JP2023153668A - Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber - Google Patents
Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber Download PDFInfo
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- JP2023153668A JP2023153668A JP2022063067A JP2022063067A JP2023153668A JP 2023153668 A JP2023153668 A JP 2023153668A JP 2022063067 A JP2022063067 A JP 2022063067A JP 2022063067 A JP2022063067 A JP 2022063067A JP 2023153668 A JP2023153668 A JP 2023153668A
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- Prior art keywords
- surface treatment
- fibers
- treatment agent
- silver
- silane coupling
- Prior art date
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- 238000000034 method Methods 0.000 title claims description 30
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- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 43
- 229910052709 silver Inorganic materials 0.000 claims abstract description 34
- 239000004332 silver Substances 0.000 claims abstract description 34
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- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 30
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- 238000006482 condensation reaction Methods 0.000 claims abstract description 22
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/58—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides
- D06M11/64—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with nitrogen or compounds thereof, e.g. with nitrides with nitrogen oxides; with oxyacids of nitrogen or their salts
- D06M11/65—Salts of oxyacids of nitrogen
-
- 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
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
- D06M13/507—Organic silicon compounds without carbon-silicon bond
-
- 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
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
本発明は繊維用表面処理剤、当該表面処理剤を用いた繊維の表面処理方法、および、当該表面処理方法により得られる皮膜を有する表面処理繊維に関する。 The present invention relates to a surface treatment agent for fibers, a method for surface treatment of fibers using the surface treatment agent, and a surface treated fiber having a film obtained by the surface treatment method.
従来、金属材料に表面処理を施す技術が種々知られている。例えば、国際公開第２０１０／０７０７２８号（特許文献１）では、耐食性、上塗り塗装性などの諸特性を有する金属材料用表面処理剤が記載されている。
当該金属材料用表面処理剤は、珪酸化合物（Ａ）と、オルガノアルコキシシラン（Ｂ）と、Ｚｒ、Ｔｉ、Ｃｏ、Ｆｅ、Ｖ、Ｃｅ、Ｍｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｎｉ、Ｃａ、Ｗ、Ｎｂ、Ｃｒ、およびＺｎからなる群から選ばれる少なくとも１種の金属元素を含む金属化合物（Ｃ）と、リン酸化合物およびフッ素化合物からなる群から選択される少なくとも１種の化合物（Ｄ）と、水（Ｅ）と、前記オルガノアルコキシシラン（Ｂ）の加水分解より生じるアルコール（Ｆ）とを含有する。
Conventionally, various techniques for surface-treating metal materials are known. For example, International Publication No. 2010/070728 (Patent Document 1) describes a surface treatment agent for metal materials having various properties such as corrosion resistance and top coatability.
The surface treatment agent for metal materials includes a silicic acid compound (A), an organoalkoxysilane (B), Zr, Ti, Co, Fe, V, Ce, Mo, Mn, Mg, Al, Ni, Ca, W, A metal compound (C) containing at least one metal element selected from the group consisting of Nb, Cr, and Zn; and at least one compound (D) selected from the group consisting of phosphoric acid compounds and fluorine compounds; It contains water (E) and alcohol (F) produced by hydrolysis of the organoalkoxysilane (B).
当該文献には、当該金属材料用表面処理剤は、前記アルコール（Ｆ）の処理剤中でのモル濃度（ｍｏｌ／Ｌ）（ＣF1）と、前記オルガノアルコキシシラン（Ｂ）に含まれるすべてのアルコキシ基が加水分解した場合に生じるアルコールの処理剤中でのモル濃度（ｍｏｌ／Ｌ）（ＣF2）との比（ＣF1／ＣF2）が０．０５～０．９の範囲に調整されることが記載されている。また、当該文献には金属材料として、建築、電気、自動車等の各種分野で使用される材料が挙げられている。 The document describes that the surface treatment agent for metal materials has a molar concentration (mol/L) (C F1 ) of the alcohol (F) in the treatment agent and all the components contained in the organoalkoxysilane (B). The ratio (C F1 /C F2 ) of the alcohol generated when the alkoxy group is hydrolyzed to the molar concentration (mol/L) (C F2 ) in the processing agent is adjusted to a range of 0.05 to 0.9. It is stated that Furthermore, this document lists materials used in various fields such as architecture, electricity, and automobiles as metal materials.
特許文献１に記載の金属材料用表面処理剤を使用することにより、耐食性、上塗り塗装性などの諸特性を有し、特に、形成された皮膜が金属材料表面との密着性に優れ、金属材料の腐食インヒビターとして働く成分を皮膜中に固定化できることが記載されている。 By using the surface treatment agent for metal materials described in Patent Document 1, it has various properties such as corrosion resistance and topcoatability, and in particular, the formed film has excellent adhesion to the surface of the metal material. It has been described that components that act as corrosion inhibitors can be immobilized in the coating.
一方で、特許文献１には繊維を表面処理することは記載されておらず、また、それによる効果も考察されていない。繊維は衣料、寝具、カーテン、衛生用品等の日用品に使用されるところ、金属材料に要求される性能とは異なる性能が求められる。例えば、今日では優れた抗菌性を有する繊維に対するニーズが増加している。 On the other hand, Patent Document 1 does not describe the surface treatment of fibers, nor does it discuss the effects thereof. Fibers are used in daily necessities such as clothing, bedding, curtains, and sanitary products, and require different performance from that of metal materials. For example, today there is an increasing need for fibers with excellent antibacterial properties.
上記事情に鑑み、本発明は一実施形態において、抗菌性および耐久性に優れ、繊維の吸水性に対する影響が少なく、繊維が変質しにくい皮膜を形成可能であり、且つ、高い液安定性を有する繊維用表面処理剤を提供することを課題とする。本発明は別の一実施形態において、当該表面処理剤を用いた繊維の表面処理方法を提供することを課題とする。本発明は更に別の一実施形態において、当該表面処理方法により得られる皮膜を有する表面処理繊維を提供することを課題とする。 In view of the above circumstances, the present invention, in one embodiment, has excellent antibacterial properties and durability, has little influence on the water absorption of fibers, can form a film that does not easily change the quality of fibers, and has high liquid stability. An object of the present invention is to provide a surface treatment agent for fibers. In another embodiment of the present invention, it is an object of the present invention to provide a method for surface treatment of fibers using the surface treatment agent. In yet another embodiment of the present invention, it is an object of the present invention to provide a surface-treated fiber having a film obtained by the surface treatment method.
本発明者らは、上記課題を解決するために鋭意検討した結果、所定のシラン化合物と、銀塩および／または銀錯体と、有機酸と、水とを所定の配合条件で配合することが、抗菌性および耐久性に優れ、繊維の吸水性に対する影響が少なく、繊維が変質しにくい皮膜を形成可能であり、且つ、高い液安定性を有する繊維用表面処理剤を得るのに有利であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors found that it is possible to blend a predetermined silane compound, a silver salt and/or a silver complex, an organic acid, and water under predetermined mixing conditions. It is advantageous for obtaining a surface treatment agent for fibers that has excellent antibacterial properties and durability, has little effect on the water absorption of fibers, can form a film that prevents fibers from deteriorating, and has high liquid stability. They discovered this and completed the present invention.
本発明は例示的に以下のように特定される。
［１］
テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の加水分解物および／または縮合反応物であるシラン化合物（Ａ）と、
銀塩および／または銀錯体（Ｂ）と、
カルボキシル基を２個以上有する有機酸（Ｃ）と、
水（Ｅ）と、を含み、
以下の１）および２）の配合条件を満足するように調製した繊維用表面処理剤。
１）前記銀塩および／または銀錯体（Ｂ）に対する前記テトラアルコキシシラン（Ａ１）と前記シランカップリング剤（Ａ２）の合計（Ａ１＋Ａ２）のモル比｛（Ａ１＋Ａ２）／Ｂ｝が１００～５００。
２）前記銀塩および／または銀錯体（Ｂ）に対する前記有機酸（Ｃ）のカルボキシル基のモル比（Ｃ／Ｂ）が５～２５。
［２］
前記シラン化合物（Ａ）として、前記テトラアルコキシシラン（Ａ１）と前記シランカップリング剤（Ａ２）の少なくとも一方の加水分解物であるアルコール（Ｄ）を含み、
前記テトラアルコキシシラン（Ａ１）と前記シランカップリング剤（Ａ２）に含まれるすべてのアルコキシ基が加水分解したと仮定した場合に生じるアルコールの前記表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄβ）に対する、前記アルコール（Ｄ）の実際の前記表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄα）の比（Ｄα／Ｄβ）が０．０５～０．９である［１］に記載の繊維用表面処理剤。
［３］
［１］または［２］に記載の繊維用表面処理剤を繊維の一部または全部と接触させて、皮膜を形成することを含む、繊維の表面処理方法。
［４］
［３］に記載の表面処理方法により得られる、皮膜を有する表面処理繊維。
The invention is exemplarily specified as follows.
[1]
A silane compound (A) which is a hydrolyzate and/or a condensation reaction product of a tetraalkoxysilane (A1) and a silane coupling agent (A2);
A silver salt and/or a silver complex (B),
an organic acid (C) having two or more carboxyl groups;
including water (E),
A surface treatment agent for fibers prepared to satisfy the following blending conditions 1) and 2).
1) The molar ratio {(A1+A2)/B} of the total (A1+A2) of the tetraalkoxysilane (A1) and the silane coupling agent (A2) to the silver salt and/or silver complex (B) is 100 to 500.
2) The molar ratio (C/B) of the carboxyl group of the organic acid (C) to the silver salt and/or silver complex (B) is 5 to 25.
[2]
The silane compound (A) contains an alcohol (D) that is a hydrolyzate of at least one of the tetraalkoxysilane (A1) and the silane coupling agent (A2),
Assuming that all the alkoxy groups contained in the tetraalkoxysilane (A1) and the silane coupling agent (A2) are hydrolyzed, the molar concentration (mol/L) of alcohol in the surface treatment agent ( In [1], the ratio (Dα/Dβ) of the actual molar concentration (mol/L) (Dα) of the alcohol (D) in the surface treatment agent to Dβ) is 0.05 to 0.9. The surface treatment agent for fibers described above.
[3]
A method for surface treatment of fibers, comprising bringing the surface treatment agent for fibers according to [1] or [2] into contact with some or all of the fibers to form a film.
[4]
A surface-treated fiber having a film obtained by the surface treatment method described in [3].
本発明の一実施形態によれば、抗菌性および耐久性に優れ、繊維の吸水性に対する影響が少なく、繊維が変質しにくい皮膜を形成可能であり、且つ、高い液安定性を有する繊維用表面処理剤を提供することができるという格別の効果が得られる。従って、本発明は、例えば衣料、衛生用品等の日用品に使用される各種繊維の抗菌用途に好適に利用することができる。 According to an embodiment of the present invention, a fiber surface is provided that has excellent antibacterial properties and durability, has little influence on the water absorption of fibers, can form a film that does not easily deteriorate fibers, and has high liquid stability. The special effect of being able to provide a processing agent is obtained. Therefore, the present invention can be suitably used for antibacterial purposes for various fibers used in daily necessities such as clothing and sanitary products.
以下、表面処理剤、表面処理方法および表面処理繊維を含む本発明の実施形態について詳細に説明する。なお、本発明は、その本発明の趣旨から逸脱しない範囲で任意に変更可能であり、下記の実施形態に限定されない。尚、本明細書にて数値範囲を示す「～」は上限値および下限値も包含する。例えば、「Ｘ～Ｙ」はＸ以上Ｙ以下であることを意味する。 Hereinafter, embodiments of the present invention including a surface treatment agent, a surface treatment method, and a surface treated fiber will be described in detail. Note that the present invention can be modified as desired without departing from the spirit of the present invention, and is not limited to the embodiments described below. Incidentally, in this specification, "~" indicating a numerical range includes the upper limit value and the lower limit value. For example, "X~Y" means greater than or equal to X and less than or equal to Y.
＜１．表面処理剤＞
本発明の一実施形態によれば、
テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の加水分解物および／または縮合反応物であるシラン化合物（Ａ）と、
銀塩および／または銀錯体（Ｂ）と、
カルボキシル基を２個以上有する有機酸（Ｃ）と、
水（Ｅ）と、
を含有する繊維用表面処理剤が提供される。
<1. Surface treatment agent>
According to one embodiment of the invention:
A silane compound (A) which is a hydrolyzate and/or a condensation reaction product of a tetraalkoxysilane (A1) and a silane coupling agent (A2);
A silver salt and/or a silver complex (B),
an organic acid (C) having two or more carboxyl groups;
Water (E) and
A surface treatment agent for fibers containing the following is provided.
［１－１．シラン化合物（Ａ）］
当該表面処理剤は、シラン化合物（Ａ）としてテトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の両方に由来する加水分解物および／または縮合反応物を含有する。テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）はそれぞれ一種を単独で使用してもよいし、二種以上を組み合わせて使用してもよい。
[1-1. Silane compound (A)]
The surface treatment agent contains, as the silane compound (A), a hydrolyzate and/or a condensation reaction product derived from both the tetraalkoxysilane (A1) and the silane coupling agent (A2). The tetraalkoxysilane (A1) and the silane coupling agent (A2) may each be used singly or in combination of two or more.
テトラアルコキシシラン（Ａ１）は、Ｓｉ（ＯＲ）4（式中、Ｒはアルキル基を表す。）の一般式で表され、Ｒは炭素数が１～４のアルキル基であることが好ましく、炭素数が１～３のアルキル基であることがより好ましく、炭素数が１～２のアルキル基であることが更により好ましい。テトラアルコキシシラン（Ａ１）の具体例としては、テトラエトキシシラン、テトラメトキシシラン、テトラノルマルプロポキシシランなどが挙げられ、中でもテトラエトキシシランが好ましい。 Tetraalkoxysilane (A1) is represented by the general formula of Si(OR) 4 (in the formula, R represents an alkyl group), R is preferably an alkyl group having 1 to 4 carbon atoms, and R is preferably an alkyl group having 1 to 4 carbon atoms. An alkyl group having 1 to 3 carbon atoms is more preferable, and an alkyl group having 1 to 2 carbon atoms is even more preferable. Specific examples of the tetraalkoxysilane (A1) include tetraethoxysilane, tetramethoxysilane, tetranormalpropoxysilane, and the like, with tetraethoxysilane being preferred.
シランカップリング剤（Ａ２）は、加水分解性基および有機官能基を有する有機ケイ素化合物である。加水分解性基としては、例えば、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、２－メトキシエトキシ基等の炭素数１～４（特に、１または２）のアルコキシ基などが例示できる。有機官能基としては、例えば、ビニル基、エポキシ基（特にグリシドキシ基）、スチリル基、メタクリル基、アクリル基、アミノ基、イソシアネート基、イソシアヌレート基、ウレイド基、メルカプト基、酸無水物基などが例示できる。これらの中でも、加水分解性基としてアルコキシ基、有機官能基としてエポキシ基および／またはアミノ基を有するシランカップリング剤が好ましい。有機官能基としては、グリシドキシ基および／またはアミノ基がより好ましい。グリシドキシ基を有するシランカップリング剤とアミノ基を有するシランカップリング剤を併用することが更により好ましい。グリシドキシ基を有するシランカップリング剤とアミノ基を有するシランカップリング剤を併用する場合は、グリシドキシ基を有するシランカップリング剤：アミノ基を有するシランカップリング剤＝１０：１～１：１のモル比とすることが好ましく、５：１～２：１のモル比とすることがより好ましい。更に、シランカップリング剤（Ａ２）は、アルコキシ基を分子中に３個有し、有機官能基を１個有するトリアルコキシシラン化合物を使用することがより好ましい。 The silane coupling agent (A2) is an organosilicon compound having a hydrolyzable group and an organic functional group. Examples of the hydrolyzable group include alkoxy groups having 1 to 4 carbon atoms (especially 1 or 2 carbon atoms) such as methoxy group, ethoxy group, propoxy group, butoxy group, and 2-methoxyethoxy group. Examples of organic functional groups include vinyl groups, epoxy groups (especially glycidoxy groups), styryl groups, methacrylic groups, acrylic groups, amino groups, isocyanate groups, isocyanurate groups, ureido groups, mercapto groups, and acid anhydride groups. I can give an example. Among these, silane coupling agents having an alkoxy group as a hydrolyzable group and an epoxy group and/or an amino group as an organic functional group are preferred. As the organic functional group, a glycidoxy group and/or an amino group are more preferred. It is even more preferable to use a silane coupling agent having a glycidoxy group and a silane coupling agent having an amino group in combination. When a silane coupling agent having a glycidoxy group and a silane coupling agent having an amino group are used together, the silane coupling agent having a glycidoxy group: the silane coupling agent having an amino group = 10:1 to 1:1 molar ratio. A molar ratio of 5:1 to 2:1 is preferred, and a molar ratio of 5:1 to 2:1 is more preferred. Furthermore, as the silane coupling agent (A2), it is more preferable to use a trialkoxysilane compound having three alkoxy groups and one organic functional group in the molecule.
シランカップリング剤（Ａ２）の好ましい実施形態の一つとして、一般式（Ｉ）：（Ｙ）3－Ｓｉ－Ｌ－Ｘで表される化合物が挙げられる。 One of the preferred embodiments of the silane coupling agent (A2) is a compound represented by the general formula (I): (Y) 3 -Si-L-X.
一般式（Ｉ）中、Ｘは、エポキシ基、アミノ基、メルカプト基、ビニル基、およびイソシアネート基から選択されるいずれかの官能基を表し、エポキシ基またはアミノ基が好ましい。 In the general formula (I), X represents any functional group selected from an epoxy group, an amino group, a mercapto group, a vinyl group, and an isocyanate group, and an epoxy group or an amino group is preferable.
一般式（Ｉ）中、Ｌは、２価の連結基、または単なる結合手を表す。Ｌで表される連結基としては、例えば、アルキレン基（炭素数１～２０が好ましい）、－Ｏ－、－Ｓ－、アリーレン基、－ＣＯ－、－ＮＨ－、－ＳＯ2－、－ＣＯＯ－、－ＣＯＮＨ－、またはこれらを二種以上組み合わせた基が挙げられる。単なる結合手の場合、一般式（Ｉ）のＸがＳｉ（ケイ素原子）と直接連結することを指す。 In general formula (I), L represents a divalent linking group or a simple bond. Examples of the linking group represented by L include alkylene group (preferably 1 to 20 carbon atoms), -O-, -S-, arylene group, -CO-, -NH-, -SO 2 -, -COO -, -CONH-, or a combination of two or more thereof. In the case of a simple bond, it means that X in general formula (I) is directly connected to Si (silicon atom).
一般式（Ｉ）中、Ｙは、それぞれ独立に、アルコキシ基を表す。なかでも、炭素数１～３のアルコキシ基が好ましい。 In general formula (I), Y each independently represents an alkoxy group. Among these, an alkoxy group having 1 to 3 carbon atoms is preferred.
シランカップリング剤（Ａ２）の具体例としては、３－グリシドキシプロピルトリメトキシシラン、および３－グリシドキシプロピルメチルジメトキシシランなどのエポキシシラン、Ｎ－（２－アミノエチル）３－アミノプロピルメチルジメトキシシラン、Ｎ－（アミノエチル）３－アミノプロピルトリメトキシシラン、および３－アミノプロピルトリエトキシシランなどのアミノシラン、３－メルカプトプロピルトリメトキシシランおよび３－メルカプトプロピルトリエトキシシランなどのメルカプトシラン、３－イソシアネートプロピルトリメトキシシラン、３－イソシアネートプロピルトリエトキシシランなどのイソシアネートシラン、ビニルトリエトキシシラン、ｐ－スチリルトリメトキシシランなどのビニル基含有シランなどが挙げられる。 Specific examples of the silane coupling agent (A2) include epoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropyl aminosilanes such as methyldimethoxysilane, N-(aminoethyl)3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane; mercaptosilanes such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; Examples include isocyanate silanes such as 3-isocyanatepropyltrimethoxysilane and 3-isocyanatepropyltriethoxysilane, and vinyl group-containing silanes such as vinyltriethoxysilane and p-styryltrimethoxysilane.
テトラアルコキシシラン（Ａ１）は加水分解すると、式Ａで表される反応式に従って、シラノール（Ｓｉ（ＯＲ）4-n（ＯＨ）n）およびアルコール（ＲＯＨ）の加水分解物が生成する。
式Ａ：Ｓｉ（ＯＲ）4＋ｎＨ2Ｏ→Ｓｉ（ＯＲ）4-n（ＯＨ）n＋ｎＲＯＨ（式中、ｎは１～４の整数）
シランカップリング剤（Ａ２）は加水分解すると、シランカップリング剤が有する加水分解性基に応じた加水分解物が生成する。加水分解性基がアルコキシ基である場合には、シラノールおよびアルコールの加水分解物が生成する。
当該表面処理剤中では加水分解によって生成したシラノールおよび／またはアルコール同士が水素結合している場合があるが、本明細書においてはそのようなものも加水分解物として取り扱う。
When tetraalkoxysilane (A1) is hydrolyzed, a hydrolyzate of silanol (Si(OR) 4-n (OH) n ) and alcohol (ROH) is produced according to the reaction formula represented by formula A.
Formula A: Si(OR) 4 +nH 2 O→Si(OR) 4-n (OH) n +nROH (in the formula, n is an integer from 1 to 4)
When the silane coupling agent (A2) is hydrolyzed, a hydrolyzate corresponding to the hydrolyzable group possessed by the silane coupling agent is generated. When the hydrolyzable group is an alkoxy group, a hydrolyzate of silanol and alcohol is produced.
In the surface treatment agent, silanols and/or alcohols generated by hydrolysis may form hydrogen bonds with each other, and in this specification, such substances are also treated as hydrolysates.
従って、当該表面処理剤は一実施形態において、シラン化合物（Ａ）として、テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の少なくとも一方の加水分解物であるアルコール（Ｄ）を含み、典型的には両者の加水分解物であるアルコール（Ｄ）を含む。そして、当該表面処理剤は好ましい実施形態において、テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）に含まれるすべてのアルコキシ基が加水分解したと仮定した場合に生じるアルコールの当該表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄβ）に対する、前記アルコール（Ｄ）の実際の当該表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄα）の比（Ｄα／Ｄβ）が０．０５～０．９である。Ｄα／Ｄβの下限は、より好ましくは０．３以上であり、更により好ましくは０．５以上である。Ｄα／Ｄβの上限は、より好ましくは０．８５以下であり、更により好ましくは０．８以下である。 Therefore, in one embodiment, the surface treatment agent contains alcohol (D), which is a hydrolyzate of at least one of tetraalkoxysilane (A1) and silane coupling agent (A2), as the silane compound (A), and Specifically, it contains alcohol (D), which is a hydrolyzate of both. In a preferred embodiment, the surface treatment agent contains alcohol generated when all the alkoxy groups contained in the tetraalkoxysilane (A1) and the silane coupling agent (A2) are hydrolyzed. The ratio (Dα/Dβ) of the actual molar concentration (mol/L) (Dα) of the alcohol (D) in the surface treatment agent to the molar concentration (mol/L) (Dβ) in the surface treatment agent is 0.05. ~0.9. The lower limit of Dα/Dβ is more preferably 0.3 or more, and even more preferably 0.5 or more. The upper limit of Dα/Dβ is more preferably 0.85 or less, and even more preferably 0.8 or less.
テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）に含まれるすべてのアルコキシ基が加水分解したと仮定した場合に生じるアルコールの当該表面処理剤中でのモル濃度（Ｄβ）は、Ａ１総モル濃度の４倍＋（Ａ２の総モル濃度）×（Ａ２の一分子に含まれるアルコキシ基の数）によって計算する。 Assuming that all the alkoxy groups contained in the tetraalkoxysilane (A1) and the silane coupling agent (A2) are hydrolyzed, the molar concentration (Dβ) of alcohol in the surface treatment agent that is generated is equal to the total mole of A1. Calculated by 4 times the concentration + (total molar concentration of A2) × (number of alkoxy groups contained in one molecule of A2).
アルコール（Ｄ）の当該表面処理剤中でのモル濃度（Ｄα）の測定は、以下の方法により行う。ＮＭＲ装置（例：ＪＮＭ－ＦＣＸ４００：日本電子株式会社製）を用いて、当該表面処理剤中のアルコール（Ｄ）に帰属するプロトンの積分値を既知モル濃度のプロトンの積分値と比較することで算出する。定量の方法としては、内部標準法を採用する。 The molar concentration (Dα) of alcohol (D) in the surface treatment agent is measured by the following method. By comparing the integral value of protons belonging to alcohol (D) in the surface treatment agent with the integral value of protons at a known molar concentration using an NMR device (e.g. JNM-FCX400: manufactured by JEOL Ltd.) calculate. The internal standard method is used as the quantitative method.
また、当該表面処理剤には、加水分解によって生成した一部のシラノールが脱水縮合反応することによって、シロキサン結合（Ｓｉ－Ｏ－Ｓｉ）を有する縮合反応物（オルガノシロキサン）を含有している場合もある。縮合反応物には、（１）テトラアルコキシシラン（Ａ１）が加水分解することで生成したシラノール同士が脱水縮合反応することによって生じた縮合反応物、（２）シランカップリング剤（Ａ２）が加水分解することで生成したシラノール同士が脱水縮合反応することによって生じた縮合反応物、（３）テトラアルコキシシラン（Ａ１）が加水分解することで生成したシラノールと、シランカップリング剤（Ａ２）が加水分解することで生成したシラノールが脱水縮合反応することによって生じた縮合反応物が挙げられる。これらは単独でまたは二種以上が組み合わさって重縮合し得る。 In addition, if the surface treatment agent contains a condensation reaction product (organosiloxane) having a siloxane bond (Si-O-Si) due to a dehydration condensation reaction of some silanols generated by hydrolysis. There is also. The condensation reaction product includes (1) a condensation reaction product produced by a dehydration condensation reaction between silanols produced by hydrolysis of the tetraalkoxysilane (A1), and (2) a silane coupling agent (A2) hydrated. A condensation reaction product produced by dehydration condensation reaction between silanols produced by decomposition, (3) silanol produced by hydrolysis of tetraalkoxysilane (A1) and silane coupling agent (A2) are hydrated. Examples include condensation reaction products produced by a dehydration condensation reaction of silanol produced by decomposition. These may be polycondensed alone or in combination of two or more.
当該表面処理剤は、液状で提供されるため、固相を形成するほどには脱水縮合は進展させないのが望ましいと考えられるが、ある程度の脱水縮合を起こさせておくことが好ましい。例えば、ＧＰＣ法による以下の測定方法で当該表面処理剤中の縮合反応物の重量平均分子量を測定したときに、１００～５０００の範囲であるのが好ましく、１５０～３０００の範囲であるのがより好ましい。
＜重量平均分子量の測定方法＞
高速ＧＰＣ装置（ＨＬＣ－８３２０ＧＰＣ：東ソー株式会社製）を用いて測定し、ＳＥＣカラム及びガードカラムの組み合わせにて重量平均分子量を求める。測定条件は以下とする。
ＳＥＣカラム：ＴＳＫｇｅｌ ＳｕｐｅｒＡＷＭ－Ｈ（東ソー株式会社製）
ガードカラム：ＴＳＫｇｕｒｄｃｏｌｕｍｎ ＳｕｐｅｒＡＷ－Ｈ（東ソー株式会社製）
検出器：ＲＩ（ＨＬＣ－８３２０ＧＰＣ内蔵検出器）
標準試料：ポリスチレン
試料注入量：０．０６％ＤＭＦ溶液３０μＬ
流速：０．５ｍＬ／ｍｉｎ
溶離液：ＤＭＦ／１００ｍＭ ＬｉＢｒ／６０ｍＭ Ｈ3ＰＯ4
Since the surface treatment agent is provided in liquid form, it is considered desirable that the dehydration condensation does not proceed to the extent that a solid phase is formed, but it is preferable to allow the dehydration condensation to occur to some extent. For example, when the weight average molecular weight of the condensation reaction product in the surface treatment agent is measured using the following measurement method using GPC method, it is preferably in the range of 100 to 5,000, and more preferably in the range of 150 to 3,000. preferable.
<Method for measuring weight average molecular weight>
Measurement is performed using a high-speed GPC device (HLC-8320GPC: manufactured by Tosoh Corporation), and the weight average molecular weight is determined using a combination of an SEC column and a guard column. The measurement conditions are as follows.
SEC column: TSKgel SuperAWM-H (manufactured by Tosoh Corporation)
Guard column: TSK guardcolumn SuperAW-H (manufactured by Tosoh Corporation)
Detector: RI (HLC-8320GPC built-in detector)
Standard sample: polystyrene Sample injection amount: 30 μL of 0.06% DMF solution
Flow rate: 0.5mL/min
Eluent: DMF/100mM LiBr/ 60mM H3PO4
［１－２．銀塩および／または銀錯体（Ｂ）］
銀塩および／または銀錯体（Ｂ）は、抗菌性能を発揮する成分である。銀塩および／または銀錯体（Ｂ）としては、例えば、カルボン酸銀、硝酸銀、炭酸銀、硫酸銀、過塩素酸銀、フッ化銀、塩化銀、塩素酸銀、クロム酸銀、シアン化銀、臭化銀、臭素酸銀、ヨウ化銀、ヨウ素酸銀等が挙げられる。好ましくは、カルボン酸の銀塩または銀錯体である。上記以外の銀塩および／または銀錯体（Ｂ）の例には、アミノ酸およびその誘導体、カルボン酸型又はホスホン酸型のキレート剤、チオールのような活性化硫黄、アミン類、窒素含有複素環類、グアニジン、スルホン酸、リン酸などの活性部位を持つ物質と銀との化合物が挙げられる。これらの化合物には、水和物も含まれる。これらは一種単独で使用してもよく、二種以上併用してもよい。
[1-2. Silver salt and/or silver complex (B)]
The silver salt and/or silver complex (B) is a component that exhibits antibacterial performance. Examples of the silver salt and/or silver complex (B) include silver carboxylate, silver nitrate, silver carbonate, silver sulfate, silver perchlorate, silver fluoride, silver chloride, silver chlorate, silver chromate, and silver cyanide. , silver bromide, silver bromate, silver iodide, silver iodate, and the like. Preferably, it is a silver salt or a silver complex of carboxylic acid. Examples of silver salts and/or silver complexes (B) other than those mentioned above include amino acids and their derivatives, carboxylic acid type or phosphonic acid type chelating agents, activated sulfur such as thiols, amines, nitrogen-containing heterocycles. Examples include compounds of silver and substances with active sites such as guanidine, sulfonic acid, and phosphoric acid. These compounds also include hydrates. These may be used alone or in combination of two or more.
［１－３．カルボキシル基を２個以上有する有機酸（Ｃ）］
理論によって本発明が限定されることを意図しないが、カルボキシル基を２個以上有する有機酸（Ｃ）は、表面処理剤中で銀イオンの安定性を向上する作用があると考えられる。中でも、カルボキシル基を２個以上有するヒドロキシ酸が好ましく、カルボキシル基を偶数個有するヒドロキシ酸がより好ましく、カルボキシル基を２個有するヒドロキシ酸が更により好ましい。有機酸（Ｃ）としては、例えば、酒石酸、リンゴ酸、クエン酸、コハク酸、マロン酸、シュウ酸、アジピン酸、フタル酸、イソフタル酸、マレイン酸、フマル酸、アスパラギン酸、グルタミン酸、ポリアクリル酸およびポリマレイン酸等が挙げられ、これらの中ではヒドロキシ酸である酒石酸、リンゴ酸およびクエン酸が好ましく、カルボキシル基を２個有するヒドロキシ酸である酒石酸およびリンゴ酸がより好ましい。有機酸（Ｃ）は一種を単独で使用してもよいし、二種以上を組み合わせて使用してもよい。
[1-3. Organic acid (C) having two or more carboxyl groups]
Although the present invention is not intended to be limited by theory, it is believed that the organic acid (C) having two or more carboxyl groups has the effect of improving the stability of silver ions in the surface treatment agent. Among these, hydroxy acids having two or more carboxyl groups are preferred, hydroxy acids having an even number of carboxyl groups are more preferred, and hydroxy acids having two carboxyl groups are even more preferred. Examples of the organic acid (C) include tartaric acid, malic acid, citric acid, succinic acid, malonic acid, oxalic acid, adipic acid, phthalic acid, isophthalic acid, maleic acid, fumaric acid, aspartic acid, glutamic acid, and polyacrylic acid. and polymaleic acid, among which hydroxy acids tartaric acid, malic acid, and citric acid are preferred, and hydroxy acids having two carboxyl groups tartaric acid and malic acid are more preferred. The organic acids (C) may be used alone or in combination of two or more.
［１－４．水（Ｅ）］
当該表面処理剤は溶媒として水を含有する。意図せず混入した物質による影響を避けるという観点から、水としては脱イオン水を用いることが好ましい。水の含有量は、表面処理剤全量に対して、７０～９９．９質量％が好ましく、９５～９９．５質量％がより好ましい。
[1-4. Water (E)]
The surface treatment agent contains water as a solvent. From the viewpoint of avoiding the influence of unintentionally mixed substances, it is preferable to use deionized water as the water. The content of water is preferably 70 to 99.9% by mass, more preferably 95 to 99.5% by mass, based on the total amount of the surface treatment agent.
［１－５．シラン化合物（Ａ）、銀塩および／または銀錯体（Ｂ）、並びに有機酸（Ｃ）の配合条件］
当該表面処理剤は、以下の１）および２）の配合条件を満足するように調製することが望ましい。
１）銀塩および／または銀錯体（Ｂ）に対するテトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の合計（Ａ１＋Ａ２）のモル比｛（Ａ１＋Ａ２）／Ｂ｝が１００～５００。
２）銀塩および／または銀錯体（Ｂ）に対する有機酸（Ｃ）のカルボキシル基のモル比（Ｃ／Ｂ）が５～２５。
[1-5. Blending conditions of silane compound (A), silver salt and/or silver complex (B), and organic acid (C)]
It is desirable that the surface treatment agent be prepared so as to satisfy the following formulation conditions 1) and 2).
1) The molar ratio {(A1+A2)/B} of the total (A1+A2) of the tetraalkoxysilane (A1) and the silane coupling agent (A2) to the silver salt and/or silver complex (B) is 100 to 500.
2) The molar ratio (C/B) of the carboxyl group of the organic acid (C) to the silver salt and/or silver complex (B) is 5 to 25.
（Ａ１＋Ａ２）／Ｂの下限は、１００以上であることが好ましく、２００以上であることがより好ましく、２５０以上であることが更により好ましい。（Ａ１＋Ａ２）／Ｂの上限は、５００以下であることが好ましく、４００以下であることがより好ましく、３００以下であることが更により好ましい。 The lower limit of (A1+A2)/B is preferably 100 or more, more preferably 200 or more, and even more preferably 250 or more. The upper limit of (A1+A2)/B is preferably 500 or less, more preferably 400 or less, and even more preferably 300 or less.
Ｃ／Ｂの下限は、５以上であることが好ましく、７以上であることがより好ましく、１０以上であることが更により好ましい。Ｃ／Ｂの上限は、２５以下であることが好ましく、２０以下であることがより好ましく、１５以下であることが更により好ましい。 The lower limit of C/B is preferably 5 or more, more preferably 7 or more, and even more preferably 10 or more. The upper limit of C/B is preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less.
また、Ａ１およびＡ２は、Ａ２に対するＡ１のモル比（Ａ１／Ａ２）が０．３０～３．００となるように配合することが好ましく、０．５０～２．００となるように配合することがより好ましく、０．７０～１．５０となるように配合することが更により好ましい。 Further, A1 and A2 are preferably blended so that the molar ratio of A1 to A2 (A1/A2) is 0.30 to 3.00, and preferably 0.50 to 2.00. is more preferable, and even more preferably blended so that the ratio is 0.70 to 1.50.
上記配合条件は、当該表面処理剤を調製するために各成分を配合する時の条件であって、当該表面処理剤に実際に存在する割合とは異なると考えられる。特に、テトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）は当該表面処理剤中で大部分は加水分解しており、更に加水分解物の一部は脱水縮合しているところ、当該表面処理剤における成分を正確に分析することは困難であるため、原料の配合条件によって当該表面処理剤を規定している。 The above blending conditions are conditions when blending each component to prepare the surface treatment agent, and are considered to be different from the proportions actually present in the surface treatment agent. In particular, most of the tetraalkoxysilane (A1) and the silane coupling agent (A2) are hydrolyzed in the surface treatment agent, and a part of the hydrolyzate is further dehydrated and condensed. Since it is difficult to accurately analyze the components in a surface treatment agent, the surface treatment agent is defined by the blending conditions of the raw materials.
当該表面処理剤は、潤滑剤、界面活性剤、顔料、染料、耐食性付与のためのインヒビター、造膜助剤、導電性向上剤、増粘剤、水系樹脂（水溶性樹脂、水分散性樹脂またはエマルジョン型樹脂）等の各種添加剤を必要に応じて含有することができる。但し、これらの各種添加剤の合計質量は、本発明が企図する所望の効果を発揮する観点から、当該表面処理剤を調製するために配合するＡ１、Ａ２、ＢおよびＣの合計質量に対して２０質量％以下であることが好ましく、１０質量％以下であることがより好ましく、例えば、０～５質量％であることが更により好ましい。 The surface treatment agents include lubricants, surfactants, pigments, dyes, inhibitors for imparting corrosion resistance, film forming aids, conductivity improvers, thickeners, water-based resins (water-soluble resins, water-dispersible resins, or water-based resins). Various additives such as emulsion type resin) can be contained as necessary. However, the total mass of these various additives is based on the total mass of A1, A2, B, and C blended to prepare the surface treatment agent, from the viewpoint of exhibiting the desired effect contemplated by the present invention. It is preferably at most 20% by mass, more preferably at most 10% by mass, and even more preferably from 0 to 5% by mass.
当該表面処理剤は、水混和性溶媒を含有してもよい。水混和性溶媒としては、水と混合した後、相分離しないものであれば特に限定されるものではない。 The surface treatment agent may contain a water-miscible solvent. The water-miscible solvent is not particularly limited as long as it does not phase separate after being mixed with water.
［１－６．製法］
当該表面処理剤は、例えば、シラン化合物（Ａ）と、銀塩および／または銀錯体（Ｂ）と、有機酸（Ｃ）と、水（Ｅ）と、必要に応じてその他の成分とを、所望の割合で配合し、撹拌することで調製可能である。また、シラン化合物（Ａ）に含まれる縮合反応物の重量平均分子量を好適な範囲に制御する上では、予めテトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の脱水縮合反応をある程度進行させておくことが好ましい。脱水縮合反応を進行させるためには加熱が有効である。加熱時の液温は６０～９０℃が好ましく、７０～８０℃がより好ましい。加熱時間は３０～１２０分が好ましく、６０～９０分がより好ましい。
[1-6. Manufacturing method]
The surface treatment agent includes, for example, a silane compound (A), a silver salt and/or a silver complex (B), an organic acid (C), water (E), and other components as necessary. It can be prepared by blending in a desired ratio and stirring. In addition, in order to control the weight average molecular weight of the condensation reaction product contained in the silane compound (A) within a suitable range, it is necessary to advance the dehydration condensation reaction between the tetraalkoxysilane (A1) and the silane coupling agent (A2) to some extent in advance. It is preferable to keep it. Heating is effective for advancing the dehydration condensation reaction. The liquid temperature during heating is preferably 60 to 90°C, more preferably 70 to 80°C. The heating time is preferably 30 to 120 minutes, more preferably 60 to 90 minutes.
＜２．表面処理方法および表面処理繊維＞
本発明の一実施形態によれば、当該表面処理剤を繊維の一部または全部と接触させて、皮膜を形成することを含む、繊維の表面処理方法が提供される。また、本発明の一実施形態によれば、当該表面処理方法により得られる、皮膜を有する表面処理繊維が提供される。当該皮膜は抗菌性および耐久性に優れ、繊維の吸水性に対する影響が少なく、繊維が変質しにくい。このため、当該皮膜を有する表面処理繊維は、衣料、ネクタイ、エプロン、水着、スポーツウェア、手袋、帽子、靴、作業服、事務服、織物、寝具、マットレス、カーテン、衛生用品、壁紙、絨毯、カーペット、床敷物、障子、紙、木材、ソファー、椅子、ハンカチ、タオル、クッション、かばん、フィルター、い草、革、風呂敷、おむつ等の繊維製品に使用される各種繊維として好適に使用可能である。
<2. Surface treatment method and surface treated fiber>
According to one embodiment of the present invention, there is provided a method for surface treatment of fibers, which includes bringing the surface treatment agent into contact with some or all of the fibers to form a film. Moreover, according to one embodiment of the present invention, there is provided a surface-treated fiber having a film obtained by the surface treatment method. The film has excellent antibacterial properties and durability, has little effect on the water absorption of the fibers, and is resistant to deterioration of the fibers. Therefore, surface-treated fibers with the film can be used for clothing, ties, aprons, swimwear, sportswear, gloves, hats, shoes, work clothes, office clothes, textiles, bedding, mattresses, curtains, sanitary products, wallpaper, carpets, It can be suitably used as various fibers used in textile products such as carpets, floor coverings, shoji screens, paper, wood, sofas, chairs, handkerchiefs, towels, cushions, bags, filters, rushes, leather, furoshiki, and diapers.
［２－１．繊維］
繊維としては、限定的ではないが、アクリル、レーヨン、ポリエステル、ポリプロピレン、ポリエチレン、ポリアミド（ナイロン）、ビニロン、ポリウレタン、ポリ塩化ビニリデン、ポリアクリロニトリル、アセテート、キュプラ、ポリ塩化ビニル、フッ素樹脂、液晶ポリマー、アラミド、セルロース、羊毛、絹、麻および綿等を紡績して得られる有機繊維が代表的である。また、ガラス繊維、人造鉱物繊維、鉱物繊維、炭素繊維およびセラミックス繊維等の無機繊維も使用可能である。但し、金属繊維は本発明において「繊維」とは取り扱わない。
[2-1. fiber]
Examples of fibers include, but are not limited to, acrylic, rayon, polyester, polypropylene, polyethylene, polyamide (nylon), vinylon, polyurethane, polyvinylidene chloride, polyacrylonitrile, acetate, cupro, polyvinyl chloride, fluororesin, liquid crystal polymer, Typical examples are organic fibers obtained by spinning aramid, cellulose, wool, silk, linen, cotton, etc. Inorganic fibers such as glass fibers, artificial mineral fibers, mineral fibers, carbon fibers, and ceramic fibers can also be used. However, metal fibers are not treated as "fibers" in the present invention.
［２－２．表面処理］
当該表面処理剤を繊維の一部または全部と接触させる方法としては、特に制限されるものではないが、例えば、浸漬法、スプレー法、ロールコート法、刷毛塗り等が挙げられる。このときの表面処理剤温度は１０～６０℃が好ましく、１５～５０℃がより好ましく、２５～４０℃が更により好ましい。接触時間は１秒～５分が好ましく、３０秒～２分がより好ましい。
[2-2. surface treatment]
The method of bringing the surface treatment agent into contact with some or all of the fibers is not particularly limited, and examples thereof include dipping, spraying, roll coating, brush coating, and the like. The temperature of the surface treatment agent at this time is preferably 10 to 60°C, more preferably 15 to 50°C, and even more preferably 25 to 40°C. The contact time is preferably 1 second to 5 minutes, more preferably 30 seconds to 2 minutes.
当該表面処理剤を繊維に接触させた後、当該表面処理剤を乾燥させることで溶媒が気化し、皮膜が形成される。乾燥方法としては、表面処理剤中の溶媒が気化すれば特に制限されない。例示的には、公知の乾燥機器、例えば、オーブン、バッチ式の乾燥炉、連続式の熱風循環式乾燥炉、コンベアー式の熱風乾燥炉、ＩＨヒーターを用いた電磁誘導加熱炉等を用いた乾燥方法等が挙げられる。乾燥温度は４０～２００℃とすることができ、好ましくは６０～１５０℃であり、より好ましくは８０～１２０℃である。（Ａ１）と（Ａ２）の脱水縮合反応を促進する上では、乾燥温度は１００℃以上が最も好ましいが、繊維の耐熱性との兼ね合いで乾燥温度は決定される。乾燥時間は１分～１２０分とすることができ、好ましくは２分～６０分とすることができる。 After bringing the surface treatment agent into contact with the fibers, the surface treatment agent is dried to vaporize the solvent and form a film. The drying method is not particularly limited as long as the solvent in the surface treatment agent is vaporized. For example, drying using a known drying device such as an oven, a batch type drying furnace, a continuous hot air circulation drying furnace, a conveyor type hot air drying furnace, an electromagnetic induction heating furnace using an IH heater, etc. Examples include methods. The drying temperature can be 40-200°C, preferably 60-150°C, more preferably 80-120°C. In order to promote the dehydration condensation reaction of (A1) and (A2), the drying temperature is most preferably 100°C or higher, but the drying temperature is determined in consideration of the heat resistance of the fiber. The drying time can be from 1 minute to 120 minutes, preferably from 2 minutes to 60 minutes.
乾燥工程により、当該表面処理剤中のシラン化合物（Ａ）は、脱水縮合反応が進行し、皮膜中のケイ素原子は主にシロキサン結合（Ｓｉ－Ｏ－Ｓｉ）を有する縮合反応物（オルガノシロキサン）を構成していると考えられ、典型的には、皮膜中のケイ素原子は重縮合によってオルガノポリシロキサンを構成していると考えられる。また、皮膜中のシロキサン結合（Ｓｉ－Ｏ－Ｓｉ）を有する縮合反応物は銀塩および／または銀錯体（Ｂ）と、カルボキシル基を２個以上有する有機酸（Ｃ）を安定的に保持する上で重量な役割（バインダー効果）を果たしていると考えられる。 Through the drying process, the silane compound (A) in the surface treatment agent undergoes a dehydration condensation reaction, and the silicon atoms in the film mainly form a condensation reaction product (organosiloxane) having siloxane bonds (Si-O-Si). Typically, the silicon atoms in the film are thought to form organopolysiloxane through polycondensation. In addition, the condensation reaction product having a siloxane bond (Si-O-Si) in the film stably retains a silver salt and/or a silver complex (B) and an organic acid having two or more carboxyl groups (C). It is thought that it plays an important role (binder effect) in the above.
［２－３．皮膜の質量］
皮膜を有する表面処理繊維における皮膜の質量（付着量）は、本発明の効果を発揮できる量であれば特に制限されるものではないが、Ｓｉの質量で皮膜形成前の繊維１ｍ2当たり１．０～５０．０ｍｇの範囲内であることが好ましく、１．５～３５ｍｇの範囲内であることがより好ましく、２．０～２０．０ｍｇの範囲内であることが特に好ましい。
[2-3. Mass of film]
The mass of the coating (amount of adhesion) in the surface-treated fibers having the coating is not particularly limited as long as it can exhibit the effects of the present invention, but the mass of Si is 1.2% per m 2 of the fiber before coating. It is preferably within the range of 0 to 50.0 mg, more preferably within the range of 1.5 to 35 mg, and particularly preferably within the range of 2.0 to 20.0 mg.
以下、実施例に基づいて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, the present invention will be explained in more detail based on Examples, but the present invention is not limited by these Examples.
［１．表面処理剤の調製］
＜処理液種Ｓ１＞
処理液種Ｓ１の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－グリシドキシプロピルトリメトキシシラン
・３－アミノプロピルトリエトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
銀濃度０．５質量％（４．６４ｍｍｏｌ／１００ｇ）に調整した硝酸銀水溶液を使用した。キレート剤として、キレスト（株）製のＨＥＤＰ（Hydroxyethylidene Diphosphonic Acid）（商品名：キレスト－ＰＨ２１０）をＡｇに対して１モル当量、およびＰＢＴＣ（Phosphonobutane Tricarboxylic Acid）（商品名：キレスト－ＰＨ４３０）をＡｇに対して２モル当量使用した。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・リンゴ酸
[1. Preparation of surface treatment agent]
<Processing liquid type S1>
The raw materials used to prepare the surface treatment agent of treatment liquid type S1 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-glycidoxypropyltrimethoxysilane ・3-aminopropyltriethoxysilane <Silver salt and/or silver complex (B)>
A silver nitrate aqueous solution whose silver concentration was adjusted to 0.5% by mass (4.64 mmol/100 g) was used. As a chelating agent, 1 molar equivalent of HEDP (Hydroxyethylidene Diphosphonic Acid) (trade name: CHILEST-PH210) manufactured by CHIREST Co., Ltd. with respect to Ag, and PBTC (Phosphonobutane Tricarboxylic Acid) (trade name: CHILEST-PH430) with respect to Ag. 2 molar equivalents were used.
<Organic acid (C) having two or more carboxyl groups>
・Malic acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ１の各種表面処理剤（実施例１、９～２８、３１～３３、比較例１～８）を得た。なお、表１中のＡ、Ｂ及びＣの「ｍｏｌ％」はＡ（＝Ａ１＋Ａ２）、Ｂ及びＣの合計を１００ｍｏｌ％としたときの値である。
８５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、１２０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ１の表面処理剤（実施例２９）を得た。
６５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、３０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ１の表面処理剤（実施例３０）を得た。
９０℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、１２０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ１の表面処理剤（比較例９）を得た。
２５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、３０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ１の表面処理剤（比較例１０）を得た。
何れの例においても処理液種Ｓ１においては、Ａ２は、３－グリシドキシプロピルトリメトキシシラン：３－アミノプロピルトリエトキシシラン＝３：１のモル比となるように配合した。表１に記載のＡ２のモル濃度は両者の合計値である。
また、処理液種Ｓ１の表面処理剤中の水の含有量は何れも９５質量％とした。
In deionized water at 75° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain various surface treatment agents of treatment liquid type S1 (Examples 1, 9 to 28, 31 to 33, and Comparative Examples 1 to 8). In addition, "mol%" of A, B, and C in Table 1 is a value when the total of A (=A1+A2), B, and C is 100 mol%.
In deionized water at 85° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 120 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S1 (Example 29).
In deionized water at 65° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 30 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S1 (Example 30).
In deionized water at 90° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 120 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S1 (Comparative Example 9).
In deionized water at 25° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 30 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S1 (Comparative Example 10).
In each example, in the treatment liquid type S1, A2 was blended in a molar ratio of 3-glycidoxypropyltrimethoxysilane:3-aminopropyltriethoxysilane=3:1. The molar concentration of A2 listed in Table 1 is the total value of both.
Further, the water content in the surface treatment agent of treatment liquid type S1 was all set to 95% by mass.
＜処理液種Ｓ２＞
処理液種Ｓ２の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－グリシドキシプロピルトリメトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・リンゴ酸
<Processing liquid type S2>
The raw materials used to prepare the surface treatment agent of treatment liquid type S2 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-glycidoxypropyltrimethoxysilane <silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Malic acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ２の表面処理剤（実施例２）を得た。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75° C., each of the above components (A1, A2, and C) was blended as shown in Table 1 and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S2 (Example 2). The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ３＞
処理液種Ｓ３の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－アミノプロピルトリエトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・リンゴ酸
<Processing liquid type S3>
The raw materials used to prepare the surface treatment agent of treatment liquid type S3 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-aminopropyltriethoxysilane <silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Malic acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ３の表面処理剤（実施例３）を得た。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S3 (Example 3). The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ４＞
処理液種Ｓ４の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－メルカプトプロピルトリエトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・リンゴ酸
<Processing liquid type S4>
The raw materials used to prepare the surface treatment agent of treatment liquid type S4 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-mercaptopropyltriethoxysilane <silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Malic acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ４の表面処理剤（実施例４）を得た。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S4 (Example 4). The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ５＞
処理液種Ｓ５の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－グリシドキシプロピルトリメトキシシラン
・３－アミノプロピルトリエトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・酒石酸
<Processing liquid type S5>
The raw materials used to prepare the surface treatment agent of treatment liquid type S5 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-glycidoxypropyltrimethoxysilane ・3-aminopropyltriethoxysilane <Silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Tartaric acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ５の表面処理剤（実施例５）を得た。処理液種Ｓ５においては、Ａ２は、３－グリシドキシプロピルトリメトキシシラン：３－アミノプロピルトリエトキシシラン＝３：１のモル比となるように配合した。表１に記載のＡ２のモル濃度は両者の合計値である。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S5 (Example 5). In treatment liquid type S5, A2 was blended in a molar ratio of 3-glycidoxypropyltrimethoxysilane:3-aminopropyltriethoxysilane=3:1. The molar concentration of A2 listed in Table 1 is the total value of both. The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ６＞
処理液種Ｓ６の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・３－イソシアネートプロピルトリメトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・酒石酸
<Processing liquid type S6>
The raw materials used to prepare the surface treatment agent of treatment liquid type S6 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・3-Isocyanatepropyltrimethoxysilane <Silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Tartaric acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填し、処理液種Ｓ６の表面処理剤（実施例６）を得た。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. The weight loss due to volatilization was compensated with deionized water to obtain a surface treatment agent of treatment liquid type S6 (Example 6). The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ７＞
処理液種Ｓ７の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・ビニルトリエトキシシラン
・３－アミノプロピルトリエトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・酒石酸
<Processing liquid type S7>
The raw materials used to prepare the surface treatment agent of treatment liquid type S7 are shown.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・Vinyltriethoxysilane ・3-aminopropyltriethoxysilane <Silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Tartaric acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填することで、処理液種Ｓ７の表面処理剤（実施例７）を得た。処理液種Ｓ７においては、Ａ２は、ビニルトリエトキシシラン：３－アミノプロピルトリエトキシシラン＝３：１のモル比となるように配合した。表１に記載のＡ２のモル濃度は両者の合計値である。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. By compensating for the weight loss due to volatilization with deionized water, a surface treatment agent of treatment liquid type S7 (Example 7) was obtained. In treatment liquid type S7, A2 was blended in a molar ratio of vinyltriethoxysilane:3-aminopropyltriethoxysilane=3:1. The molar concentration of A2 listed in Table 1 is the total value of both. The water content in the surface treatment agent was 95% by mass.
＜処理液種Ｓ８＞
処理液種Ｓ８の表面処理剤の調製に用いた原料を示す。
＜テトラアルコキシシラン（Ａ１）＞
・テトラエトキシシラン（ＴＥＯＳ）
＜シランカップリング剤（Ａ２）＞
・ビニルトリエトキシシラン
・３－グリシドキシプロピルトリメトキシシラン
＜銀塩および／または銀錯体（Ｂ）＞
処理液種Ｓ１と同じ。
＜カルボキシル基を２個以上有する有機酸（Ｃ）＞
・酒石酸
<Processing liquid type S8>
The raw materials used to prepare the surface treatment agent of treatment liquid type S8 are shown below.
<Tetraalkoxysilane (A1)>
・Tetraethoxysilane (TEOS)
<Silane coupling agent (A2)>
・Vinyltriethoxysilane ・3-glycidoxypropyltrimethoxysilane <Silver salt and/or silver complex (B)>
Same as processing liquid type S1.
<Organic acid (C) having two or more carboxyl groups>
・Tartaric acid
７５℃の脱イオン水中で、上記の各成分（Ａ１、Ａ２、およびＣ）を試験番号に応じて表１に記載の通りに配合し、７０分撹拌した。室温へ冷却後、更に表１に記載の通りにＢを添加し溶解させた。揮発した重量減少分を脱イオン水で補填することで、処理液種Ｓ８の表面処理剤（実施例８）を得た。処理液種Ｓ８においては、Ａ２は、ビニルトリエトキシシラン：３－グリシドキシプロピルトリメトキシシラン＝３：１のモル比となるように配合した。表１に記載のＡ２のモル濃度は両者の合計値である。当該表面処理剤中の水の含有量は９５質量％とした。 In deionized water at 75°C, each of the above components (A1, A2, and C) was blended as shown in Table 1 according to the test number, and stirred for 70 minutes. After cooling to room temperature, B was further added and dissolved as shown in Table 1. By compensating for the weight loss due to volatilization with deionized water, a surface treatment agent (Example 8) of treatment liquid type S8 was obtained. In treatment liquid type S8, A2 was blended in a molar ratio of vinyltriethoxysilane:3-glycidoxypropyltrimethoxysilane=3:1. The molar concentration of A2 listed in Table 1 is the total value of both. The water content in the surface treatment agent was 95% by mass.
＜条件１：（Ａ１＋Ａ２）／Ｂ＞
銀塩および／または銀錯体（Ｂ）に対するテトラアルコキシシラン（Ａ１）とシランカップリング剤（Ａ２）の合計（Ａ１＋Ａ２）のモル比｛（Ａ１＋Ａ２）／Ｂ｝を、原料配合条件から算出した。結果を表１に示す。
<Condition 1: (A1+A2)/B>
The molar ratio {(A1+A2)/B} of the total (A1+A2) of the tetraalkoxysilane (A1) and the silane coupling agent (A2) to the silver salt and/or silver complex (B) was calculated from the raw material blending conditions. The results are shown in Table 1.
＜条件２：Ｃ／Ｂ＞
銀塩および／または銀錯体（Ｂ）に対する有機酸（Ｃ）のカルボキシル基のモル比（Ｃ／Ｂ）を、原料配合条件から算出した。結果を表１に示す。
<Condition 2: C/B>
The molar ratio (C/B) of the carboxyl group of the organic acid (C) to the silver salt and/or silver complex (B) was calculated from the raw material blending conditions. The results are shown in Table 1.
＜条件３：Ｄα／Ｄβ＞
上記の方法で調製した各表面処理剤について、アルコールのモル濃度（ｍｏｌ／Ｌ）（Ｄα）をＮＭＲ装置（例：ＪＮＭ－ＦＣＸ４００：日本電子株式会社製）を用いて測定した。これにより、Ａ１およびＡ２に含まれるすべてのアルコキシ基が加水分解したと仮定した場合に生じるアルコールの表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄβ）に対するＤαの比（Ｄα／Ｄβ）を求めた。結果を表１に示す。
<Condition 3: Dα/Dβ>
For each surface treatment agent prepared by the above method, the molar concentration (mol/L) (Dα) of alcohol was measured using an NMR device (eg, JNM-FCX400, manufactured by JEOL Ltd.). As a result, the ratio of Dα to the molar concentration (mol/L) (Dβ) of alcohol in the surface treatment agent, which is generated when all the alkoxy groups contained in A1 and A2 are hydrolyzed (Dα/Dβ). I asked for The results are shown in Table 1.
＜重量平均分子量＞
上記の方法で調製した各表面処理剤について、先述したＧＰＣ法により重量平均分子量を測定した。結果を表２に示す。
<Weight average molecular weight>
The weight average molecular weight of each surface treatment agent prepared by the above method was measured by the GPC method described above. The results are shown in Table 2.
［２．繊維の表面処理］
ＪＩＳ Ｌ１９３０：２０１４付属書Ｈに規定されているＩ型（綿１００％織物）およびＩＩＩ型（ポリエステル１００％編み物）の洗濯試験用負荷布を用意した。当該負荷布を、上記の方法で調製した２５℃の各表面処理剤に浸して１分経過後に絞り、繊維１ｇに対して表面処理剤が１ｇ付着している状態に調整した。その後、オーブンに入れ、表２に記載の最高到達乾燥温度で２分乾燥した。これにより皮膜を有する表面処理繊維を得た。尚、表面処理繊維は以下の特性評価に必要な数用意した。以下の評価試験のうち、「繊維の変質」はＩ型（綿）の負荷布を使用した表面処理繊維とＩＩＩ型（ポリエステル）の負荷布を使用した表面処理繊維の両方に対して行い、その他の評価試験はＩ型（綿）の負荷布を使用した表面処理繊維に対してのみ行った。
[2. Fiber surface treatment]
Load fabrics for washing tests of type I (100% cotton woven fabric) and type III (100% polyester knitted fabric) specified in JIS L1930:2014 Annex H were prepared. The loaded cloth was immersed in each surface treatment agent prepared by the above method at 25° C. and squeezed after 1 minute, so that 1 g of surface treatment agent was attached to 1 g of fiber. Thereafter, it was placed in an oven and dried for 2 minutes at the maximum drying temperature listed in Table 2. As a result, a surface-treated fiber having a film was obtained. In addition, the number of surface-treated fibers required for the following characteristic evaluation was prepared. Among the following evaluation tests, "fiber alteration" was performed on both surface-treated fibers using Type I (cotton) loaded fabric and surface-treated fibers using Type III (polyester) loaded fabric, and other The evaluation test was conducted only on surface-treated fibers using Type I (cotton) loaded fabric.
［３．皮膜付着量］
表面処理繊維における皮膜付着量の指標としてＳｉ量を測定した。具体的には、波長分散型蛍光Ｘ線分析装置（株式会社リガク製、型式：ＺＳＸ－ＰｒｉｍｕｓＩＩＩ）を使用し、以下の分析条件で表面処理繊維１ｍ2当たりに付着したＳｉ量（ｍｇ）を定量分析した。
管球：Ｒｈ
分光結晶：ＰＥＴ
分析径：３０ｍｍφ
電圧－電流：５０ｋｖ ５０ｍＡ
具体的には、まず、波長分散型蛍光Ｘ線分析装置で測定されたＳｉの強度から検量線法にてＳｉＯ2の質量を求めた。検量線は、所定量のＳｉＯ2を添加したウレタン樹脂（ＨＹＤＲＡＮ ＳＰ－５１０ ＤＩＣ株式会社製）を塗布した塗装板を作製し、塗装板１ｍ2あたりのＳｉＯ2付着量を用いて検量線を作成した。求めたＳｉＯ2の質量からＳｉに換算して［ＳｉＯ2質量×Ｓｉの原子量／ＳｉＯ2の分子量（２８．１／６０．１）］、Ｓｉの質量を算出した。結果を表２に示す。
[3. Amount of film attached]
The amount of Si was measured as an index of the amount of film deposited on the surface-treated fibers. Specifically, using a wavelength-dispersive fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., model: ZSX-Primus III), we quantified the amount of Si (mg) attached per 1 m 2 of surface-treated fibers under the following analysis conditions. analyzed.
Tube: Rh
Spectroscopic crystal: PET
Analysis diameter: 30mmφ
Voltage-current: 50kv 50mA
Specifically, first, the mass of SiO 2 was determined by a calibration curve method from the Si intensity measured with a wavelength dispersive X-ray fluorescence spectrometer. The calibration curve was created by preparing a painted plate coated with urethane resin (HYDRAN SP-510 manufactured by DIC Corporation) to which a predetermined amount of SiO 2 was added, and using the amount of SiO 2 attached per 1 m 2 of the painted plate. did. The mass of Si was calculated from the obtained mass of SiO 2 by converting it into Si [mass of SiO 2 × atomic weight of Si/molecular weight of SiO 2 (28.1/60.1)]. The results are shown in Table 2.
［４．特性評価］
＜抗菌性能（洗濯前）＞
上記の表面処理方法で得られた各表面処理繊維について、ＪＩＳ Ｌ１９０２：２０１５に準拠して、抗菌性能を評価した。具体的には、大腸菌および黄色ブドウ球菌を表面処理繊維にそれぞれ別々に接種し、３７℃で１８時間培養した。培養後の表面処理繊維をバイアル瓶に入れ、洗い出し液を加えて菌を洗い流し、生菌数を測定した。また、表面処理を行っていない上記負荷布（コントロール）についても、同じ方法で菌の接種、培養および生菌数の測定を行った。表面処理繊維とコントロールを比較することで抗菌活性値を算出した。抗菌性能の評価は以下の基準で行った。結果を表２に示す。
◎：２菌種ともに抗菌活性値が３．０以上
〇：抗菌活性値の低い菌種の抗菌活性値が３．０未満２．０以上
△：抗菌活性値が高い菌種の抗菌活性値が２．０以上であるが抗菌活性値の低い菌種の抗菌活性値が２．０未満
×：２菌種ともに抗菌活性値が２．０未満
[4. Characteristic evaluation]
<Antibacterial performance (before washing)>
The antibacterial performance of each surface treated fiber obtained by the above surface treatment method was evaluated in accordance with JIS L1902:2015. Specifically, Escherichia coli and Staphylococcus aureus were separately inoculated onto the surface-treated fibers and cultured at 37°C for 18 hours. After culturing, the surface-treated fibers were placed in a vial, a washing solution was added to wash away the bacteria, and the number of viable bacteria was measured. In addition, for the above-mentioned loaded cloth (control) that had not been subjected to surface treatment, bacteria were inoculated, cultured, and the number of viable bacteria was measured in the same manner. Antibacterial activity values were calculated by comparing the surface-treated fibers and the control. The antibacterial performance was evaluated based on the following criteria. The results are shown in Table 2.
◎: The antibacterial activity value of both bacterial species is 3.0 or more 〇: The antibacterial activity value of the bacterial species with low antibacterial activity value is less than 3.0 and 2.0 or more △: The antibacterial activity value of the bacterial species with high antibacterial activity value is 2.0 or more, but the antibacterial activity value of the bacterial species with low antibacterial activity value is less than 2.0 ×: The antibacterial activity value of both bacterial species is less than 2.0
＜抗菌性能（洗濯３０回後）＞
上記の表面処理方法で得られた各表面処理繊維を、ＪＩＳ Ｌ１９３０：２０１４の付属書Ｆに準拠し、Ｎｏ．Ｃ４Ｇの洗濯方法にて洗濯を３０回実施した。また、表面処理を行っていない上記負荷布（コントロール）についても、同じ方法で洗濯を３０回実施した。その後、上述した「抗菌性能（洗濯前）」に記載の方法と同じ方法で菌の接種、培養および生菌数の測定を行い、抗菌活性値を算出した。抗菌性能の評価は以下の基準で行った。結果を表２に示す。
◎：２菌種ともに抗菌活性値が３．０以上
〇：抗菌活性値の低い菌種の抗菌活性値が３．０未満２．０以上
△：抗菌活性値が高い菌種の抗菌活性値が２．０以上であるが抗菌活性値の低い菌種の抗菌活性値が２．０未満
×：２菌種ともに抗菌活性値が２．０未満
<Antibacterial performance (after 30 washes)>
Each surface-treated fiber obtained by the above-mentioned surface treatment method was treated with No. Washing was carried out 30 times using the C4G washing method. In addition, the load cloth (control) which had not been surface-treated was also washed 30 times in the same manner. Thereafter, bacteria were inoculated, cultured, and the number of viable bacteria was measured in the same manner as described in "Antibacterial Performance (Before Washing)" above, and the antibacterial activity value was calculated. The antibacterial performance was evaluated based on the following criteria. The results are shown in Table 2.
◎: The antibacterial activity value of both bacterial species is 3.0 or more 〇: The antibacterial activity value of the bacterial species with low antibacterial activity value is less than 3.0 and 2.0 or more △: The antibacterial activity value of the bacterial species with high antibacterial activity value is 2.0 or more, but the antibacterial activity value of the bacterial species with low antibacterial activity value is less than 2.0 ×: The antibacterial activity value of both bacterial species is less than 2.0
＜吸水性＞
上記の表面処理方法で得られた各表面処理繊維の吸水性を評価した。ＪＩＳ Ｌ １９０７：２０１０（滴下法）に準拠し、表面処理繊維に水を１滴滴下させ、水滴が吸収されるまでの時間（秒）を測定した。同様の測定を表面処理を行っていない上記負荷布（コントロール）に対しても行った。両者の値を比較し、時間差を以下の基準で評価した。結果を表２に示す。
◎：コントロールと比較して１秒未満
〇：コントロールと比較して１秒以上２秒未満
△：コントロールと比較して２秒以上３秒未満
×：コントロールと比較して３秒以上
<Water absorption>
The water absorbency of each surface-treated fiber obtained by the above-mentioned surface treatment method was evaluated. In accordance with JIS L 1907:2010 (dropping method), one drop of water was dropped on the surface-treated fiber, and the time (seconds) until the water drop was absorbed was measured. Similar measurements were also carried out on the above-mentioned loaded fabric (control) which had not been subjected to surface treatment. The two values were compared and the time difference was evaluated using the following criteria. The results are shown in Table 2.
◎: Less than 1 second compared to the control 〇: 1 second or more and less than 2 seconds compared to the control △: 2 seconds or more and less than 3 seconds compared to the control ×: 3 seconds or more compared to the control
＜液安定性＞
上記の実施例及び比較例に係る各表面処理剤について、脱イオン水の添加量を変えた以外は、同じ調製方法を実施することにより、実施例及び比較例に係る各表面処理剤の５０倍濃縮液をそれぞれ作製した。得られた濃縮液をＪＰボトル（ＰＰ広口瓶）に入れて密封し、常温で６カ月暗室で保管した。その後、濃縮液の外観を、ＪＩＳ Ｋ ０１０１：１９９８「工業用水試験方法」に準拠して、ホルマジン標準液を用いた透過光濁度と、白金・コバルトによる色度を測定し、以下の基準で評価した。結果を表２に示す。
◎：濁度２度以下且つ色度５度以下
〇：濁度２度超且つ色度５度超５０度以下
△：濁度２度超１００度以下且つ色度５度超５０度以下
×：濁度１００度超且つ色度５０度超
<Liquid stability>
By carrying out the same preparation method for each surface treatment agent according to the above Examples and Comparative Examples, except for changing the amount of deionized water added, Concentrated solutions were prepared respectively. The obtained concentrate was placed in a JP bottle (PP wide-mouth bottle), sealed, and stored in a dark room at room temperature for 6 months. After that, the appearance of the concentrated liquid was measured in accordance with JIS K 0101:1998 "Industrial Water Testing Methods" for transmitted light turbidity using a formazin standard solution and chromaticity using platinum and cobalt. evaluated. The results are shown in Table 2.
◎: Turbidity is 2 degrees or less and chromaticity is 5 degrees or less 〇: Turbidity is more than 2 degrees and chromaticity is more than 5 degrees and less than 50 degrees △: Turbidity is more than 2 degrees and less than 100 degrees and chromaticity is more than 5 degrees and less than 50 degrees ×: Turbidity over 100 degrees and chromaticity over 50 degrees
＜繊維の変質＞
上記の表面処理方法で得られた各表面処理繊維に対して以下の条件で耐候性試験を行った。
耐候性試験機：スガ試験機(株)製スーパーキセノンウエザーメーターＳＸ７５
光源：キセノンアークランプ７．５ｋＷ
照射照度：１８０Ｗ／ｍ2
インナーフィルター：石英
アウターフィルター：＃２７５
ブラックパネル温度（ＢＰＴ）：６３℃
試験モード：（照射２時間サイクル中に１８分降雨モード）×６０サイクル
耐候性試験後の表面処理繊維に対して、目視で外観観察すること及び手触りで繊維の変質を評価した。評価は以下の基準で行った。結果を表２に示す。
◎：耐候試験前後において風合いの変化および変色が認められない。
○：耐候試験前後において風合いに変化はないが変色が確認される。
△：耐候試験前後において変色は確認されないが風合いの変化が確認される。
×：耐候試験前後において風合いの変化および変色が確認される。
<Fiber alteration>
A weather resistance test was conducted on each surface treated fiber obtained by the above surface treatment method under the following conditions.
Weather resistance tester: Super xenon weather meter SX75 manufactured by Suga Test Instruments Co., Ltd.
Light source: xenon arc lamp 7.5kW
Irradiation intensity: 180W/m 2
Inner filter: Quartz Outer filter: #275
Black panel temperature (BPT): 63℃
Test mode: (Rainfall mode for 18 minutes during 2-hour irradiation cycle) x 60 cycles After the weather resistance test, the surface-treated fibers were evaluated for deterioration by visual observation of their appearance and touch. Evaluation was performed based on the following criteria. The results are shown in Table 2.
◎: No change in texture or discoloration is observed before and after the weathering test.
○: There is no change in texture before and after the weathering test, but discoloration is observed.
Δ: No discoloration is observed before and after the weathering test, but a change in texture is observed.
×: Changes in texture and discoloration are observed before and after the weathering test.
Claims (4)
銀塩および／または銀錯体（Ｂ）と、
カルボキシル基を２個以上有する有機酸（Ｃ）と、
水（Ｅ）と、を含み、
以下の１）および２）の配合条件を満足するように調製した繊維用表面処理剤。
１）前記銀塩および／または銀錯体（Ｂ）に対する前記テトラアルコキシシラン（Ａ１）と前記シランカップリング剤（Ａ２）の合計（Ａ１＋Ａ２）のモル比｛（Ａ１＋Ａ２）／Ｂ｝が１００～５００。
２）前記銀塩および／または銀錯体（Ｂ）に対する前記有機酸（Ｃ）のカルボキシル基のモル比（Ｃ／Ｂ）が５～２５。 A silane compound (A) which is a hydrolyzate and/or a condensation reaction product of a tetraalkoxysilane (A1) and a silane coupling agent (A2);
A silver salt and/or a silver complex (B),
an organic acid (C) having two or more carboxyl groups;
including water (E),
A surface treatment agent for fibers prepared to satisfy the following blending conditions 1) and 2).
1) The molar ratio {(A1+A2)/B} of the total (A1+A2) of the tetraalkoxysilane (A1) and the silane coupling agent (A2) to the silver salt and/or silver complex (B) is 100 to 500.
2) The molar ratio (C/B) of the carboxyl group of the organic acid (C) to the silver salt and/or silver complex (B) is 5 to 25.
前記テトラアルコキシシラン（Ａ１）と前記シランカップリング剤（Ａ２）に含まれるすべてのアルコキシ基が加水分解したと仮定した場合に生じるアルコールの前記表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄβ）に対する、前記アルコール（Ｄ）の実際の前記表面処理剤中でのモル濃度（ｍｏｌ／Ｌ）（Ｄα）の比（Ｄα／Ｄβ）が０．０５～０．９である請求項１に記載の繊維用表面処理剤。 The silane compound (A) contains an alcohol (D) that is a hydrolyzate of at least one of the tetraalkoxysilane (A1) and the silane coupling agent (A2),
Assuming that all the alkoxy groups contained in the tetraalkoxysilane (A1) and the silane coupling agent (A2) are hydrolyzed, the molar concentration (mol/L) of alcohol in the surface treatment agent ( According to claim 1, the ratio (Dα/Dβ) of the actual molar concentration (mol/L) (Dα) of the alcohol (D) in the surface treatment agent to Dβ) is 0.05 to 0.9. The surface treatment agent for fibers described above.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022063067A JP2023153668A (en) | 2022-04-05 | 2022-04-05 | Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber |
| PCT/JP2023/011981 WO2023195363A1 (en) | 2022-04-05 | 2023-03-24 | Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2022063067A JP2023153668A (en) | 2022-04-05 | 2022-04-05 | Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber |
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| Publication Number | Publication Date |
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| JP2023153668A true JP2023153668A (en) | 2023-10-18 |
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| JP2022063067A Pending JP2023153668A (en) | 2022-04-05 | 2022-04-05 | Surface treating agent for fibers, method for treating surface of fiber, and surface-treated fiber |
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| WO (1) | WO2023195363A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006055763B4 (en) * | 2006-11-21 | 2011-06-22 | Militz, Detlef, 15366 | Process for metallizing polyester, metallized polyester and its use |
| JP2008127372A (en) * | 2006-11-24 | 2008-06-05 | Nitto Boseki Co Ltd | Antibacterial processing method and product of the same |
| CN102257178B (en) * | 2008-12-16 | 2014-05-07 | 日本帕卡濑精株式会社 | Surface treating agent for metallic materials |
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