JP6227872B2 - Hydrophilization treatment agent and hydrophilization treatment method - Google Patents
Hydrophilization treatment agent and hydrophilization treatment method Download PDFInfo
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- JP6227872B2 JP6227872B2 JP2013001257A JP2013001257A JP6227872B2 JP 6227872 B2 JP6227872 B2 JP 6227872B2 JP 2013001257 A JP2013001257 A JP 2013001257A JP 2013001257 A JP2013001257 A JP 2013001257A JP 6227872 B2 JP6227872 B2 JP 6227872B2
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- 239000004743 Polypropylene Substances 0.000 description 1
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- 239000012933 diacyl peroxide Substances 0.000 description 1
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- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- UCYFZDNMZYZSPN-UHFFFAOYSA-N docosyl(trimethyl)azanium Chemical class CCCCCCCCCCCCCCCCCCCCCC[N+](C)(C)C UCYFZDNMZYZSPN-UHFFFAOYSA-N 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BNKAXGCRDYRABM-UHFFFAOYSA-N ethenyl dihydrogen phosphate Chemical compound OP(O)(=O)OC=C BNKAXGCRDYRABM-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 229960002989 glutamic acid Drugs 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229930182470 glycoside Natural products 0.000 description 1
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940100491 laureth-2 Drugs 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
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- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- BHQZSXXOSYWJSZ-UHFFFAOYSA-N n,n-dimethyl-3-octadecoxypropan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCOCCCN(C)C BHQZSXXOSYWJSZ-UHFFFAOYSA-N 0.000 description 1
- ICZKASVWFUJTEI-UHFFFAOYSA-N n,n-dimethyldocosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN(C)C ICZKASVWFUJTEI-UHFFFAOYSA-N 0.000 description 1
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- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- 229920001444 polymaleic acid Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
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- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
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- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
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- 229940079781 sodium cocoyl glutamate Drugs 0.000 description 1
- 229940045990 sodium laureth-2 sulfate Drugs 0.000 description 1
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- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
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- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical class CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- USFMMZYROHDWPJ-UHFFFAOYSA-N trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium Chemical compound CC(=C)C(=O)OCC[N+](C)(C)C USFMMZYROHDWPJ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は、親水化処理剤に関し、更に詳しくは、固体表面を親水化処理し、水に濡れやすくする親水化処理剤及び親水化処理方法に関する。 The present invention relates to a hydrophilization treatment agent, and more particularly to a hydrophilization treatment agent and a hydrophilization treatment method that make a solid surface hydrophilic and easily wet.
従来、固体表面に防汚性を付与する方法としては、撥水化処理と親水化処理の相異なる方法が知られている。
撥水化処理は、ガラス、金属、繊維等の固体表面に撥水性を持たせる表面処理を行い、水に含まれる汚れを付着させないようにする技術である。例えば、衣類を洗濯後、柔軟仕上げ剤で処理したり、スキーウェア等に撥水剤をスプレーして防水効果を持たせたり、自動車の塗装面をワックス掛けしたりすることが広く行われている。
しかしながら、撥水化処理では、表面を完全に撥水化させることは難しく、度重なる水との接触により、水に含まれる汚れが固体表面に蓄積するため、十分な防汚効果を発揮することが難しい。
Conventionally, as a method for imparting antifouling properties to a solid surface, different methods of water repellent treatment and hydrophilic treatment are known.
The water repellency treatment is a technique for applying a surface repellency to a solid surface of glass, metal, fiber, or the like so that dirt contained in water does not adhere. For example, after washing clothes, they are treated with a soft finish, sprayed with water repellent on skiwear, etc. to give a waterproof effect, and painted surfaces of automobiles are waxed. .
However, with water-repellent treatment, it is difficult to make the surface completely water-repellent, and due to repeated contact with water, dirt contained in the water accumulates on the solid surface, so it exhibits a sufficient antifouling effect Is difficult.
一方、固体表面の親水化処理、すなわち、固体表面の水に対する接触角を低下させ、固体表面を水に対して濡れ易くする処理をすると、当該処理後に固体表面に付着した汚れが洗浄時に落とし易くなったり、汚れの再汚染防止効果が期待できる他、ガラス・鏡等の防曇効果、帯電防止、浴槽及びトイレ表面等の防汚性付与等が期待できる。
固体表面の親水化処理剤及び方法としては、いくつかの提案がなされている。
例えば、特許文献１には、特定の構造を有するベンゾトロポロン類を含有する親水化処理剤と、それを用いる固体表面の親水化処理方法剤が開示されている。
特許文献２には、特定の共重合体を含有する水性組成物の２種を適用する硬質表面処理方法が開示されている。
特許文献３には、ポリオキシエチレンラウリルエーテルカルボン酸ナトリウム等の化合物を含有する親水化処理剤が開示されている。
しかるに、親水化技術を応用した商品は意外なことに少なく、広く一般に普及しているとは言いがたい。これは十分満足できる効果を有する親水化剤がないことに起因している。
On the other hand, if the surface of the solid surface is hydrophilized, that is, the contact angle of the solid surface with water is decreased to make the solid surface easily wetted with water, dirt attached to the solid surface after the treatment is easily removed during cleaning. In addition to anti-fogging and anti-contamination effects, anti-fogging effects such as glass and mirrors, anti-static properties, anti-fouling properties such as bath and toilet surfaces can be expected.
Several proposals have been made for a hydrophilic treatment agent and method for a solid surface.
For example, Patent Document 1 discloses a hydrophilization treatment agent containing a benzotropolone having a specific structure and a solid surface hydrophilization treatment agent using the same.
Patent Document 2 discloses a hard surface treatment method to which two kinds of aqueous compositions containing a specific copolymer are applied.
Patent Document 3 discloses a hydrophilizing agent containing a compound such as sodium polyoxyethylene lauryl ether carboxylate.
However, there are surprisingly few products that apply hydrophilization technology, and it cannot be said that they are widely spread. This is due to the absence of a hydrophilizing agent that has a sufficiently satisfactory effect.
本発明は、固体表面に対して優れた親水化能力を有する親水化処理剤、及びそれを用いる親水化処理方法を提供することを課題とする。 An object of the present invention is to provide a hydrophilization treatment agent having an excellent hydrophilization ability for a solid surface, and a hydrophilization treatment method using the same.
発明者らは、特定構造の高分子化合物、多価有機酸、及び水を含有する親水化処理剤が、固体表面に対して優れた親水化力を有することを見出した。
すなわち、本発明は、下記［１］及び［２］を提供する。
［１］下記一般式（１）で表されるモノマー由来の繰り返し単位（ａ）を有する高分子化合物（Ａ）、多価有機酸（Ｂ）、及び水（Ｃ）を含有する親水化処理剤であって、高分子化合物（Ａ）の質量平均分子量が１，０００〜２０，０００であり、高分子化合物（Ａ）を構成する全繰り返し単位中における繰り返し単位（ａ）の含有量が６０モル％以上であり、酸性基を有するモノマー由来の繰り返し単位（ｂ）の含有量が５モル％以下である、親水化処理剤。
The inventors have found that a hydrophilizing agent containing a polymer compound having a specific structure, a polyvalent organic acid, and water has an excellent hydrophilizing power for a solid surface.
That is, the present invention provides the following [1] and [2].
[1] A hydrophilizing agent containing a polymer compound (A) having a repeating unit (a) derived from a monomer represented by the following general formula (1), a polyvalent organic acid (B), and water (C) The mass average molecular weight of the polymer compound (A) is 1,000 to 20,000, and the content of the repeating unit (a) in all repeating units constituting the polymer compound (A) is 60 mol. %, And the content of the repeating unit (b) derived from the monomer having an acidic group is 5 mol% or less.
［２］固体表面を上記［１］に記載の親水化処理剤を含有する溶液に接触させる、固体表面の親水化処理方法。
[2] A method for hydrophilizing a solid surface, wherein the solid surface is contacted with a solution containing the hydrophilizing agent according to [1].
本発明によれば、固体表面に対して優れた親水化力を有する親水化処理剤、及びそれを用いる親水化処理方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the hydrophilization processing agent which has the hydrophilization power outstanding with respect to the solid surface, and the hydrophilization processing method using the same can be provided.
［高分子化合物（Ａ）］
本発明で用いられる高分子化合物（Ａ）は、該高分子化合物（Ａ）を構成する全繰り返し単位中における、下記一般式（１）で表されるモノマー由来の繰り返し単位（ａ）（以下、単に「繰り返し単位（ａ）」ともいう）の組成が６０モル％以上であり、酸性基を有するモノマー由来の繰り返し単位（ｂ）（以下、単に「繰り返し単位（ｂ）」ともいう）の組成が５モル％以下であり、質量平均分子量が１，０００〜２０，０００であるものである。
高分子化合物（Ａ）は、繰り返し単位（ａ）を含有し、必要に応じて、繰り返し単位（ｂ）、及びその他のモノマー由来の繰り返し単位（ｃ）を含んでいてもよい。
また、高分子化合物（Ａ）は、単独重合体であってもよいし、共重合体であってもよい。高分子化合物（Ａ）が共重合体である場合、繰り返し単位の配列は、ランダム、ブロック、又はグラフトのいずれであってもよい。さらに、高分子化合物（Ａ）の構造は直鎖状、分岐状のいずれでもよい。
[Polymer Compound (A)]
The polymer compound (A) used in the present invention is a repeating unit (a) derived from a monomer represented by the following general formula (1) in all repeating units constituting the polymer compound (A) (hereinafter, The composition of the repeating unit (b) derived from a monomer having an acidic group (hereinafter also simply referred to as “repeating unit (b)”) is 60 mol% or more. It is 5 mol% or less, and a mass average molecular weight is 1,000-20,000.
The polymer compound (A) contains a repeating unit (a), and may contain a repeating unit (b) and a repeating unit (c) derived from another monomer as necessary.
Further, the polymer compound (A) may be a homopolymer or a copolymer. When the polymer compound (A) is a copolymer, the arrangement of repeating units may be random, block, or graft. Furthermore, the structure of the polymer compound (A) may be either linear or branched.
＜一般式（１）で表されるモノマー由来の繰り返し単位（ａ）＞ <Repeating unit (a) derived from monomer represented by formula (1)>
一般式（１）において、Ｒ1は、親水化処理剤の親水化力を高める観点から、メチル基が好ましい。
Ｒ2は、一般式（１）で表されるモノマーの入手の容易さの観点から、炭素数が１〜３のアルカンジイル基が好ましく、具体的には、メチレン基、エタン−１，２−ジイル基（エチレン基）、プロパン−１，２−ジイル基、プロパン−１，３−ジイル基（トリメチレン基）が挙げられるが、エチレン基がより好ましい。
Ｒ3、Ｒ4は、一般式（１）で表されるモノマーの入手の容易さの観点から、それぞれ独立に、炭素数１〜５のアルキル基が好ましく、親水化処理剤の親水化力を高める観点から、炭素数１〜３のアルキル基がより好ましく、メチル基、エチル基が更に好ましく、メチル基がより更に好ましい。
Ｒ5は、一般式（１）で表されるモノマーの入手の容易さの観点から、炭素数１〜５のアルキル基が好ましく、親水化処理剤の親水化力を高める観点から、メチル基、エチル基がより好ましい。
In general formula (1), R 1 is preferably a methyl group from the viewpoint of increasing the hydrophilizing power of the hydrophilizing agent.
R 2 is preferably an alkanediyl group having 1 to 3 carbon atoms from the viewpoint of easy availability of the monomer represented by the general formula (1), and specifically includes a methylene group, ethane-1,2- Examples include a diyl group (ethylene group), a propane-1,2-diyl group, and a propane-1,3-diyl group (trimethylene group), and an ethylene group is more preferable.
R 3 and R 4 are each independently preferably an alkyl group having 1 to 5 carbon atoms from the viewpoint of easy availability of the monomer represented by the general formula (1). From the viewpoint of enhancing, an alkyl group having 1 to 3 carbon atoms is more preferable, a methyl group and an ethyl group are more preferable, and a methyl group is still more preferable.
R 5 is preferably an alkyl group having 1 to 5 carbon atoms from the viewpoint of easy availability of the monomer represented by the general formula (1), and from the viewpoint of enhancing the hydrophilizing power of the hydrophilizing agent, An ethyl group is more preferable.
一般式（１）において、Ｘは、親水化処理剤の親水化力を高める観点から、酸素原子が好ましい。
Ｙ-は、ハロゲンイオン、硫酸イオン、炭素数１〜３のアルキル基を有するアルキル硫酸エステルイオン、炭素数１〜３のアルキル基で置換されていてもよい芳香族スルホン酸イオン、ヒドロキシイオン、リン酸イオン、ギ酸イオン、又は酢酸イオンが好ましく、塩素イオン等のハロゲンイオン、又は炭素数１〜３のアルキル基を有するアルキル硫酸エステルイオンがより好ましい。
高分子化合物（Ａ）を構成する全繰り返し単位中における繰り返し単位（ａ）の含有量は、６０モル％以上であれば、親水化処理剤の固体表面に対する親水化力に優れ、８０モル％以上であることが好ましく、その上限は１００モル％である。
In the general formula (1), X is preferably an oxygen atom from the viewpoint of increasing the hydrophilizing power of the hydrophilizing agent.
Y − represents a halogen ion, a sulfate ion, an alkyl sulfate ester ion having an alkyl group having 1 to 3 carbon atoms, an aromatic sulfonate ion optionally substituted with an alkyl group having 1 to 3 carbon atoms, a hydroxy ion, phosphorus An acid ion, a formate ion, or an acetate ion is preferable, and a halogen ion such as a chlorine ion or an alkyl sulfate ester ion having a C 1-3 alkyl group is more preferable.
If the content of the repeating unit (a) in all the repeating units constituting the polymer compound (A) is 60 mol% or more, the hydrophilicity of the hydrophilizing agent on the solid surface is excellent, and 80 mol% or more. It is preferable that the upper limit is 100 mol%.
＜酸性基を有するモノマー由来の繰り返し単位（ｂ）＞
繰り返し単位（ｂ）が有する酸性基とは、カルボキシ基、スルホン酸基、リン酸基等を意味する。
酸性基を有するモノマー由来の繰り返し単位（ｂ）としては、例えば、（メタ）アクリル酸、マレイン酸、イタコン酸、フマル酸、クロトン酸、スチレンスルホン酸、２−アクリルアミド−２−メチルプロパンスルホン酸、３−スルホプロピル（メタ）アクリル酸エステル、ビニルホスホン酸、ビニルホスフェート等の酸性基を有するモノマー由来の繰り返し単位が挙げられる。
高分子化合物（Ａ）を構成する全繰り返し単位中における繰り返し単位（ｂ）の含有量は、５モル％以下であれば、親水化処理剤は固体表面に対する親水化力に優れ、１モル％以下であることが好ましく、０モル％であることがより好ましい。
<Repeating unit (b) derived from monomer having acidic group>
The acidic group that the repeating unit (b) has means a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like.
As the repeating unit (b) derived from the monomer having an acidic group, for example, (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, crotonic acid, styrenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, The repeating unit derived from the monomer which has acidic groups, such as 3-sulfopropyl (meth) acrylic acid ester, vinyl phosphonic acid, vinyl phosphate, is mentioned.
If the content of the repeating unit (b) in all repeating units constituting the polymer compound (A) is 5 mol% or less, the hydrophilizing agent is excellent in hydrophilizing power on the solid surface, and 1 mol% or less. It is preferable that it is 0 mol%.
本発明において、前記一般式（１）で表されるモノマー、又は酸性基を有するモノマー由来の繰り返し単位とは、前記一般式（１）で表されるモノマー、又は酸性基を有するモノマーを重合させて得られる高分子化合物における繰り返し単位構造をいう。また以下において、繰り返し単位（ａ）又は繰り返し単位（ｂ）を構成するモノマーとは、それぞれ前記一般式（１）で表されるモノマー、又は前記酸性基を有するモノマーのことをいう。 In the present invention, the monomer represented by the general formula (1) or the repeating unit derived from the monomer having an acidic group is obtained by polymerizing the monomer represented by the general formula (1) or the monomer having an acidic group. The repeating unit structure in the polymer compound obtained in this way. In the following, the monomer constituting the repeating unit (a) or the repeating unit (b) refers to a monomer represented by the general formula (1) or a monomer having an acidic group.
＜繰り返し単位（ｃ）＞
高分子化合物（Ａ）は、繰り返し単位（ａ）を構成するモノマー、及び繰り返し単位（ｂ）を構成するモノマー以外のモノマー由来の繰り返し単位（ｃ）を含んでいてもよい。
繰り返し単位（ｃ）を構成するモノマーの具体例としては、アクリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド、ヒドロキシエチルアクリルアミド等のアクリルアミドモノマー；メタクリルアミド、イソプロピルメタクリルアミド、Ｎ−ブトキシメチルメタクリルアミド、Ｎ−メトキシメチルメタクリルアミド等のメタクリルアミドモノマー；メチルアクリレート、ブチルアクリレート、ラウリルアクリレート、メトキシポリエチレングリコール（１〜５モル付加）アクリレート等のアクリレートモノマー；メチルメタクリレート、エチルメタクリレート、ブチルメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、メトキシポリエチレングリコール（１〜５モル付加）メタクリレート等のメタクリレートモノマー；エチレン、プロピレン等のオレフィンモノマー；スチレン等のスチレンモノマーに由来する繰り返し単位が挙げられる。これらの中では、親水化処理剤の固体表面に対する親水化力を高める観点から、アクリルアミド、メトキシポリエチレングリコール（１〜３モル付加）アクリレート、メトキシポリエチレングリコール（１〜３モル付加）メタクリレート、及びスチレンから選ばれる１種又は２種以上に由来する繰り返し単位が好ましい。
<Repeating unit (c)>
The polymer compound (A) may contain a monomer constituting the repeating unit (a) and a repeating unit (c) derived from a monomer other than the monomer constituting the repeating unit (b).
Specific examples of the monomer constituting the repeating unit (c) include acrylamide monomers such as acrylamide, dimethylacrylamide, diethylacrylamide, and hydroxyethylacrylamide; methacrylamide, isopropylmethacrylamide, N-butoxymethylmethacrylamide, N-methoxymethylmethacrylate Methacrylamide monomers such as amides; Acrylate monomers such as methyl acrylate, butyl acrylate, lauryl acrylate, methoxypolyethylene glycol (1-5 mole addition) acrylate; Methyl methacrylate, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, stearyl methacrylate, methoxypolyethylene glycol (1-5 mole addition) Methacrylate such as methacrylate Monomer; and the repeating unit derived from a styrene monomer such as styrene, ethylene, olefin monomers such as propylene. Among these, from the viewpoint of increasing the hydrophilizing power of the hydrophilizing agent to the solid surface, from acrylamide, methoxypolyethylene glycol (1-3 mol addition) acrylate, methoxypolyethylene glycol (1-3 mol addition) methacrylate, and styrene. The repeating unit derived from the 1 type (s) or 2 or more types selected is preferable.
＜高分子化合物（Ａ）の物性＞
高分子化合物（Ａ）のカチオン電荷密度は、本発明の親水化処理剤の親水化力を高める観点から、好ましくは３ｍｅｑ／ｇ以上であり、より好ましくは３．５ｍｅｑ／ｇ以上、更に好ましくは３．７ｍｅｑ／ｇ以上であり、その上限は、好ましくは６．７ｍｅｑ／ｇ以下、より好ましくは６ｍｅｑ／ｇ以下、更に好ましくは５．５ｍｅｑ／ｇ以下である。上記の観点から、高分子化合物（Ａ）のカチオン電荷密度は、より好ましくは３〜６．７ｍｅｑ／ｇ、更に好ましくは３．５〜６ｍｅｑ／ｇ、より更に好ましくは３．７〜５．５ｍｅｑ／ｇである。
ここでカチオン電荷密度（ｍｅｑ／ｇ）とは、ポリマー１ｇ当たりのカチオン性基のモル数×１０００で表され、高分子化合物（Ａ）を製造する場合には、用いた原料から算出することもできる。
高分子化合物（Ａ）の質量平均分子量は、本発明の親水化処理剤の親水化力を高める観点から、１，０００〜２０，０００である。前記質量平均分子量は、好ましくは、２，０００以上、より好ましく３，０００以上であり、その上限は、好ましくは１８，０００以下、より好ましくは１５，０００以下である。上記の観点から、高分子化合物（Ａ）の質量平均分子量は、２，０００〜１８，０００が好ましく、３，０００〜１５，０００がより好ましい。なお、本発明における質量平均分子量はゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定したポリエチレングリコール換算の質量平均分子量であり、測定条件の詳細は実施例に示すとおりである。
<Physical properties of polymer compound (A)>
The cationic charge density of the polymer compound (A) is preferably 3 meq / g or more, more preferably 3.5 meq / g or more, still more preferably, from the viewpoint of increasing the hydrophilization power of the hydrophilic treatment agent of the present invention. 3.7 meq / g or more, and the upper limit thereof is preferably 6.7 meq / g or less, more preferably 6 meq / g or less, and still more preferably 5.5 meq / g or less. From the above viewpoint, the cationic charge density of the polymer compound (A) is more preferably 3 to 6.7 meq / g, still more preferably 3.5 to 6 meq / g, and still more preferably 3.7 to 5.5 meq. / G.
Here, the cation charge density (meq / g) is represented by the number of moles of cationic groups per gram of polymer × 1000, and when the polymer compound (A) is produced, it may be calculated from the raw material used. it can.
The mass average molecular weight of the polymer compound (A) is 1,000 to 20,000 from the viewpoint of increasing the hydrophilicity of the hydrophilic treatment agent of the present invention. The mass average molecular weight is preferably 2,000 or more, more preferably 3,000 or more, and the upper limit thereof is preferably 18,000 or less, more preferably 15,000 or less. From the above viewpoint, the mass average molecular weight of the polymer compound (A) is preferably 2,000 to 18,000, and more preferably 3,000 to 15,000. In addition, the mass average molecular weight in this invention is a polyethylene glycol conversion mass average molecular weight measured by gel permeation chromatography (GPC), and the details of the measurement conditions are as shown in the Examples.
＜高分子化合物（Ａ）の製造法＞
高分子化合物（Ａ）は公知の方法により製造することができる。例えば、一般式（１）で表されるモノマーと、所望に応じて、繰り返し単位（ｂ）を構成するモノマー、及び繰り返し単位（ｃ）を構成するモノマーから選ばれる１種以上のモノマーを含む原料モノマーを、溶液重合法で重合させることにより製造することができる。
上記の溶液重合に用いられる溶媒としては、例えば、芳香族系炭化水素（トルエン、キシレン等）、低級アルコール（エタノール、イソプロパノール等）、ケトン（アセトン、メチルエチルケトン）、テトラヒドロフラン、ジエチレングリコールジメチルエーテル等を使用することができる。溶媒量は、原料モノマー全量に対し０．５〜２０質量倍が好ましく、１〜１０質量倍が好ましい。
<Method for producing polymer compound (A)>
The polymer compound (A) can be produced by a known method. For example, the raw material containing the monomer represented by the general formula (1), and, if desired, one or more monomers selected from the monomer constituting the repeating unit (b) and the monomer constituting the repeating unit (c) The monomer can be produced by polymerizing by a solution polymerization method.
Examples of the solvent used for the solution polymerization include aromatic hydrocarbons (toluene, xylene, etc.), lower alcohols (ethanol, isopropanol, etc.), ketones (acetone, methyl ethyl ketone), tetrahydrofuran, diethylene glycol dimethyl ether, and the like. Can do. 0.5-20 mass times is preferable with respect to the raw material monomer whole quantity, and, as for the amount of solvent, 1-10 mass times is preferable.
重合開始剤としては、公知のラジカル重合開始剤を用いることができ、例えば、２，２’−アゾビス（２，４−ジメチルバレロニトリル）、２，２’−アゾビス（２−メチルプロパンアミジン）・二塩酸、２，２’−アゾビス（イソブチロニトリル）、１，１’−アゾビス（シクロヘキサン−１−カルボニトリル）等のアゾ系重合開始剤、ｔ−ブチルヒドロペルオキシド等のヒドロ過酸化物類、過酸化ジｔ−ブチル等の過酸化ジアルキル類、ドデカノイルペルオキシド等の過酸化ジアシル類、メチルエチルケトンペルオキシド等のケトンペルオキシド類、過硫酸ナトリウムなどの過硫酸塩類等が挙げられる。
重合開始剤の量は、原料モノマー全量に対し０．００１〜５モル倍が好ましく、０．０２〜１モル倍が好ましい。
重合反応は、不活性ガス気流下、好ましくは６０〜１８０℃、より好ましくは６５〜１２０℃の温度範囲で行うのが好ましく、反応時間は好ましくは０．５〜２０時間、より好ましくは１〜１２時間が好ましい。
得られた高分子化合物（Ａ）は必要に応じて公知の方法で精製することもできる。
As the polymerization initiator, a known radical polymerization initiator can be used. For example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylpropaneamidine). Azo polymerization initiators such as dihydrochloric acid, 2,2′-azobis (isobutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), hydroperoxides such as t-butyl hydroperoxide And dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as dodecanoyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, and persulfates such as sodium persulfate.
The amount of the polymerization initiator is preferably 0.001 to 5 mol times, more preferably 0.02 to 1 mol times based on the total amount of raw material monomers.
The polymerization reaction is preferably carried out in an inert gas stream at a temperature range of preferably 60 to 180 ° C, more preferably 65 to 120 ° C, and the reaction time is preferably 0.5 to 20 hours, more preferably 1 to 1. 12 hours is preferred.
The obtained polymer compound (A) can be purified by a known method as necessary.
［多価有機酸（Ｂ）］
本発明に用いられる多価有機酸（Ｂ）とは、１分子内に２個以上の酸性基を有する化合物であり、酸性基とは、カルボキシ基、スルホン酸基、リン酸基等を意味する。
多価有機酸（Ｂ）としては、例えば、シュウ酸、マレイン酸、クエン酸、アジピン酸、セバシン酸、リンゴ酸、エチレンジアミン四酢酸、ニトリロ三酢酸、ポリアクリル酸、ポリメタクリル酸、ポリマレイン酸、ポリ２−アクリルアミド―２−メチルプロパンスルホン酸、ポリｐ−スチレンスルホン酸等が挙げられる。これらの中では、親水化処理剤の親水化力を高める観点から、エチレンジアミン四酢酸、及びポリアクリル酸から選ばれる１種又は２種が好ましい。
前記ポリアクリル酸の質量平均分子量は、親水化処理剤の親水化力を高める観点から、好ましくは１，０００以上、好ましくは１，２００以上、より好ましくは１，５００以上であり、その上限は、好ましくは２０，０００以下、より好ましくは１０，０００以下、更に好ましく５，０００以下である。上記の観点から、前記ポリアクリル酸の質量平均分子量は、１，０００〜２０，０００が好ましく、１，２００〜１０，０００がより好ましく、１，５００〜５，０００が更に好ましい。
多価有機酸（Ｂ）は、塩の形であってもよい。多価有機酸（Ｂ）の塩としては、アルカリ金属塩、アルカリ土類金属塩、アミン塩が挙げられる。これらの中では、多価有機酸（Ｂ）の水への溶解性の問題、及び親水化処理剤の親水化力を高める観点から、アルカリ金属塩又はアミン塩であることが好ましく、ナトリウム塩、カリウム塩、又はアンモニウム塩であることがより好ましい。
[Polyvalent organic acid (B)]
The polyvalent organic acid (B) used in the present invention is a compound having two or more acidic groups in one molecule, and the acidic group means a carboxy group, a sulfonic acid group, a phosphoric acid group, or the like. .
Examples of the polyvalent organic acid (B) include oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyacrylic acid, polymethacrylic acid, polymaleic acid, poly Examples include 2-acrylamido-2-methylpropane sulfonic acid and poly p-styrene sulfonic acid. Among these, from the viewpoint of increasing the hydrophilizing power of the hydrophilizing agent, one or two selected from ethylenediaminetetraacetic acid and polyacrylic acid are preferable.
The weight average molecular weight of the polyacrylic acid is preferably 1,000 or more, preferably 1,200 or more, more preferably 1,500 or more, from the viewpoint of increasing the hydrophilizing power of the hydrophilizing agent, and the upper limit is Preferably, it is 20,000 or less, More preferably, it is 10,000 or less, More preferably, it is 5,000 or less. In view of the above, the mass average molecular weight of the polyacrylic acid is preferably 1,000 to 20,000, more preferably 1,200 to 10,000, and still more preferably 1,500 to 5,000.
The polyvalent organic acid (B) may be in the form of a salt. Examples of the salt of the polyvalent organic acid (B) include alkali metal salts, alkaline earth metal salts, and amine salts. Among these, from the viewpoint of increasing the solubility of the polyvalent organic acid (B) in water and increasing the hydrophilizing power of the hydrophilizing agent, an alkali metal salt or an amine salt is preferable, a sodium salt, More preferably, it is a potassium salt or an ammonium salt.
［親水化処理剤］
本発明の親水化処理剤は、前記一般式（１）で表されるモノマー由来の繰り返し単位（ａ）を有する高分子化合物（Ａ）、多価有機酸（Ｂ）、及び水（Ｃ）を含有する。
高分子化合物（Ａ）は１種又は２種以上を用いることができ、親水化処理剤中の高分子化合物（Ａ）の含有量は、親水化処理剤の親水化力を高める観点から、好ましくは０．０１質量％以上、より好ましくは０．２質量％以上であり、その上限は、好ましくは５質量％以下、好ましくは２質量％以下、より好ましくは１質量％以下である。上記の観点から、親水化処理剤中の高分子化合物（Ａ）の含有量は、０．０１〜２５質量％が好ましく、０．１〜２質量％がより好ましく、０．２〜１質量％が更に好ましい。
多価有機酸（Ｂ）は１種又は２種以上を用いることができ、親水化処理剤中の含有量に特に限定はないが、その含有量は、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、更に好ましくは０．２質量％以上であり、その上限は、好ましくは２５質量％以下、より好ましくは５質量％以下、更に好ましく４質量％以下、より更に好ましくは３質量％以下である。上記の観点から、親水化処理剤中の多価有機酸（Ｂ）の含有量は、０．０１〜２５質量％が好ましく、溶解性と親水化力向上を両立させる観点から０．１〜５質量％がより好ましく、０．２〜４質量％が更に好ましく、０．２〜３質量％がより更に好ましい。
[Hydrophilic treatment agent]
The hydrophilic treatment agent of the present invention comprises a polymer compound (A) having a repeating unit (a) derived from the monomer represented by the general formula (1), a polyvalent organic acid (B), and water (C). contains.
1 type (s) or 2 or more types can be used for a high molecular compound (A), and the content of the high molecular compound (A) in a hydrophilization processing agent is preferable from a viewpoint of raising the hydrophilization power of a hydrophilization processing agent. Is 0.01% by mass or more, more preferably 0.2% by mass or more, and the upper limit thereof is preferably 5% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less. From the above viewpoint, the content of the polymer compound (A) in the hydrophilic treatment agent is preferably 0.01 to 25% by mass, more preferably 0.1 to 2% by mass, and 0.2 to 1% by mass. Is more preferable.
The polyvalent organic acid (B) can be used singly or in combination of two or more. The content in the hydrophilizing agent is not particularly limited, but the content is preferably 0.01% by mass or more. Preferably it is 0.1% by mass or more, more preferably 0.2% by mass or more, and the upper limit is preferably 25% by mass or less, more preferably 5% by mass or less, still more preferably 4% by mass or less, and still more preferably. Is 3% by mass or less. From the above viewpoint, the content of the polyvalent organic acid (B) in the hydrophilization treatment agent is preferably 0.01 to 25% by mass, and 0.1 to 5 from the viewpoint of achieving both improvement in solubility and hydrophilization power. % By mass is more preferable, 0.2 to 4% by mass is still more preferable, and 0.2 to 3% by mass is still more preferable.
また、本発明の親水化処理剤中の高分子化合物（Ａ）と多価有機酸（Ｂ）の質量比（（Ａ）／（Ｂ））は、本発明の親水化処理剤の親水化力を高める観点から、より好ましくは１／２０以上、より好ましくは１／１０以上、更に好ましくは１／５以上であり、その上限は、好ましくは２０／１以下、より好ましくは１０／１以下、更に好ましくは５／１以下である。上記の観点から、質量比（（Ａ）／（Ｂ））は、１／２０〜２０／１が好ましく、１／１０〜１０／１がより好ましく、１／５〜５／１が更に好ましい。
本発明の親水化処理剤中の水（Ｃ）の含有量に特に限定はないが、その含有量は、親水化力を高める観点から、５０〜９９．９質量％が好ましく、８０〜９９．５質量％がより好ましく、８５〜９９．２質量％が更に好ましい。
Moreover, the mass ratio ((A) / (B)) of the polymer compound (A) and the polyvalent organic acid (B) in the hydrophilization treatment agent of the present invention is the hydrophilization power of the hydrophilization treatment agent of the present invention. Is more preferably 1/20 or more, more preferably 1/10 or more, still more preferably 1/5 or more, and the upper limit thereof is preferably 20/1 or less, more preferably 10/1 or less, More preferably, it is 5/1 or less. From the above viewpoint, the mass ratio ((A) / (B)) is preferably 1/20 to 20/1, more preferably 1/10 to 10/1, and further preferably 1/5 to 5/1.
The content of water (C) in the hydrophilization treatment agent of the present invention is not particularly limited, but the content is preferably 50 to 99.9% by mass from the viewpoint of enhancing the hydrophilization power, and 80 to 99.99. 5 mass% is more preferable, and 85-99.2 mass% is still more preferable.
［その他の成分］
本発明の親水化処理剤には、本発明の目的を阻害しない範囲で、界面活性剤、エチルアルコール、イソプロピルアルコール等の低級アルコール；トルエンスルホン酸塩、キシレンスルホン酸塩、尿素等の可溶化剤；粘土鉱物、水溶性高分子化合物等の粘度調整剤（但し、高分子化合物（Ａ）又は多価有機酸（Ｂ）であるものを除く）；方解石、珪石、リン酸カルシウム、ゼオライト、炭酸カルシウム、ポリエチレン、ナイロン、ポリスチレン等の水不溶性研磨剤；グリセリン、ソルビトール等の保湿剤；カチオン化セルロース等の感触向上剤（但し、高分子化合物（Ａ）であるものを除く）；炭酸ナトリウム、珪酸ナトリウム等のアルカリビルダー；酵素、色素、香料、防腐・防かび剤等を添加することができる。
[Other ingredients]
The hydrophilic treatment agent of the present invention includes a surfactant, a lower alcohol such as ethyl alcohol and isopropyl alcohol; a solubilizer such as toluene sulfonate, xylene sulfonate, urea and the like as long as the object of the present invention is not impaired. Viscosity modifiers such as clay minerals and water-soluble polymer compounds (excluding those that are polymer compounds (A) or polyvalent organic acids (B)); calcite, quartzite, calcium phosphate, zeolite, calcium carbonate, polyethylene Water-insoluble abrasives such as nylon, polystyrene, etc .; Moisturizers such as glycerin and sorbitol; Touch improvers such as cationized cellulose (excluding those that are polymer compounds (A)); Sodium carbonate, sodium silicate, etc. Alkali builder: Enzymes, pigments, fragrances, preservatives and fungicides can be added.
＜界面活性剤＞
本発明の親水化処理剤は、界面活性剤と併用する方が好ましい。また、固体表面に汚れ物質、特に疎水性の高い例えば油性の汚れ物質が付着している場合には、本発明の親水化処理剤と界面活性剤を併用することにより、界面活性剤により疎水性の高い汚れ物質が除去された固体表面を親水化できるため、より効率的に固体表面の親水化処理が可能になる。
用いられる界面活性剤としては、通常液体洗浄剤に用いられる界面活性剤であれば特に限定はない。界面活性剤としてはアニオン性、非イオン性、カチオン性及び両性界面活性剤が挙げられる。
界面活性剤は、洗浄性の観点から、疎水性部位としてアルキル基又はアルケニル基を有することが好ましく、その炭素数は、好ましくは８以上、より好ましくは炭素数１０以上であり、その上限は、好ましくは２０以下、より好ましくは１６以下である。
<Surfactant>
The hydrophilic treatment agent of the present invention is preferably used in combination with a surfactant. In addition, when a dirt substance, particularly an oily dirt substance having a high hydrophobic property is adhered to the solid surface, the surfactant can be made hydrophobic by using the hydrophilizing agent of the present invention in combination with the surfactant. Since the solid surface from which the high-contamination contaminants are removed can be hydrophilized, the solid surface can be hydrophilized more efficiently.
The surfactant to be used is not particularly limited as long as it is a surfactant that is usually used for a liquid detergent. Surfactants include anionic, nonionic, cationic and amphoteric surfactants.
From the viewpoint of detergency, the surfactant preferably has an alkyl group or an alkenyl group as a hydrophobic site, and the carbon number thereof is preferably 8 or more, more preferably 10 or more, and the upper limit is Preferably it is 20 or less, More preferably, it is 16 or less.
（陰イオン性界面活性剤）
陰イオン性界面活性剤としては、疎水性部位を有する硫酸エステル塩、スルホン酸塩、カルボン酸塩、リン酸エステル塩、及びアミノ酸塩から選ばれる１種又は２種以上が好ましい。
具体的には、アルキル硫酸塩、アルケニル硫酸塩、ポリオキシアルキレンアルキルエーテル硫酸塩、ポリオキシアルキレンアルケニルエーテル硫酸塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸塩等の疎水性部位を有する硫酸エステル塩；スルホコハク酸アルキルエステル塩、ポリオキシアルキレンスルホコハク酸アルキルエステル塩、アルカンスルホン酸塩、アシルイセチオネート、アシルメチルタウレート等の疎水性部位を有するスルホン酸塩；炭素数８以上１６以下の高級脂肪酸塩、ポリオキシアルキレンアルキルエーテル酢酸塩等の疎水性部位を有するカルボン酸塩；アルキルリン酸塩、ポリオキシアルキレンアルキルエーテルリン酸塩等の疎水性部位を有するリン酸エステル塩；アシルグルタミン酸塩、アラニン誘導体、グリシン誘導体、アルギニン誘導体等の疎水性部位を有するアミノ酸塩等が挙げられる。
(Anionic surfactant)
The anionic surfactant is preferably one or more selected from sulfate ester salts, sulfonate salts, carboxylate salts, phosphate ester salts, and amino acid salts having a hydrophobic site.
Specifically, sulfate esters having a hydrophobic site such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid Alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, alkane sulfonate, acyl isethionate, sulfonate having a hydrophobic site such as acyl methyl taurate; higher fatty acid salt having 8 to 16 carbon atoms, poly Carboxylate having a hydrophobic moiety such as oxyalkylene alkyl ether acetate; Phosphate ester salt having a hydrophobic moiety such as alkyl phosphate and polyoxyalkylene alkyl ether phosphate; Acyl glutamate, alanine derivatives Glycine derivatives, amino acid salts and the like having a hydrophobic moiety, such as arginine derivatives.
これら陰イオン性界面活性剤の中では、ラウリル硫酸ナトリウム等のアルキル硫酸塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウム（ラウレス−２硫酸ナトリウム）等のポリオキシエチレンアルキルエーテル硫酸塩、ラウリン酸カリウム等の高級脂肪酸塩、ポリオキシエチレンラウリルエーテル酢酸ナトリウム（ラウレス−４，５酢酸ナトリウム）等のポリオキシエチレンアルキルエーテル酢酸塩、ラウレス−２スルホコハク酸ナトリウム等のスルホコハク酸アルキルエステル塩、Ｎ−アシル−Ｌ−グルタミン酸ナトリウム（ココイルグルタミン酸ナトリウム）等のアシルグルタミン酸塩アシルイセチオネート、及びアシルメチルタウレートから選ばれる１種又は２種以上が好ましく、ポリオキシエチレンアルキルエーテル硫酸塩又はアルキル硫酸塩がより好ましい。 Among these anionic surfactants, alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene lauryl ether sulfate (sodium laureth-2 sulfate), and higher grades such as potassium laurate Fatty acid salts, polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate (sodium laureth-4,5 acetate), sulfosuccinic acid alkyl ester salts such as sodium laureth-2 sulfosuccinate, N-acyl-L-glutamic acid One or more selected from acyl glutamate acyl isethionate such as sodium (sodium cocoyl glutamate) and acyl methyl taurate are preferred, polyoxyethylene alkyl ether sulfate or Alkyl sulfate are more preferred.
（非イオン性界面活性剤）
非イオン性界面活性剤としては、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシアルキレン（硬化）ヒマシ油等のポリエチレングリコール型と、ショ糖脂肪酸エステル、ポリグリセリンアルキルエーテル、ポリグリセリン脂肪酸エステル、アルキルグリコシド等の多価アルコール型及び脂肪酸アルカノールアミド等が挙げられる。
これらの中では、ポリオキシアルキレンアルキルエーテル、ポリオキシエチレン硬化ヒマシ油、脂肪酸アルカノールアミド、及びアルキルグリコシドから選ばれる１種又は２種以上が好ましく、アルキルグルコシドがより好ましい。
(Nonionic surfactant)
Nonionic surfactants include polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, Examples include polyethylene glycol types such as oxyalkylene (cured) castor oil, polyhydric alcohol types such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkylglycoside, and fatty acid alkanolamide.
Among these, one or more selected from polyoxyalkylene alkyl ether, polyoxyethylene hydrogenated castor oil, fatty acid alkanolamide, and alkyl glycoside are preferable, and alkyl glucoside is more preferable.
（両性界面活性剤）
両性界面活性剤としては、イミダゾリン系ベタイン、アルキルジメチルアミノ酢酸ベタイン、脂肪酸アミドプロピルベタイン、スルホベタイン等のベタイン系界面活性剤、及びアルキルジメチルアミンオキサイド等のアミンオキサイド型界面活性剤等が挙げられる。 これらの中では、界面活性剤組成物の洗浄性及び洗浄時の泡量の観点から、イミダゾリン系ベタイン、アルキルジメチルアミノ酢酸ベタイン、脂肪酸アミドプロピルベタイン、及びアルキルヒドロキシスルホベタインから選ばれる１種又は２種以上が好ましい。
(Amphoteric surfactant)
Examples of amphoteric surfactants include betaine surfactants such as imidazoline betaines, alkyldimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and sulfobetaines, and amine oxide surfactants such as alkyldimethylamine oxides. Among these, one or two selected from imidazoline betaine, alkyldimethylaminoacetic acid betaine, fatty acid amidopropyl betaine, and alkylhydroxysulfobetaine from the viewpoint of the detergency of the surfactant composition and the amount of foam during washing. More than species are preferred.
（陽イオン性界面活性剤）
陽イオン性界面活性剤としては、アミド基、エステル基又はエーテル基で分断されていてもよい炭素数１２〜２８、好ましくは炭素数１６〜２２炭化水素基を有する第４級アンモニウム塩、ピリジニウム塩、又は３級アミンの鉱酸又は有機酸の塩が挙げられる。
具体的には、セチルトリメチルアンモニウム塩、ステアリルトリメチルアンモニウム塩、ベヘニルトリメチルアンモニウム塩、オクダデシロキシプロピルトリメチルアンモニウム塩等のモノ長鎖アルキルトリメチルアンモニウム塩や、ジステアリルジメチルアンモニウム塩、ジイソテトラデシルジメチルアンモニウム塩等のジ長鎖アルキルジメチルアンモニウム塩や、ステアリルジメチルアミン、ベヘニルジメチルアミン、オクタデシロキシプロピルジメチルアミンの酸塩等のモノ長鎖アルキルジメチルアミン塩が挙げられる。
上記の界面活性剤は、単独で又は２種以上を混合して使用することができ、本発明の親水化処理剤中に、０．５〜８０質量％配合するのが好ましく、２〜３０質量％配合するのがより好ましい。
(Cationic surfactant)
As the cationic surfactant, a quaternary ammonium salt or pyridinium salt having a hydrocarbon group having 12 to 28 carbon atoms, preferably 16 to 22 carbon atoms, which may be separated by an amide group, an ester group or an ether group. Or a salt of a tertiary amine mineral acid or organic acid.
Specifically, mono-long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, okdadecyloxypropyltrimethylammonium salt, distearyldimethylammonium salt, diisotetradecyldimethylammonium Examples thereof include dilong-chain alkyldimethylammonium salts such as salts, and monolong-chain alkyldimethylamine salts such as stearyldimethylamine, behenyldimethylamine, and octadecyloxypropyldimethylamine acid salts.
Said surfactant can be used individually or in mixture of 2 or more types, It is preferable to mix | blend 0.5-80 mass% in the hydrophilic treatment agent of this invention, and 2-30 mass. % Is more preferable.
＜親水化処理剤の製造＞
本発明の親水化処理剤は、前記の高分子化合物（Ａ）、多価有機酸（Ｂ）、水（Ｃ）、及び必要に応じて前述したその他の成分を加えて、公知の方法により攪拌、混合することにより得ることができる。混合装置としては、例えば、ホモジナイザー、超音波分散機、高圧分散機等を用いることができる。
親水化処理剤は、固体表面の種類や処理目的に応じて、適宜組成割合を調整することができる。また、濃厚溶液を調製しておき、使用時に希釈して用いることもできる。
得られる親水化処理剤の２０℃におけるｐＨは、取扱いの安全性、及び固体表面の損傷防止の観点から、好ましくは２〜１１、より好ましくは３〜１０、更に好ましくは４〜８である。ｐＨ調節剤としては、塩酸、硫酸等の無機酸や、クエン酸、コハク酸、リンゴ酸、フマル酸、酒石酸、マロン酸、マレイン酸等の有機酸等の酸剤；水酸化ナトリウム、水酸化カリウム、アンモニアやその誘導体、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等のアミン塩等、炭酸ナトリウム、炭酸カリウム等のアルカリ剤が挙げられる。また、酸剤とアルカリ剤を組み合わせて緩衝剤系として用いることもできる。
<Manufacture of hydrophilic treatment agent>
The hydrophilic treatment agent of the present invention is agitated by a known method by adding the above-described polymer compound (A), polyvalent organic acid (B), water (C), and other components described above as necessary. Can be obtained by mixing. As the mixing device, for example, a homogenizer, an ultrasonic disperser, a high-pressure disperser, or the like can be used.
The composition ratio of the hydrophilizing agent can be appropriately adjusted according to the type of solid surface and the purpose of treatment. In addition, a concentrated solution can be prepared and diluted at the time of use.
The pH of the resulting hydrophilization treatment agent at 20 ° C. is preferably 2 to 11, more preferably 3 to 10, and still more preferably 4 to 8, from the viewpoints of handling safety and prevention of damage to the solid surface. Examples of pH regulators include acid agents such as inorganic acids such as hydrochloric acid and sulfuric acid, and organic acids such as citric acid, succinic acid, malic acid, fumaric acid, tartaric acid, malonic acid and maleic acid; sodium hydroxide, potassium hydroxide And ammonia, derivatives thereof, amine salts such as monoethanolamine, diethanolamine, and triethanolamine, and alkali agents such as sodium carbonate and potassium carbonate. Also, a combination of an acid agent and an alkali agent can be used as a buffer system.
［親水化処理方法］
本発明の固体表面の親水化処理方法は、固体表面を本発明の親水化処理剤を含有する溶液に接触させることを特徴とする。
ここで「固体表面」の「固体」とは、特に制限はなく、ガラス、陶器、磁器、琺瑯、タイル、セラミックス；アルミニウム、ステンレス、真鍮等の金属；ポリエチレン、ポリプロピレン、メラミン樹脂、ポリアミド樹脂、ＡＢＳ樹脂、ＦＲＰ等の合成樹脂；木綿、絹、羊毛等の天然繊維；ポリエステル、ナイロン、レーヨン等の合成繊維；毛髪、爪、歯等の固体を意味する。
本発明方法を適用しうる好適な固体表面としては、前記のセラミックス、金属、合成樹脂から選ばれる１種又は２種以上の疎水性硬質表面が挙げられる。
また、親水化処理剤を含有する溶液としては、取扱いの安全性の観点から、水溶液が好ましい。
親水化処理剤を含有する溶液中の親水化処理剤の含有量は、処理条件にもよるが、表面親水化効果の観点から、前記高分子化合物（Ａ）の含有量が、親水化処理剤を含有する溶液中、好ましくは０．０１質量％以上、より好ましくは０．０５質量％以上、更に好ましくは０．１質量％以上となる量であり、その上限は、好ましくは１５質量％以下、より好ましくは１０質量％以下、更に好ましくは５質量％以下となる量である。上記の観点から、親水化処理剤を含有する溶液中の前記高分子化合物（Ａ）の含有量は、０．０１〜１５質量％が好ましく、０．０５〜１０質量％がより好ましく、０．１〜５質量％が更に好ましい。
[Hydrophilic treatment method]
The method for hydrophilizing a solid surface of the present invention is characterized in that the solid surface is brought into contact with a solution containing the hydrophilizing agent of the present invention.
Here, the “solid” of the “solid surface” is not particularly limited, and glass, ceramic, porcelain, glazed, tile, ceramics; metals such as aluminum, stainless steel, brass; polyethylene, polypropylene, melamine resin, polyamide resin, ABS Synthetic resins such as resin and FRP; natural fibers such as cotton, silk and wool; synthetic fibers such as polyester, nylon and rayon; solids such as hair, nails and teeth.
Suitable solid surfaces to which the method of the present invention can be applied include one or more hydrophobic hard surfaces selected from the ceramics, metals, and synthetic resins.
The solution containing the hydrophilizing agent is preferably an aqueous solution from the viewpoint of handling safety.
The content of the hydrophilic treatment agent in the solution containing the hydrophilic treatment agent depends on the treatment conditions, but from the viewpoint of the surface hydrophilic effect, the content of the polymer compound (A) In an aqueous solution, preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and the upper limit thereof is preferably 15% by mass or less. The amount is more preferably 10% by mass or less, and still more preferably 5% by mass or less. From the above viewpoint, the content of the polymer compound (A) in the solution containing the hydrophilic treatment agent is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, and 1-5 mass% is still more preferable.
固体表面と親水化処理剤を含有する溶液の接触方法は、特に限定されない。例えば、次の（i）〜（iii）の方法等が挙げられる。
（i）親水化処理剤を含有する溶液に固体を浸漬させる方法
（ii）親水化処理剤を含有する溶液を固体表面に噴霧又は塗布する方法
（iii）親水化処理剤を含有する溶液で常法に従い固体表面を洗浄する方法
前記（i）の方法では、固体表面の親水化効果の観点から、親水化処理剤を含有する溶液中に固体表面を、好ましくは５〜５０℃、より好ましくは１０〜４０℃の温度で、好ましくは０．５〜６０分間、より好ましくは１〜５０分間浸漬するのが好ましい。
前記（ii）の方法において、親水化処理剤を含有する溶液を固体表面に適用する方法は、硬質表面の広さ（面積）等に応じて適宜選択できる。通常は、親水化処理剤を固体表面にスプレーした後、乾燥する方法が好ましいが、例えば、１０ｃｍ2あたり０．０１〜０．１ｍＬの親水化処理剤の０．５質量％水溶液をスプレーした後、スポンジ等を用いて薄く塗りのばして処理することもできる。
前記（iii）の方法では、親水化処理剤及び界面活性剤を含有する洗浄剤組成物の形態で使用し、固体表面と接触させるのが好ましい。かかる洗浄剤組成物の形態とする場合、取扱いの安全性、及び固体表面の損傷防止の観点から、そのｐＨは４〜１０が好ましく、４〜８がより好ましい。
界面活性剤としては、前述したものを使用することができる。
The method for contacting the solid surface with the solution containing the hydrophilizing agent is not particularly limited. For example, the following methods (i) to (iii) may be mentioned.
(I) A method of immersing a solid in a solution containing a hydrophilizing agent (ii) A method of spraying or applying a solution containing a hydrophilizing agent on the surface of a solid (iii) A solution containing a hydrophilizing agent is usually used Method of washing the solid surface according to the method In the method (i), from the viewpoint of the effect of hydrophilizing the solid surface, the solid surface is preferably contained in a solution containing a hydrophilizing agent, preferably 5 to 50 ° C., more preferably It is preferable to immerse at a temperature of 10 to 40 ° C., preferably 0.5 to 60 minutes, more preferably 1 to 50 minutes.
In the method (ii), the method of applying the solution containing the hydrophilizing agent to the solid surface can be appropriately selected according to the width (area) of the hard surface. Usually, the method of drying after spraying the hydrophilizing agent on the solid surface is preferable. For example, after spraying a 0.5% by mass aqueous solution of 0.01 to 0.1 mL of hydrophilizing agent per 10 cm 2. It is also possible to apply a thin coating using a sponge or the like.
In the method (iii), it is preferably used in the form of a cleaning composition containing a hydrophilizing agent and a surfactant and brought into contact with a solid surface. When it is set as the form of this cleaning composition, 4-10 are preferable and 4-8 are more preferable from a viewpoint of the safety of handling and damage prevention of a solid surface.
As the surfactant, those described above can be used.
また、本発明の親水化処理により固体表面の水に対する静止接触角が、疎水性硬質表面、好ましくは塩化ビニルの場合は５０°以下、特に４０°以下になることが好ましい。また、親水性硬質表面、好ましくはガラスの場合、３０°以下、特に２５°以下になることが好ましい。ここで、疎水性硬質表面とは、水に対する静止接触角が７０°以上であることを意味し、親水性硬質表面とは７０°未満であることを意味する。 In addition, it is preferable that the static contact angle with respect to water of the solid surface by the hydrophilization treatment of the present invention is 50 ° or less, particularly 40 ° or less in the case of a hydrophobic hard surface, preferably vinyl chloride. In the case of a hydrophilic hard surface, preferably glass, it is preferably 30 ° or less, particularly preferably 25 ° or less. Here, the hydrophobic hard surface means that the static contact angle with respect to water is 70 ° or more, and the hydrophilic hard surface means less than 70 °.
以下の合成例及び実施例における各物性の測定条件をまとめて以下に示す。
＜質量平均分子量測定条件＞
高分子化合物の質量平均分子量は、高分子化合物を溶離液に溶解した０．５質量％溶液をゲル浸透クロマトグラフィー（ＧＰＣ）により下記条件で測定したポリエチレングリコール換算の質量平均分子量である。
（ＧＰＣ測定条件）
・カラム：東ソー株式会社製、ＴＳＫｇｅｌα−Ｍ、２本を直列につないで使用。
・溶離液：５０ｍｍｏｌ／Ｌ臭化リチウム、１％酢酸、エタノール／水＝３／７ｖｏｌ
・流速：０．６ｍＬ／ｍｉｎ、
・カラム温度：４０℃、
・検出器：示差屈折率計
・標準ポリマー；ポリエチレングリコール（東ソー株式会社又は西尾工業株式会社製）
The measurement conditions for each physical property in the following synthesis examples and examples are summarized below.
<Mass average molecular weight measurement conditions>
The mass average molecular weight of the polymer compound is a mass average molecular weight in terms of polyethylene glycol, measured by gel permeation chromatography (GPC) using a 0.5% by mass solution obtained by dissolving the polymer compound in the eluent.
(GPC measurement conditions)
-Column: Tosoh Co., Ltd., TSKgelα-M, used by connecting two in series.
Eluent: 50 mmol / L lithium bromide, 1% acetic acid, ethanol / water = 3/7 vol
・ Flow rate: 0.6 mL / min,
Column temperature: 40 ° C
-Detector: differential refractometer-Standard polymer: Polyethylene glycol (Tosoh Corporation or Nishio Kogyo Co., Ltd.)
合成例１（高分子化合物（Ａ）−（１）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）５０．０ｇ、及び重合溶媒としてイソプロピルアルコール２００．０ｇと、重合開始剤として２，２’−アゾビス（２，４−ジメチルバレロニトリル）（和光純薬工業株式会社製、商品名：Ｖ−６５）６．０ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（１）を得た。高分子化合物（Ａ）−（１）中の繰り返し単位（ａ）、（ｂ）の含有量、カチオン電荷密度、質量平均分子量を表１にまとめて示す。
Synthesis Example 1 (Synthesis of polymer compound (A)-(1))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 200.0 g of isopropyl alcohol as a polymerization solvent, and a polymerization initiator 6.0 g of 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-65) was charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(1) was obtained by reprecipitation with 3000.0 g of acetone and drying. Table 1 summarizes the contents of the repeating units (a) and (b), the cationic charge density, and the mass average molecular weight in the polymer compound (A)-(1).
合成例２（高分子化合物（Ａ）−（２）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）４０．８ｇ、メトキシポリエチレングリコール（２モル）メタクリレート７．４ｇ、及び重合溶媒としてイオン交換水１１．２ｇとエタノール１０１．１ｇと、重合開始剤としてドデカノイルペルオキシド７．８ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（２）を得た。結果を表１に示す。
Synthesis Example 2 (Synthesis of polymer compound (A)-(2))
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 40.8 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 7.4 g of methoxypolyethylene glycol (2 mol) methacrylate, and a polymerization solvent Were charged with 11.2 g of ion-exchanged water and 101.1 g of ethanol, and 7.8 g of dodecanoyl peroxide as a polymerization initiator, and a polymerization reaction was carried out at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(2) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例３（高分子化合物（Ａ）−（３）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）５０．０ｇ、スチレン０．８ｇ、及び重合溶媒としてイオン交換水１１８．６ｇ、重合開始剤として過硫酸ナトリウム４．８ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（３）を得た。結果を表１に示す。
Synthesis Example 3 (Synthesis of polymer compound (A)-(3))
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 50.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 0.8 g of styrene, and 118.6 g of ion-exchanged water as a polymerization solvent. Then, 4.8 g of sodium persulfate was charged as a polymerization initiator, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(3) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例４（高分子化合物（Ａ）−（４）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）４０．７ｇ、アクリルアミド（ＡＡｍ）７．４ｇ、及び重合溶媒としてイオン交換水１１２．３ｇと、重合開始剤として過硫酸ナトリウム６．２ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（４）を得た。結果を表１に示す。
Synthesis Example 4 (Synthesis of polymer compound (A)-(4))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introducing tube, 40.7 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 7.4 g of acrylamide (AAm), and ion-exchanged water as a polymerization solvent 112.3 g and 6.2 g of sodium persulfate as a polymerization initiator were charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(4) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例５（高分子化合物（Ａ）−（５）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、メタクリル酸エチルジメチルエチルアンモニウムエチル硫酸塩（ＭＯＥＤＥＳ）３８．６ｇ、アクリルアミド（ＡＡｍ）５．３ｇ、及び重合溶媒としてイオン交換水１０２．３ｇと、重合開始剤として過硫酸ナトリウム４．４ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（５）を得た。結果を表１に示す。
Synthesis Example 5 (Synthesis of polymer compound (A)-(5))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 38.6 g of ethyl dimethyl ethyl ammonium ethyl sulfate (MOEDES), 5.3 g of acrylamide (AAm), and ion-exchanged water as a polymerization solvent 102.3 g and 4.4 g of sodium persulfate as a polymerization initiator were charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(5) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例６（高分子化合物（Ａ）−（６）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、メタクリル酸ジメチルアミノエチル（ＤＭＡＥＭＡ）４０．０ｇ、及び重合溶媒としてイオン交換水９．３ｇとエタノール８４．０ｇと、重合開始剤としてＶ−６５（和光純薬工業株式会社製）６．３ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（６）を得た。結果を表１に示す。
Synthesis Example 6 (Synthesis of polymer compound (A)-(6))
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 40.0 g of dimethylaminoethyl methacrylate (DMAEMA), 9.3 g of ion-exchanged water and 84.0 g of ethanol as a polymerization solvent, polymerization started As an agent, 6.3 g of V-65 (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(6) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例７（高分子化合物（Ａ）−（９）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、メタクリル酸エチルジメチルエチルアンモニウムエチル硫酸塩（ＭＯＥＤＥＳ）１４０．４ｇ、及び重合溶媒としてイオン交換水２５９．３ｇと、重合開始剤として２，２’−アゾビス（２−メチルプロパンアミジン）・二塩酸（和光純薬工業株式会社製、商品名：Ｖ−５０）１．４ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（９）を得た。結果を表１に示す。
Synthesis Example 7 (Synthesis of polymer compound (A)-(9))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 140.4 g of ethyl dimethyl ethyl ammonium ethyl sulfate (MOEDES), 259.3 g of ion-exchanged water as a polymerization solvent, and a polymerization initiator 2,4′-azobis (2-methylpropaneamidine) · dihydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., trade name: V-50) (1.4 g) was charged, and the polymerization reaction was carried out at 85 ° C. for 6 hours. . Thereafter, the polymer compound (A)-(9) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例８（高分子化合物（Ａ）−（１０）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）１００．０ｇ、及び重合溶媒としてエタノール６６．７ｇと、重合開始剤としてＶ−６５（和光純薬工業株式会社製）０．１ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（１０）を得た。結果を表１に示す。
Synthesis Example 8 (Synthesis of polymer compound (A)-(10))
In a reactor equipped with a stirrer, reflux condenser, thermometer, and nitrogen introduction tube, 100.0 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 66.7 g of ethanol as a polymerization solvent, and V as a polymerization initiator. -65 (made by Wako Pure Chemical Industries Ltd.) 0.1g was prepared, and the polymerization reaction was performed at 85 degreeC for 6 hours. Thereafter, the polymer compound (A)-(10) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例９（高分子化合物（Ａ）−（９）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）４５．３ｇ、メタクリル酸３．８ｇ、及び重合溶媒としてイオン交換水１１４．５ｇと、重合開始剤として過硫酸ナトリウム５．２ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（９）を得た。結果を表１に示す。
Synthesis Example 9 (Synthesis of polymer compound (A)-(9))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 45.3 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 3.8 g of methacrylic acid, and ion-exchanged water 114. 5 g and 5.2 g of sodium persulfate as a polymerization initiator were charged, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(9) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例１０（高分子化合物（Ａ）−（１０）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド（ＱＤＭ）３７．３ｇ、アクリルアミド１０．２ｇ、及び重合溶媒としてイオン交換水１１０．７ｇと、重合開始剤として過硫酸ナトリウム６．８ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（１０）を得た。結果を表１に示す。
Synthesis Example 10 (Synthesis of polymer compound (A)-(10))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 37.3 g of 2-methacryloyloxy-ethyltrimethylammonium chloride (QDM), 10.2 g of acrylamide, and 110.7 g of ion-exchanged water as a polymerization solvent. Then, 6.8 g of sodium persulfate was charged as a polymerization initiator, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(10) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
合成例１１（高分子化合物（Ａ）−（１１）の合成）
攪拌機、還流冷却器、温度計、窒素導入管を備えた反応器に、メタクリル酸エチルジメチルエチルアンモニウムエチル硫酸塩（ＭＯＥＤＥＳ）３６．２ｇ、アクリルアミド７．４ｇ、及び重合溶媒としてイオン交換水１０１．８ｇと、重合開始剤として過硫酸ナトリウム５．０ｇを仕込み、８５℃にて６時間重合反応を行った。その後、アセトン３０００．０ｇで再沈殿させた後に乾燥させることで高分子化合物（Ａ）−（１１）を得た。結果を表１に示す。
Synthesis Example 11 (Synthesis of polymer compound (A)-(11))
In a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 36.2 g of ethyldimethylethylammonium ethylsulfate (MOEDES), 7.4 g of acrylamide, and 101.8 g of ion-exchanged water as a polymerization solvent Then, 5.0 g of sodium persulfate was charged as a polymerization initiator, and a polymerization reaction was performed at 85 ° C. for 6 hours. Thereafter, the polymer compound (A)-(11) was obtained by reprecipitation with 3000.0 g of acetone and drying. The results are shown in Table 1.
実施例１（親水化処理剤の製造）
合成例（１）で得た高分子化合物（Ａ）−（１）３．７５ｇ、ポリアクリル酸１．２５ｇ、及びイオン交換水４９５ｇを混合し、親水化処理剤を得た。
得られた本発明の親水化処理剤の親水化能を、下記の方法で処理した固体表面の接触角測定から評価した。
Example 1 (Production of hydrophilizing agent)
3.75 g of the polymer compound (A)-(1) obtained in Synthesis Example (1), 1.25 g of polyacrylic acid, and 495 g of ion-exchanged water were mixed to obtain a hydrophilic treatment agent.
The hydrophilicity of the obtained hydrophilic treatment agent of the present invention was evaluated by measuring the contact angle of the solid surface treated by the following method.
＜接触角測定条件＞
水平に固定した予め清浄にしたテストピース（材質：硬質ポリ塩化ビニル、２５ｍｍ×７５ｍｍ、株式会社エンジニアリングテストサービス製、商品名：塩化ビニルテストピース）に親水化処理剤１ｍＬを滴下して５分間静置した後、イオン交換水約２００ｍＬで軽くすすいで風乾した。
このテストピースの処理部分表面のイオン交換水に対する静止接触角を、協和界面科学株式会社製の自動接触角計ＤＭ−５００を用いて、添加量１０μＬ、添加６秒後の接触角を測定した。測定は２枚のテストピースについて、１枚のテストピース当たり５回行い、その平均値を用いた。
処理後の接触角が低いほど、水に濡れやすい、即ち、固体表面が親水化されていることを示す。結果を表１に示す。
<Contact angle measurement conditions>
1 mL of a hydrophilizing agent was dropped on a pre-cleaned test piece (material: hard polyvinyl chloride, 25 mm x 75 mm, manufactured by Engineering Test Service Co., Ltd., trade name: vinyl chloride test piece) that was fixed horizontally and left still for 5 minutes. After being placed, it was lightly rinsed with about 200 mL of ion exchange water and air-dried.
The contact angle with respect to the ion-exchanged water on the surface of the treated part of this test piece was measured using an automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd., and the contact angle after 6 seconds of addition was 10 μL. The measurement was performed 5 times per one test piece for two test pieces, and the average value was used.
The lower the contact angle after the treatment, the easier it is to get wet with water, that is, the solid surface is hydrophilized. The results are shown in Table 1.
実施例２〜７及び比較例１〜１１
高分子化合物（Ａ）、多価有機酸（Ｂ）の種類と配合量を表１に示すように変化させたほかは、実施例１と同様の操作を行って、親水化処理剤を得た。
得られた親水化処理剤の親水化能を、実施例１と同様の操作を行って、評価した。結果を表１に示す。
なお、親水化処理剤の配合時に原料として水溶液を用いた場合、表中の数値は、水溶液の配合量ではなく、配合した水溶液中に含まれる原料の値に換算した数値である。
Examples 2-7 and Comparative Examples 1-11
Except having changed the kind and compounding quantity of a high molecular compound (A) and polyhydric organic acid (B) as shown in Table 1, operation similar to Example 1 was performed and the hydrophilic treatment agent was obtained. .
The hydrophilicity of the obtained hydrophilic treatment agent was evaluated by performing the same operation as in Example 1. The results are shown in Table 1.
When an aqueous solution is used as a raw material at the time of blending the hydrophilic treatment agent, the numerical values in the table are not the blending amount of the aqueous solution but the numerical values converted into the raw material values contained in the blended aqueous solution.
表１中の、略号は以下のとおりである。
・ＱＤＭ：２−メタクリロイルオキシ−エチルトリメチルアンモニウムクロリド
・ＰＥＧ（２）ＭＡ：メトキシポリエチレングリコール（２モル）メタクリレート
・Ｓｔ：スチレン
・ＡＡｍ：アクリルアミド
・ＤＭＡＥＭＡ：メタクリル酸ジメチルアミノエチル
・ＭＯＥＤＥＳ：メタクリル酸エチルジメチルエチルアンモニウムエチル硫酸塩
・ＭＡＡ：メタクリル酸
Abbreviations in Table 1 are as follows.
-QDM: 2-methacryloyloxy-ethyltrimethylammonium chloride-PEG (2) MA: methoxypolyethylene glycol (2 mol) methacrylate-St: styrene-AAm: acrylamide-DMAEMA: dimethylaminoethyl methacrylate-MOEDES: ethyldimethyl methacrylate Ethyl ammonium ethyl sulfate / MAA: Methacrylic acid
表１から、実施例１〜７で得られた親水化処理剤は、及び比較例１〜１１で得られた親水化処理剤に比べて、親水化処理後の静止接触角が３９°以下と低く、固体表面に対する親水化力が優れていることが分かる。 From Table 1, the hydrophilization treatment agents obtained in Examples 1 to 7 and the hydrophilization treatment agents obtained in Comparative Examples 1 to 11 have a static contact angle of 39 ° or less after the hydrophilization treatment. It is low and it turns out that the hydrophilization power with respect to the solid surface is excellent.
本発明によれば、固体表面に対して優れた親水化力を有する親水化処理剤を提供することができる。
また、本発明の親水化処理方法によれば、疎水性の固体表面に対して優れた親水性を付与することができ、しかもその持続効果も優れている。また、親水性が優れているため固体表面に付着した汚れ、特に疎水性汚れを水で容易に洗い流すことができるため、本発明の方法は防汚処理として利用することもできる。
ADVANTAGE OF THE INVENTION According to this invention, the hydrophilization processing agent which has the outstanding hydrophilization power with respect to the solid surface can be provided.
Moreover, according to the hydrophilic treatment method of the present invention, excellent hydrophilicity can be imparted to the hydrophobic solid surface, and the sustaining effect is also excellent. In addition, since the hydrophilicity is excellent, dirt attached to the solid surface, particularly hydrophobic dirt, can be easily washed away with water, so that the method of the present invention can also be used as an antifouling treatment.
Claims (7)
（式中、Ｒ１は水素原子又はメチル基、Ｒ２は炭素数が１〜６のアルカンジイル基、Ｒ３、Ｒ４及びＲ５はそれぞれ独立に、炭素数１〜５のアルキル基、ベンジル基、又はアルキル基の炭素数が１〜５のアルキルベンジル基、Ｘは酸素原子又はＮＨ基、Ｙ−は陰イオンを示す。） Polymer compound (A) having a cation charge density of 3.9 meq / g to 5.5 meq / g having a repeating unit (a) derived from a monomer represented by the following general formula (1), a polyvalent organic acid (B) and a hydrophilization treatment agent containing water (C), wherein the polymer compound (A) has a mass average molecular weight of 1,000 to 20,000, and constitutes the polymer compound (A). The hydrophilic treatment agent, wherein the content of the repeating unit (a) in all repeating units is 60 mol% or more and the content of the repeating unit (b) derived from the monomer having an acidic group is 1 mol% or less.
Wherein R 1 is a hydrogen atom or a methyl group, R 2 is an alkanediyl group having 1 to 6 carbon atoms, R 3 , R 4 and R 5 are each independently an alkyl group having 1 to 5 carbon atoms, benzyl group, or an alkyl benzyl group having 1 to 5 carbon atoms in the alkyl group, X is an oxygen atom or an NH group, Y - represents an anion).
The hydrophilic treatment method according to claim 6 , wherein the hydrophobic hard surface is a surface of ceramic, metal, or synthetic resin.
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