JP6815092B2 - Surface treatment agent - Google Patents
Surface treatment agent Download PDFInfo
- Publication number
- JP6815092B2 JP6815092B2 JP2016079545A JP2016079545A JP6815092B2 JP 6815092 B2 JP6815092 B2 JP 6815092B2 JP 2016079545 A JP2016079545 A JP 2016079545A JP 2016079545 A JP2016079545 A JP 2016079545A JP 6815092 B2 JP6815092 B2 JP 6815092B2
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- Japan
- Prior art keywords
- carbon atoms
- structural unit
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- treatment agent
- surface treatment
- Prior art date
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- 239000012756 surface treatment agent Substances 0.000 title claims description 85
- 125000004432 carbon atom Chemical group C* 0.000 claims description 68
- 239000007787 solid Substances 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 41
- 229920001577 copolymer Polymers 0.000 claims description 35
- 125000002947 alkylene group Chemical group 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 22
- 230000003068 static effect Effects 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229910001504 inorganic chloride Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 15
- 229920000642 polymer Polymers 0.000 description 71
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 63
- 239000000243 solution Substances 0.000 description 24
- 235000019441 ethanol Nutrition 0.000 description 23
- 230000002708 enhancing effect Effects 0.000 description 22
- 238000004519 manufacturing process Methods 0.000 description 21
- 239000000178 monomer Substances 0.000 description 21
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- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
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- 238000005406 washing Methods 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229940071104 xylenesulfonate Drugs 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Description
本発明は、表面処理剤、表面処理剤組成物、及び固体表面の処理方法に関する。 The present invention relates to surface treatment agents, surface treatment agent compositions, and methods for treating solid surfaces.
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 property to a solid surface, different methods of water repellent treatment and hydrophilic treatment are known.
The water-repellent treatment is a technique for surface-treating a solid surface such as glass, metal, or fiber to have water repellency so that dirt contained in water does not adhere. For example, it is widely practiced to wash clothes and then treat them with a soft finish, spray ski wear or the like with a water repellent to give a waterproof effect, or wax the painted surface of an automobile. ..
However, it is difficult to completely make the surface water-repellent by the water-repellent treatment, and the dirt contained in the water accumulates on the solid surface due to repeated contact with water, so that a sufficient antifouling effect is exhibited. 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ち易くなったり、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、熱交換器のアルミニウムフィンの着霜防止、浴槽及びトイレ表面等の防汚性付与等が期待できる。 On the other hand, if the solid surface is hydrophilized, that is, the solid surface is treated to reduce the contact angle with water and make the solid surface wet easily, the dirt adhering to the solid surface after the treatment is easily removed during cleaning. In addition to being expected to prevent recontamination of dirt and stains, it is also expected to have anti-fog effect on glass and mirrors, anti-static effect, prevention of frost formation on aluminum fins of heat exchangers, and anti-fouling properties on bath and toilet surfaces. it can.
固体表面の処理剤及び処理方法としては、いくつかの提案がなされている。
例えば、特許文献１には、ヒドロキシアルキル（メタ）アクリルアミドとジメチルアクリルアミドと含フッ素化合物とを共重合してなる含フッ素共重合体、及びヒドロキシル基と結合を形成し得る官能基を有する化合物を含むコーティング剤が記載されている。
特許文献２には、粒径が１ｎｍから１００ｎｍの親水性シリカを含み、有機バインダーとして、非プロトン性カチオン樹脂、並びにアルコール及び／又はエーテル系溶剤を含む超親水性コーティング剤が記載されている。
Several proposals have been made as treatment agents and treatment methods for solid surfaces.
For example, Patent Document 1 includes a fluorine-containing copolymer obtained by copolymerizing hydroxyalkyl (meth) acrylamide, dimethylacrylamide, and a fluorine-containing compound, and a compound having a functional group capable of forming a bond with a hydroxyl group. Coating agents are listed.
Patent Document 2 describes a super-hydrophilic coating agent containing hydrophilic silica having a particle size of 1 nm to 100 nm, and as an organic binder, an aprotic cationic resin and an alcohol and / or an ether solvent.
また、特許文献３には、カチオン両性ポリマーとアニオン有用物質とを含む組成物を用いた毛髪の洗浄方法等が記載され、特許文献４には、スルホベタインを構成単位とし、さらに疎水性不飽和単量体由来の構成単位を含むブロック重合体からなる親水化処理剤が記載されている。 Further, Patent Document 3 describes a method for washing hair using a composition containing a cationic amphoteric polymer and an anionic useful substance, and Patent Document 4 contains sulfobetaine as a constituent unit and further hydrophobic unsaturated. A hydrophilization treatment agent composed of a block polymer containing a constituent unit derived from a monomer is described.
本発明は、固体表面に高い親水性を付与する表面処理剤、表面処理剤組成物、及び固体表面の処理方法を提供する。 The present invention provides a surface treatment agent, a surface treatment agent composition, and a method for treating a solid surface, which imparts high hydrophilicity to a solid surface.
本発明は、下記式（１）で表される構成単位（Ａ）、及び下記式（２）で表される構成単位（Ｂ）を含む共重合体からなる表面処理剤に関する。 The present invention relates to a surface treatment agent composed of a copolymer containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2).
〔式中、
Ｒ１〜Ｒ３：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｒ４：炭素数１以上４以下のアルキレン基、又は−Ｙ１−ＯＰＯ３ −−Ｙ２−
Ｙ１、Ｙ２：同一又は異なって、炭素数１以上４以下のアルキレン基
Ｒ５、Ｒ６：同一又は異なって、炭素数１以上４以下の炭化水素基
Ｘ１：Ｏ又はＮＲ７であり、Ｒ７は水素原子又は炭素数１以上４以下の炭化水素基
Ｘ２：水素原子、炭素数１以上４以下の炭化水素基、Ｒ１７ＳＯ３ −、又はＲ１７ＣＯＯ−を示す。ただし、Ｒ４が炭素数１以上４以下のアルキレン基のとき、Ｘ２はＲ１７ＳＯ３ −、又はＲ１７ＣＯＯ−、Ｒ１７は炭素数１以上４以下のアルキレン基であり、Ｒ４が−Ｙ１−ＯＰＯ３ −−Ｙ２−のとき、Ｘ２は水素原子又は炭素数１以上４以下の炭化水素基である。〕
[In the formula,
R 1 to R 3 : Same or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R 4 : alkylene group having 1 to 4 carbon atoms, or −Y 1 −OPO 3 − −Y 2 −
Y 1 , Y 2 : Same or different, alkylene group with 1 or more and 4 or less carbon atoms R 5 , R 6 : Same or different, hydrocarbon group with 1 or more and 4 or less carbon atoms X 1 : O or NR 7 . , R 7 is a hydrogen atom or a C 1 to 4 hydrocarbon group X 2: a hydrogen atom, 1 to 4 of the hydrocarbon group having a carbon number, R 17 SO 3 -, or R 17 COO - shows the. Provided that when R 4 is an alkylene group having 1 to 4 carbon atoms, X 2 is R 17 SO 3 -, or R 17 COO -, R 17 is an alkylene group having 1 to 4 carbon atoms, R 4 is When −Y 1 −OPO 3 − −Y 2− , X 2 is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. ]
〔式中、
Ｒ８〜Ｒ１０：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｘ３：Ｏ又はＮＨ基
Ｒ１１：炭素数１以上４以下のアルキレン基
Ｘ４：Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｒ１２〜Ｒ１６は、同一又は異なって、水素原子又は炭素数１以上４以下の炭化水素基、Ｘ５は陰イオンを示す。〕
[In the formula,
R 8 to R 10 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms X 3 : O or NH group R 11 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms X 4 : N + R 12 R 13 R 14 X 5 or NR 15 R 16 , where R 12 to R 16 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X 5 is an anion. ]
また、本発明は、前記式（１）で表される構成単位（Ａ）、及び前記式（２）で表される構成単位（Ｂ）を含む共重合体を含有する表面処理剤組成物に関する。 The present invention also relates to a surface treatment agent composition containing a copolymer containing a structural unit (A) represented by the formula (1) and a structural unit (B) represented by the formula (2). ..
また、本発明は、前記式（１）で表される構成単位（Ａ）及び前記式（２）で表される構成単位（Ｂ）を含む共重合体、並びに水を含有する処理液を、固体表面に接触させる、固体表面の処理方法に関する。 In addition, the present invention uses a copolymer containing the structural unit (A) represented by the formula (1) and the structural unit (B) represented by the formula (2), and a treatment liquid containing water. The present invention relates to a method for treating a solid surface, which is brought into contact with the solid surface.
本発明によれば、固体表面に高い親水性を付与する表面処理剤、表面処理剤組成物、及び固体表面の処理方法が提供される。 According to the present invention, there are provided a surface treatment agent, a surface treatment agent composition, and a method for treating a solid surface, which impart high hydrophilicity to a solid surface.
＜表面処理剤＞
本発明の表面処理剤は、前記式（１）で表される構成単位（Ａ）と前記式（２）で表される構成単位（Ｂ）とを含む共重合体（以下、表面処理剤用重合体という）からなる。
前記式（１）で表される構成単位（Ａ）は、ベタイン基を有する不飽和単量体を由来とする構成単位であってよい。また、前記式（２）で表される構成単位（Ｂ）は、カチオン基を有する不飽和単量体を由来とする構成単位であってよい。
<Surface treatment agent>
The surface treatment agent of the present invention is a copolymer containing a structural unit (A) represented by the formula (1) and a structural unit (B) represented by the formula (2) (hereinafter, for a surface treatment agent). It consists of a polymer).
The structural unit (A) represented by the formula (1) may be a structural unit derived from an unsaturated monomer having a betaine group. Further, the structural unit (B) represented by the above formula (2) may be a structural unit derived from an unsaturated monomer having a cationic group.
［表面処理剤用重合体］
（表面処理剤用重合体の重量平均分子量）
表面処理剤用重合体の重量平均分子量は、表面処理剤用重合体の親水化性能を高める観点から、好ましくは５００以上、より好ましくは５０００以上、更に好ましくは１万以上、より更に好ましくは３万以上であり、製造性（配合物の粘度等）向上の観点から、好ましくは２０万以下、より好ましくは１０万以下、更に好ましくは７万以下、より更に好ましくは６万以下である。この重量平均分子量は、実施例に記載の方法で測定することができる。
[Polymer for surface treatment agent]
(Weight average molecular weight of polymer for surface treatment agent)
The weight average molecular weight of the polymer for surface treatment agent is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 3 from the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent. From the viewpoint of improving manufacturability (viscosity of the compound, etc.), it is preferably 200,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, and even more preferably 60,000 or less. This weight average molecular weight can be measured by the method described in Examples.
（構成単位Ａと構成単位Ｂのモル比）
表面処理剤用重合体の構成単位Ａと構成単位Ｂのモル比は、表面への吸着性を高める観点から、構成単位（Ａ）／構成単位（Ｂ）で、５０／５０以上９９．９／０．１以下が好ましく、５５／４５以上９９．９／０．１以下がより好ましい。構成単位（Ａ）／構成単位（Ｂ）のモル比は、同様の観点から、好ましくは５０／５０以上、より好ましくは５５／４５以上、更に好ましくは６０／４０以上、更により好ましくは７５／２５以上、更により好ましくは９０／１０以上であり、表面処理剤用重合体の親水化性能を高める観点から好ましくは９８／２以下、より好ましくは９６／４以下である。
(Mole ratio of constituent unit A and constituent unit B)
The molar ratio of the structural unit A and the structural unit B of the polymer for surface treatment agent is 50/50 or more and 99.9 / in terms of the structural unit (A) / structural unit (B) from the viewpoint of enhancing the adsorptivity to the surface. It is preferably 0.1 or less, and more preferably 55/45 or more and 99.9 / 0.1 or less. From the same viewpoint, the molar ratio of the structural unit (A) / structural unit (B) is preferably 50/50 or more, more preferably 55/45 or more, still more preferably 60/40 or more, still more preferably 75 /. It is 25 or more, more preferably 90/10 or more, and preferably 98/2 or less, more preferably 96/4 or less, from the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent.
［構成単位Ａ］
（構成単位Ａの含有量）
表面処理剤用重合体中の構成単位Ａの含有量は、表面処理剤用重合体の親水化性能を高める観点から、好ましくは９０質量％以上、より好ましくは９２質量％以上、更に好ましくは９４質量％以上であり、表面への吸着性を高める観点から、好ましくは９９質量％以下、より好ましくは９８質量％以下、更に好ましくは９５質量％以下である。
[Structural unit A]
(Content of constituent unit A)
The content of the structural unit A in the polymer for surface treatment agent is preferably 90% by mass or more, more preferably 92% by mass or more, still more preferably 94, from the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent. It is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less, from the viewpoint of enhancing the adsorptivity to the surface.
（構成単位Ａの構成）
表面処理剤用重合体の構成単位Ａは、下記式（１）で表される構成単位である。
(Structure of configuration unit A)
The structural unit A of the polymer for surface treatment agent is a structural unit represented by the following formula (1).
〔式中、
Ｒ１〜Ｒ３：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｒ４：炭素数１以上４以下のアルキレン基、又は−Ｙ１−ＯＰＯ３ −−Ｙ２−
Ｙ１、Ｙ２：同一又は異なって、炭素数１以上４以下のアルキレン基
Ｒ５、Ｒ６：同一又は異なって、炭素数１以上４以下の炭化水素基
Ｘ１：Ｏ又はＮＲ７であり、Ｒ７は水素原子又は炭素数１以上４以下の炭化水素基
Ｘ２：水素原子、炭素数１以上４以下の炭化水素基、Ｒ１７ＳＯ３ −、又はＲ１７ＣＯＯ−を示す。ただし、Ｒ４が炭素数１以上４以下のアルキレン基のとき、Ｘ２はＲ１７ＳＯ３ −、又はＲ１７ＣＯＯ−、Ｒ１７は炭素数１以上４以下のアルキレン基であり、Ｒ４が−Ｙ１−ＯＰＯ３ −−Ｙ２−のとき、Ｘ２は水素原子又は炭素数１以上４以下の炭化水素基である。〕
[In the formula,
R 1 to R 3 : Same or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R 4 : alkylene group having 1 to 4 carbon atoms, or −Y 1 −OPO 3 − −Y 2 −
Y 1 , Y 2 : Same or different, alkylene group with 1 or more and 4 or less carbon atoms R 5 , R 6 : Same or different, hydrocarbon group with 1 or more and 4 or less carbon atoms X 1 : O or NR 7 . , R 7 is a hydrogen atom or a C 1 to 4 hydrocarbon group X 2: a hydrogen atom, 1 to 4 of the hydrocarbon group having a carbon number, R 17 SO 3 -, or R 17 COO - shows the. Provided that when R 4 is an alkylene group having 1 to 4 carbon atoms, X 2 is R 17 SO 3 -, or R 17 COO -, R 17 is an alkylene group having 1 to 4 carbon atoms, R 4 is When −Y 1 −OPO 3 − −Y 2− , X 2 is a hydrogen atom or a hydrocarbon group having 1 or more and 4 or less carbon atoms. ]
式（１）において、不飽和単量体の入手性の観点、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、Ｒ１及びＲ２は、それぞれ、水素原子が好ましい。
式（１）において、Ｒ３は、不飽和単量体の入手性の観点、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、水素原子又はメチル基が好ましく、メチル基がより好ましい。
式（１）において、Ｘ１は、不飽和単量体の入手性の観点、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、Ｏが好ましい。Ｒ４の炭素数１以上４以下のアルキレン基は、同様の観点から、炭素数２又は３のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。
式（１）において、Ｒ４は、親水化性能を高める観点から、炭素数１以上４以下のアルキレン基が好ましく、炭素数２又は３のアルキレン基がより好ましい。
式（１）において、Ｙ１、Ｙ２は、それぞれ、炭素数２又は３のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。
式（１）において、Ｒ５、Ｒ６は、同不飽和単量体の入手性の観点、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、それぞれ、メチル基、エチル基が好ましく、メチル基がより好ましい。
式（１）において、Ｘ２は、水素原子、炭素数１以上４以下の炭化水素基、Ｒ１７ＳＯ３ −、又はＲ１７ＣＯＯ−であるが、Ｒ４が炭素数１以上４以下のアルキレン基のとき、Ｘ２はＲ１７ＳＯ３ −、又はＣＯＯ−であり、Ｒ４が−Ｙ１−ＯＰＯ３ −−Ｙ２−のとき、Ｘ２は水素原子又は炭素数１以上４以下の炭化水素基である。Ｒ４が−Ｙ１−ＯＰＯ３ −−Ｙ２−のとき、親水化性能を高める観点から、Ｘ２は炭素数１以上４以下の炭化水素基が好ましく、メチル基がより好ましい。Ｒ４が炭素数１以上４以下のアルキレン基のとき、同様の観点から、Ｘ２はＲ１７ＳＯ３ −が好ましい。
また、Ｒ１７は，炭素数１以上３以下のアルキレン基が好ましく、炭素数２以上３以下のアルキレン基がより好ましい。
In the formula (1), R 1 and R 2 are respectively from the viewpoint of the availability of the unsaturated monomer, the viewpoint of the polymerizable property of the monomer, and the viewpoint of enhancing the hydrophilicity performance of the polymer for the surface treatment agent. A hydrogen atom is preferred.
In the formula (1), R 3 is a hydrogen atom or a methyl group from the viewpoint of availability of unsaturated monomer, polymerizability of monomer, and enhancement of hydrophilicity performance of polymer for surface treatment agent. Is preferable, and a methyl group is more preferable.
In the formula (1), X 1 is preferably O from the viewpoint of availability of unsaturated monomer, polymerizability of monomer, and enhancement of hydrophilicity performance of polymer for surface treatment agent. From the same viewpoint, the alkylene group having 1 to 4 carbon atoms of R4 is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably an alkylene group having 2 carbon atoms.
In the formula (1), R 4 is preferably an alkylene group having 1 or more and 4 or less carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms, from the viewpoint of enhancing the hydrophilicity performance.
In the formula (1), Y 1 and Y 2 are preferably an alkylene group having 2 or 3 carbon atoms, respectively, and more preferably an alkylene group having 2 carbon atoms.
In the formula (1), R 5 and R 6 are each from the viewpoint of availability of the unsaturated monomer, the viewpoint of the polymerizable property of the monomer, and the viewpoint of enhancing the hydrophilic performance of the polymer for surface treatment agent, respectively. , Methyl group, ethyl group is preferable, and methyl group is more preferable.
In the formula (1), X 2 is a hydrogen atom, 1 or more and 4 or less carbon atoms hydrocarbon group, R 17 SO 3 -, or R 17 COO - is a alkylene R 4 is having 1 to 4 carbon atoms When the group, X 2 is R 17 SO 3 − or COO − , and when R 4 is −Y 1 −OPO 3 − −Y 2 −, X 2 is a hydrogen atom or a hydrocarbon having 1 or more carbon atoms and 4 or less carbon atoms. It is a hydrogen group. When R 4 is −Y 1 −OPO 3 − −Y 2 −, from the viewpoint of enhancing the hydrophilicity performance, X 2 is preferably a hydrocarbon group having 1 or more carbon atoms and 4 or less carbon atoms, and more preferably a methyl group. When R 4 is an alkylene group having 1 or more carbon atoms and 4 or less carbon atoms, R 17 SO 3 − is preferable for X 2 from the same viewpoint.
Further, R 17 preferably has an alkylene group having 1 or more and 3 or less carbon atoms, and more preferably an alkylene group having 2 or more and 3 or less carbon atoms.
［構成単位Ｂ］
（構成単位Ｂの含有量）
表面処理剤用重合体中の構成単位Ｂの含有量は、表面への吸着性を高める観点から、好ましくは１質量％以上、より好ましくは２質量％以上、更に好ましくは５質量％以上であり、表面処理剤用重合体の親水化性能を高める観点から、好ましくは１０質量％以下、より好ましくは８質量％以下、更に好ましくは６質量％以下である。
[Structural unit B]
(Content of constituent unit B)
The content of the structural unit B in the polymer for surface treatment agent is preferably 1% by mass or more, more preferably 2% by mass or more, still more preferably 5% by mass or more, from the viewpoint of enhancing the adsorptivity to the surface. From the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent, it is preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 6% by mass or less.
（構成単位Ｂの構成）
表面処理剤用重合体の構成単位Ｂは、下記式（２）で表される構成単位である。
(Structure of configuration unit B)
The structural unit B of the polymer for surface treatment agent is a structural unit represented by the following formula (2).
〔式中、
Ｒ８〜Ｒ１０：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｘ３：Ｏ又はＮＨ基
Ｒ１１：炭素数１以上４以下のアルキレン基
Ｘ４：Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｒ１２〜Ｒ１６は、同一又は異なって、水素原子又は炭素数１以上４以下の炭化水素基、Ｘ５は４陰イオン
を示す。〕
[In the formula,
R 8 to R 10 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms X 3 : O or NH group R 11 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms X 4 : N + R 12 R 13 R 14 X 5 or NR 15 R 16 , R 12 to R 16 represent the same or different hydrocarbon atoms or hydrocarbon groups having 1 to 4 carbon atoms, and X 5 represents 4 anions. ]
式（２）において、不飽和単量体の入手性の観点、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、Ｒ８及びＲ９は、それぞれ、水素原子が好ましい。
式（２）において、Ｒ１０は、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、水素原子又はメチル基が好ましく、メチル基がより好ましい。
式（２）において、Ｘ３は、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、Ｏが好ましい。
式（２）において、Ｒ１１は、単量体の重合性の観点及び表面処理剤用重合体の親水化性能を高める観点から、炭素数２又は３のアルキレン基が好ましく、炭素数２のアルキレン基がより好ましい。
式（２）において、Ｘ４は、表面処理剤用重合体の親水化性能を高める観点及び４級化反応の容易性の観点から、Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５が好ましく、Ｒ１２、Ｒ１３、Ｒ１４は、同様の観点から、それぞれ、メチル基、エチル基が好ましい。
式（２）において、Ｒ１５、Ｒ１６は、表面処理剤用重合体の親水化性能を高める観点及び４級化反応の容易性の観点から、メチル基、エチル基が好ましく、メチル基がより好ましい。
式（２）において、Ｘ５は陰イオンであり、ハロゲンイオン又はＣ２Ｈ５ＳＯ４ −が好ましく、Ｃ２Ｈ５ＳＯ４ −がより好ましい。
In the formula (2), from the viewpoint of availability of unsaturated monomer, polymerizability of monomer, and enhancement of hydrophilicity performance of polymer for surface treatment agent, R 8 and R 9 are respectively. A hydrogen atom is preferred.
In the formula (2), R 10 is preferably a hydrogen atom or a methyl group, and more preferably a methyl group, from the viewpoint of the polymerizable property of the monomer and the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent.
In the formula (2), X 3, from the viewpoint of increasing the hydrophilic properties of the polymerizable aspects and surface treatment agent for polymer of a monomer, O is preferred.
In the formula (2), R 11 is preferably an alkylene group having 2 or 3 carbon atoms, preferably an alkylene group having 2 carbon atoms, from the viewpoint of the polymerizable property of the monomer and the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent. Groups are more preferred.
In the formula (2), X 4 is N + R 12 R 13 R 14 X 5 or NR 15 R 16 from the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent and the ease of the quaternization reaction. N + R 12 R 13 R 14 X 5 is preferable, and R 12 , R 13 and R 14 are preferably a methyl group and an ethyl group, respectively, from the same viewpoint.
In the formula (2), R 15 and R 16 are preferably a methyl group or an ethyl group, preferably a methyl group, from the viewpoint of enhancing the hydrophilicity performance of the polymer for surface treatment agent and the ease of the quaternization reaction. preferable.
In formula (2), X 5 is an anion, preferably a halogen ion or C 2 H 5 SO 4 −, and more preferably C 2 H 5 SO 4 − .
［構成単位Ａ及び構成単位Ｂ以外の構成単位］
表面処理剤用重合体は、本発明の効果を損なわない範囲で、構成単位Ａ及び構成単位Ｂ以外の構成単位を含有してもよい。構成単位Ａ及び構成単位Ｂ以外の構成単位としては、スルホベタイン基を有する不飽和単量体以外の不飽和単量体に由来する構成単位が好ましく、スチレン等の疎水性不飽和単量体に由来する構成単位がより好ましい。
表面処理剤用重合体中の構成単位Ａ及び構成単位Ｂ以外の構成単位の含有量は、好ましくは１質量％以下、より好ましくは、０．５質量％以下、更に好ましくは０．１質量％以下、より更に好ましくは、０．０５質量％以下である。表面処理剤用重合体中の構成単位Ａ及び構成単位Ｂ以外の構成単位の含有量は、０質量％であってもよい。
表面処理剤用重合体中の構成単位Ａ及び構成単位Ｂの合計の含有量は、好ましくは９９質量％以上、より好ましくは９９．５質量％以上、更に好ましくは９９．９質量％以上、より更に好ましくは９９．９５質量％以上である。表面処理剤用重合体中の構成単位Ａ及び構成単位Ｂの合計の含有量は、１００質量％であってもよい。
[Constructive units other than structural unit A and structural unit B]
The polymer for a surface treatment agent may contain a structural unit other than the structural unit A and the structural unit B as long as the effect of the present invention is not impaired. As the structural unit other than the structural unit A and the structural unit B, a structural unit derived from an unsaturated monomer other than the unsaturated monomer having a sulfobetaine group is preferable, and a hydrophobic unsaturated monomer such as styrene is used. The resulting building block is more preferred.
The content of the structural units other than the structural unit A and the structural unit B in the polymer for the surface treatment agent is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.1% by mass. Hereinafter, even more preferably, it is 0.05% by mass or less. The content of the structural units other than the structural unit A and the structural unit B in the polymer for the surface treatment agent may be 0% by mass.
The total content of the structural unit A and the structural unit B in the polymer for surface treatment agent is preferably 99% by mass or more, more preferably 99.5% by mass or more, still more preferably 99.9% by mass or more, and more. More preferably, it is 99.95% by mass or more. The total content of the structural unit A and the structural unit B in the polymer for the surface treatment agent may be 100% by mass.
［表面処理剤用重合体の製造方法］
本発明の表面処理剤用重合体を製造する方法としては、どのような方法を採っても良いが、具体的には以下の（ｉ）、（ii）のような方法が挙げられる。原料の入手性と、製造の容易さの観点から、（ii）の方法が好ましい。
（ｉ）ベタイン基とカチオン基を有する不飽和単量体を共重合して得る方法
（ii）アミノ基とカチオン基を有する不飽和単量体を共重合させたあとに、ベタイン化剤によって４級化を行って得る方法
[Method for producing polymer for surface treatment agent]
Any method may be adopted as a method for producing the polymer for a surface treatment agent of the present invention, and specific examples thereof include the following methods (i) and (ii). The method (ii) is preferable from the viewpoint of availability of raw materials and ease of production.
(I) Method obtained by copolymerizing an unsaturated monomer having a betaine group and a cationic group (ii) After copolymerizing an unsaturated monomer having an amino group and a cationic group, 4 by a betaine agent How to get by classifying
＜表面処理剤組成物＞
本発明の表面処理剤組成物は、前記本発明の表面処理剤用重合体を含有する。表面処理剤用重合体は１種又は２種以上を用いることができる。
本発明の表面処理剤組成物は、前記本発明の表面処理剤用重合体、及び水を含有することが好ましい。
本発明の表面処理剤組成物における本発明の表面処理剤用重合体の具体例及び好ましい態様は、本発明の表面処理剤と同じである。
<Surface treatment agent composition>
The surface treatment agent composition of the present invention contains the polymer for surface treatment agents of the present invention. One kind or two or more kinds of polymers for surface treatment agents can be used.
The surface treatment agent composition of the present invention preferably contains the polymer for the surface treatment agent of the present invention and water.
Specific examples and preferred embodiments of the polymer for a surface treatment agent of the present invention in the surface treatment agent composition of the present invention are the same as those of the surface treatment agent of the present invention.
表面処理剤組成物中の表面処理剤用重合体の含有量は、表面処理剤組成物の親水化性能を高める観点から、好ましくは０．０１質量％以上、より好ましくは０．１質量％以上、より好ましくは０．２質量％以上であり、増粘により均一な処理が抑制され、表面処理剤組成物の親水化性能が低下するのを防止する観点から、好ましくは５質量％以下、好ましくは２．０質量％以下、より好ましくは１．０質量％以下である。
本発明の表面処理剤組成物が水を含有する場合、水は該組成物の残部であり、該組成物中の水の含有量は、水と水以外の成分との合計が１００質量％となる量である。
The content of the polymer for surface treatment agent in the surface treatment agent composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, from the viewpoint of enhancing the hydrophilic performance of the surface treatment agent composition. , More preferably 0.2% by mass or more, and preferably 5% by mass or less from the viewpoint of suppressing uniform treatment by thickening and preventing deterioration of the hydrophilization performance of the surface treatment agent composition. Is 2.0% by mass or less, more preferably 1.0% by mass or less.
When the surface treatment agent composition of the present invention contains water, water is the rest of the composition, and the content of water in the composition is 100% by mass in total of water and components other than water. Is the amount.
本発明の表面処理剤組成物は、表面処理剤組成物の親水化性能を高める観点から、界面活性剤を含有することができる。界面活性剤を用いることにより、表面処理剤組成物が固体表面に濡れ広がりやすくなり、親水化性能が向上する。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、界面活性剤を用いることにより、界面活性剤により疎水性の高い汚れ物質が除去され、固体表面の親水化性能が向上する。
表面処理剤組成物中の界面活性剤の含有量は、表面処理剤組成物の親水化性能を高める観点から、好ましくは０．０１質量％以上、より好ましく０．０３質量％以上、より好ましくは０．０５質量％以上であり、表面処理剤用重合体の固体表面への吸着が阻害され、親水化性能が低下するのを防止する観点から、好ましくは３０質量％以下、好ましくは２０質量％以下、より好ましくは１０質量％以下である。さらに抑泡の観点から、好ましくは１質量％以下、より好ましくは０．５質量％以下、更に好ましくは０．３質量％以下、より更に好ましくは０．１質量％以下である。
The surface treatment agent composition of the present invention can contain a surfactant from the viewpoint of enhancing the hydrophilicity performance of the surface treatment agent composition. By using the surfactant, the surface treatment agent composition is easily wetted and spread on the solid surface, and the hydrophilicity performance is improved. Further, when a dirt substance, particularly an oily dirt substance having high hydrophobicity, is attached to the solid surface, by using a surfactant, the dirt substance having high hydrophobicity is removed by the surfactant, and the solid Surface hydrophilization performance is improved.
The content of the surfactant in the surface treatment agent composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, more preferably more preferably 0.03% by mass or more, from the viewpoint of enhancing the hydrophilization performance of the surface treatment agent composition. The content is 0.05% by mass or more, preferably 30% by mass or less, preferably 20% by mass, from the viewpoint of preventing the adsorption of the surfactant polymer to the solid surface from being inhibited and the hydrophilicity performance from being lowered. Hereinafter, it is more preferably 10% by mass or less. Further, from the viewpoint of foam suppression, it is preferably 1% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.3% by mass or less, still more preferably 0.1% by mass or less.
用いられる界面活性剤としては、液体洗浄剤などの固体表面に適用される処理剤に通常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、陰イオン性界面活性剤、非イオン性界面活性剤、陽イオン性界面活性剤及び両性界面活性剤から選ばれる界面活性剤が挙げられる。 The surfactant used is not particularly limited as long as it is a surfactant usually used for a treatment agent applied to a solid surface such as a liquid cleaning agent. Examples of the surfactant include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
本発明の表面処理剤組成物は、本発明の表面処理剤用重合体の水への溶解性を高める観点から、塩化ナトリウムなどの溶解促進剤を含有することが好ましい。溶解促進剤は塩化物、更に無機塩化物が好ましい。本発明の表面処理剤組成物は、溶解促進剤、好ましくは塩化物、より好ましくは塩化ナトリウムを、好ましくは０．１質量％以上、より好ましくは０．３質量％以上、そして、好ましくは１０質量％以下、より好ましくは３．０質量％
以下含有する。
The surface treatment agent composition of the present invention preferably contains a dissolution accelerator such as sodium chloride from the viewpoint of increasing the solubility of the polymer for surface treatment agent of the present invention in water. The dissolution accelerator is preferably chloride, more preferably inorganic chloride. The surface treatment agent composition of the present invention contains a dissolution accelerator, preferably chloride, more preferably sodium chloride, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and preferably 10. Weight% or less, more preferably 3.0% by mass
It contains the following.
本発明の表面処理剤組成物には、本発明の目的を阻害しない範囲で、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の多価カルボン酸；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、ジエチレングリコールモノブチルエーテル等の溶剤；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、表面処理剤用重合体を除く）；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、表面処理剤用重合体を除く）；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。 The surface treatment agent composition of the present invention contains oxalic acid, maleic acid, citrate, adipic acid, sebacic acid, malic acid, ethylenediamine tetraacetic acid, nitrilotriacetic acid, and polyacrylic acid, as long as the object of the present invention is not impaired. , Polycarboxylic acids such as polymethacrylic acid, polymaleic acid, poly2-acrylamide-2-methylpropanesulfonic acid, polyp-styrenesulfonic acid; lower alcohols such as ethyl alcohol and isopropyl alcohol, solvents such as diethylene glycol monobutyl ether; Solubilizers such as toluene sulfonate, xylene sulfonate, urea; viscosity modifiers such as clay minerals, water-soluble polymer compounds (excluding polymers for surface treatment agents); calcified stones, silicates, calcium phosphate, zeolites , Water-insoluble abrasives such as calcium carbonate, polyethylene, nylon, polystyrene; moisturizers such as glycerin, sorbitol; feel improvers such as cationized cellulose (excluding polymers for surface treatment agents); sodium carbonate, sodium silicate Alkaline builders such as; enzymes, pigments, fragrances, antiseptic / antifungal agents, etc. can be added.
本発明の表面処理剤組成物は、本発明の表面処理剤用重合体、水及び必要に応じて前述した界面活性剤や多価有機酸等の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。
表面処理剤組成物は、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。
The surface treatment agent composition of the present invention is stirred by a known method by adding the polymer for the surface treatment agent of the present invention, water and, if necessary, other components such as the above-mentioned surfactant and polyhydric organic acid. , Can be obtained by mixing.
The composition ratio of the surface treatment agent composition can be appropriately adjusted according to the type of solid surface and the purpose of treatment. It is also possible to prepare a concentrated solution and dilute it at the time of use.
得られる表面処理剤組成物の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以上、より好ましくは３以上、より好ましくは４以上であり、好ましくは１１以下、より好ましくは１０以下、より好ましくは８以下である。ｐＨ調節剤としては、塩酸、硫酸等の無機酸や、前述の有機酸等の酸剤；水酸化ナトリウム、水酸化カリウム等のアルカリ金属水酸化物、炭酸ナトリウム、炭酸カリウム等のアルカリ金属炭酸塩等の無機アルカリ化合物、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有機アルカリ化合物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。 The pH of the obtained surface treatment agent composition at 20 ° C. is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, and preferably 4 or more, from the viewpoint of handling safety and prevention of damage to the solid surface. It is 11 or less, more preferably 10 or less, and more preferably 8 or less. Examples of the pH adjuster include inorganic acids such as hydrochloric acid and sulfuric acid, acid agents such as the above-mentioned organic acids; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Examples thereof include inorganic alkaline compounds such as ammonia and derivatives thereof, and alkaline agents such as organic alkaline compounds such as monoethanolamine, diethanolamine and triethanolamine. Further, an acid agent and an alkaline agent can be combined and used as a buffer system.
＜固体表面の処理方法＞
本発明の固体表面の処理方法は、前記本発明の表面処理剤用重合体、及び水を含有する処理液を、固体表面に接触させる。
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等の固体を意味する。
本発明の処理方法を適用しうる好適な固体表面としては、親水性固体表面、あるいは疎水性固体表面が挙げられ、親水性固体表面がより好ましい。ここで、固体表面についての「親水性」とは、水に対する静止接触角が７０°未満であることを意味する。なお、この静止接触角は、実施例に記載の方法で測定することができる。
本発明で好適な固体表面は、ガラス、陶器、磁器、ステンレス及びシリコンウエハーから選ばれる１種又は２種以上の硬質表面が挙げられる。
<Solid surface treatment method>
In the method for treating a solid surface of the present invention, the polymer for a surface treatment agent of the present invention and a treatment liquid containing water are brought into contact with the solid surface.
Here, the "solid" of the "solid surface" is not particularly limited, and is limited to glass, pottery, porcelain, aquarium, tile, ceramics; metals such as aluminum, stainless steel, and brass; polyethylene, polypropylene, melamine resin, polyamide resin, and ABS. Resin, synthetic resin such as FRP; natural fiber such as cotton, silk, wool; solid such as synthetic fiber such as polyester, nylon, and rayon.
Suitable solid surfaces to which the treatment method of the present invention can be applied include hydrophilic solid surfaces and hydrophobic solid surfaces, with hydrophilic solid surfaces being more preferred. Here, "hydrophilic" for a solid surface means that the static contact angle with water is less than 70 °. The static contact angle can be measured by the method described in the examples.
Suitable solid surfaces in the present invention include one or more hard surfaces selected from glass, pottery, porcelain, stainless steel and silicon wafers.
本発明の固体表面の処理方法に用いられる処理液は、本発明の表面処理剤用重合体を、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、そして、好ましくは５質量％以下、より好ましくは２質量％以下、更に好ましくは１質量％以下含有する。 The treatment liquid used in the method for treating a solid surface of the present invention is the polymer for a surface treatment agent of the present invention, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0. It is contained in an amount of 2% by mass or more, preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.
また、本発明の固体表面の処理方法に用いられる処理液は、本発明の表面処理剤用重合体の水への溶解性を高める観点から、塩化ナトリウムなどの溶解促進剤を含有することが好ましい。本発明の固体表面の処理方法に用いられる処理液は、溶解促進剤、好ましくは塩化物を、より好ましくは塩化ナトリウムを、好ましくは０．１質量％以上、より好ましくは０．５質量％以上、そして、好ましくは３．０質量％以下、より好ましくは１．５質量％以下含有する。 Further, the treatment liquid used in the method for treating a solid surface of the present invention preferably contains a dissolution accelerator such as sodium chloride from the viewpoint of enhancing the solubility of the polymer for a surface treatment agent of the present invention in water. .. The treatment liquid used in the method for treating a solid surface of the present invention is a dissolution accelerator, preferably chloride, more preferably sodium chloride, preferably 0.1% by mass or more, more preferably 0.5% by mass or more. , And preferably 3.0% by mass or less, more preferably 1.5% by mass or less.
また、本発明の表面処理剤組成物が本発明の固体表面の処理方法に用いられる処理液であってもよい。また、本発明の表面処理剤組成物を希釈して本発明の固体表面の処理方法に用いられる処理液を調製してもよい。 Further, the surface treatment agent composition of the present invention may be a treatment liquid used in the method for treating a solid surface of the present invention. Further, the surface treatment agent composition of the present invention may be diluted to prepare a treatment liquid used in the method for treating a solid surface of the present invention.
固体表面と処理液との接触方法は、特に限定されない。例えば、次の（ｉ）〜（ii）の方法が挙げられる。
（ｉ）処理液に固体を浸漬させる方法
（ii）処理液を固体表面に噴霧又は塗布する方法
The contact method between the solid surface and the treatment liquid is not particularly limited. For example, the following methods (i) to (ii) can be mentioned.
(I) Method of immersing a solid in a treatment liquid (ii) Method of spraying or coating a solid surface with a treatment liquid
前記（ｉ）の方法において、浸漬する時間は、親水化性能を高める観点及び経済性の観点から、好ましくは０．５分以上、より好ましくは１分以上であり、好ましくは６０分以下、より好ましくは５０分以下である。
前記（ii）の方法において、処理液を固体表面に噴霧又は塗布する方法は、硬質表面の広さ（面積）等に応じて適宜選択できる。処理液を固体表面にスプレー等で噴霧した後、乾燥する方法が好ましい。必要に応じて、噴霧した後、水ですすいでもよい。また、噴霧した後、スポンジ等を用いて薄く塗りのばしてもよい。
固体表面に噴霧又は塗布する処理液の量は、例えば、表面処理剤用重合体の含有量が０．５質量％の処理液の場合、好ましくは１０ｃｍ２あたり０．０１ｍＬ以上０．１ｍＬ以下である。
In the method (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, preferably 60 minutes or less, from the viewpoint of enhancing the hydrophilicity performance and economic efficiency. It is preferably 50 minutes or less.
In the method (ii), the method of spraying or coating the treatment liquid on the solid surface can be appropriately selected depending on the size (area) of the hard surface and the like. A method of spraying the treatment liquid on the solid surface with a spray or the like and then drying is preferable. If necessary, it may be sprayed and then rinsed with water. Further, after spraying, it may be spread thinly with a sponge or the like.
The amount of the treatment liquid to be sprayed or applied to the solid surface is, for example, 0.01 mL or more and 0.1 mL or less per 10 cm 2 in the case of a treatment liquid containing 0.5% by mass of the polymer for surface treatment agent. is there.
固体表面に接触させる処理液の温度は、親水化性能を高める観点、処理方法の容易性の観点から、好ましくは５℃以上、より好ましくは１０℃以上、更に好ましくは１５℃以上であり、好ましくは５０℃以下、より好ましくは４０℃以下、更に好ましくは３０℃以下である。 The temperature of the treatment liquid to be brought into contact with the solid surface is preferably 5 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 15 ° C. or higher, from the viewpoint of enhancing the hydrophilicity performance and the ease of the treatment method. Is 50 ° C. or lower, more preferably 40 ° C. or lower, still more preferably 30 ° C. or lower.
また、処理が固体表面に親水性を付与することを目的とする場合、本発明の処理液により処理された固体表面の水に対する静止接触角が、好ましくは５０°以下、より好ましくは４０°以下、更に好ましくは３０°以下、より更に好ましくは２５°以下である。
また、本発明の処理液を接触させた後の固体表面の静止接触角は、前記処理液を接触させる前の静止接触角の７０％以下、更に５０％以下、更に４５％以下であることが好ましい。
また、本発明の処理液により処理された固体表面は、親水化性能などを高める観点から、均一に処理されていることが好ましい。表面処理の均一性は、処理後の固体表面を目視で観察することにより判断できる。
When the treatment aims to impart hydrophilicity to the solid surface, the static contact angle of the solid surface treated with the treatment liquid of the present invention with water is preferably 50 ° or less, more preferably 40 ° or less. , More preferably 30 ° or less, and even more preferably 25 ° or less.
Further, the static contact angle of the solid surface after the treatment liquid of the present invention is brought into contact is 70% or less, 50% or less, and 45% or less of the static contact angle before the treatment liquid is brought into contact. preferable.
Further, the solid surface treated with the treatment liquid of the present invention is preferably uniformly treated from the viewpoint of enhancing the hydrophilicity performance and the like. The uniformity of the surface treatment can be judged by visually observing the solid surface after the treatment.
以下の製造例、実施例及び比較例において、「％」は「質量％」を意味する。各種物性等の測定は以下の方法により行った。 In the following production examples, examples and comparative examples, "%" means "mass%". Various physical properties were measured by the following methods.
製造例１〔共重合体Ａ１の製造〕
（工程１）
内容量１０００ｍＬの４つ口フラスコにエタノール（和光純薬工業（株）製）を１２６．３０ｇ入れ、７８℃に昇温して還流させた。ここにメタクリル酸２−（ジメチルアミノ）エチル（和光純薬工業（株）製）１８１．１２ｇ、メタクリル酸２−（ジメチルアミノ）エチルジエチル硫酸塩（花王（株）製／９０％水溶液）２３．６０ｇ、エタノール５３．２０ｇを混合させた溶液と、２，２’−アゾビス（２−メチルブチロニトリル）（和光純薬工業（株）製）５．８３ｇ、エタノール１０．００ｇを混合させた溶液をそれぞれ２時間かけて滴下した。４時間熟成させた後に冷却し、ポリマー溶液を得た。
Production Example 1 [Production of copolymer A1]
(Step 1)
126.30 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 78 ° C. to reflux. Here, 181.12 g of 2- (dimethylamino) ethyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) and 2- (dimethylamino) ethyldiethyl sulfate (manufactured by Kao Co., Ltd./90% aqueous solution) 23. A solution in which 60 g and 53.20 g of ethanol are mixed, and 5.83 g of 2,2'-azobis (2-methylbutyronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.) and 10.00 g of ethanol are mixed. Was added dropwise over 2 hours. After aging for 4 hours, it was cooled to obtain a polymer solution.
（工程２）
内容量１０００ｍＬの４つ口フラスコに、得られたポリマー溶液を９４．７０ｇ、炭酸水素ナトリウム（和光純薬工業（株）製）３．１５ｇ、水を１５０．００ｇ添加し、５０℃に昇温した。そこに１，３−プロパンスルトン（東京化成（株）製）３８．７０ｇを１時間かけて滴下して反応を行った。３時間熟成させた後に、９０℃／２０ｋＰａで２時間減圧加熱することでエタノールを留去し、共重合体Ａ１を含有する水溶液を得た。
(Step 2)
To a 4-necked flask with an internal volume of 1000 mL, add 94.70 g of the obtained polymer solution, 3.15 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 150.00 g of water, and raise the temperature to 50 ° C. did. 38.70 g of 1,3-propane sultone (manufactured by Tokyo Kasei Co., Ltd.) was added dropwise thereto over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain an aqueous solution containing the copolymer A1.
製造例２〔共重合体Ａ２の製造〕
（工程１）
内容量１０００ｍＬの４つ口フラスコにエタノールを９４．４６ｇ入れ、７８℃まで昇温して還流させた。そこにメタクリル酸２-(ジメチルアミノ)エチル２６７．５２ｇ、メタクリル酸２-(ジメチルアミノ)エチルジエチル硫酸塩１４７．２０ｇ、エタノール７８．２９ｇを混合させた溶液と、２,２'-アゾビス(２-メチルブチロニトリル)４．０９ｇ、エタノール９．５４ｇを混合させた溶液を別々に２時間かけて滴下して重合した。４時間熟成させた後に冷却し、ポリマー溶液を得た。
（工程２）
内容量１０００ｍＬの４つ口フラスコに、得られたポリマー溶液を３０７．８２ｇ、炭酸水素ナトリウム７．１５ｇ、水を３９４．５６ｇ入れて５０℃まで昇温した。そこに１,３-プロパンスルトン１１１．２０ｇを１時間かけて滴下して反応を行った。３時間熟成させた後に、９０℃/２０ｋＰａで２時間減圧加熱することでエタノールを留去し、共重合体Ａ２を含有するポリマー水溶液を得た。
Production Example 2 [Production of copolymer A2]
(Step 1)
94.46 g of ethanol was placed in a four-necked flask having an internal volume of 1000 mL, the temperature was raised to 78 ° C., and the mixture was refluxed. A solution prepared by mixing 267.52 g of 2- (dimethylamino) ethyl methacrylate, 147.20 g of 2- (dimethylamino) ethyldiethyl sulfate, and 78.29 g of ethanol, and 2,2'-azobis (2). A mixed solution of 4.09 g of -methylbutyronitrile) and 9.54 g of ethanol was separately added dropwise over 2 hours for polymerization. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
307.82 g of the obtained polymer solution, 7.15 g of sodium hydrogen carbonate, and 394.56 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. 111.20 g of 1,3-propane sultone was added dropwise thereto over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the copolymer A2.
製造例３〔共重合体Ａ３の製造〕
（工程１）
内容量１０００ｍＬの４つ口フラスコにエタノールを８１．４７ｇ入れ、７８℃まで昇温して還流させた。そこにメタクリル酸２-(ジメチルアミノ)エチル１７２．３７ｇ、メタクリル酸２-(ジメチルアミノ)エチルジエチル硫酸塩２５２．９２ｇ、エタノール８０．２９ｇを混合させた溶液と、２,２'-アゾビス(２-メチルブチロニトリル)４．２２ｇ、エタノール９．８４ｇを混合させた溶液を別々に２時間かけて滴下して重合した。４時間熟成させた後に冷却し、ポリマー溶液を得た。
（工程２）
内容量１０００ｍＬの４つ口フラスコに、得られたポリマー溶液を３０７．６９ｇ、炭酸水素ナトリウム４．６１ｇ、水を３６９．１４ｇ入れて５０℃まで昇温した。そこに１,３-プロパンスルトン７１．６５ｇを１時間かけて滴下して反応を行った。３時間熟成させた後に、９０℃/２０ｋＰａで２時間減圧加熱することでエタノールを留去し、共重合体Ａ３を含有するポリマー水溶液を得た。
Production Example 3 [Production of copolymer A3]
(Step 1)
81.47 g of ethanol was placed in a four-necked flask having an internal volume of 1000 mL, the temperature was raised to 78 ° C., and the mixture was refluxed. A solution prepared by mixing 172.37 g of 2- (dimethylamino) ethyl methacrylate, 252.92 g of 2- (dimethylamino) ethyldiethyl sulfate, and 80.29 g of ethanol, and 2,2'-azobis (2). A mixed solution of 4.22 g of -methylbutyronitrile) and 9.84 g of ethanol was separately added dropwise over 2 hours for polymerization. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
307.69 g of the obtained polymer solution, 4.61 g of sodium hydrogen carbonate, and 369.14 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. 71.65 g of 1,3-propane sultone was added dropwise thereto over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the copolymer A3.
製造例４〔共重合体Ａ４の製造〕
（工程１）
内容量１０００ｍＬの４つ口フラスコにエタノールを１２７．１５ｇ入れ、７８℃まで昇温して還流させた。そこにメタクリル酸２-(ジメチルアミノ)エチル１８７．００ｇ、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ライド(Ａｌｄｒｉｃｈ製/８０％水溶液)１６．２６ｇ、エタノール５３．６０ｇを混合させた溶液と、２,２'-アゾビス(２-メチルブチロニトリル)６．０２ｇ、エタノール１０．００ｇを混合させた溶液を別々に２時間かけて滴下して重合した。４時間熟成させた後に冷却し、ポリマー溶液を得た。
（工程２）
内容量１０００ｍＬの４つ口フラスコに、得られたポリマー溶液を９５．４２ｇ、炭酸水素ナトリウム３．５０ｇ、水を１５０．００ｇ入れて５０℃まで昇温した。そこに１,３-プロパンスルトン３９．９６ｇを１時間かけて滴下して反応を行った。３時間熟成させた後に、９０℃/２０ｋＰａで２時間減圧加熱することでエタノールを留去し、共重合体Ａ４を含有するポリマー水溶液を得た。
Production Example 4 [Production of copolymer A4]
(Step 1)
127.15 g of ethanol was placed in a four-necked flask having an internal volume of 1000 mL, the temperature was raised to 78 ° C., and the mixture was refluxed. A solution obtained by mixing 187.00 g of 2- (dimethylamino) ethyl methacrylate, 16.26 g of methacryloyloxyethyl trimethylammonium chloride (manufactured by Aldrich / 80% aqueous solution), and 53.60 g of ethanol, and 2,2'-azobis. A mixed solution of 6.02 g of (2-methylbutyronitrile) and 10.00 g of ethanol was separately added dropwise over 2 hours for polymerization. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
95.42 g of the obtained polymer solution, 3.50 g of sodium hydrogen carbonate, and 150.00 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. 39.96 g of 1,3-propane sultone was added dropwise thereto over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the copolymer A4.
製造例５〔共重合体Ａ５の製造〕
５０ｍＬナスフラスコにスターラーチップ、２-メタクリロイルオキシエチルホスホリルコリン（シグマアルドリッチ製）４．８２ｇ、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ライド０．２２ｇ、２,２'-アゾビス(２-メチルプロピオンアミジン)ニ塩酸塩０．０９ｇ、水１１．５０ｇを入れ、三方コックで栓をし、７０℃に加熱し重合を行った。４時間反応させた後に冷却し、共重合体Ａ５を含有するポリマー水溶液を得た。
Production Example 5 [Production of copolymer A5]
Stirrer chip, 2-methacryloyloxyethyl phosphorylcholine (manufactured by Sigma Aldrich) 4.82 g, methacryloyloxyethyl trimethylammonium chloride 0.22 g, 2,2'-azobis (2-methylpropion amidine) dihydrochloride in a 50 mL eggplant flask. 09 g and 11.50 g of water were added, stoppered with a three-way cock, and heated to 70 ° C. for polymerization. After reacting for 4 hours, the mixture was cooled to obtain an aqueous polymer solution containing the copolymer A5.
製造例６〔共重合体Ａ６の製造〕
内容量５００ｍＬの４つ口フラスコに水５７．４７ｇ入れ、７０℃まで昇温させた。そこにＮ-（２-カルボキシエチル）-Ｎ-メタクリロキシエチル-Ｎ，Ｎ-ジメチルアンモニウムベタイン（大阪有機化学工業（株）製）４７．７６ｇ、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ライド２．８０ｇ、水４７．５０ｇを混合させた溶液と、２,２'-アゾビス(２-メチルプロピオンアミジン)二塩酸塩（和光純薬工業（株）製）１．１７ｇ、水１０．００ｇを混合させた溶液を別々に２時間かけて滴下して重合した。４時間熟成させた後に冷却し、共重合体Ａ６を含有するポリマー水溶液を得た。
Production Example 6 [Production of copolymer A6]
57.47 g of water was placed in a four-necked flask having an internal volume of 500 mL, and the temperature was raised to 70 ° C. There, N- (2-carboxyethyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine (manufactured by Osaka Organic Chemical Industries, Ltd.) 47.76 g, methacryloyloxyethyl trimethylammonium chloride 2.80 g, water 47 Separate solution of .50 g mixed solution and 2,2'-azobis (2-methylpropion amidine) dihydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) 1.17 g and water of 10.00 g. It was added dropwise over 2 hours to polymerize. After aging for 4 hours, it was cooled to obtain an aqueous polymer solution containing the copolymer A6.
製造例７〔重合体Ｂ１の製造〕
（工程１）
内容量５００ｍＬの４つ口フラスコにエタノールを５３．２３ｇ入れ、７８℃まで昇温して還流させた。そこにメタクリル酸２-(ジメチルアミノ)エチル１５０．００ｇ、エタノール１６．６０ｇを混合させた溶液と、２,２'-アゾビス(２-メチルブチロニトリル)０．９２ｇ、エタノール１０．００ｇを混合させた溶液を別々に２時間かけて滴下して重合した。４時間熟成させた後に冷却し、ポリマー溶液を得た。
（工程２）
内容量１０００ｍＬの４つ口フラスコに、得られたポリマー溶液を７５．７６ｇ、炭酸水素ナトリウム３．４７ｇ、水を１５０．００ｇ入れて５０℃まで昇温した。そこに１,３-プロパンスルトン４２．７３ｇを１時間かけて滴下して反応を行った。３時間熟成させた後に、９０℃/２０ｋＰａで２時間減圧加熱することでエタノールを留去し、重合体Ｂ１を含有するポリマー水溶液を得た。
Production Example 7 [Production of polymer B1]
(Step 1)
53.23 g of ethanol was placed in a four-necked flask having an internal volume of 500 mL, the temperature was raised to 78 ° C., and the mixture was refluxed. A solution prepared by mixing 150.00 g of 2- (dimethylamino) ethyl methacrylate and 16.60 g of ethanol is mixed with 0.92 g of 2,2'-azobis (2-methylbutyronitrile) and 10.00 g of ethanol. The resulting solutions were separately added dropwise over 2 hours for polymerization. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
75.76 g of the obtained polymer solution, 3.47 g of sodium hydrogen carbonate, and 150.00 g of water were placed in a four-necked flask having an internal volume of 1000 mL, and the temperature was raised to 50 ° C. 42.73 g of 1,3-propane sultone was added dropwise thereto over 1 hour to carry out the reaction. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90 ° C./20 kPa for 2 hours to obtain a polymer aqueous solution containing the polymer B1.
製造例８〔共重合体Ｂ２の製造〕
（工程１）
ナスフラスコにスターラーチップ、メタクリル酸ブチル（和光純薬工業（株）製）２．００ｇ、メタクリル酸２-(ジメチルアミノ)エチル１９．９０ｇ、２,２'-アゾビス(２-メチルブチロニトリル)０．１４ｇ、メチルエチルケトン（和光純薬工業（株）製）２１．９０ｇを入れ、３０分間窒素バブリングを行った。その後、６７℃で８時間反応を行い、溶液を空気にさらしながら氷冷した後、乾燥によりポリマー固体を得た。
（工程２）
ナスフラスコに得られたポリマー固体６．００ｇ、２,２,２-トリフルオロエタノール（シグマアルドリッチ製）２４．００ｇ、１,３-プロパンスルトン４．７１ｇを入れ、ポリマーを溶解させた。５０℃で５時間反応を行い、乾燥によりランダム共重合体Ｂ２のポリマー固体を得た。
Production Example 8 [Production of copolymer B2]
(Step 1)
Stirrer chip, butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.) 2.00 g, 2- (dimethylamino) ethyl methacrylate 19.90 g, 2,2'-azobis (2-methylbutyronitrile) in eggplant flask 0.14 g and 21.90 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) were added, and nitrogen bubbling was performed for 30 minutes. Then, the reaction was carried out at 67 ° C. for 8 hours, the solution was ice-cooled while being exposed to air, and then dried to obtain a polymer solid.
(Step 2)
6.00 g of the obtained polymer solid, 24.00 g of 2,2,2-trifluoroethanol (manufactured by Sigma-Aldrich) and 4.71 g of 1,3-propane sultone were placed in an eggplant flask to dissolve the polymer. The reaction was carried out at 50 ° C. for 5 hours, and drying was performed to obtain a polymer solid of the random copolymer B2.
得られた共重合体Ａ１〜Ａ６、重合体Ｂ１、共重合体Ｂ２の構造、モル比、及び重量平均分子量を表１に示す。表１中のモル比は、構成単位ＡとＢの合計におけるモル比であり、反応時の仕込み比に基づく。 Table 1 shows the structures, molar ratios, and weight average molecular weights of the obtained copolymers A1 to A6, the polymer B1, and the copolymer B2. The molar ratio in Table 1 is the molar ratio in the total of the constituent units A and B, and is based on the charging ratio at the time of reaction.
共重合体Ａ１〜Ａ６の重量平均分子量は、以下の条件のゲル浸透クロマトグラフィー（プルラン）で測定した。
カラム：ＴＳＫｇｅｌ α-Ｍ（東ソー(株)製）を２本直列に連結して使用した。
カラム温度：４０℃
溶離液：０．１５ｍｏｌＮａ２ＳＯ４／１％ＣＨ３ＣＯＯＨ／水
流量：１．０ｍｌ／分 検出器：示差屈折率計
The weight average molecular weights of the copolymers A1 to A6 were measured by gel permeation chromatography (pullulan) under the following conditions.
Column: Two TSKgel α-M (manufactured by Tosoh Corporation) were connected in series and used.
Column temperature: 40 ° C
Eluent: 0.15 molNa 2 SO 4 /1% CH 3 COOH / water Flow rate: 1.0 ml / min Detector: Differential refractometer
重合体Ｂ１、共重合体Ｂ２の重量平均分子量は、以下の条件のゲル浸透クロマトグラフィー（プルラン）で測定した。
ＳＬＳ（静的光散乱法）による分子量測定を行った。重量平均分子量（Ｍｗ）は光散乱光度計「ＤＬＳ−７０００」（大塚電子（株）製）を用いて、下記の条件で静的光散乱を測定し、Ｚｉｍｍ−ｐｌｏｔを作製することで算出した。また、分子量の算出に必要な屈折率増分は、示差屈折率計「ＤＲＭ３０００」（大塚電子（株）製）を用いて測定した。
波長：６３２．８ｎｍ（ヘリウムーネオンレーザー）
散乱角：３０°から１５０°まで１０°おきに測定した。
平均温度：２５°
溶媒：トリフルオロエタノール
The weight average molecular weights of the polymer B1 and the copolymer B2 were measured by gel permeation chromatography (pullulan) under the following conditions.
The molecular weight was measured by SLS (static light scattering method). The weight average molecular weight (Mw) was calculated by measuring static light scattering under the following conditions using a light scattering photometer "DLS-7000" (manufactured by Otsuka Electronics Co., Ltd.) and producing a Zimm-plot. .. The refractive index increment required for calculating the molecular weight was measured using a differential refractometer "DRM3000" (manufactured by Otsuka Electronics Co., Ltd.).
Wavelength: 632.8 nm (helium-neon laser)
Scattering angle: Measured every 10 ° from 30 ° to 150 °.
Average temperature: 25 °
Solvent: Trifluoroethanol
実施例及び比較例
上記製造法により得られた共重合体Ａ１〜Ａ６、重合体Ｂ１、又は共重合体Ｂ２の０．２ｇを、塩化ナトリウム１．０ｇと共にイオン交換水９８．８ｇに溶解して処理液を調製した。この処理液を用いて、以下の方法で静的接触角及び水膜形成性を評価した。
比較例１は、塩化ナトリウム１．０ｇ及びイオン交換水９９．０ｇを混合した処理液を用いて、以下の方法で静的接触角及び水膜形成性を評価した。
結果を表２に示した。
Examples and Comparative Examples 0.2 g of the copolymers A1 to A6, the polymer B1 or the copolymer B2 obtained by the above production method was dissolved in 98.8 g of ion-exchanged water together with 1.0 g of sodium chloride. A treatment solution was prepared. Using this treatment liquid, the static contact angle and water film forming property were evaluated by the following methods.
In Comparative Example 1, the static contact angle and the water film forming property were evaluated by the following method using a treatment solution in which 1.0 g of sodium chloride and 99.0 g of ion-exchanged water were mixed.
The results are shown in Table 2.
（１）静止接触角
２つの異なる基板に対する静止接触角を測定した。
予め清浄にした基板を水平に固定し、処理液１ｍＬを滴下して２０秒間静置した後、イオン交換水約２００ｍＬで軽くすすいで風乾した。
基板の処理部分表面のイオン交換水に対する静止接触角を、自動接触角計「ＤＭ−５００」（協和界面科学株式会社製）を用いて、添加量１０μＬ、添加６秒後の条件にて測定した。
１枚の基板当たり１０回接触角の測定を行い、１０回の測定値の平均値をその基板の静止接触角とした。接触角が小さいほど、親水化性能に優れる。
試験に用いた基板は以下のとおりである。
ステンレス：「ステンレステストピース」（（株）エンジニアリングテストサービス製、材質：JIS G 4305 SUS304、２５ｍｍ×７５ｍｍ）
シリコンウエハー：「シリコンウエハー」（ニコラ社製、材質：シリコン、２５ｍｍ×７５ｍｍ）
(1) Static contact angle The static contact angle with respect to two different substrates was measured.
The pre-cleaned substrate was fixed horizontally, 1 mL of the treatment solution was added dropwise, and the mixture was allowed to stand for 20 seconds, then lightly rinsed with about 200 mL of ion-exchanged water and air-dried.
The static contact angle of the surface of the treated portion of the substrate with respect to ion-exchanged water was measured using an automatic contact angle meter "DM-500" (manufactured by Kyowa Interface Science Co., Ltd.) under the conditions of an addition amount of 10 μL and 6 seconds after the addition. ..
The contact angle was measured 10 times per substrate, and the average value of the 10 measurements was taken as the static contact angle of the substrate. The smaller the contact angle, the better the hydrophilic performance.
The substrates used in the test are as follows.
Stainless steel: "Stainless steel test piece" (manufactured by Engineering Test Service Co., Ltd., material: JIS G 4305 SUS304, 25 mm x 75 mm)
Silicon wafer: "Silicon wafer" (manufactured by Nicola, material: silicon, 25 mm x 75 mm)
（２）水膜形成性
（１）の静止接触角の測定において、イオン交換水約２００ｍＬで軽くすすいだ後、風乾する前に、テストピース上に残る水がテストピースの全面を覆った状態になっている時間を、水膜の形成時間とした。水膜の形成時間が長いほど、親油性の汚れが表面に接触しにくく、防汚性能に優れる。さらに、水膜の形成時間が１０秒以上のものを○、１０秒未満のものを×とした。
(2) Water film forming property In the measurement of the static contact angle of (1), after lightly rinsing with about 200 mL of ion-exchanged water and before air-drying, the water remaining on the test piece covers the entire surface of the test piece. The time during which the water film was formed was defined as the water film formation time. The longer the water film formation time, the less lipophilic stains come into contact with the surface, and the better the antifouling performance. Further, those having a water film formation time of 10 seconds or more were evaluated as ◯, and those having a water film formation time of less than 10 seconds were evaluated as x.
表２中、構成単位Ａ、Ｂは、便宜的に、下記の化合物に由来する構成単位として示してある。
ＳＢＭＡ：Ｎ−（３−スルホプロピル）−Ｎ−メタクリロキシエチル−Ｎ，Ｎ−ジメチルアンモニウムベタイン
ＭＯＥＤＥＳ：メタクリル酸２−（ジメチルアミノ）エチルジエチル硫酸塩
ＱＤＭ：メタクリル酸２−（ジメチルアミノ）メチルジエチル硫酸塩
ＭＰＣ：２−メタクリロキシエチルホスホリルコリン
ＣＢＭＡ：Ｎ−（３−カルボキシプロピル）−Ｎ−メタクリロキシエチル−Ｎ，Ｎ−ジメチルアンモニウムベタイン
ＢＭＡ：ｎ−ブチルメタクリレート
In Table 2, the structural units A and B are shown as structural units derived from the following compounds for convenience.
SBMA: N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine MOEDES: 2- (dimethylamino) ethyldiethyl sulfate QDM: 2- (dimethylamino) methyldiethyl methacrylate Sulfate MPC: 2-methacryloxyethyl phosphorylcholine CBMA: N- (3-carboxypropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine BMA: n-butyl methacrylate
表２から明らかなように、実施例１〜６は、比較例１〜３に比べて、ステンレス、シリコンウエハーに対する静止接触角が低下し、水膜形成性にも優れている事から、表面の親水化性能に優れていることがわかる。 As is clear from Table 2, in Examples 1 to 6, as compared with Comparative Examples 1 to 3, the static contact angle with respect to the stainless steel and silicon wafers is lowered, and the water film forming property is also excellent. It can be seen that the hydrophilicity performance is excellent.
Claims (13)
前記共重合体における構成単位（Ａ）と構成単位（Ｂ）のモル比が、構成単位（Ａ）／構成単位（Ｂ）で、７５／２５以上９９．９／０．１以下である、
表面処理剤。
〔式中、
Ｒ１〜Ｒ３：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｒ４：炭素数１以上４以下のアルキレン基
Ｒ５、Ｒ６：同一又は異なって、炭素数１以上４以下の炭化水素基
Ｘ１：Ｏ又はＮＲ７であり、Ｒ７は水素原子又は炭素数１以上４以下の炭化水素基
Ｘ２：Ｒ１７ＳＯ３ −であり、Ｒ１７は炭素数１以上４以下のアルキレン基である。〕
〔式中、
Ｒ８〜Ｒ１０：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｘ３：Ｏ又はＮＨ基
Ｒ１１：炭素数１以上４以下のアルキレン基
Ｘ４：Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｒ１２〜Ｒ１６は、同一又は異なって、水素原子又は炭素数１以上４以下の炭化水素基、Ｘ５は陰イオン
を示す。〕 A surface treatment agent composed of a copolymer containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2).
The molar ratio of the structural unit (A) to the structural unit (B) in the copolymer is 75/25 or more and 99.9 / 0.1 or less in terms of the structural unit (A) / structural unit (B).
Surface treatment agent.
[In the formula,
R 1 to R 3 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms R 4 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms R 5 , R 6 : Same or different, 1 or more carbon atoms 4 the following hydrocarbon groups X 1: O or NR 7, R 7 is a hydrogen atom or a C 1 to 4 hydrocarbon group X 2: R 17 SO 3 - and is, R 17 is 1 or more and 4 carbon atoms The following alkylene groups. ]
[In the formula,
R 8 to R 10 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms X 3 : O or NH group R 11 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms X 4 : N + R 12 R 13 R 14 X 5 or NR 15 R 16 , where R 12 to R 16 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X 5 is an anion. ]
前記共重合体における構成単位（Ａ）と構成単位（Ｂ）のモル比が、構成単位（Ａ）／構成単位（Ｂ）で、７５／２５以上９９．９／０．１以下である、
表面処理剤組成物。
〔式中、
Ｒ１〜Ｒ３：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｒ４：炭素数１以上４以下のアルキレン基
Ｒ５、Ｒ６：同一又は異なって、炭素数１以上４以下の炭化水素基
Ｘ１：Ｏ又はＮＲ７であり、Ｒ７は水素原子又は炭素数１以上４以下の炭化水素基
Ｘ２：Ｒ１７ＳＯ３ −であり、Ｒ１７は炭素数１以上４以下のアルキレン基である。〕
〔式中、
Ｒ８〜Ｒ１０：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｘ３：Ｏ又はＮＨ基
Ｒ１１：炭素数１以上４以下のアルキレン基
Ｘ４：Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｒ１２〜Ｒ１６は、同一又は異なって、水素原子又は炭素数１以上４以下の炭化水素基、Ｘ５は陰イオン
を示す。〕 A surface treatment agent composition containing a copolymer containing a structural unit (A) represented by the following formula (1) and a structural unit (B) represented by the following formula (2).
The molar ratio of the structural unit (A) to the structural unit (B) in the copolymer is 75/25 or more and 99.9 / 0.1 or less in terms of the structural unit (A) / structural unit (B).
Surface treatment agent composition.
[In the formula,
R 1 to R 3 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms R 4 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms R 5 , R 6 : Same or different, 1 or more carbon atoms 4 the following hydrocarbon groups X 1: O or NR 7, R 7 is a hydrogen atom or a C 1 to 4 hydrocarbon group X 2: R 17 SO 3 - and is, R 17 is 1 or more and 4 carbon atoms The following alkylene groups. ]
[In the formula,
R 8 to R 10 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms X 3 : O or NH group R 11 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms X 4 : N + R 12 R 13 R 14 X 5 or NR 15 R 16 , where R 12 to R 16 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X 5 is an anion. ]
前記共重合体における構成単位（Ａ）と構成単位（Ｂ）のモル比が、構成単位（Ａ）／構成単位（Ｂ）で、７５／２５以上９９．９／０．１以下である、
固体表面の処理方法。
〔式中、
Ｒ１〜Ｒ３：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｒ４：炭素数１以上４以下のアルキレン基
Ｒ５、Ｒ６：同一又は異なって、炭素数１以上４以下の炭化水素基
Ｘ１：Ｏ又はＮＲ７であり、Ｒ７は水素原子又は炭素数１以上４以下の炭化水素基
Ｘ２：Ｒ１７ＳＯ３ −であり、Ｒ１７は炭素数１以上４以下のアルキレン基である。〕
〔式中、
Ｒ８〜Ｒ１０：同一又は異なって、水素原子又は炭素数１もしくは２のアルキル基
Ｘ３：Ｏ又はＮＨ基
Ｒ１１：炭素数１以上４以下のアルキレン基
Ｘ４：Ｎ＋Ｒ１２Ｒ１３Ｒ１４Ｘ５又はＮＲ１５Ｒ１６であり、Ｒ１２〜Ｒ１６は、同一又は異なって、水素原子又は炭素数１以上４以下の炭化水素基、Ｘ５は陰イオン
を示す。〕 A copolymer containing the structural unit (A) represented by the following formula (1) and the structural unit (B) represented by the following formula (2), and a treatment liquid containing water are brought into contact with the solid surface. A method for treating solid surfaces
The molar ratio of the structural unit (A) to the structural unit (B) in the copolymer is 75/25 or more and 99.9 / 0.1 or less in terms of the structural unit (A) / structural unit (B).
A method for treating a solid surface.
[In the formula,
R 1 to R 3 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms R 4 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms R 5 , R 6 : Same or different, 1 or more carbon atoms 4 the following hydrocarbon groups X 1: O or NR 7, R 7 is a hydrogen atom or a C 1 to 4 hydrocarbon group X 2: R 17 SO 3 - and is, R 17 is 1 or more and 4 carbon atoms The following alkylene groups. ]
[In the formula,
R 8 to R 10 : Same or different, hydrocarbon atom or alkyl group with 1 or 2 carbon atoms X 3 : O or NH group R 11 : alkylene group with 1 or more carbon atoms and 4 or less carbon atoms X 4 : N + R 12 R 13 R 14 X 5 or NR 15 R 16 , where R 12 to R 16 are the same or different, a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, and X 5 is an anion. ]
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