JP2015034253A - Method for treating hard surface - Google Patents
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- JP2015034253A JP2015034253A JP2013166469A JP2013166469A JP2015034253A JP 2015034253 A JP2015034253 A JP 2015034253A JP 2013166469 A JP2013166469 A JP 2013166469A JP 2013166469 A JP2013166469 A JP 2013166469A JP 2015034253 A JP2015034253 A JP 2015034253A
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- 238000000034 method Methods 0.000 title claims abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 126
- 239000000203 mixture Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 17
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000004381 surface treatment Methods 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 abstract description 16
- 230000003373 anti-fouling effect Effects 0.000 abstract description 14
- 230000002688 persistence Effects 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 description 8
- -1 polypropylene Polymers 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011151 fibre-reinforced plastic Substances 0.000 description 2
- 230000005660 hydrophilic surface Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 210000002374 sebum Anatomy 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
本発明は、硬質表面の処理方法及び硬質表面用処理剤組成物に関する。 The present invention relates to a hard surface treatment method and a hard surface treatment composition.
我々を取り巻く住環境設備には、プラスチック、金属等を材料とした各種硬質表面が存在し、これら硬質表面は生活場面に於いて様々な汚れが付着する環境に晒されている。特に水周り設備に於いては、浴室の皮脂・湯垢汚れ、レンジフード、ガスコンロ、シンク周りにおける油汚れなど、日常的に残留し易い汚れが発生しており、これらの汚れを洗浄除去する家事行動は生活者の大きな負担となっている。 The living environment equipment that surrounds us has various hard surfaces made of plastic, metal, etc., and these hard surfaces are exposed to an environment where various types of dirt adhere in daily life. In particular, in water-related facilities, dirt that tends to remain on a daily basis, such as sebum and scale stains in the bathroom, range hoods, gas stoves, and oil stains around the sink, has been generated. Is a heavy burden on consumers.
中でも、疎水性の汚れは除去し難く、残留し易い汚れであることが一般に知られている。疎水性汚れが付着、残留し易く、除去し難い原因のひとつとして、住環境に用いられているポリ塩化ビニル、ポリプロピレン、ステンレスなど硬質表面の多くが疎水性の性質を帯びていることが挙げられる。つまり、疎水性の硬質表面は、疎水性汚れとの親和性が高いために、汚れが残留、蓄積し易く、更には洗浄除去し難い性質を伴うものとなっている。 Among them, it is generally known that hydrophobic dirt is difficult to remove and is likely to remain. One of the reasons that hydrophobic dirt is likely to adhere and remain and is difficult to remove is that many hard surfaces such as polyvinyl chloride, polypropylene, and stainless steel used in living environments have hydrophobic properties. . That is, since the hydrophobic hard surface has a high affinity with the hydrophobic dirt, the dirt is likely to remain and accumulate, and it is difficult to wash and remove.
疎水性硬質表面からの疎水性汚れの除去や、疎水性硬質表面への汚れの残留ないし汚れの再付着の防止においてより高い効果を得るための方法として、改質剤を硬質表面に塗布し疎水性の硬質表面を親水性の性質を帯びるように表面改質する方法が考えられる。 As a method to obtain a higher effect in removing hydrophobic dirt from the hydrophobic hard surface and preventing soil residue or dirt reattachment to the hydrophobic hard surface, a modifier is applied to the hard surface to make it hydrophobic. It is conceivable to modify the surface of the hydrophilic hard surface so as to have hydrophilic properties.
特許文献１には、アニオン重合体とカチオン重合体及びノニオン重合体を含有し、優れた親水性と持続性を付与できる親水性表面処理膜を提供する親水性表面処理組成物が開示されている。特許文献２には、プラスチックや金属等の硬質表面を処理する組成物が開示されており、汚れはがしの効果が長い期間持続することが記載されている。特許文献３には、プラスチックや金属等の硬質表面洗浄組成物が開示されている。特許文献４には、２種類の共重合体を２段階で処理する硬質表面処理方法が記載されている。 Patent Document 1 discloses a hydrophilic surface treatment composition that contains an anionic polymer, a cationic polymer, and a nonionic polymer, and provides a hydrophilic surface treatment film that can impart excellent hydrophilicity and durability. . Patent Document 2 discloses a composition for treating a hard surface such as plastic or metal, and describes that the effect of removing the stain lasts for a long period of time. Patent Document 3 discloses a hard surface cleaning composition such as plastic or metal. Patent Document 4 describes a hard surface treatment method in which two types of copolymers are treated in two stages.
しかしながら、疎水性硬質表面の防汚性効果の点からは、生活者が満足するレベルの更なる高い防汚効果が期待されていた。また、防汚効果の持続性に優れることも望まれており、例えば、防汚処理された硬質表面が水と接触した後でも防汚効果が維持できることが望まれる。 However, from the viewpoint of the antifouling effect of the hydrophobic hard surface, a further high antifouling effect that is expected to satisfy consumers has been expected. It is also desired that the antifouling effect is excellent in sustainability. For example, it is desired that the antifouling effect can be maintained even after the hard surface subjected to the antifouling treatment comes into contact with water.
本発明の課題は、疎水性硬質表面を改質して、優れた防汚性を付与でき、且つ防汚性の持続性にも優れた硬質表面の処理方法を提供することである。 An object of the present invention is to provide a method for treating a hard surface, which can impart a superior antifouling property by modifying a hydrophobic hard surface and has excellent antifouling properties.
本発明は、エチレンイミンをモノマー単位として含む重量平均分子量１００，０００以上、１，０００，０００以下の重合体（Ａ）、アクリル酸、メタクリル酸及びこれらの塩から選ばれるモノマーをモノマー単位として含む重量平均分子量２，０００以上、４，５００以下の重合体（Ｂ）、及び水を混合して重合体（Ａ）と重合体（Ｂ）の複合体を形成させ、該複合体を含む液体混合物を硬質表面に適用する、硬質表面の処理方法に関する。 The present invention includes, as a monomer unit, a monomer selected from a polymer (A) having ethyleneimine as a monomer unit and having a weight average molecular weight of 100,000 or more and 1,000,000 or less, acrylic acid, methacrylic acid, and salts thereof. A polymer (B) having a weight average molecular weight of 2,000 or more and 4,500 or less and water are mixed to form a complex of the polymer (A) and the polymer (B), and a liquid mixture containing the complex The present invention relates to a method for treating a hard surface.
また、本発明は、エチレンイミンをモノマー単位として含む重量平均分子量１００，０００以上、１，０００，０００以下の重合体（Ａ）〔以下、重合体（Ａ）という〕、アクリル酸、メタクリル酸及びこれらの塩から選ばれるモノマーをモノマー単位として含む重量平均分子量２，０００以上、４，５００以下の重合体（Ｂ）〔以下、重合体（Ｂ）という〕とから形成された複合体、並びに水を含有する、硬質表面用液体処理剤組成物に関する。 Further, the present invention relates to a polymer (A) (hereinafter referred to as polymer (A)) having a weight average molecular weight of from 100,000 to 1,000,000 containing ethyleneimine as a monomer unit, acrylic acid, methacrylic acid and A complex formed from a polymer (B) [hereinafter referred to as polymer (B)] having a weight average molecular weight of 2,000 or more and 4,500 or less containing a monomer selected from these salts as a monomer unit, and water The liquid processing agent composition for hard surfaces containing this.
本発明によれば、疎水性硬質表面に対して優れた防汚性を付与でき、且つ防汚性の持続性にも優れた硬質表面の処理方法が提供される。 ADVANTAGE OF THE INVENTION According to this invention, the processing method of the hard surface which can provide the outstanding antifouling property with respect to a hydrophobic hard surface, and was excellent also in the antifouling durability.
＜重合体（Ａ）＞
重合体（Ａ）は、エチレンイミンをモノマー単位として含む重量平均分子量１００，０００以上、１，０００，０００以下の重合体である。重合体（Ａ）は、エチレンイミンに由来するモノマー単位を、全モノマー単位中、８０モル％以上、更に９０モル％以上含む重合体が好ましい。重合体（Ａ）としては、エチレンイミンのホモポリマーであるポリエチレンイミンが挙げられる。また、エチレンイミン及びエチレンイミンと共重合可能なモノマーの共重合体が挙げられる。エチレンイミンと共重合可能なモノマーとして、アルキレンアミン、アミドアミン、エーテルアミンが挙げられる。重合体（Ａ）は、ポリエチレンイミンが好ましい。エチレンイミンは、下記式（Ａ１）で表される化合物であり、ポリエチレンイミンはそのホモポリマーである。
<Polymer (A)>
The polymer (A) is a polymer having ethyleneimine as a monomer unit and having a weight average molecular weight of 100,000 or more and 1,000,000 or less. The polymer (A) is preferably a polymer containing monomer units derived from ethyleneimine in an amount of 80 mol% or more, and more preferably 90 mol% or more, based on all monomer units. Examples of the polymer (A) include polyethyleneimine which is a homopolymer of ethyleneimine. Moreover, the copolymer of the monomer which can be copolymerized with ethyleneimine and ethyleneimine is mentioned. Examples of the monomer copolymerizable with ethyleneimine include alkylene amine, amido amine, and ether amine. The polymer (A) is preferably polyethyleneimine. Ethyleneimine is a compound represented by the following formula (A1), and polyethyleneimine is a homopolymer thereof.
（Ａ）成分は、（Ｂ）成分との複合体に耐水性を持たせるという観点から、重量平均分子量が１００，０００以上であり、また、（Ｂ）成分との複合体を含む液体混合物を硬質表面に適用する際の取り扱い性の観点から、重量平均分子量が１，０００，０００以下である。（Ａ）成分の重量平均分子量は、５００，０００以上が好ましく、６００，０００以上がより好ましく、７００，０００以上が更に好ましく、そして９００，０００以下が好ましく、８５０，０００以下がより好ましく、８００，０００以下が更に好ましい。 The component (A) has a weight average molecular weight of 100,000 or more from the viewpoint of imparting water resistance to the complex with the component (B), and a liquid mixture containing the complex with the component (B). From the viewpoint of handleability when applied to a hard surface, the weight average molecular weight is 1,000,000 or less. The weight average molecular weight of the component (A) is preferably 500,000 or more, more preferably 600,000 or more, still more preferably 700,000 or more, preferably 900,000 or less, more preferably 850,000 or less, 800 Is more preferable.
なお、重合体（Ａ）の重量平均分子量は、光散乱法により測定されたものである。 The weight average molecular weight of the polymer (A) is measured by a light scattering method.
重合体（Ａ）は、重量平均分子量６００，０００以上、９００，０００以下のポリエチレンイミンがより好ましい。 The polymer (A) is more preferably a polyethyleneimine having a weight average molecular weight of 600,000 or more and 900,000 or less.
＜重合体（Ｂ）＞
重合体（Ｂ）は、アクリル酸、メタクリル酸及びこれらの塩から選ばれるモノマーをモノマー単位として含む重量平均分子量２，０００以上、４，５００以下の重合体である。重合体（Ｂ）は、アクリル酸、メタクリル酸及びこれらの塩から選ばれるモノマーに由来するモノマー単位を、全モノマー単位中、７５モル％以上、更に８０モル％以上含む重合体が好ましい。
<Polymer (B)>
The polymer (B) is a polymer having a weight average molecular weight of 2,000 or more and 4,500 or less containing a monomer selected from acrylic acid, methacrylic acid and salts thereof as a monomer unit. The polymer (B) is preferably a polymer containing a monomer unit derived from a monomer selected from acrylic acid, methacrylic acid and salts thereof in an amount of 75 mol% or more, and more preferably 80 mol% or more in all monomer units.
重合体（Ｂ）としては、アクリル酸のホモポリマーであるポリアクリル酸及びその塩から選ばれる重合体が挙げられる。また、アクリル酸、メタクリル酸及びこれらの塩から選ばれるモノマーと、これらのモノマーと共重合可能なモノマーとの共重合体が挙げられる。前記共重合可能なモノマーとして、マレイン酸が挙げられる。 Examples of the polymer (B) include polymers selected from polyacrylic acid, which is a homopolymer of acrylic acid, and salts thereof. Moreover, the copolymer of the monomer chosen from acrylic acid, methacrylic acid, and these salts, and the monomer copolymerizable with these monomers is mentioned. Examples of the copolymerizable monomer include maleic acid.
重合体（Ｂ）としては、ポリアクリル酸、ポリメタクリル酸、及びそれらの塩から選ばれる重合体が好ましく、ポリアクリル酸及びその塩から選ばれる重合体がより好ましい。なお、重合体（Ｂ）の塩は、ナトリウム塩、カリウム塩などのアルカリ金属塩が好ましい。 As the polymer (B), a polymer selected from polyacrylic acid, polymethacrylic acid, and salts thereof is preferable, and a polymer selected from polyacrylic acid and salts thereof is more preferable. The salt of the polymer (B) is preferably an alkali metal salt such as sodium salt or potassium salt.
本発明の（Ｂ）成分は、重量平均分子量が２，０００以上、４，５００以下である。重合体（Ｂ）の重量平均分子量は、耐水性の観点から、２１００以上が好ましく、２２００以上がより好ましく、２３００以上が更に好ましく、そして、（A）成分との混合性を高める観点から、４０００以下が好ましく、３０００以下がより好ましく、２５００以下が更に好ましい。 The component (B) of the present invention has a weight average molecular weight of 2,000 or more and 4,500 or less. The weight average molecular weight of the polymer (B) is preferably 2100 or more, more preferably 2200 or more, further preferably 2300 or more from the viewpoint of water resistance, and 4000 from the viewpoint of improving the mixing property with the component (A). The following is preferable, 3000 or less is more preferable, and 2500 or less is still more preferable.
なお、重合体（Ｂ）の重量平均分子量は、０．２ｍｏｌ／Ｌリン酸バッファー／アセトニトリル＝９／１（容量比）を溶離液とし、カラムはＧ４０００ＰＷＸＬおよびＧ２５００ＰＷＸＬを２本連結して、ゲルパーミェーションクロマトグラフィーでポリアクリル酸Ｎａを標準物質として求めた値である。 The weight average molecular weight of the polymer (B) was 0.2 mol / L phosphate buffer / acetonitrile = 9/1 (volume ratio) as an eluent, and the column was composed of two G4000PWXL and G2500PWXL. This is a value obtained by measuring polyacrylic acid Na as a standard substance by the migration chromatography.
＜硬質表面の処理方法＞
本発明では、重合体（Ａ）、重合体（Ｂ）、及び水を混合して、重合体（Ａ）と重合体（Ｂ）の複合体（以下、複合体という場合もある）を形成させ、該複合体を含む液体混合物を硬質表面に適用して硬質表面を処理する。重合体（Ａ）と重合体（Ｂ）は、静電相互作用による複合体を形成し、これが系から析出することによって、処理対象の硬質表面に付着し、当該硬質表面の親水性を向上させる。なお、前記液体混合物は、本発明の硬質表面用液体処理剤組成物として使用できるものである。また、前記液体混合物は、複合体、水の他に、重合体（Ａ）及び／又は重合体（Ｂ）を含有していてもよい。また、前記液体混合物は、複合体、水、重合体（Ａ）、重合体（Ｂ）以外の成分を含有していてもよい。
<Hard surface treatment method>
In the present invention, the polymer (A), the polymer (B), and water are mixed to form a complex of the polymer (A) and the polymer (B) (hereinafter sometimes referred to as a complex). The liquid mixture containing the composite is applied to the hard surface to treat the hard surface. The polymer (A) and the polymer (B) form a complex due to electrostatic interaction, and deposit from the system, thereby adhering to the hard surface to be treated and improving the hydrophilicity of the hard surface. . In addition, the said liquid mixture can be used as the liquid processing agent composition for hard surfaces of this invention. The liquid mixture may contain a polymer (A) and / or a polymer (B) in addition to the composite and water. The liquid mixture may contain components other than the composite, water, the polymer (A), and the polymer (B).
複合体を形成するにあたり、重合体（Ａ）と重合体（Ｂ）の質量比は、（Ｂ）／（Ａ）で、０．６５以上、３．０以下が好ましい。この質量比は、重合体（Ａ）及び重合体（Ｂ）の電荷の比率がおよそ０．５以上、２以下となる組成である。 In forming the composite, the mass ratio of the polymer (A) to the polymer (B) is (B) / (A), and is preferably from 0.65 to 3.0. This mass ratio is a composition in which the charge ratio of the polymer (A) and the polymer (B) is about 0.5 or more and 2 or less.
また、重合体（Ａ）、重合体（Ｂ）、及び水を混合して得られる、複合体を形成させるための混合物では、重合体（Ａ）と重量比（Ｂ）の合計の含有量は、０．３質量％以上が好ましく、０．５質量％以上がより好ましい。また、５質量％以下が好ましく、３質量％以下がより好ましい。 Moreover, in the mixture for forming a complex obtained by mixing the polymer (A), the polymer (B), and water, the total content of the polymer (A) and the weight ratio (B) is 0.3 mass% or more is preferable, and 0.5 mass% or more is more preferable. Moreover, 5 mass% or less is preferable and 3 mass% or less is more preferable.
本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有する混合物のｐＨを変化させることにより、重合体（Ａ）と重合体（Ｂ）の複合体を形成させることが好ましい。更に、本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有する混合物のｐＨを低下させることにより、重合体（Ａ）と重合体（Ｂ）の複合体を形成させることが好ましい。すなわち、本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有する混合物を調製し、該混合物のｐＨを低下させることで、重合体（Ａ）と重合体（Ｂ）の複合体を形成させることが好ましい。 In the present invention, it is preferable to form a complex of the polymer (A) and the polymer (B) by changing the pH of the mixture containing the polymer (A), the polymer (B) and water. Furthermore, in the present invention, a complex of the polymer (A) and the polymer (B) can be formed by lowering the pH of the mixture containing the polymer (A), the polymer (B) and water. preferable. That is, in the present invention, by preparing a mixture containing the polymer (A), the polymer (B) and water, and lowering the pH of the mixture, the composite of the polymer (A) and the polymer (B) It is preferable to form a body.
本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有する透明な混合物を調製し、該混合物のｐＨを、該混合物が白濁するまで低下させることで、重合体（Ａ）と重合体（Ｂ）の複合体を形成させることができる。重合体（Ａ）と重合体（Ｂ）と水とを、（Ｂ）／（Ａ）の質量比が０．６５以上、３．０以下で混合する場合、混合物のｐＨを１０．４以下にすることで、複合体が形成される。 In the present invention, a transparent mixture containing the polymer (A), the polymer (B) and water is prepared, and the pH of the mixture is lowered until the mixture becomes cloudy, whereby the polymer (A) and A complex of the polymer (B) can be formed. When the polymer (A), the polymer (B), and water are mixed at a mass ratio of (B) / (A) of 0.65 to 3.0, the pH of the mixture is 10.4 or less. By doing so, a complex is formed.
重合体（Ａ）、重合体（Ｂ）及び水を含有する混合物について、「透明」とは、波長６００ｎｍで１ｃｍの光路長における透過率が水に対して５０％以上であることをいう。
また、重合体（Ａ）、重合体（Ｂ）及び水を含有する混合物について、「白濁」とは、波長６００ｎｍで１ｃｍの光路長における透過率が水に対して５０％未満、更に３０％以下、更に１０％以下であることをいう。
透過率の測定は、例えば、Ｕ−３２００ Ｓｐｅｃｔｒｏｐｈｏｔｏｍｅｔｅｒ（ＨＩＴＡＣＨＩ製）、石英セルを用いて、６００ｎｍにおける精製水の透過率を１００％として測定することができる。
About the mixture containing a polymer (A), a polymer (B), and water, "transparent" means that the transmittance | permeability in the optical path length of 1 cm with a wavelength of 600 nm is 50% or more with respect to water.
Moreover, about the mixture containing a polymer (A), a polymer (B), and water, "white turbidity" means that the transmittance | permeability in the optical path length of 1 cm with a wavelength of 600 nm is less than 50% with respect to water, and also 30% or less Furthermore, it means 10% or less.
The transmittance can be measured using, for example, U-3200 Spectrophotometer (manufactured by HITACHI) and a quartz cell with the transmittance of purified water at 600 nm as 100%.
本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有し、重合体（Ａ）と重合体（Ｂ）の合計含有量が０．３質量％以上、５質量％以下であり、重合体（Ｂ）／重合体（Ａ）の質量比が０．６５以上、３．０以下である透明な混合物を調製し、該混合物のｐＨを該混合物が白濁するまで低下させることで、重合体（Ａ）と重合体（Ｂ）の複合体を形成させることができる。 In the present invention, the polymer (A), the polymer (B) and water are contained, and the total content of the polymer (A) and the polymer (B) is 0.3% by mass or more and 5% by mass or less. Preparing a transparent mixture having a polymer (B) / polymer (A) mass ratio of 0.65 or more and 3.0 or less, and lowering the pH of the mixture until the mixture becomes cloudy, A complex of the polymer (A) and the polymer (B) can be formed.
本発明では、重合体（Ａ）、重合体（Ｂ）及び水を含有し、重合体（Ａ）と重合体（Ｂ）の合計含有量が０．３質量％以上、５質量％以下であり、（Ｂ）／（Ａ）の質量比が０．６５以上、３．０以下であり、ｐＨが１０．４超である透明な混合物を調製し、該混合物のｐＨを１０．４以下に低下させて白濁させることで、（Ａ）と（Ｂ）の複合体を形成させることができる。 In the present invention, the polymer (A), the polymer (B) and water are contained, and the total content of the polymer (A) and the polymer (B) is 0.3% by mass or more and 5% by mass or less. A transparent mixture having a mass ratio of (B) / (A) of 0.65 or more and 3.0 or less and a pH of more than 10.4 is prepared, and the pH of the mixture is lowered to 10.4 or less. By making it cloudy, the complex of (A) and (B) can be formed.
複合体を含む液体混合物のｐＨは、硬質表面に適用する際の作業性などの観点から、７以上、更に８以上が好ましく、複合体を形成し防汚性を高める観点から、１０以下、更に９以下が好ましい。なお、ｐＨは、本発明の処理方法を実施する際の液体混合物の温度におけるものでよく、又は２０℃で測定されたものであってもよい。 The pH of the liquid mixture containing the composite is preferably 7 or more, more preferably 8 or more from the viewpoint of workability when applied to a hard surface, and 10 or less from the viewpoint of forming the composite and enhancing the antifouling property. 9 or less is preferable. In addition, pH may be at the temperature of the liquid mixture when the treatment method of the present invention is performed, or may be measured at 20 ° C.
ｐＨの低下により複合物を形成させる場合は、硬質表面に適用する複合体を含む液体混合物のｐＨが前記範囲となるように、ｐＨの低下の度合いを調整することが好ましい。 When the composite is formed by lowering the pH, it is preferable to adjust the degree of lowering the pH so that the pH of the liquid mixture containing the composite applied to the hard surface falls within the above range.
本発明では、重合体（Ａ）及び重合体（Ｂ）から形成された複合体を含む液体混合物を、例えば、台所の硬質表面、浴室の硬質表面などで用いられている疎水性の硬質表面に接触させて複合体を付着させることによって該硬質表面を改質し、親水性を向上させるものである。本発明の処理方法の対象となる硬質表面は、浴室の硬質表面が好ましい。 In the present invention, the liquid mixture containing the composite formed from the polymer (A) and the polymer (B) is applied to a hydrophobic hard surface used, for example, in a hard surface of a kitchen or a hard surface of a bathroom. The hard surface is modified by bringing the composite into contact with it to improve hydrophilicity. The hard surface targeted for the treatment method of the present invention is preferably a hard surface of a bathroom.
重合体（Ａ）及び重合体（Ｂ）から形成された複合体を含む液体混合物を硬質表面に適用する方法は、前記液体混合物を硬質表面に塗布する方法、前記液体混合物を硬質表面に噴霧する方法、前記液体混合物に硬質表面を有する物品を浸漬する方法などが挙げられる。前記液体混合物を適用した後、所定時間、例えば、１分以上、更に３分以上、更に５分以上静置することが好ましい。静置後、水洗することによって、親水性を付与することができる。 A method of applying a liquid mixture comprising a polymer (A) and a composite formed from a polymer (B) to a hard surface is a method of applying the liquid mixture to a hard surface, and spraying the liquid mixture onto the hard surface And a method of immersing an article having a hard surface in the liquid mixture. After applying the liquid mixture, it is preferable to stand still for a predetermined time, for example, 1 minute or more, further 3 minutes or more, and further 5 minutes or more. Hydrophilicity can be imparted by washing with water after standing.
本発明の硬質表面の処理方法には、重合体（Ａ）と重合体（Ｂ）とから形成された複合体、並びに水を含有する、硬質表面用液体処理剤組成物を用いることができる。硬質表面用液体処理剤組成物のｐＨは、２０℃で、７以上、更に８以上が好ましく、１０以下、更に９以下が好ましい。また、前記硬質表面用液体処理剤組成物の前駆組成物として、重合体（Ａ）、重合体（Ｂ）、及び水を含有する処理剤用組成物を用いることができる。処理剤用組成物を用いる場合は、硬質表面上で重合体（Ａ）と重合体（Ｂ）との複合体を形成させることができる。 In the method for treating a hard surface of the present invention, a liquid treatment agent composition for hard surface containing a composite formed from the polymer (A) and the polymer (B) and water can be used. The pH of the hard surface liquid treating agent composition is 20 ° C., preferably 7 or more, more preferably 8 or more, and preferably 10 or less, and more preferably 9 or less. Moreover, the composition for processing agents containing a polymer (A), a polymer (B), and water can be used as a precursor composition of the liquid processing agent composition for hard surfaces. When using the composition for processing agents, the composite body of a polymer (A) and a polymer (B) can be formed on a hard surface.
本発明の対象となる硬質表面としては、プラスチック、セラミックス及び金属から選ばれる材質からなる疎水性の硬質表面が挙げられる。具体的には、プラスチックとして、繊維強化プラスチック（ＦＲＰ）、ポリ塩化ビニル、ポリプロピレン、ポリエチレン、ＡＢＳ、ポリアミドが挙げられる。また、金属として、ステンレスが挙げられる。ここで、疎水性の硬質表面とは、硬質表面に１μｌのイオン交換水の水滴を処理表面に着滴させ、着滴３秒後から１秒間隔で１０回接触角を測定し、その平均値が６０°以上である硬質表面をいう。静止接触角の測定は、全自動接触角計を用いて行うことができる。一例として、協和界面科学株式会社製の全自動接触角計ＤＭ−５００が挙げられる。 Examples of the hard surface targeted by the present invention include a hydrophobic hard surface made of a material selected from plastics, ceramics, and metals. Specifically, examples of the plastic include fiber reinforced plastic (FRP), polyvinyl chloride, polypropylene, polyethylene, ABS, and polyamide. Moreover, stainless steel is mentioned as a metal. Here, the hydrophobic hard surface means that 1 μl of ion-exchanged water droplets are deposited on the hard surface and the contact angle is measured 10 times at intervals of 1 second from 3 seconds after the landing, and the average value is obtained. Refers to a hard surface having an angle of 60 ° or more. The measurement of the static contact angle can be performed using a fully automatic contact angle meter. As an example, there is a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd.
＜実施例１＞
表１の重合体（Ａ）を０．２１質量％、重合体（Ｂ）を０．２９質量％、残部の水を含有する水溶液（ｐＨ１１．４）を調製した。この水溶液は透過率が５０％以上であった。この水溶液に、１ＭのＨＣｌ水溶液を滴下してｐＨを低下させていくと、ｐＨ１０．４で複合体が析出し、白濁した。この混合物は透過率が５０％未満であった。ｐＨが８．５になるまで１ＭのＨＣｌ水溶液を滴下した。この白濁したｐＨ８．５の混合物を、以下の親水化性能の評価に用いた。このｐＨは２５℃で測定されたものであった。
<Example 1>
An aqueous solution (pH 11.4) containing 0.21% by mass of the polymer (A) in Table 1, 0.29% by mass of the polymer (B), and the remaining water was prepared. This aqueous solution had a transmittance of 50% or more. When 1M HCl aqueous solution was dropped into this aqueous solution to lower the pH, the complex was precipitated at a pH of 10.4 and became cloudy. This mixture had a transmittance of less than 50%. A 1M aqueous HCl solution was added dropwise until the pH was 8.5. This cloudy mixture of pH 8.5 was used for the following evaluation of hydrophilization performance. This pH was measured at 25 ° C.
＜比較例１〜３＞
表１の重合体（Ａ）、（Ｂ）を合計で０．５質量％、残部の水を含有する混合物を、以下の親水化性能の評価に用いた。該混合物は白濁した外観を呈していた。なお、重合体（Ａ）、（Ｂ）は、系中の正負の電荷比率が等比となるように配合した。また、表１には、便宜的に重合体（Ａ）、（Ｂ）に該当しない重合体もそれらの欄に示した（以下同様）。
<Comparative Examples 1-3>
A mixture containing a total of 0.5% by mass of the polymers (A) and (B) in Table 1 and the remaining water was used for the evaluation of the following hydrophilization performance. The mixture had a cloudy appearance. The polymers (A) and (B) were blended so that the positive and negative charge ratios in the system were equal. In Table 1, polymers not corresponding to the polymers (A) and (B) are also shown in these columns for convenience (the same applies hereinafter).
＜比較例４〜７＞
表１重合体（Ａ）と重合体（Ｂ）の欄の化合物とを、対象基板に滴下、混合して、以下の親水化性能を評価した。その際、同体積の重合体（Ａ）水溶液と、重合体（Ｂ）の欄の化合物の水溶液の２液を混合すると、ちょうど系中の電荷比が重合体（Ａ）の電荷に対して、重合体（Ｂ）の欄の化合物の電荷が２倍となり、かつ重合体（Ａ）濃度が０．５質量％となるよう、それぞれの水溶液の濃度を調整し、ピペットを用いて０．５ｍｌずつ採取し、同時に対象基板に滴下した。
<Comparative Examples 4-7>
Table 1 Polymer (A) and the compound in the column of polymer (B) were added dropwise to the target substrate and mixed to evaluate the following hydrophilization performance. At that time, when two liquids of the polymer (A) aqueous solution of the same volume and the aqueous solution of the compound in the column of the polymer (B) are mixed, the charge ratio in the system is exactly the charge of the polymer (A), Adjust the concentration of each aqueous solution so that the charge of the compound in the polymer (B) column is doubled and the concentration of the polymer (A) is 0.5% by mass, and 0.5 ml each using a pipette. The sample was collected and simultaneously dropped onto the target substrate.
＜親水化性能（接触角）＞
ＰＶＣ板（株式会社エンジニアリングテストサービス製、形状は２５ｍｍ×７５ｍｍ×１ｍｍ）に、実施例又は比較例の混合物又は水溶液を合計１ｍｌ塗布ないし滴下して５分間静置した後、２５℃のイオン交換水で１０秒間すすぎ、自然乾燥させた。２５℃４０％ＲＨに調温調湿された測定室にて、上記処理を行ったＰＶＣ板のイオン交換水に対する静止接触角（初期静止接触角とする）を測定した。測定には協和界面科学株式会社製の全自動接触角計ＤＭ−５００を使用し、１μｌのイオン交換水の水滴を処理表面に着滴させ、着滴３秒後から１秒間隔で１０回接触角を測定し、その平均値をデータとして記載した。さらに、初期接触角を測定した後のＰＶＣ板を、２５℃の水道水（流速５０ｍｌ／秒）で６０秒間すすいだ後に、同様に静止接触角（追加すすぎ後の接触角とする）を測定した。初期接触角が小さいほど、親水性が高く防汚性に優れることを意味する。また、追加すすぎ後の接触角が、初期静止接触角に近いほど、耐水性に優れ、防汚性の持続性にも優れることを意味する。なお、処理前のＰＶＣ板の静止接触角は、８５°であった。
<Hydrophilicity (contact angle)>
A PVC plate (manufactured by Engineering Test Service Co., Ltd., shape: 25 mm × 75 mm × 1 mm) was applied or dripped with a total of 1 ml of the mixture or aqueous solution of the example or comparative example and allowed to stand for 5 minutes, and then ion-exchanged water at 25 ° C. For 10 seconds and allowed to air dry. The static contact angle (referred to as the initial static contact angle) with respect to the ion-exchanged water of the PVC plate subjected to the above treatment was measured in a measurement chamber adjusted to a temperature of 25 ° C and 40% RH. For the measurement, a fully automatic contact angle meter DM-500 manufactured by Kyowa Interface Science Co., Ltd. was used, and 1 μl of ion-exchanged water droplets were deposited on the treated surface, and contacted 10 times at 1-second intervals after 3 seconds of deposition. The angle was measured and the average value was recorded as data. Further, the PVC plate after the initial contact angle was measured was rinsed for 60 seconds with 25 ° C. tap water (flow rate 50 ml / second), and then the static contact angle (referred to as the contact angle after additional rinsing) was also measured. . A smaller initial contact angle means higher hydrophilicity and better antifouling properties. Further, the closer the contact angle after the additional rinsing is to the initial static contact angle, the better the water resistance and the better the antifouling property. In addition, the static contact angle of the PVC board before a process was 85 degrees.
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