WO2002061012A1 - Surface modifier for hard surface - Google Patents

Abstract

A surface modifier for hard surfaces, an antifogging agent, a waterdrop repellant, a cleaning facilitator, and a rapid-drying-property imparter which each comprises a copolymer obtained by the copolymerization of an anionic vinyl monomer (a), a nitrogenous vinyl monomer (b), and a hydrophobic vinyl monomer (c). They impart highly long-lasting, antifogging, waterdrop repellent, easy-to-clean, and rapid-drying properties.

Description

 Specification

Surface modifiers for hard surfaces

 The present invention is a surface modification that imparts properties such as excellent anti-fogging property, water drop preventing property (water drop forming preventing property), easy cleaning property and quick drying property to various hard surfaces such as glass and plastic. Agent, anti-fogging agent, water droplet inhibitor (water droplet formation inhibitor), easy-cleaning agent, and quick-drying agent.

 This specification is based on a patent application filed in Japan (“Japanese Patent Application No. 2001-1024”), and the contents of the Japanese application are incorporated as a part of this specification. Shall be. Background art

 If a mirror, window glass, or transparent plastic is used in a high-temperature and high-humidity environment or in an environment where the temperature difference between the outer surface and the inner surface is large, water vapor will finely aggregate on these surfaces, and as a result, these surfaces Cloudy. In addition, especially when these are used outdoors, raindrops cause water droplets to adhere to these surfaces and obstruct visibility, and if these attached raindrops remain on these surfaces, they may cause streaks or spots of scale. In addition, raindrops containing sand dust and vehicle waste gas may cause problems such as adhesion of dirt on the surface.

 In addition, if water droplets remain on the bathroom wall, organic matter will adhere to the bathroom walls and vegetation will proliferate, causing problems such as adverse effects on health. In order to solve these problems, various surface modifiers have been developed to provide anti-fog properties, anti-water-drop properties, easy-to-clean, and quick-dry properties to hard surfaces such as mirrors, window glasses, and plastics as described above. Have been.

For example, as the anti-fogging property, a method of using a surfactant to prevent fogging has been conventionally known. However, with this method, the anti-fog property is And there was a problem with its durability.

 Further, antifogging agents and detergents using polymers are disclosed in the following publications (1) to (3).

 (1) JP-A-57-187347: An antifogging agent containing a specific copolymer and an inorganic sol as essential components is disclosed.

 (2) Japanese Patent Application Laid-Open No. 62-260895: A liquid aqueous detergent containing an amphoteric polymer compound is disclosed. It is disclosed that this detergent is mainly intended for an antistatic effect and also has an antifogging property.

(3) Japanese Patent Application Laid-Open No. 3-275705: Acryloyloxy Group (Meyer) Using a polyfunctional monomer having an acryloyloxy group to form a polymer in a network form Anti-fogging agents that exhibit antistatic ability have been disclosed.

 However, the anti-fogging agent described in (1) has a problem in stability such as gelation depending on conditions such as pH and temperature.

 The detergent described in (2) has a problem that the antifogging property is insufficient because the main purpose is an antistatic property. Further, since the compounded amphoteric polymer compound has a high water solubility, there is a problem that this detergent lacks anti-fogging durability.

 The anti-fogging agent described in (3) crosslinks the polymer compound, and thus easily becomes a gel in a solvent, for example, and there is a problem in blending this into a stable liquid product. Further, when applied to the surface of an object, there is also a problem that it is difficult to form a uniform film and sufficient antifogging property cannot be exhibited. Thus, the antifogging agent according to the above (1) to (3), In the case of detergents, the antifogging property and its durability were not sufficient.

Here, the durability of the antifogging property is a phenomenon in which the antifogging property is given to the hard surface by the antifogging agent, and then the antifogging property decreases with time due to the influence of water or the like. For example, a mirror in a bathroom, even if its surface is treated with an anti-fog agent, it will not get wet if it is splashed with water or rinsed with water. May run down and become cloudy soon. Even if the surface of a window glass or the like is treated with an anti-fogging agent, the anti-fogging agent may gradually flow down due to condensation formed in rainy white or winter, and the anti-fogging property may be lost.

 In addition, the following publications (4) and (5) disclose inventions aimed at improving the durability of antifogging properties.

 (4) Japanese Patent Application Laid-Open No. 3-223330: A plastic that cures by heating is mixed with an antifogging agent consisting of a specific polymer before curing, and then cured to cure. A heat-curable antifogging agent that imparts properties is disclosed.

 (5) Japanese Patent Application Publication No. 2000-94056: A film-type molded article provided with anti-fogging property using a photocatalyst such as titanium oxide is disclosed.

 However, the antifogging agent described in (4) requires mixing with a plastic and curing treatment, and has a problem that the treatment method is not simple and its application range is limited.

 The molded article described in (5) has drawbacks of lack of simplicity and easiness, such as the necessity of irradiation with ultraviolet rays and the necessity of uniformly applying the film to the target surface.

 As surface modifiers for imparting water droplet prevention properties, water droplet adhesion inhibitors and detergents are disclosed in the following publications (6) and (7).

 (6) Japanese Patent Application Laid-Open No. 3-127696 discloses that addition of an alcohol or a surfactant to a water-soluble cationic polymer prevents adhesion of water droplets. .

 (7) Japanese Patent Application Laid-Open No. 4-246493 discloses a raindrop-preventing agent which contains a nonionic fluorine-based surfactant, a cationic polymer and a monovalent fatty acid alcohol as essential components. It has been disclosed.

However, in those described in (6) and (7), the high Since the molecule is cationic, a precipitate may be formed when used in combination with an anionic surfactant. In addition, the cationic polymer has a very high adsorptivity to glass as described in (7) above. Therefore, the charged portion is directed toward the glass surface, and the surface on the air side is water. Since the number of polar groups capable of causing the summation is reduced, the polymer itself has a disadvantage that its ability to prevent water droplets (the ability to prevent water droplet formation) is reduced.

 Further, as a surface modifier imparting easy-cleaning properties, for example, easy-cleaning agents are disclosed in the following publications (8) and (9).

 (8) Japanese Patent Application Laid-Open No. 5-331494 discloses a finishing liquid for hand wiping, which contains alcohols and siloxane as essential components.

 (9) Japanese Patent Application Laid-Open No. 2000-1214150 discloses an easy-cleaning agent which is modified with a compound having a functional group in an optical semiconductor layer to promote easy-cleaning properties.

 However, the one described in (8) was intended to remove fingerprints, sebum, and the like, and was therefore unsatisfactory for solid-state stains such as scales.

 In addition, the method described in (9) lacks simplicity and simplicity because it is necessary to form a film by heating and to chemically modify this film in order to exhibit easy cleaning. There were drawbacks.

 In addition, methods for imparting quick drying properties are disclosed in the following publications (10) and (11).

 (10) JP-A-2000-3446333 discloses that a fluorine-based oil agent such as perfluoropolyether and a silicon derivative are added to impart quick drying property.

 (11) Japanese Patent Application Laid-Open No. 2000-1992 599 discloses a method of imparting quick drying with a composition containing a highly volatile solvent such as ethanol as a main solvent. I have.

However, the method described in (10) is a component for imparting quick drying property to the composition. Is a hydrophobic substance, and it is assumed that the composition to which quick-drying has been applied is applied to the object, then wiped with a towel or dried with a dryer. However, when this composition is used on a hard surface, the hard surface repels water and becomes water-drop-like, which causes problems such as leaving a water-drop-shaped pattern after drying.

 Since the method described in (11) uses a highly volatile solvent as a main solvent, it has a problem in storage stability. Disclosure of the invention

 Therefore, the present invention provides an anti-fogging agent capable of obtaining a highly durable anti-fogging property, a water drip preventing agent capable of obtaining a highly durable anti-fogging property, and a highly durable and easy-to-clean which can easily remove dirt. It is an object of the present invention to provide a surface modifier such as an agent and a quick-drying agent capable of drying the surface quickly.

 Specifically, an antifogging agent that does not reduce the antifogging property even by the adhesion of water, an antifogging agent that does not reduce the antidropping property even by the adhesion of water droplets, and the easy cleaning property does not decrease by the adhesion of rain etc. It is an object of the present invention to provide a quick-drying agent that does not decrease in quick-drying property when exposed to an easy-cleaning agent and water.

 In addition, surface modifiers such as anti-fogging agents, water-drop preventing agents, easy-cleaning agents, and quick-drying agents that can easily and easily provide anti-fogging properties, water-drop preventing properties, easy-cleaning properties, and quick-drying properties. The task is to provide.

 The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that an anti-fogging agent, a water droplet preventing agent, an easy-cleaning agent, and a quick-drying agent comprising a copolymer containing a specific vinyl monomer as an essential component. It has been found that the above problem can be solved by using an agent, and the present invention has been completed.

That is, the surface modifier for hard surfaces of the present invention is a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b), and a hydrophobic vinyl monomer (c). It is characterized by containing a polymer. Further, the antifogging agent for a hard surface of the present invention is an anionic vinyl monomer

(a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Further, the water droplet inhibitor for hard surfaces of the present invention is a copolymer prepared by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b), and a hydrophobic vinyl monomer (c). It is characterized by containing a polymer.

 Further, the easy cleaning agent for hard surfaces of the present invention is a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). It is characterized by including coalescence.

 The quick-drying agent for hard surfaces of the present invention is a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). It is characterized by containing a polymer.

 These surface modifier, anti-fogging agent, water droplet inhibitor, easy-cleaning agent, and quick-drying additive may be composed of only the above-mentioned copolymer, or may be a composition containing the copolymer. Good. This copolymer has (a) / (b) = 80 Z20 to 500 mol%, (c) / ((a) + (b) + (c)) = 0.10 to 20 It is preferred that they are copolymerized at a ratio of mass%. BEST MODE FOR CARRYING OUT THE INVENTION

 In the present invention, the anionic vinyl monomer (a) is a vinyl monomer having an acidic anionic functional group or a salt thereof, for example, a vinyl monomer having a hydroxyl group or a salt thereof. Examples thereof include salts, vinyl monomers having a sulfonic acid group, and salts thereof.

 Examples of the vinyl monomer having a carboxyl group (hereinafter, may be referred to as an acid type) include, for example, acrylic acid, maleic acid, maleic acid, fumaric acid, and the like.

In addition, a salt in which hydrogen of a carboxyl group is substituted with an alkali metal or the like (hereinafter, sometimes referred to as a salt form) can be used, and the salt is formed. Suitable counter ions are, for example, alkali metals, ammonium, organic amines and the like. Examples of the alkali metal include Na, K and the like. Examples of the organic amines include monoethanolamine, triethylamine, and the like.

 As the vinyl monomer having a sulfonic acid group (hereinafter sometimes referred to as an acid type), those represented by the following general formula (1) are suitable.

 R

 C— C— A— X— Y 1)

Ο In the general formula (1), I represents hydrogen or an alkyl group having 1 to 2 carbon atoms, and Y represents a sulfonic acid group (one SO ₃ H).

 A represents an oxygen atom or NH, and X represents a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched unsaturated hydrocarbon chain.

 Vinyl monomers having a sulfonic acid group include acrylamide sulfonic acid, methacrylamide sulfonic acid, acrylamide ethane sulfonic acid, methyl acrylamide sulfonic acid, and acrylamide propane sulfonic acid. , Methyl acrylamide propyl sulfonic acid, 2-acrylamide 2-methyl propyl sulfonic acid, 2-methacrylamide 12-methyl propane sulfonic acid, methane sulfonic acid acrylate, methane sulfonic acid methacrylate, Examples include ethanesulfonic acid acrylate, ethanesulfonic acid methacrylate, propanesulfonic acid acrylate, and propanesulfonic acid methacrylate.

In the above formula (1), a salt in which hydrogen of a sulfonic acid group is substituted with an alkali metal or the like (hereinafter, also referred to as a salt type) may be used. As a counter ion constituting the salt, For example, alkali metals, ammonia, organic amines and the like are suitable. Alkali metal Na, K and the like can be exemplified. Examples of the organic amines include monoethanolamine and triethylamine.

 Among these compounds, the following compounds can be exemplified as preferred as the anionic vinyl monomer (a) from the viewpoint of effectively exhibiting antifogging properties.

 That is, acrylic acid, methacrylic acid, acrylic acid salt, methacrylic acid salt, acrylamide methanesulfonic acid, methacrylic acid methanesulfonic acid, acrylamide dimethylsulfonic acid, 2-methylacrylamide 2-sulfonic acid, 2-acrylamide-2-methylpropanesulfonate, 2-methylacrylamide-1 2-methylpropanesulfonic acid, 2-acrylamide 2-methylpropanesulfonic acid , 2-methylacrylamide 2-methylpropanesulfonate, methanesulfonic acid acrylate, and methanesulfonic acid methacrylate are preferred, and acrylic acid, methacrylic acid, and acrylate are more preferred. 2-methacrylic acid 2-methacrylic acid 2-methacrylic acid 2-methylpropanesulfonic acid Propanesulfonic acid, 2 - Accession Riruami Dawe 2 - methyltransferase propane sulfonate, 2 - main Yuku Riruami dough 2 - Mechirupuro pan sulfonate, and the like.

 Further, as described above, as the anionic vinyl monomer (a), any of an acid type and a salt type can be used, each of which may be used alone, or a mixture of an acid type and a salt type may be used. Can also. Further, after the acid-type anionic vinyl monomer (a) is copolymerized with the vinyl monomers (b) and (c) of other essential components described below, the carboxyl group and / or sulfonic acid Some or all of the groups can be neutralized with an alkaline agent to form a salt form.

As the anionic vinyl monomer (a), one kind of compound may be used, or two or more different kinds of compounds may be used in combination. The nitrogen-containing vinyl monomer (b) contains a nitrogen atom such as an amino group or a substituted amino group and has a basic cationic functional group. Quaternary ammonium salts and the like are preferred. For example, a tertiary amine of a monofunctional monomer represented by the following general formula (2-1), a quaternary ammonium salt represented by the following general formula (2-2), Examples thereof include quaternary ammonium salts of a bifunctional monomer represented by the formula (3). In the case of a tertiary amine, for example, when dissolved or dispersed in a solvent, the structure of the proton is dissociated depending on the pH, and the dissociated structure is also a nitrogen-containing vinyl monomer. Included in (b).

RR ¹

H ₂ C = C— C— A— X— N— R ² '■ (2-1)

 O

In the general formula (2-1), RA and X are the same as those in the general formula (1). R ² represents an alkyl group having 1 to 2 carbon atoms. Note that RR ² may be the same or different.

Specific examples of the tertiary amine represented by the general formula (2-1) include, for example, dimethylaminoethyl acrylate, dimethylaminoethyl methyl acrylate, and dimethylaminopropyl acrylate. Acrylate, dimethylaminopropyl methacrylate, dimethylaminobutyl acrylate, dimethylaminobutyl methacrylate, getylaminoethyl acrylate, dimethylaminoethyl methyl acrylate, dimethylaminoethyl acrylate Dimethylaminoethyl methacrylamide, dimethylaminopropyl acrylamide, dimethylaminopropyl methacrylamide, dimethylaminobutyl acrylamide, dimethylaminobutyl methacrylamide, dimethylaminoethyl acrylamide, getylaminoethyl acrylamide, Etc. can and exemplified child E Ji Ruami Noechirumetaku Riruami de. RR ¹

H ₂ C = C—— C- ■ A—— X—— N—— R (2-2) o R 3

In - (2 2), R, A s X, R \ R 2 , the above general formula general formula - are the same as those of (2 1). R ³ is the same as R ² . Note that RRR ³ may be the same or different. Although the county anion that forms a salt is not shown in the general formula (2-2), the county anion is a negative ion, for example, a halogen ion, a sulfate ion, an organic acid ion, or the like. can do. Among them, chloride ion, bromine ion, alkyl sulfate ion, citrate ion and the like are preferable.

Specific examples of the quaternary ammonium salt represented by the general formula (2-2) include, for example, trimethylaminoethyl acrylate, trimethylaminoethyl methacrylate, and trimethylaminopropyl acrylate. Relate, Trimethylaminopropyl methacrylate, Trimethylaminobutyl acrylate, Trimethylaminobutyl methacrylate, Triethylaminoethyl methacrylate, Triethylaminoethyl methacrylate, Triethylaminoethyl methacrylate, Trimethylaminoethylacrylamide chloride, Trimethylaminoethylmethacrylamide chloride, Trimethylaminopropylacrylamide chloride, Trimethylaminopropylmethyl chloride acrylamide, Trimethylaminobutyl chloride chloride, Trimethylaminobutylacrylamide Lilamide Trimethylaminobutyl methacrylamide, triethylaminoethyl acrylamide, triethylaminoethyl methacrylamide, and the like, preferably dimethylaminoethyl methyl methacrylate, preferably dimethylaminoethyl acrylate , Trimethylaminoethyl methyl chloride, trimethylaminoethyl ethyl acrylate, trichloride Methylaminopropyl methyl amide, trimethylaminopropyl acrylamide, and the like.

 More preferably, trimethylaminoethyl methyl chloride, trimethylaminopropyl methyl chloride, acrylamide, and the like can be exemplified.

 Although a specific example in which the counter anion is chloride ion is shown here, the present invention is not limited to this, and a quaternary ammonium salt having another counter anion as exemplified above may be appropriately used. it can.

一般式 （ 3 ) において、 R、 R ²、 および R ³は上記一般式 （ 2— 2 ) 中のものと同様である。 Z ¹および Z ²は炭素数 1 ~ 3の直鎖状のアル キレン基を示し、 Z ¹と Z ²は同じ構造でも、 異なっていても良い。 な お、 一般式 （ 3 ) において、 塩を構成するカウンターァニオンは示さ れていないが、 上述の一般 （ 2— 2 ) で示される第 4級アンモニゥム 塩の場合と同様のカウン夕ーァニオンを例示することができる。

In the general formula (3), R, R ² and R ³ are the same as those in the general formula (2-2). Z ¹ and Z ^{2 each} represent a linear alkylene group having 1 to 3 carbon atoms, and Z ¹ and Z ² may have the same structure or may be different. In the general formula (3), the counter anion constituting the salt is not shown, but the same counter anion as in the case of the quaternary ammonium salt represented by the above general (2-2) is exemplified. can do.

 Specific examples of the quaternary ammonium salt represented by the general formula (3) include diaryldimethylammonium chloride, diaryldimethylammonium chloride, and diarylgetylammonium chloride. And garyrgetilammonium bromide.

 More preferably, diaryldimethylammonium chloride, diaryldimethylammonium bromide and the like can be mentioned.

As the nitrogen-containing vinyl monomer (b), one compound may be used, or two or more different compounds may be used in combination. As the hydrophobic vinyl monomer (c), for example, a compound represented by the general formula (4) or a silicon macromer represented by the general formula (5) can be used.

 R

H ₂ C = C—C II-A— Xl. ■. "." _(Λ

 (Four)

ο In the general formula (4), R and A are the same as those in the general formula (2-1). X ¹ represents a linear or branched alkyl group having 3 to 15 carbon atoms, or a linear or branched unsaturated hydrocarbon chain, of the compound represented by the general formula (4). Specific examples include propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, hexyl acrylate, and hexyl methacrylate. Relate, 2—ethylhexyl acrylate, 2—ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, propyl acrylyl amide, provir methacrylonitrile Mid, butyl acrylamide, butyl methyl acrylamide, t-butyl acrylamide t - butyl methyl Yuku Riruami de, to Kishiruaku Rirua mi de, to Kishirume Yuku Riruami de, Okuchiruaku Riruami de, can be used Okuchi Rumetaku Riruami de, Lau Riruaku Riruami de, and Lau Rirume Yuku Lil Ami de.

Among them, propyl acrylate, propyl methacrylate, butyl methacrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, hexyl acrylate, hexyl acrylate, and hexyl methacrylate And 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, and more preferably butyl acrylate, butyl methacrylate, t-butyl acrylate, t-butyl methacrylate. A relay or the like can be used.

H

 . . • (Five)

—In the general formula (5), R is the same as that in the general formula (2-1), and R ⁴ is a group having 1 to 6, preferably 1 to 4 carbon atoms which may contain an ether group. Represents a divalent aliphatic group, and R ⁵ represents an aliphatic group having 1 to 30 carbon atoms, preferably 2 to 18 carbon atoms, or a fluoroalkyl group having 1 to 22 carbon atoms (h is 0, It represents a number of 1 or 2, and j represents a number of 0 to 500, preferably 10 to 300.

 The weight average molecular weight of the silicon macromer represented by the general formula (5) is from 300 to 40,000, preferably from 100 to 200, from the viewpoint of the durability of the copolymer and the compatibility with the polymerization solvent. It is assumed to be ten thousand. The mass average molecular weight is determined by fe determined by GPC (gel permeation chromatography).

 As the hydrophobic vinyl monomer (C), one type of compound may be used, or two or more types of compounds may be used in combination. In the present invention, the blending ratio (composition) of the anionic vinyl monomer (a), the nitrogen-containing vinyl monomer (b) and the hydrophobic vinyl monomer (c) of the copolymer is as follows: The following ranges are preferred from the viewpoints of prevention, easy cleaning, quick drying, and durability.

 That is, (a) / (b) is preferably 80/20 to 50/50 (mol%), and more preferably 70/30 to 50/50 (mol%). ).

 If the proportion of (a) is too large, the durability tends to decrease, and if the proportion of (b) is too large, the antifogging properties, water drop prevention properties, easy cleaning properties and quick drying properties tend to decrease.

(C) / ((a) + (b) + (c)) is 0.1 to 20 (% by mass) Is more preferably 0.2 to 15 (% by mass), and still more preferably 0.3 to 10 (% by mass). When the amount is less than 0.1% by mass, the coating film is easily dissolved in water, and the antifogging property, water drop preventing property, easy cleaning property, and quick drying durability tend to decrease. If this is exceeded, the solubility and dispersibility of the surface modifying agent, anti-fog agent, anti-dropping agent, easy-cleaning agent and quick-drying agent in water and other solvents will be reduced, and the liquid surface modifier, anti-fog In some cases, it may be difficult to produce an agent, an anti-dripping agent, an easy-cleaning composition, or a quick-drying agent.

 When calculating the mass ratio, the anionic vinyl monomer (a) is based on the total mass in both the acid type and the salt type, and the nitrogen-containing vinyl monomer (b) is the quaternary ammonium salt. In the case of, the calculation is based on the total mass including the county anion.

 Then, the masses of the vinyl monomers (a), (b), and (c) are measured so as to satisfy this composition, and charged into a reactor and copolymerized to obtain a copolymer satisfying this composition. Obtainable.

 As described above, the surface modifier, antifogging agent, anti-waterdrop agent, easy-cleaning agent, and quick-drying agent of the present invention contain vinyl monomers (a), (b), and (c) as essential components. However, another vinyl monomer copolymerizable with the vinyl monomers (a), (b) and (c) is further copolymerized so as not to impair the performance of the copolymer of the present invention. It can also be used as a surface modifier, anti-fogging agent, water droplet inhibitor, easy-cleaning agent, and quick-drying additive.

 As the other monomer, for example, a vinyl monomer (d) represented by the general formula (6) is suitable.

一般式 （ 6 ) において、 R、 Aは前記一般式 （ 2— 1 ) 中のものと 同様である。 Y¹は （CH₂CH₂0) _nBを示し、 ここでの nは 1〜 3 0の数を示し、 Bは水素または C H ₃を示す。

In the general formula (6), R and A are the same as those in the general formula (2-1). The same is true. Y ¹ represents (CH ₂ CH ₂₀ ) _n B, wherein n represents a number of 1 to 30, and B represents hydrogen or CH ₃ .

 Specific examples of the vinyl monomer (d) include methoxypolyethylene glycol acrylate (ethylene part, 1 to 30) and methoxypolyethylene glycol methacrylate (ethylene part, 1 to 30). I can do it.

 When the vinyl monomer (d) is copolymerized, the proportion of the vinyl monomer (d) in all the vinyl monomers constituting the copolymer is determined by a surface modifier, an anti-fog agent, and a water droplet inhibitor. From the viewpoint of the durability of the easy-cleaning agent and the quick-drying agent to water and the like, it is preferably from 0.1 to 15 (% by mass), more preferably from 0.2 to 10 (% by mass).

 When the vinyl monomer (d) is used, the mass of the vinyl monomer (d) is measured so as to satisfy this range, and the reaction with the vinyl monomers (a), (b) and (c) is performed. In a vessel, copolymerize.

 The weight average molecular weight of the copolymer is from 100,000 to 2,000,000, preferably from 300,000 to 15 from the viewpoints of anti-fogging property, anti-water drop property, easy-cleaning property, fast drying durability and coating property. It is assumed to be 100,000. Here, the mass average molecular weight is a value measured by GPC.

 Note that the copolymer may be a random copolymer or a block copolymer.

 In addition, the copolymer can be used as a surface modifier, an anti-fogging agent, a water droplet inhibitor, an easy-cleaning agent, a quick-drying agent using only one type, or a mixture of two or more types having different compositions. It can also be used as an antifogging agent, anti-drop agent, easy-cleaning agent, and quick-drying additive.

 As the polymerization method of the copolymer, known polymerization methods such as solution polymerization, bulk polymerization, and precipitation polymerization are used.

The polymerization temperature varies depending on the polymerization method, the solvent used in solution polymerization, and the like, but is generally 30 ° C to 110 ° C, preferably 50 ° C; The polymerization time is from 1 hour to 24 hours, preferably from 2 hours to 10 hours.

The polymerization initiator used for the polymerization is not particularly limited as long as it has the ability to initiate radical polymerization, and various conventionally known ones can be used. For example, base peroxide Nzoiru, 2, 2 '- Azobisui Sopuchironi DOO Lil, 2, 2' - Azobisu (2 - Mechirupuchironi DOO Lil), 2, 2 ^f - Azobisu (2, 4 - Jimechiruno Reroni DOO Lil), 2, 2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), potassium persulfate, sodium persulfate, ammonium persulfate, Examples thereof include hydrogen oxide, and preferred are sodium persulfate and 2,2′-azobis (2-methylbutyronitrile).

 The copolymer used in the present invention may be a copolymer alone, and may be used as a surface modifier, an anti-fogging agent, an anti-dropping agent, an easy-cleaning agent, or a quick-drying agent.For example, the copolymer may be used as a solvent. The composition may be dissolved or dispersed to form a liquid composition, and this composition may be used as a surface modifier, an anti-fogging agent, a water drop inhibitor, an easy-cleaning agent, or a quick-drying agent. By applying this to various hard surfaces, a very thin coating film made of the copolymer is formed on the surface, and the hard surface has good antifogging property, water droplet preventing property, Washability, quick drying, etc. can be imparted.

 The coating film thus formed has an appropriate hydrophilicity (wetting property) on its surface, so a thin water film is formed on this surface, preventing fogging, preventing water droplets from adhering, and easily cleaning. Water can be imparted, and the formed water film is thin, so that quick drying can be imparted.

 In the present invention, as the water droplet preventing agent, for example, an agent for forming a water droplet into a water film and preventing a water droplet from being formed can be exemplified as a preferable one.

In addition, as a quick-drying agent, for example, by forming water droplets into a uniform thin water film, the surface area of water is reduced, excess water is flowed in advance, and Fast-drying agents that can dry quickly because they hold only water can be exemplified as preferred.

 Therefore, in the present invention, the “surface modifier” preferably modifies the wettability of the hard surface and has the above-mentioned favorable properties such as anti-fogging property, water drop preventing property, easy cleaning property and quick drying property. It is applied to hard surfaces.

 Examples of the hard surface include window glass for buildings and vehicles; mirrors for bathrooms and wash basins; glass lenses and plastic lenses for glasses; glass and acrylic products for water tanks and the like. .

 When the surface modifier, anti-fogging agent, water droplet inhibitor, easy-cleaning agent, and quick-drying agent are liquid compositions, the amount of the copolymer in the liquid composition is 0.01 to 3 0 mass%, more preferably 0.01 to 20 mass%. If the amount is less than 0.01% by mass, the antifogging property, the water droplet preventing property, the easy washing property, and the quick drying property cannot be imparted. If the amount is more than 30% by mass, the solubility and the dispersibility of the copolymer are reduced. May decrease.

 The solvent is preferably water, or a mixed solvent of water and an alcohol such as ethanol that is soluble. The reason for this is that a surface modifier, anti-fogging agent, anti-dropping agent, easy-cleaning agent, and quick-drying agent are applied to hard surfaces, etc., and after the copolymer coating film is formed, it evaporates quickly. This is because it is more preferable.

 The form of the surface modifier, the antifogging agent, the anti-dropping agent, the easy-to-clean agent, and the quick-drying agent may be liquid, granular, gel, or the like, and the form is not particularly limited. When provided in the form of granules or gels, for example, products that are appropriately dissolved or dispersed in a solvent at the time of use and used may be considered.

In addition, from the point of simplicity of use, it is preferable that it is liquid. Surface modifiers, anti-fogging agents, water droplet inhibitors, and quick-drying agents are used, for example, for the purpose of imparting detergency and the like, and easy-to-detergents are also used for enhancing the cleaning effect. Surfactants such as cationic surfactants, nonionic surfactants, and amphoteric surfactants Wear.

 In addition, other components can be blended within a range that does not impair the antifogging property, water drop preventing property, easy cleaning property, and quick drying property. Examples of such components include a plasticizer such as ethyl carbitol; a chelating agent such as ethylenediaminetetraacetic acid (EDTA); a pH adjuster such as monoethanolamine and citrate; and a fragrance.

 In the case of a form other than the liquid form, a solvent such as ethanol can be further added as necessary.

It is preferable that the compounding amount of these other components is such that the antifogging property, the water drop preventing property, the easy cleaning property and the quick drying property are not hindered, and it is not particularly limited ₍ the surface modifying agent of the present invention). A composition of a surface modifier, an anti-fog agent, an anti-drop agent, an easy-to-clean agent, and a quick-drying agent by blending a surfactant, an anti-fogging agent, a water-drop preventing agent, an easy-to-clean agent, and a quick-drying agent. In this case, it is possible to provide a cleaning agent having both good anti-fogging properties, good anti-fogging properties, excellent water-proof properties, easy cleaning properties, and quick drying properties.

 Next, the present invention will be described specifically with reference to examples.

 1. Composition of copolymer

 The composition of the copolymer used in each experimental example is shown below by mass% of the vinyl monomer. The anionic vinyl monomer (a) used was of the acid type. The ratio in {} is mol% of (a) / (b).

 The copolymers 1 to 29 correspond to the numbers 1 to 29 in the experimental examples, respectively. In Experimental Example 30, no copolymer was used.

 Among them, Experimental Examples 1 to 28 using Copolymers 1 to 28 correspond to Examples, Copolymer 29 is a polymer polymerized for comparison, and Experimental Examples 29 and 30 are It is a comparative example.

Copolymer 1; methacrylic acid (hereinafter abbreviated as MAA) / trimethyl chloride Luminoethyl methyl acrylate (hereinafter abbreviated as DMC) / 2-ethylhexyl acrylate (hereinafter abbreviated as 2EHA) = 38.2 / 61.5

0.3 {60/40} copolymer 2; MAA / DMC / t-butyl methyl acrylate (hereinafter abbreviated as t-BMA) = 37.2 / 59.8 / 3 {60/40} copolymer 3; MAA / DMC / t-BMA = 35.7 / 57.3 / 7 {60/40} copolymer 4: MAA / DMC / butyl acrylate (hereinafter abbreviated as BA) = 41.8 / 43.2 / 15 {70/30} copolymer Polymer 5; MAA / trimethylaminopropyl acrylamide

… {60/40} 共重合体 6 ； MAA/塩化 ト リメチルァミノプロピルメ夕ク リルアミ ド(Hereinafter abbreviated as AAPTAC)

… {60/40} copolymer 6; MAA / trimethylaminopropyl chloride methyl amide

(Hereinafter abbreviated as MAPTAC) /t-BMA=35.8/61.2/3 · ·-{60/40} copolymer 7; MAA / diaryldimethylammonium chloride (hereinafter abbreviated as DADMAC) ZMA BMA = 34.6 / 65.2 / 0.2 ··· {50/50} copolymer 8; MAA / DADMAC / BA = 44.2 / 55.4 / 0.4 {60/40} copolymer 9; acrylic acid (hereinafter, referred to as / AAPTAC / t-butylmethacrylamide (abbreviated as t-BMAA) = 38.1 / 46.9Z

15 {70/30} copolymer 10; AA / MAPTAC / t-BMAA = 31.2 / 63.8 / 5 ··· {60/40} copolymer 11; 2-methyl-2-acrylamide propanesulfonic acid ( Less than,

AMPS / DMC / BA = 63/27/10 {70/30} copolymer 12; AMPS / DMC / BA = 63.7 / 21.3 / 15 {75/25} copolymer 13; AMPS / DMC / t-BMA = 57/38/5 {60/40} copolymer 14; AMPS / DMC / t-BMA = 69/30/1 {70/30} copolymer 15; AMPS / DMC / HA = 49.5 / 49.5 / 1 {50/50} copolymer 16; AMPS / AAPTAC / butyl methyl acrylate (hereinafter abbreviated as BMA) ^ /. {50/50} copolymer 17; AMPS / AAPTAC / hexylmethacrylate (hereinafter referred to as HMA = 51/34/15 {60/40} copolymer 18; AMPS / AAPTAC / t-BMA = 48.6 / 48.4 / 3 {50/50} copolymer 19; AMPS / AAPTAC / HMA = 59.5 /39.5/1 {60/40} copolymer 20; AMPS / MAPTAC / t-BMA = 48.1 / 51.4 / 0.5 {50/50} copolymer 21; AMPS / MAPTAC / t-BMA = 55.6 / 39.4 / 5 {60/40} copolymer 22; AMPS / MAPTAC / HMA = 61.6 / 35.4 / 3 {65/35} copolymer 24; AMPS / DADMAC / BMA = 65.7 / 34.1 / 0.2 {60/40} copolymer 25; AMPS / DMC / t-BMA / methoxypolyether (p = 23) methacrylate = 47.3 / 47.4 / 0.3 / 5 {50/50}

* 1 (p = 23): Meaning of ethylene part number 23.

Copolymer 26; MAA / DMCZt-BMAZ methoxypolyether (p = 9 * ² ) methyl acrylate = 34.5 / 55.5 / 5/5 {60/40}

* 2 (p = 9): Means 9 ethylene parts.

Copolymer 27; MAA / DMC / BA / Siraf. Lane * ³ (made by Chidso Corporation) = 37.9 /60.9/0.2/1 {60/40}

* 3: Compound represented by the general formula (5), h = 2, j = ll, R: methyl group, R ⁴ : propyl group, R ⁵ : butyl group.

Copolymer 28; MAA / DMCZt-BMA / maleic acid = 26.4 / 63.6 / 5 Copolymer 29; MAA / dimethylaminoethyl methacrylate (hereinafter abbreviated as DM) = 5.7 / 94.3 ·- {10/90}

2. Copolymerization method

 The copolymer 1 was polymerized as follows.

 In a separate flask equipped with a cooling reflux tube, thermometer, nitrogen inlet tube and stirrer, add 15.28 g of MAA, 24.60 g of DMC, 0.12 of 2EHA :, 0.69 g of sodium persulfate, and 200 g of ion-exchanged water. The mixture was stirred at room temperature (about 20 ° C) for 30 minutes while introducing nitrogen.

Next, the temperature of the reaction system was raised to 85 ° C, and the reaction was performed for 6 hours. And raw The product was taken out of the reactor and reprecipitated with hexane to obtain 39 g of a copolymer 1 solid.

 The weight average molecular weight of the obtained copolymer 1 (surface modifier) was 60,000.

 Copolymers other than Copolymers 9, 12, 17, 17 and 30 were produced by the same polymerization method as Copolymer 1.

 Then, copolymers 9, 12, 17, 17 and 30 were produced in the same manner as copolymer 1 except that a mixed solvent of water / ethanol (70/30% by mass) was used as a solvent. did.

 3. Evaluation method

 Surface modifiers having the compositions shown in Tables 1 to 5 were produced. The surface modifier is liquid and is a solution or dispersion of the copolymer.

 In Tables 1 to 5, polyoxyethylene (ethylene part 30) lauryl alcohol is a nonionic surfactant, sodium dodecylbenzenesulfonate is an anionic surfactant, and N, N-dimethyl-N- Dodecyl-1-N-carboxymethylammonium benzoin is an amphoteric surfactant, ethanol and water are solvents, and monoethanolamine is a pH adjuster.

 Then, the following tests were performed and evaluated.

Anti-fog properties:

 The glass plate (10 cm long x 10 cm wide) was coated with lmL of each of the antifoggants shown in Tables 1 to 5 and then wiped and dried using Kimwipe (trade name, paper for experiment).

 Then, the glass plate was placed on boiling water at a height of 10 cm from the surface of the water. At this time, the surface treated with the anti-fogging agent was oriented toward the water surface, and was arranged at an angle of 60 ° with respect to the water surface.

The appearance of the surface of the glass plate was visually evaluated in the following three stages. 3 Does not cloud

 2 Half of the glass surface is cloudy

 The entire surface of the glass is fogged. Antifogging durability:

 The glass plate on which the antifogging agent was applied and dried in the same manner as in the antifogging test was rinsed with tap water for 10 seconds (flow rate 300 mL / min), and then dried again. Then, evaluation was made in the same manner as in the test for antifogging property. Water droplet prevention

 A glass plate (10 cm in length and 10 cm in width) was coated with 1 mL of the water droplet inhibitor of each concentration shown in Tables 1 to 5, then wiped with a Kimwipe and dried.

 Next, water was sprayed in a mist state from a distance of 10 cm from the glass plate using a mist sprayer, and the appearance of the glass surface was visually evaluated according to the following three grades.

 3 Water droplets cannot be formed, forming a water film, and the other side is seen well. 2 Some water droplets remain and the other side is hard to see.

 1 Water droplets remain on the entire surface, making the opposite side difficult to see. Water drop prevention durability:

 The glass plate to which the water droplet inhibitor was applied and dried in the same manner as above was rinsed with tap water for 10 seconds (flow rate 300 mL / min), and then dried again. Then, the evaluation was made in the same manner as the evaluation of the water droplet prevention property described above. Easy cleaning:

 A glass plate (length 10 cm x width 10 cm) was coated with lmL of the easy-cleaning agent of each concentration shown in Tables 1 to 5, wiped with Kimwipe, and dried.

Then, a 0.5 mM chloride solution was added to the glass plate from the pasteur bit. Nine drops of the shim solution were dropped. After drying and gently wiping with a Kimwipe, the appearance of the glass surface was visually evaluated on the following three scales.

 3 Dirt is removed.

 2 Some dirt remains

 1 Dirt is not removed. Durability of easy cleaning:

 The glass plate to which the easy-cleaning agent was applied and dried in the same manner as above was rinsed with tap water for 10 seconds (flow rate 300 mL / min), and then dried again. Then, the evaluation was performed in the same manner as the evaluation of the easy-cleaning property described above. Quick drying:

 A glass plate (10 cm in length and 10 cm in width) was coated with 1 mL of quick-drying additive of each concentration shown in Tables 1 to 5, and then wiped with a Kimwipe and dried.

 Next, water is sprayed in a mist from a location 10 cm away from the glass plate using a mist sprayer.The glass plate is allowed to stand for 10 minutes, and then the dryness of the glass surface is visually evaluated according to the following three levels. did.

 3 It is dry.

 2 Water remains partially.

 1 Water is scattered all over the surface. Fast drying durability

 The glass plate to which the quick-drying agent was applied and dried as described above was rinsed with tap water for 10 seconds (flow rate 300 mL / min), and then dried again. And it evaluated similarly to the above-mentioned evaluation of quick-drying property.

The test results are shown in Tables 1 to 5. (The numbers of the experimental examples in the table match the numbers of the copolymers.) Component f Lightning amount%

 丄 ά ο

 Ο 4 0 D 仕 H 里 里 里 ^ Mouth ^! 0 U, π 1 U. 0 U. 4 ϋ. 0 U, 51 Li / Jan Nareno J Li Purinore Nore J-Nore 0.30. Ύ 0.50 0.3

Pair ^ Annole Hen, Nono ¾ _ _ Sorter 0.10 0.5 0.5 0.3 0.3

Ν ^ Ν- メ テ

 Tsumetano 0.04 0.04 0.04 0.04 0.04 Seletano 10 10 10 10 10 10 10

0.50, 50.5, 0.50, 0.50, 5, 0, 5 Water 88.56 88.26 88.66 88.8 88.46 88.7 88.16 Fogging 3 3 3 3 3 3 3 S-proof durable 3 3 3 3 3 3 3 Drip-proof 3 3 3 3 3 3 3 Drip-proof durable 3 3 3 3 3 3 3 Easy cleaning 3 3 3 3 3 3 3 Valency Easy cleaning durability 3 3 3 3 3 3 3 Quick drying 3 3 3 3 3 3 3 Quick drying durability 3 3 3 3 3 3 3

Ingredient (% by weight)

 8 9 10 11 12 13 14 Copolymer 0.5 0, 7 0.5 0.5 0.4 0.50, 51 boroxixylene (30) peryl alcohol 0, 3 0.3 0.50 . 3

Gumi Sodium dodecylbenzene sulphonate 0, 1 0.5 0.5 0.3 0.3 Dimethyl-N-carboxymethylammonium

 ゥ Mbetaine 0.04 0.04 0.04 0.04 0.04

 Monoethanolamine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Water 88.56 88.26 88.66 88.88 88.46 88.7 88.16 Anti-fog 3 3 3 3 3 3 3 Anti-fog durability 3 3 3 3 3 3 3 Rated drip-proof 3 3 3 3 3 3 3 3

 Drip-proof durability 3 3 3 3 3 3 3 Easy cleaning 3 3 3 3 3 3 3 Valency Easy cleaning durability 3 3 3 3 3 3 3

 Quick drying 3 3 3 3 3 3 "3 Quick drying durability 3 3 3 3 3 3 3

02 Ingredient (% by weight)

 1 fi 1 7 1 R 1 q 2 n 9 1 Co-polymer

 Polyoxyethylene (30) lauryl alcohol

Gumi Sodium dodecylbenzenesulfonate 0 1 υ

Ν, Ν-dimethyl-N-carboxymethylammonium

Ω 4 Π 04 ^{4 4} ± ⁴ 10 10 10 10 10 10 10

 Monoethanolamine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Water 88.56 88.26 88.66 88.88 88.46 88.7 88.16 Anti-fog property 3 3 3 3 3 3 3 Anti-violence durability 3 3 3 3 3 3 3 Evaluation drip-proof 3 3 3 3 3 3 3

 Drip-proof durability 3 3 3 3 3 3 3 Easy cleaning 3 3 3 3 3 3 3 Valuable cleaning durability 3 3 3 3 3 3 3

 Quick drying 3 3 3 3 3 3 3 Quick drying durability 3 3 3 3 3 3 3

03 Ingredient (% by weight)

 22 23 24 25 26 27 28 Copolymer 0.5 0.7 0.7 0.5 0.4, 50, 51 Boroxyethylene (30) lauryl alcohol 0.3 0.3 0.3, 5 0.3

Gumi Sodium dodecylbenzenesulfonate 0.1 0.5 0.5 0.3 0.3

Ν, Ν-dimethyl-Ν-carboxymethyl ammonium

 ゥ Mubtaine 0.04 0.04 0.04 0.04 0.0 Ethanol 10 10 10 10 10 10 10

 Monoethanolamine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 50.5 Water 88.56 88.26 88.66 88.88 88.46 88.7 88.16 Antifogging property 3 3 3 3 3 3 3 Anti-fog durability 3 3 3 3 3 3 3 Evaluation Drip-proof 3 3 3 3 3 3 3

 Drip-proof durability 3 3 3 3 3 3 3 Easy cleaning 3 3 3 3 3 3 3 Valency Easy cleaning durability 3 3 3 3 3 3 3

 Quick drying 3 3 3 3 3 3 3 Quick drying durability 3 3 3 3 3 3 3

β 4 Ingredient (% by weight)

29 30 Copolymer 0.50 Boroxyethylene (30) lauryl alcohol 0.3

Gumi Sodium dodecylbenzenesnolephonate 0.1 0, 3

N, N-dimethyl-N-carboxymethyl ammonium

 ゥ Mbetaine 0.04 0.0 0.0 Composition Ethanol 1 0 1 0

 Monoethanolamine 0.5 0.5 0.5 Water 88.56 88.96 Anti-fog 2

 Anti-fog durability 1

Water drop prevention 2

 Water droplet prevention durability 1

 Easy cleaning 2

Easy cleaning durability 1

 Quick drying 2

 Quick drying durability 1

Five From these results, in Examples 1 to 28 satisfying the preferred composition of the vinyl monomers (a), (b) and (c), good characteristics were obtained, and a preferable surface modification was obtained. Filling agent It was clarified that an anti-fogging agent, a water droplet preventing agent, an easy-cleaning agent, and a quick-drying agent could be provided. On the other hand, the characteristics of Experimental Example 29 containing no vinyl monomer (c) and Experimental Example 30 containing no copolymer were deteriorated. INDUSTRIAL APPLICABILITY As described above, by using the surface modifier of the present invention, surfaces such as various hard surfaces such as glass and plastic can be modified, and the durability is excellent. , Water-drop prevention, easy-cleaning, and quick-drying properties.

 In addition, the use of the anti-fogging agent, water-drop preventing agent, easy-cleaning agent, and quick-drying imparting agent of the present invention allows the hard surface to have excellent anti-fogging properties, water-drop preventing properties, and easy cleaning properties. And quick-drying properties.

Claims

The scope of the claims 1. A hard surface characterized by containing a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Surface modifier.  2. When the copolymer is (a) / (b) = 80/20 to 50/50 mol%, (c) / ((a) + (b) + (c)) = 0. The surface modifier for hard surfaces according to claim 1, wherein the surface modifier is copolymerized at a ratio of 1 to 20% by mass.  3. A hard surface characterized by containing a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Anti-fog agent.  4. The copolymer is (a) / (b) = 80Z20-50 / 50 mol%, (0) / ((&) + (13) + (0)) = 0. The antifogging agent according to claim 3, wherein the antifogging agent is copolymerized at a ratio of 1 to 20% by mass.  5. A hard surface characterized by containing a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Water drop inhibitor.  6. When the copolymer has (a) / (b) = 80/20 to 50/50 mol%, (c) / ((a) + (b) + (c)) = 0. The water droplet preventive according to claim 5, which is copolymerized at a ratio of 1 to 20% by mass.  7. A hard surface characterized by containing a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Easy cleaning agent. 8. (a) / (b) = 80/20 to 50/50 mol%, (c) / ((a) + (b) + (c)) = 0. 1 to 20% by mass 8. The easy-cleaning agent according to claim 7, which is copolymerized at a ratio of:  9. A rigid material characterized by containing a copolymer obtained by copolymerizing an anionic vinyl monomer (a), a nitrogen-containing vinyl monomer (b) and a hydrophobic vinyl monomer (c). Quick-drying agent for surfaces. 1 0. The copolymer, (a) / (b) = 8 0/2 0~ 5 0/5 0 mol%, (c) / (( a) + (b) + (c)) = 0 The quick-drying agent according to claim 9, wherein the agent is copolymerized at a ratio of 1 to 20% by mass.