JP2019094433A - Hydrophilization treatment agent - Google Patents

Abstract

To provide a hydrophilization treatment agent that exhibits an excellent hydrophilization ability and a hydrophilization treatment agent composition containing the same.SOLUTION: A hydrophilization treatment agent contains a copolymer containing a specific constitutional unit (A) having a betaine group and a constitutional unit (B) having an aromatic group.SELECTED DRAWING: None

Description

  The present invention relates to a hydrophilizing agent, a hydrophilizing agent composition, and a method of hydrophilizing a solid surface.

Conventionally, as a method of imparting antifouling properties to a solid surface, different methods of water repelling treatment and hydrophilizing treatment are known.
The water repelling treatment is a technique for performing surface treatment to give water repellence to a solid surface such as glass, metal, fiber and the like so that dirt contained in water is not attached. For example, after washing clothes, they are treated with a softener, sprayed with a water repellent on ski wear, etc. to have a waterproof effect, or waxed on the painted surface of a car. .
However, in water repellent treatment, it is difficult to make the surface completely water repellent, and due to repeated contact with water, dirt contained in water accumulates on the solid surface, thus exhibiting a sufficient antifouling effect. Is difficult.

  On the other hand, if the solid surface is rendered hydrophilic, that is, the contact surface of the solid surface with water is reduced to make the solid surface easy to wet with water, the dirt adhering to the solid surface after the treatment tends to fall off during cleaning. In addition to being expected to have the effect of preventing soil re-contamination, anti-fogging effect of glass and mirror, antistatic prevention, prevention of frost formation on aluminum fins of heat exchanger, anti-soiling property of bath and toilet surfaces etc. Can be expected.

Several proposals have been made for hydrophilic surface treatment agents and methods for solid surfaces.
For example, Patent Document 1 discloses an aqueous antifouling composition containing an amphoteric polyelectrolyte. Patent Document 2 discloses a cleaning or rinsing composition containing a surfactant and a specific polybetaine. Patent Document 3 discloses a hydrophilic resin containing an acrylic resin obtained by copolymerizing a polymerizable unsaturated monomer having a specific betaine structure and a specific polymerizable unsaturated monomer, a hydrophilic crosslinked polymer particle and a crosslinking agent. A treatment composition has been disclosed. U.S. Pat. No. 5,075,059 comprises applying to the support a composition comprising an amphiphilic block copolymer, wherein the amphiphilic brooc copolymer is formed from a hydrophilic block of specific structure and an ethylenically unsaturated hydrophobic monomer. Methods are disclosed to improve the wettability / hydrophilicity of hydrophobic supports containing hydrophobic blocks. Patent Document 5 includes a polymer segment A-1 derived from an unsaturated monomer containing a repeating unit derived from a hydrophobic unsaturated monomer, and a repeating unit derived from an unsaturated monomer having a sulfobetaine group. Hydrophilization comprising a block polymer A having a polymer segment A-2 derived from an unsaturated monomer and having a content of the polymer segment A-1 of 0.05% by mass or more and 75% by mass or less Treatment agents are disclosed. Patent Document 6 discloses a surface treatment agent comprising a copolymer comprising a specific structural unit (A) having a betaine group and a specific structural unit (B) having a cationic group.

JP 2001-181601 A Japanese Patent Application Publication No. 2006-514150 JP, 2012-25820, A Japanese Patent Application Publication No. 2009-545642 JP, 2015-105313, A JP, 2017-190381, A

However, the product to which the hydrophilization technology is applied is surprisingly small, and it can not be said that it is widely and widely used. In particular, there is an increasing demand for a hydrophilizing agent that can easily hydrophilize the surface of a material with low surface free energy such as polypropylene and polyethylene.
An object of the present invention is to provide a hydrophilization treatment agent that exhibits excellent hydrophilization ability and a hydrophilization treatment agent composition containing the same.

  The present invention relates to a hydrophilic consisting of a copolymer (hereinafter also referred to as the copolymer of the present invention) containing a structural unit (A) represented by the following formula (a1) and a structural unit (B) having an aromatic group Related to chemical treatment agents.

[In the formula,
R ^1a , R ^2a and R ^{3a are the} same or different and each is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ^4a : an alkylene group having 1 to 4 carbon atoms, or -Z ¹ -OPO ₃ ^-- Z ^2-
Z ¹ and Z ^{2 are the} same or different and have 1 to 4 carbon atoms as an alkylene group R ^5a or R ^6a : the same or different and each having 1 to 4 carbon atoms and a hydrocarbon group X ¹ : O or NR ^7a And R ^7a represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ^8a SO ₃ ⁻ or R ^8a COO ⁻ . However, when R ^4a is an alkylene group having 1 to 4 carbon atoms, X ² is R ^8a SO ₃ ⁻ or R ^8a COO ⁻ , R ^8a is an alkylene group having 1 to 4 carbon atoms, and R ^4a is In the case of -Z ¹ -OPO ₃ ^-- Z ^2- , X ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

  The present invention also relates to a hydrophilizing agent composition containing the hydrophilizing agent of the present invention and water.

  The present invention also relates to a method for hydrophilizing a solid surface, wherein the hydrophilic treatment agent composition of the present invention is brought into contact with a solid surface having a surface free energy of 5 mN / m to 35 mN / m.

  The hydrophilization treatment agent composition containing the hydrophilization treatment agent of the present invention is excellent in hydrophilization performance (hereinafter, also referred to as the effect of the present invention). The hydrophilizing agent composition containing the hydrophilizing agent of the present invention can hydrophilize the surface of a substance with low surface free energy, such as polypropylene and polyethylene, in a simple manner.

<Hydrophilizing agent>
The hydrophilizing agent of the present invention comprises the copolymer of the present invention.
The copolymer of the present invention comprises the constituent unit (A) represented by the above formula (a1) and the constituent unit (B) having an aromatic group.

The structural unit (A) is a structural unit having a sulfobetaine group, a carbobetaine group, or a phosphobetaine group.
In the formula (a1), R ^1a and R ^2a are preferably hydrogen atoms from the viewpoint of the availability of unsaturated monomers, the viewpoint of the polymerizability of the monomers, and the viewpoint of enhancing the hydrophilization performance of the hydrophilizing treatment agent. From the same viewpoint, R ^3a is preferably a hydrogen atom or a methyl group, more preferably a methyl group. X ¹ is preferably O from the same viewpoint. From the same point of view, R ^4a is preferably an alkylene group having 2 or 3 carbon atoms, and more preferably a dimethylene group having 2 carbon atoms. From the same point of view, R ^5a and R ^6a are preferably a methyl group or an ethyl group, more preferably a methyl group.
In the formula (a1), from the same ^{viewpoint, R 4a} is an alkylene group having 1 to 4 carbon atoms, ^{X 2} is ^R 8a SO ₃ ^- or ^R 8a COO ^- is ^{preferably, R 4a} carbon atoms a 1 to 4 alkylene group, ^{X 2} is ^R 8a SO ₃ ^- and more preferably.

  From the viewpoint of enhancing hydrophilic performance, the copolymer of the present invention preferably has a proportion of structural unit (A) in all structural units of 80 mol% or more, more preferably 85 mol% or more, still more preferably 90 mol% or more And preferably 99 mol% or less, more preferably 98 mol% or less, and still more preferably 95 mol% or less.

  The structural unit (B) is a structural unit having an aromatic group. The aromatic group of the structural unit (B) may have a substituent such as a hydroxyl group. As the structural unit (B), a structural unit represented by the following formula (b1) (hereinafter, also referred to as a structural unit (b1)) and / or a structural unit derived from styrene (hereinafter, also referred to as a structural unit (b2)) It can be mentioned.

[In the formula,
R ^1b , R ^2b , R ^3b : identical or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R ^4b : hydrocarbon group having 6 to 22 total carbon atoms having an aromatic group Y ¹ : O or NR a ^5b, R ^5b is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]

The structural unit (b1) is a structural unit derived by polymerizing an unsaturated monomer (hereinafter also referred to as an unsaturated monomer b) represented by the following general formula (b1 ′), and a general formula R ^1b , R ^2b , R ^3b , R ^4b and Y ¹ in (b1) and in the general formula (b1 ′) are all synonymous.

In the formula (b1) and the formula (b1 ′), R ^1b and R ^2b from the viewpoint of the availability of unsaturated monomer, the viewpoint of the polymerizability of the monomer and the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent Is preferably a hydrogen atom. From the same point of view, R ^3b is preferably a hydrogen atom or a methyl group, more preferably a methyl group. Y ¹ is preferably O from the same viewpoint. The total carbon number of the hydrocarbon group of R ^4b is 6 or more and 22 or less, preferably 18 or less. The aromatic group of R ^4b may be substituted by one or more hydroxyl groups. ^Examples of R ^4b include aralkyl groups such as benzyl group, phenethyl group and 3,4-dihydroxyphenethyl group, aryl groups such as phenyl group, and alkyl-substituted aryl groups. R ^{4 b} is preferably an aralkyl group from the viewpoint of enhancing the adsorptivity to the surface.

  Examples of the unsaturated monomer b include benzyl (meth) acrylate and N- (3,4-dihydroxyphenylethyl) (meth) acrylamide. In the present specification, “(meth) acrylic” means acrylic, methacrylic or both of them.

  In the copolymer of the present invention, the proportion of the structural unit (B) in all the structural units is preferably 0.1 mol% or more, more preferably 1 mol% or more, from the viewpoint of enhancing the adsorptivity to the surface. It is preferably 1.5 mol% or more, more preferably 2 mol% or more, still more preferably 3 mol% or more, still more preferably 5 mol% or more, and preferably 20 mol% or less, more preferably 18 mol % Or less, more preferably 15 mol% or less, still more preferably 12 mol% or less, still more preferably 10 mol% or less.

  The copolymer of the present invention has a structural unit (A) / structural unit (B) which is a molar ratio of the structural unit (A) and the structural unit (B), from the viewpoint of enhancing the hydrophilization performance of the copolymer. It is preferably 50/50 or more, more preferably 60/40 or more, further preferably 75/25 or more, and preferably 99/1 or less, more preferably 98/2 or less, still more preferably 95/5 or less.

  The weight average molecular weight of the copolymer of component A is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, from the viewpoint of enhancing the hydrophilization performance, and manufacturability From the viewpoint of improving (the viscosity of the composition, etc.), it is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, still more preferably 300,000 or less. This weight average molecular weight can be measured by the method described in the examples.

  From the viewpoint of enhancing the hydrophilization performance of the copolymer of the present invention, the proportion of the total of the structural unit (A) and the structural unit (B) in all the structural units is 50 mol% or more, and further 60 More than 70% by mole, more than 75% by mole, more than 80% by mole, still more than 90% by mole, and less than 100% by mole, further less than 99.9% by mole, still more than 99% by mole Hereinafter, it can be selected from 98 mol% or less.

  The copolymer of the present invention may contain a structural unit (hereinafter also referred to as a structural unit (C)) other than the structural unit (A) and the structural unit (B) within the range not impairing the effects of the present invention. As a monomer used as a structural unit (C), unsaturated monomers, such as methacryloyl oxyethyl dimethyl ethyl ammonium ethyl sulfate (MOEDES), are mentioned. As the monomer to be the structural unit (C), methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, (meth ) T-butyl acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-decyl (meth) acrylate (Meth) acrylic acid esters such as lauryl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate and benzyl (meth) acrylate Or N-ethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-t-butyl (meth) acrylate Amide, N, N-diethyl (meth) include (meth) acrylamides such as acrylamide.

  The weight average molecular weight of the copolymer of the present invention is preferably 500 or more, more preferably 5000 or more, still more preferably 10,000 or more, still more preferably 30,000 or more, from the viewpoint of enhancing the hydrophilization performance, and manufacturability From the viewpoint of improving (the viscosity of the composition, etc.), it is preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 400,000 or less, still more preferably 300,000 or less. This weight average molecular weight can be measured by the method described in the examples.

  The hydrophilizing agent of the present invention can be applied to the surface of various substances. For example, it can be applied to the surface of a substance having a surface free energy of 5 mN / m or more and 35 mN / m or less. Here, the surface free energy is obtained by measuring the contact angle θ with a liquid of known surface tension γ with respect to the solid surface to be measured, plotting the surface tension γ and the cosine of the contact angle (cos θ) to cos θ = 1 It measured using the Zisman method which makes extrapolation value of Ct critical surface tension (gamma) c (surface free energy).

<Hydrophilizing treatment composition>
The hydrophilizing agent composition of the present invention contains the hydrophilizing agent of the present invention and water. That is, the hydrophilization treatment agent composition of the present invention contains water, and a copolymer including the structural unit (A) represented by the above formula (a1) and the structural unit (B) having an aromatic group. It is a hydrophilization treatment agent composition. The hydrophilic treatment agent can be used alone or in combination of two or more.
The content of the hydrophilization treatment agent in the hydrophilization 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 hydrophilization performance of the hydrophilization treatment agent composition And more preferably 0.2% by mass or more, and from the viewpoint of preventing uniform treatment by thickening and preventing deterioration of the hydrophilization performance, preferably 5% by mass or less, preferably 2.0% by mass The content is preferably at most 1.0% by mass.

  The content of water in the hydrophilic treatment agent composition is preferably 30% by mass or more, and more preferably 50% by mass, from the viewpoint of preventing uniform treatment by thickening and preventing reduction in hydrophilicity performance. Or more, more preferably 70% by mass or more, and from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing treatment composition, preferably 99.7% by mass or less, preferably 99.5% by mass or less, more preferably 99% by mass % Or less.

[Surfactant]
From the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment composition, the hydrophilization treatment composition of the present invention preferably contains a surfactant. By using a surfactant, the hydrophilization treatment composition easily wets and spreads on the solid surface, and the hydrophilization performance is improved. In addition, when a dirt substance, particularly a highly hydrophobic, for example, oily dirt substance is attached to a solid surface, the surfactant removes the highly hydrophobic dirt substance by using the surfactant, and the solid substance is solid. The surface hydrophilization performance is improved.
The content of the surfactant in the hydrophilizing treatment composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, from the viewpoint of enhancing the hydrophilization performance of the hydrophilizing treatment agent composition. The content is preferably 0.05% by mass or more, and from the viewpoint of preventing the adsorption of the copolymer of the present invention to the solid surface to be reduced, and reducing the hydrophilization performance, preferably 30% by mass or less, preferably 20%. It is not more than mass%, more preferably not more than 10 mass%. Furthermore, it is preferably 1% by mass or less, more preferably less than 0.5% by mass, still more preferably 0.3% by mass or less, and still more preferably 0.1% by mass or less from the viewpoint of foam control.

The surfactant to be used is not particularly limited as long as it is a surfactant generally used for liquid detergents. Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
The surfactant preferably has an alkyl group or an alkenyl group as the hydrophobic moiety from the above-mentioned viewpoint, and the carbon number thereof is preferably 8 or more, more preferably 10 or more, and the upper limit is preferably 20. Or less, more preferably 16 or less.

(Anionic surfactant)
The anionic surfactant is preferably one or more selected from a sulfate, a sulfonate, a carboxylate, a phosphate, and an amino acid salt having a hydrophobic site.
Specifically, sulfuric acid ester salts having a hydrophobic moiety such as alkyl sulfates, alkenyl sulfates, polyoxyalkylene alkyl ether sulfates, polyoxyalkylene alkenyl ether sulfates, polyoxyalkylene alkyl phenyl ether sulfates; sulfosuccinic acid Alkyl ester salts, polyoxyalkylene sulfosuccinic acid alkyl ester salts, alkane sulfonates, internal olefin sulfonates, sulfonates having a hydrophobic site such as acyl isethionate, acyl methyl taurate, etc. having 8 to 16 carbon atoms Fatty acid salts of carboxylic acids, carboxylic acid salts having hydrophobic sites such as polyoxyalkylene alkyl ether acetates; phosphoric acid ester salts having hydrophobic sites such as alkyl phosphates and polyoxyalkylene alkyl ether phosphates; Glutamic acid salts, alanine derivatives, glycine derivatives, amino acid salts and the like having a hydrophobic moiety, such as arginine derivatives.

  Among these anionic surfactants, alkyl sulfates such as sodium lauryl sulfate, sodium polyoxyethylene lauryl ether sulfate (sodium laureth-2 sulfate) from the viewpoint of improving the hydrophilization performance of the hydrophilization treatment composition And so forth, higher fatty acid salts such as potassium laurate and sodium myristate, and polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate (sodium laureth-4,5 acetate); Sulfosuccinate alkyl ester salts such as sodium laureth-2 sulfosuccinate, acyl glutamate salts such as N-acyl-L-glutamate sodium (sodium cocoylglutamate), acyl isethionate, and acyl methyl taurate? One or more preferably chosen, one or more selected from polyoxyethylene alkyl ether sulfuric acid salts and higher fatty acid salts are more preferred.

(Nonionic surfactant)
As nonionic surfactants, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbite fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, poly Polyethylene glycol type nonionic surfactants such as oxyalkylene (hardened) castor oil, and polyhydric alcohol type nonionic surfactants such as sucrose fatty acid ester, polyglycerin alkyl ether, polyglycerin fatty acid ester, alkyl glycoside and the like Examples include fatty acid alkanolamides and the like.
Among these nonionic surfactants, from the viewpoint of improving the hydrophilization performance of the hydrophilization treatment composition, it is selected from polyoxyalkylene alkyl ethers, polyoxyethylene hydrogenated castor oils, fatty acid alkanolamides, and alkyl glycosides. 1 type, or 2 or more types are preferable, and 1 type or 2 or more types selected from polyoxyethylene alkyl ether and alkyl glucoside are more preferable.

(Ampholytic surfactant)
Examples of the amphoteric surfactant include imidazoline type betaines, alkyl dimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, betaine type surfactants such as sulfobetaine, and amine oxide type surfactants such as alkyldimethylamine oxide.
Among these amphoteric surfactants, from the viewpoint of improving the hydrophilization performance of the hydrophilization treatment composition, it is selected from imidazoline type betaines, alkyl dimethylaminoacetic acid betaines, fatty acid amidopropyl betaines, and alkyl hydroxy sulfobetaines 1 The species or two or more species are preferable, and fatty acid amidopropyl betaines such as lauric acid amidopropyl-N, N-dimethyl-acetic acid betaine are more preferred.

(Cationic surfactant)
As a cationic surfactant, a quaternary ammonium salt having a hydrocarbon group having 12 to 28 carbon atoms, preferably 16 to 22 carbon atoms, which may be separated by an amide group, an ester group or an ether group , Pyridinium salts, or salts of mineral acids or organic acids of tertiary amines.
Specifically, long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, ochdadecyloxypropyltrimethylammonium salt; long-chain alkyldimethylbenzylammonium salts such as stearyldimethylbenzylammonium salt Di-long chain alkyl dimethyl ammonium salts such as distearyl dimethyl ammonium salt, diiso tetradecyl dimethyl ammonium salt; mono long chain alkyl dimethyl amine salts such as stearyl dimethyl amine, behenyl dimethyl amine, acid salt of octadecyl oxypropyl dimethyl amine Can be mentioned.
Among these cationic surfactants, long-chain alkyldimethylbenzyl ammonium salts are preferable from the viewpoint of improving the hydrophilization performance of the hydrophilization treatment composition.

[Other ingredients]
In the hydrophilic treatment composition of the present invention, oxalic acid, maleic acid, citric acid, adipic acid, sebacic acid, malic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, polyacrylic acid, as long as the object of the present invention is not impaired. Polyhydric carboxylic acids such as acids, polymethacrylic acid, polymaleic acid, poly 2-acrylamido-2-methylpropane sulfonic acid, poly p-styrene sulfonic acid; Lower alcohols such as ethyl alcohol and isopropyl alcohol; solvents such as diethylene glycol monobutyl ether Salts for improving the solubility of hydrophilic treatment agents such as NaCl in water; solubilizers such as toluene sulfonates, xylene sulfonates and ureas; viscosity modifiers such as clay minerals and water-soluble polymer compounds However, except for the copolymer of the present invention); calcite, silica, calcium phosphate, zeolite, carbon Water-insoluble abrasives such as calcium, polyethylene, nylon and polystyrene; moisturizers such as glycerin and sorbitol; feel improvers such as cationized cellulose (but excluding the copolymer of the present invention); sodium carbonate, sodium silicate and the like Alkali builders; enzymes, dyes, flavors, preservatives, fungicides, etc. can be added.

[Production of Hydrophilizing Treatment Composition]
The hydrophilization treatment agent composition of the present invention comprises the copolymer of the present invention, water and, if necessary, other components such as the surfactant and the polyvalent organic acid mentioned above, and is stirred and mixed by a known method. It can be obtained by
The composition ratio of the hydrophilization treatment agent composition can be appropriately adjusted in accordance with the type of solid surface and the treatment purpose. In addition, concentrated solutions can be prepared and diluted before use.

  The pH of the resulting hydrophilized treatment composition at 20 ° C. is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, from the viewpoint of safety in handling and prevention of damage to the solid surface, preferably Is 11 or less, more preferably 10 or less, more preferably 8 or less. As pH adjusters, 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; alkali metal carbonates such as sodium carbonate and potassium carbonate And alkali agents such as ammonia and derivatives thereof, and organic alkali compounds such as monoethanolamine, diethanolamine and triethanolamine. Moreover, an acid agent and an alkali agent can be combined and used as a buffer system.

  The hydrophilizing treatment composition of the present invention can be applied to the surface of various substances. For example, it can be applied to the surface of a substance having a surface free energy of 5 mN / m or more and 35 mN / m or less.

<Hydrophilization treatment method>
The present invention provides a method of hydrophilizing a solid surface, wherein the hydrophilizing treatment composition of the present invention is brought into contact with the solid surface.
Furthermore, the present invention provides a method for hydrophilizing a solid surface, wherein the hydrophilic treatment agent composition of the present invention is brought into contact with a solid surface having a surface free energy of 5 mN / m to 35 mN / m.
Here, "solid" of "solid surface" is not particularly limited, and glass, pottery, porcelain, glaze, tile, ceramics; metals such as aluminum, stainless steel, brass, etc .; polyethylene, polypropylene, melamine resin, polyamide resin, ABS Resin, synthetic resin such as FRP, natural fiber such as cotton, silk, wool etc. Synthetic fiber such as polyester, nylon, rayon etc .; Solid such as hair, nail, teeth etc.
Suitable solid surfaces to which the method of the present invention can be applied include hydrophobic hard surfaces, and further, one or more hydrophobic hard surfaces selected from ceramics, metals and synthetic resins. Here, a hydrophobic hard surface means that the static contact angle to water is 70 ° or more, and a hydrophilic hard surface means that it is less than 70 °. In addition, a stationary contact angle can be measured by the method as described in an Example.

  Furthermore, suitable solid surfaces to which the method of the present invention can be applied include solid surfaces having a surface free energy of 5 mN / m or more and 35 mN / m or less. Specifically, polyolefins such as polypropylene and polyethylene can be mentioned. The solid surface having a surface free energy of 5 mN / m or more and 35 mN / m or less is preferably a solid surface of polypropylene and / or polyethylene.

  In the hydrophilization treatment method of the present invention, the hydrophilization treatment agent composition is preferably an aqueous solution from the viewpoint of handling stability.

  The hydrophilic treatment agent composition of the present invention to be brought into contact with the surface is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, still more preferably 0.2% by mass of the copolymer of the present invention From the viewpoint of suppressing the uniform treatment by thickening and preventing the hydrophilizing performance of the hydrophilizing treatment composition from being reduced, the content is preferably 5.0% by mass or less, more preferably 2. The content is 0% by mass or less, more preferably 1.0% by mass or less.

  In the hydrophilization treatment method of the present invention, the hydrophilization treatment agent composition is preferably applied on a solid surface for 0.1 seconds or more, more preferably 0.5 seconds or more, still more preferably 1 second or more, and preferably 30. The contact is carried out for not more than a minute, more preferably not more than 15 minutes, still more preferably not more than 10 minutes.

  Moreover, in the hydrophilization treatment method of the present invention, after the hydrophilization treatment composition is brought into contact with the solid surface, it is preferably 10 seconds or more, more preferably 1 minute or more, still more preferably 2 minutes or more, and preferably It may be left for 30 minutes or less, more preferably for 15 minutes or less, still more preferably for 10 minutes or less. The temperature for standing is preferably 0 ° C. or more and 40 ° C. or less.

  In the hydrophilization treatment method of the present invention, it is preferable to rinse the solid surface with water after the hydrophilization treatment composition is brought into contact with the solid surface, preferably after being allowed to stand as described above. After rinsing, the solid surface can be dried.

The method of contacting the solid surface with the hydrophilizing treatment composition is not particularly limited. For example, the following methods (i) to (iii) may be mentioned.
(I) A method of immersing the solid in the hydrophilizing treatment composition (ii) a method of spraying or applying the hydrophilizing treatment composition onto the solid surface (iii) washing the solid surface according to a conventional method with the hydrophilizing treatment composition The temperature at which the solid surface is subjected to the hydrophilization treatment with the hydrophilization treatment agent composition is preferably 5 ° C. or more, more preferably from the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment agent composition and the ease of treatment method Is 10 ° C. or more, more preferably 15 ° C. or more, preferably 50 ° C. or less, more preferably 40 ° C. or less, more preferably 30 ° C. or less.
In the method (i), the immersion time is preferably 0.5 minutes or more, more preferably 1 minute or more, from the viewpoint of enhancing the hydrophilization performance of the hydrophilization treatment composition and from the economical viewpoint. Preferably it is 60 minutes or less, More preferably, it is 50 minutes or less.
In the method (ii), the method of spraying or applying the hydrophilizing treatment composition to a solid surface can be appropriately selected depending on the size (area) of the hard surface and the like. It is preferable to spray the hydrophilic treatment composition on a solid surface by a method such as spraying, and then to dry it. If necessary, after spraying, it may be rinsed with water. Moreover, after spraying, you may apply thinly using sponge etc.
The amount of the hydrophilizing treatment composition to be sprayed or applied onto the solid surface is preferably, for example, 0 per 10 cm ² of the hydrophilizing treatment composition having a content of the copolymer of the present invention of 0.5% by mass. .01 mL or more and 0.1 mL or less.
In the method (iii) above, it is preferable to use in the form of a detergent composition containing the copolymer of the present invention and a surfactant, and to contact with a solid surface. In the form of such a detergent composition, the pH is preferably 4 or more, preferably 10 or less, and more preferably 8 or less, from the viewpoint of safety in handling and prevention of damage to the solid surface.
As the surfactant, those described above can be used.

In addition, the static contact angle to water of the solid surface subjected to the hydrophilization treatment by the hydrophilization treatment agent composition of the present invention is preferably 50 ° or less, more preferably when the surface free energy of the solid surface exceeds 35 mN / m. Preferably it is 40 degrees or less, More preferably, it is 30 degrees or less, More preferably, it is 25 degrees or less.
In addition, the static contact angle to water of the solid surface subjected to the hydrophilization treatment by the hydrophilization treatment agent composition of the present invention is preferably 70 when the surface free energy of the solid surface is 5 mN / m to 35 mN / m. Or less, more preferably 65 or less, more preferably 60 or less, more preferably 55 or less.
Moreover, it is preferable that the solid surface which was hydrophilized by the hydrophilization processing agent composition of this invention is uniformly processed from a viewpoint of improving hydrophilization performance. The uniformity of the surface treatment can be judged by visually observing the solid surface after treatment.

  In the following production examples, examples and comparative examples, "%" means "mass%". The measurement of various physical properties was performed by the following method. In addition, the compounds used in each production example are the same manufacturer as long as they are the same compounds.

Production Example 1 (Production of Copolymer 1)
(Composition of DOPAMAm)
In a separable flask, 50.00 g of dopamine hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.), 28.00 g of sodium hydrogencarbonate (manufactured by Wako Pure Chemical Industries, Ltd.), sodium borate (manufactured by Wako Pure Chemical Industries, Ltd.) 70.00 g, 700.0 g of ion-exchanged water was added, and the mixture was stirred at room temperature. Separately, 34.22 g of methacrylic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) and 155.6 g of tetrahydrofuran (manufactured by Wako Pure Chemical Industries, Ltd.) were prepared in a dropping funnel and dropped over 1 hour. Several drops of NaOH (1 M) (manufactured by Wako Pure Chemical Industries, Ltd.) were added to make the pH alkaline to 8.0 or more, and the mixture was aged at room temperature for 12 hours. Thereafter, HCl (6 M) (manufactured by Wako Pure Chemical Industries, Ltd.) was added to acidify the pH to 2.0 or less, and magnesium sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and dried. Ethyl acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the dried solution, extraction and washing were performed with a separatory funnel, and an ethyl acetate solution was isolated. Thereafter, purification was carried out by recrystallization to obtain an intended white powder.

(Synthesis of copolymer 1)
[2- (Methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide (manufactured by Aldrich) 18.38 in a 100 mL eggplant flask. g, 1.618 g of DOPAMAm synthesized in the preceding paragraph, 0.1816 g of V-65B (manufactured by Wako Pure Chemical Industries, Ltd.), 46.49 g of trifluoroethanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and degassing by nitrogen bubbling The The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with acetone (manufactured by Wako Pure Chemical Industries, Ltd.). The precipitated polymer was vacuum dried at 80 ° C. to obtain copolymer 1.

Production Example 2 (Production of Copolymer 2)
In a 100 mL eggplant flask, 8.34 g of [2- (methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide], in the preceding paragraph The synthesized DOPAMAm 1.653 g, V-65B 0.093 g, and trifluoroethanol 23.24 g were added, and degassing was performed by nitrogen bubbling. The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with an acetone solvent. The precipitated polymer was vacuum dried at 80 ° C. to obtain copolymer 2.

Production Example 3 (Production of Copolymer 3)
In a 100-mL eggplant flask, 9.345 g of [2- (methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide], benzyl methacrylate 0.655 g (manufactured by Wako Pure Chemical Industries, Ltd.), 0.092 g of V-65B, and 23.24 g of trifluoroethanol were charged, and degassing was performed by nitrogen bubbling. The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with an acetone solvent. The precipitated polymer was vacuum dried at 80 ° C. to obtain copolymer 3.

Production Example 4 (Production of Copolymer 4)
[2- (Methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide] 8.638 g, benzyl methacrylate in a 100 mL eggplant flask 1.362 g, V-65B 0.096 g, and trifluoroethanol 23.24 g were charged, and degassing was performed by bubbling nitrogen. The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with an acetone solvent. The precipitated polymer was vacuum dried at 80 ° C. to obtain copolymer 4.

Production Example 5 (Production of Copolymer 5)
In a 100 mL eggplant flask, 9.602 g of [2- (methacryloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide [[2- (Methacryloyloxy) ethyl] dimethyl]-(3-sulfopropyl) ammonium hydroxide], styrene ( 0.398 g of Wako Pure Chemical Industries, Ltd., 0.095 g of V-65B, and 23.24 g of trifluoroethanol were charged, and degassing was performed by nitrogen bubbling. The oil bath was set to 65 ° C. and the eggplant flask was set to initiate polymerization. The polymerization was terminated after 6 hours, and reprecipitation was carried out with an acetone solvent. The precipitated polymer was vacuum dried at 80 ° C. to obtain copolymer 5.

Production Example 6 (Production of Copolymer 6)
(Step 1)
In a 1000 mL four-necked flask, 46.40 g of ethanol (manufactured by Wako Pure Chemical Industries, Ltd.) was charged, and the temperature was raised to 78 ° C. to reflux. Here, 128.0 g of methacrylic acid 2- (dimethylamino) ethyl (manufactured by Wako Pure Chemical Industries, Ltd.), 14.12 g of methacrylic acid 2- (dimethylamino) ethyl diethyl sulfate (manufactured by Kao Corp. / 90% aqueous solution), A mixed solution of 9.340 g of benzyl methacrylate and 20.90 g of ethanol, and a mixed solution of 2.080 g of 2,2'-azobis (2-methylbutyronitrile) (Wako Pure Chemical Industries, Ltd.) and 10.00 g of ethanol Was added dropwise over 2 hours. After aging for 4 hours, it was cooled to obtain a polymer solution.

(Step 2)
230.8 g of the obtained polymer solution, 6.837 g of sodium hydrogen carbonate (manufactured by Wako Pure Chemical Industries, Ltd.), and 310.7 g of water were added to a 1000 mL four-necked flask, and the temperature was raised to 50 ° C. The reaction was carried out by dropping 106.4 g of 1,3-propane sultone (manufactured by Tokyo Kasei Co., Ltd.) over 2 hours. 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 a copolymer 6.

Production Example 7 (Production of Polymer 7)
(Step 1)
53.23 g of ethanol was put into a 500 mL four-necked flask, and the temperature was raised to 78 ° C. to reflux. A mixed solution of 150.0 g of 2- (dimethylamino) ethyl methacrylate and 16.60 g of ethanol, and a mixed solution of 0.920 g of 2,2'-azobis (2-methylbutyronitrile) and 10.00 g of ethanol are mixed therein. Separately, it was dropped and polymerized over 2 hours. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
In a 1000 mL four-necked flask, 75.76 g of the obtained polymer solution, 3.470 g of sodium hydrogen carbonate and 150.0 g of water were charged, and the temperature was raised to 50 ° C. The reaction was carried out by dropping 42.73 g of 1,3-propane sultone thereto over 2 hours. After aging for 3 hours, ethanol was distilled off by heating under reduced pressure at 90/20 kPa for 2 hours to obtain an aqueous solution containing polymer 7

Production Example 8 (Production of Copolymer 8)
(Step 1)
In an eggplant flask, a stirrer chip, 2.000 g of butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 19.90 g of 2- (dimethylamino) ethyl methacrylate, 0.140 g of 2,2'-azobis (2-methylbutyronitrile) Then, 21.90 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and nitrogen bubbling was performed for 30 minutes. Then, the reaction was carried out at 67 ° C. for 8 hours, and the solution was cooled on ice while exposing to air, and then dried to obtain a polymer solid.
(Step 2)
In an eggplant flask, 6.000 g of the obtained polymer solid, 24.00 g of 2,2,2-trifluoroethanol, and 4.710 g of 1,3-propane sultone were charged to dissolve the polymer. The reaction was carried out at 50 ° C. for 5 hours, and drying gave copolymer 8 as a solid.

Production Example 9 (Production of Copolymer 9)
(Step 1)
In an eggplant flask, a stirrer chip, 7.875 g of butyl methacrylate (manufactured by Wako Pure Chemical Industries, Ltd.), 13.13 g of 2- (dimethylamino) ethyl methacrylate, 0.140 g of 2,2'-azobis (2-methylbutyronitrile) Then, 21.90 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and nitrogen bubbling was performed for 30 minutes. Then, the reaction was carried out at 67 ° C. for 8 hours, and the solution was cooled on ice while exposing to air, and then dried to obtain a polymer solid.
(Step 2)
In an eggplant flask, 6.000 g of the obtained polymer solid, 24.00 g of 2,2,2-trifluoroethanol, and 3.520 g of 1,3-propane sultone were charged to dissolve the polymer. The reaction was carried out at 50 ° C. for 5 hours, and drying gave a copolymer 9 as a solid.

Production Example 10 (Production of Copolymer 10)
(Step 1)
In a 1000 mL four-necked flask, 126.3 g of ethanol was charged, and the temperature was raised to 78 ° C. to reflux. Here, a solution obtained by mixing 181.1 g of 2- (dimethylamino) ethyl methacrylate, 47.20 g of 2- (dimethylamino) ethyl diethyl sulfate methacrylate, and 53.20 g of ethanol, and 2,2'-azobis (2-methylbutyric acid) A solution in which 5.830 g of ronitrile) and 10.00 g of ethanol were mixed was added dropwise over 2 hours. After aging for 4 hours, it was cooled to obtain a polymer solution.
(Step 2)
In a 1000 mL four-necked flask, 94.70 g of the obtained polymer solution, 3.150 g of sodium hydrogen carbonate, and 150.0 g of water were added, and the temperature was raised to 50 ° C. The reaction was carried out by dropwise addition of 38.70 g of 1,3-propane sultone over 2 hours. 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 10.

<Measurement of weight average molecular weight>
The weight average molecular weights of the copolymers 1 to 6, 8 to 10 and the polymer 7 were measured for molecular weight 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 preparing Zimm-plot. . Moreover, the refractive index increment required for calculation of molecular weight was measured using a differential refractometer "DRM 3000" (manufactured by Otsuka Electronics Co., Ltd.).
Wavelength: 632.8 nm (helium-neon laser)
Scattering angle: measured at 10 ° intervals from 30 ° to 150 °.
Average temperature: 25 °
Solvent: trifluoroethanol

Examples 1 to 6, Comparative Examples 1 to 5
Using the copolymer or polymer obtained in the above production example, a hydrophilic treatment agent composition is prepared to have the composition of Table 1, and the hydrophilic treatment of Examples 1 to 6 and Comparative Examples 2 to 5 is carried out. The agent composition was obtained. The comparative example 1 did not mix | blend anything other than water. In addition, water used ion exchange water. In addition, water was used in such an amount that the composition of the composition was 100% by mass (represented as balance in the table).
The following evaluations were used using the hydrophilization treatment agent composition of Examples 1-6, the water of Comparative Example 1, and the hydrophilization treatment agent compositions of Comparative Examples 2 to 5.

[Test method (evaluation of hydrophilic surface formation)]
The test piece cleaned in advance was fixed horizontally, and 1 mL of the hydrophilizing treatment composition was dropped and allowed to stand for 5 minutes, and then lightly rinsed with about 200 mL of ion exchanged water and air-dried.
The static contact angle of the treated surface of this test piece to ion exchange water was measured using an automatic contact angle meter “DM-500” (manufactured by Kyowa Interface Science Co., Ltd.) under the condition of addition amount 10 μL, 6 seconds after addition. It was measured.
The measurement was performed 5 times per test piece using two test pieces, and the average value of 10 measurement values was used.
The smaller the contact angle, the better the hydrophilization performance. The results are shown in Table 1.
The following test pieces were used.
PP: "PP test piece" (manufactured by Nippon Test Panel, 25 mm x 75 mm)
PE: PE Test Piece (made by Nippon Test Panel, 25 mm x 75 mm)
Vinyl chloride :: “vinyl chloride test piece” (manufactured by Engineering Test Service Co., Ltd., material: hard polyvinyl chloride, 25 mm × 75 mm)
Aluminum: “Aluminum Test Piece” (manufactured by Engineering Test Service, 25 mm × 75 mm)
SUS: "Stainless steel test piece" (manufactured by Engineering Test Service Co., Ltd., material: JIS G 4305 SUS 304, 25 mm x 75 mm)
Glass: "Glass test piece" (Akebono Shokai, Material: Glass plate (four-sided corner cutting), 60 mm x 60 mm)

The symbols of the constitutional units in the table mean the following monomers. The constituent units in the copolymer are constituent units corresponding to these monomers.
SBMA: N- (3-sulfopropyl) -N-methacryloxyethyl-N, N-dimethylammonium betaine DOPAMAm: dopamine methacrylamide BzMA: benzyl methacrylate benzyl St: styrene MOEDES methacryloyloxyethyldimethylethylammonium Ethyl sulfate · BMA: n-butyl methacrylate

  As apparent from Table 1, in Examples 1 to 6, since the contact angle at the surface with low surface free energy such as PP and PE is lower than in Comparative Examples 1 to 5, hydrophilicity of the surface is obtained. It is understood that it is excellent in

Claims (8)

The hydrophilic-ized processing agent which consists of a copolymer containing the structural unit (A) represented with following formula (a1), and the structural unit (B) which has an aromatic group.

[In the formula,
R ^1a , R ^2a and R ^{3a are the} same or different and each is a hydrogen atom or an alkyl group having 1 or 2 carbon atoms R ^4a : an alkylene group having 1 to 4 carbon atoms, or -Z ¹ -OPO ₃ ^-- Z ^2-
Z ¹ and Z ^{2 are the} same or different and have 1 to 4 carbon atoms as an alkylene group R ^5a or R ^6a : the same or different and each having 1 to 4 carbon atoms and a hydrocarbon group X ¹ : O or NR ^7a And R ^7a represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms X ² : a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, R ^8a SO ₃ ⁻ or R ^8a COO ⁻ . However, when R ^4a is an alkylene group having 1 to 4 carbon atoms, X ² is R ^8a SO ₃ ⁻ or R ^8a COO ⁻ , R ^8a is an alkylene group having 1 to 4 carbon atoms, and R ^4a is In the case of -Z ¹ -OPO ₃ ^-- Z ^2- , X ² is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ] The hydrophilizing agent according to claim 1, wherein the structural unit (B) having an aromatic group is a structural unit represented by the following formula (b1) and / or a structural unit derived from styrene.

[In the formula,
R ^1b , R ^2b , R ^3b : identical or different, hydrogen atom or alkyl group having 1 or 2 carbon atoms R ^4b : hydrocarbon group having 6 to 22 total carbon atoms having an aromatic group Y ¹ : O or NR a ^5b, R ^5b is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]   The hydrophilic treatment agent according to claim 1 or 2, wherein the copolymer is a random copolymer of the structural unit (A) and the structural unit (B).   The hydrophilization treatment agent in any one of Claims 1-3 whose ratio of the said structural unit (B) in all the structural units of the said copolymer is 0.1 mol% or more and 35 mol% or less.   A hydrophilization treatment agent composition comprising the hydrophilization treatment agent according to any one of claims 1 to 4 and water.   A method for hydrophilizing a solid surface, comprising bringing the hydrophilic treatment agent composition according to claim 5 into contact with a solid surface having a surface free energy of 5 mN / m to 35 mN / m.   The method for hydrophilizing a solid surface according to claim 6, wherein the solid surface having a surface free energy of 5 mN / m to 35 mN / m is a solid surface of polypropylene and / or polyethylene.   The method for hydrophilizing a solid surface according to claim 6 or 7, wherein the hydrophilizing agent composition is brought into contact with the solid surface, and then the solid surface is rinsed with water.