JP2023074399A - Surface modification method - Google Patents

Abstract

To provide a surface modification method and a treatment agent set for surface modification which can impart a high modification effect to a target surface, and are excellent in sustainability of the modification effect, and a surface homogenization method which can satisfactorily homogenize a target surface.SOLUTION: There are provided [1] a surface modification method which includes a step 1 of applying a nitrogen-containing polycyclic compound (A) to a target surface, and then forming a polymer of the compound (A), and a step 2 of applying a treatment agent I containing a compound (B) having an amino group or a thiol group to the polymer of the compound (A) on the target surface formed in the step 1, wherein the compound (A) is at least one selected from an indole compound represented by a formula (1) and its salt, and an indoline compound represented by a formula (2) and its salt; [2] a treatment agent set for surface modification which contains a treatment agent I' containing a nitrogen-containing polycyclic compound (A), and a treatment agent I containing a compound (B) having an amino group or a thiol group, wherein the compound (A) is at least one selected from an indole compound represented by a formula (1) and its salt, and an indoline compound represented by a formula (2) and its salt; and [3] a surface homogenization method which includes a step 1 of applying a nitrogen-containing polycyclic compound (A) to a target surface, and then forming a polymer of the compound (A), wherein the compound (A) is at least one selected from an indole compound represented by the formula (1) and its salt, and an indoline compound represented by the formula (2) and its salt.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a surface modification method, a surface modification treatment agent set, and a surface homogenization method.

Conventionally, methods for controlling the wettability of solid surfaces, such as hydrophilization and water-repellent treatments, are known as methods for modifying solid surfaces. These methods are expected to have effects such as anti-fogging of glass and mirrors, anti-static of plastics, anti-frost of aluminum fins of heat exchangers, antifouling of bathtub and toilet surfaces, etc. It has been used in the industrial field, and studies have been conducted on methods for modifying the surface of solids.

For example, in US Pat. No. 5,200,402, a method for depositing a coating material to reduce or prevent biofilm formation on a surface includes contacting the surface with a solution mixture of a dopamine coating material to form a dopamine coating on the surface, A method of reducing biofilm formation is described.
In Patent Document 2, the object is to provide a method for producing a composite material that can be used in a wide range of fields and is suitable for controlling physical properties of the interface and adding functions such as prevention of adhesion of contaminants. Compound A having an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic group containing a compound A is bonded to a substrate, and the compound A and the compound B are bonded to manufacture a composite material method is described.
US Patent No. 5,330,003 discloses a method of forming a hydrophilic coating covalently bonded to the surface of a substrate, said method comprising: (a) a surface, components A and B, optional component C, optional component D and contacting with a mixture comprising a radical initiator, wherein component A comprises one or more C2-C16 hydrophilic monomers each comprising one or more alkene and/or alkyne groups, and component B comprises two one or more hydrophilic polymers each containing one or more alkene and/or alkyne groups and component C, if present, one or more beneficial chemicals each containing one or more alkene or alkyne groups material and component D, if present, comprises one or more low molecular weight crosslinkers each comprising two or more functional groups independently selected from thiol, alkene, and alkyne groups; and (b) alkene and/or alkyne groups of components A, B and C (if present) and component D (if present) to form crosslinked copolymers of components A, B, and optionally C and D; initiating radical polymerization involving the functional groups of (if any), wherein said copolymer is covalently attached to a surface; and (c) optionally comprising one or more beneficial chemicals. A method is described comprising the step of incorporating component E into a hydrophilic coating, wherein component E does not form a copolymer with components A, B, C (if present) and D (if present). It is

WO2011/005258 JP-A-10-287862 Japanese Patent Publication No. 2016-508776

However, it has been found that the techniques of Patent Documents 1 to 3 are not sufficiently effective in modifying the target surface. In addition, regarding the modification effect of the target surface, it is required that the modification effect imparted is not easily reduced even if washing etc. are performed after the modification treatment, and improvement of the sustainability of the modification effect is also required. there is
Furthermore, when modifying the target surface using a treatment agent, the degree of hydrophilicity and hydrophobicity of the target surface varies depending on the material of the target surface, so the desired hydrophilization effect can be achieved regardless of the degree of hydrophilicity and hydrophobicity of the target surface. Alternatively, it may be required to impart a hydrophobic effect. However, it is necessary to change the treatment agent to be used depending on the degree of hydrophilicity/hydrophobicity, and there are also restrictions on changing the treatment agent depending on the type of material of the target surface and the composition of the material. Therefore, it is also required to homogenize the target surface regardless of the material.
The present invention provides a surface modification method and a surface modification treatment agent set capable of imparting a high modification effect to a target surface and having excellent durability of the modification effect, and homogenizing the target surface satisfactorily. An object of the present invention is to provide a surface homogenization method capable of

［式（１）中、Ｒ¹は、それぞれ独立に、水酸基又はアセトキシ基を示し、Ｒ²は水素原子、又は－ＣＯＯＲ（Ｒは水素原子、メチル基又はエチル基）を示し、Ｒ³は水素原子、アセチル基、メチル基、又はエチル基を示す。］

［式（２）中、Ｒ¹～Ｒ³は、前記式（１）と同じである。］ The present inventors used a nitrogen-containing polycyclic compound containing a specific catechol structure to homogenize a target surface, and also used a nitrogen-containing polycyclic compound containing a specific catechol structure and a compound having an amino group or a thiol group. It was found that the above problems can be solved by using the above for the modification treatment of the target surface.
That is, the present invention provides the following [1] to [3].
[1] A surface modification method for modifying a target surface,
Step 1 of applying a nitrogen-containing polycyclic compound (A) containing a catechol structure to a target surface, and then forming a polymer of the nitrogen-containing polycyclic compound (A);
A step 2 of applying a treatment agent I containing a compound (B) having an amino group or a thiol group to the polymer of the nitrogen-containing polycyclic compound (A) on the target surface formed in step 1,
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , surface modification methods.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ]

［式（１）中、Ｒ¹は、それぞれ独立に、水酸基又はアセトキシ基を示し、Ｒ²は水素原子、又は－ＣＯＯＲ（Ｒは水素原子、メチル基又はエチル基）を示し、Ｒ³は水素原子、アセチル基、メチル基、又はエチル基を示す。］

［式（２）中、Ｒ¹～Ｒ³は、前記式（１）と同じである。］ [2] A treatment agent I' containing a nitrogen-containing polycyclic compound (A) containing a catechol structure, and a treatment agent I containing a compound (B) having an amino group or a thiol group,
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , treatment agent set for surface modification.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ]

［式（１）中、Ｒ¹は、それぞれ独立に、水酸基又はアセトキシ基を示し、Ｒ²は水素原子、又は－ＣＯＯＲ（Ｒは水素原子、メチル基又はエチル基）を示し、Ｒ³は水素原子、アセチル基、メチル基、又はエチル基を示す。］

［式（２）中、Ｒ¹～Ｒ³は、前記式（１）と同じである。］ [3] A surface homogenization method for homogenizing a target surface, comprising:
A step 1 of applying a nitrogen-containing polycyclic compound (A) containing a catechol structure to a target surface and then forming a polymer of the nitrogen-containing polycyclic compound (A);
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , surface homogenization method.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ]

According to the present invention, a surface modification method and a treatment agent set for surface modification, which can impart a high modification effect to a target surface and are excellent in the durability of the modification effect, and a surface modification treatment agent set, and a target surface. A surface homogenization method can be provided that can homogenize.

[Surface homogenization method and surface modification method]
The surface homogenization method of the present invention is a surface homogenization method for homogenizing a target surface, and is a nitrogen-containing polycyclic compound (A) containing a catechol structure on the target surface (hereinafter simply "compound (A)" or (Also referred to as "nitrogen-containing polycyclic compound (A)") is applied, and then a step 1 of forming a polymer of said nitrogen-containing polycyclic compound (A), is at least one selected from the indole compound represented by the formula (1) and its salt, and the indoline compound represented by the compound represented by the formula (2) and its salt.
Further, the surface modification method of the present invention is a surface modification method for modifying a target surface, and after applying the nitrogen-containing polycyclic compound (A) containing a catechol structure to the target surface, Step 1 of forming a polymer of the cyclic compound (A), and a compound ( B) a step 2 of applying a treatment agent I containing (hereinafter also simply referred to as “compound (B)”), wherein the nitrogen-containing polycyclic compound (A) is represented by the formula (1) is at least one selected from indole compounds and salts thereof, and indoline compounds represented by the formula (2) and salts thereof.
In the present invention, the “catechol structure” means a catechol (1,2-diphenol) structure and a structure in which at least one hydroxyl group of the structure is substituted with an acetoxy group.

According to the present invention, the target surface can be homogenized satisfactorily, a high modification effect can be imparted to the target surface, and an effect of excellent sustainability of the modification effect can be expressed. . Although the reason why such an effect is produced is not clear, it is considered as follows.
In the present invention, after applying a nitrogen-containing polycyclic compound containing a specific catechol structure to the target surface in step 1, a polymer of the nitrogen-containing polycyclic compound is formed. And this polymer contains an amino group, a catechol structure, and a benzene ring structure. Therefore, when the target surface is a hydrophilic surface, the polymer of the nitrogen-containing polycyclic compound is adsorbed by the coordination bond or hydrogen bond resulting from the amino group or catechol structure, and the target surface is a hydrophobic surface. In some cases, hydrophobic interactions between the alkyl groups or aromatic rings on the surface of interest and the benzene rings of the polymer of the nitrogen-containing polycyclic compound cause the polymer to adsorb, resulting in the hydrophilicity and hydrophobicity of the surface of interest. It is considered that the polymer of the nitrogen-containing polycyclic compound can homogenize the surface properties regardless of the degree.
In addition, the polymer of the nitrogen-containing polycyclic compound formed on the target surface contains a quinone structure. Therefore, by applying a treatment agent containing a compound having an amino group or a thiol group to the polymer of the nitrogen-containing polycyclic compound on the target surface formed in step 1, the compound having an amino group or a thiol group is a Schiff base reaction between the amino group or thiol group of the compound and the carbonyl group of the quinone structure of the polymer, or a Michael addition reaction between the amino group or thiol group of the compound and the quinone structure of the polymer It is thought that the compound can be efficiently and strongly adsorbed to the surface of the object through the process, enhance the modification effect due to the characteristics of the compound having an amino group or a thiol group, and improve the sustainability of the modification effect.
Furthermore, since the nitrogen-containing polycyclic compound used in step 1 contains a specific catechol structure, it has high reactivity and can efficiently form a polymer of the nitrogen-containing polycyclic compound in a short time. , the homogenization of the target surface can be improved, the modification effect can be enhanced, and the sustainability of the modification effect can be improved.

(Step 1)
In the step 1, from the viewpoint of homogenizing the target surface well, enhancing the modification effect imparted to the target surface, and improving the sustainability of the modification effect, the target surface contains a nitrogen-containing multi-layer containing a catechol structure. After applying the cyclic compound (A), it is a step of forming a polymer of the nitrogen-containing polycyclic compound (A).
The polymer of the nitrogen-containing polycyclic compound (A), from the viewpoint of homogenizing the target surface well, enhancing the modification effect imparted to the target surface, and improving the sustainability of the modification effect, It preferably has a crosslinked structure. The crosslinked structure is preferably a three-dimensional network crosslinked structure.
When the polymer of the nitrogen-containing polycyclic compound (A) has a crosslinked structure, the polymer of the nitrogen-containing polycyclic compound (A) is dissolved in a solvent that dissolves the nitrogen-containing polycyclic compound (A). do not.

<Target surface>
The target surface to be homogenized or modified by the present invention is preferably a solid surface.
In the present invention, "solid surface" means the interface between a solid and the atmosphere.
The solid is not particularly limited, and polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polymethyl methacrylate (PMMA), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytetrafluoro Synthetic resins such as ethylene (PTFE), polycarbonate (PC), polyurethane (PU), acrylonitrile/butadiene/styrene copolymer (ABS), polyamide (PA), melamine resin, FRP; natural fibers such as cotton, silk, and wool synthetic fibers such as polyester, nylon and rayon; metals such as aluminum, stainless steel (SUS) and brass; glass, earthenware, porcelain, enamel, tiles, ceramics, wood, hair, nails and teeth. The shape of the solid surface is not particularly limited.

The target surface to be homogenized or modified by the method of the present invention can be either a hydrophobic surface or a hydrophilic surface.
In the present invention, "hydrophobic surface" means that the contact angle is 70° or more, and "hydrophilic surface" means that the contact angle is less than 70°. The contact angle can be measured by the method described in Examples.
For example, when the compound (B) having an amino group or a thiol group has a function of imparting a hydrophilic effect, the target surface is preferably a hydrophobic surface. Moreover, when the compound (B) having an amino group or a thiol group has a function of imparting a hydrophobic effect, the target surface is preferably a hydrophilic surface.
The hydrophobic surface preferably includes at least one selected from synthetic resins, metals, and ceramics.
The hydrophilic surface preferably includes glass.

The surface modification method of the present invention is preferably applied to the surface of hair as the target surface. As a result, the hair surface can be well homogenized, a high modification effect can be imparted to the hair surface, the modification effect can be maintained even after washing the hair, and the feel of the hair can be improved. can.
In general, the hair surface has a structure in which highly hydrophobic cuticle pieces are laminated, while the vicinity of the edges of the cuticle pieces is hydrophilic. It is required to homogenize both of these parts well and impart a high modification effect.
In the present invention, when the target surface is the surface of hair, the polymer of the nitrogen-containing polycyclic compound (A) containing a catechol structure can be efficiently and firmly adsorbed on the surface of the hair, and the surface of the hair can be improved. It is considered that the property of the compound (B) having an amino group or a thiol group can be homogenized to enhance the property of the compound (B) and improve the durability of the property. From this point of view, it is preferable to use the surface modification method of the present invention as a method for modifying the surface of hair, wherein the target surface is the surface of hair.

<Treatment agent I'>
(Nitrogen-containing polycyclic compound (A) containing a catechol structure)
As a method for applying the nitrogen-containing polycyclic compound (A) containing a catechol structure to the target surface in step 1, a treatment agent I′ containing the nitrogen-containing polycyclic compound (A) containing a catechol structure can be used. preferable. That is, in the surface modification method of the present invention, a treating agent I′ containing a nitrogen-containing polycyclic compound (A) containing a catechol structure and a treating agent containing a compound (B) having an amino group or a thiol group I is preferably used as a treatment agent set for surface modification.

［式（１）中、Ｒ¹は、それぞれ独立に、水酸基又はアセトキシ基を示し、Ｒ²は水素原子、又は－ＣＯＯＲ（Ｒは水素原子、メチル基又はエチル基）を示し、Ｒ³は水素原子、アセチル基、メチル基、又はエチル基を示す。］

［式（２）中、Ｒ¹～Ｒ³は、前記式（１）と同じである。］ The nitrogen-containing polycyclic compound (A) has the following formula ( It is at least one selected from an indole compound represented by 1) and its salt, and an indoline compound represented by the following formula (2) and its salt. The nitrogen-containing polycyclic compound (A) can be used singly or in combination of two or more.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ]

In the above formulas (1) and (2), specific examples or preferred embodiments of R ¹ to R ³ are from the viewpoint of homogenizing the target surface well and enhancing the modification effect imparted to the target surface. From the viewpoint of improving the sustainability of quality effects, the followings are considered.
R ¹ is preferably hydroxyl.
R ² is preferably a hydrogen atom or --COOH, more preferably a hydrogen atom.
R ³ is preferably a hydrogen atom.

Examples of the indole compound represented by the formula (1) include 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, methyl 5,6-dihydroxyindole-2-carboxylate, 5,6- Ethyl dihydroxyindole-2-carboxylate, N-methyl-5,6-dihydroxyindole, N-methyl-5,6-dihydroxyindole-2-carboxylic acid, N-ethyl-5,6-dihydroxyindole, N-ethyl -5,6-dihydroxyindole-2-carboxylic acid, N-acetyl-5,6-dihydroxyindole, N-acetyl-5,6-dihydroxyindole-2-carboxylic acid, 5-acetoxy-6-hydroxyindole, 5 -acetoxy-6-hydroxyindole-2-carboxylic acid and the like.

Examples of the indoline compound represented by the formula (2) include 5,6-dihydroxyindoline, 5,6-dihydroxyindoline-2-carboxylic acid, methyl 5,6-dihydroxyindoline-2-carboxylate, 5,6- Ethyl dihydroxyindoline-2-carboxylate, N-methyl-5,6-dihydroxyindoline, N-methyl-5,6-dihydroxyindoline-2-carboxylic acid, N-ethyl-5,6-dihydroxyindoline, N-ethyl -5,6-dihydroxyindoline-2-carboxylic acid, N-acetyl-5,6-dihydroxyindoline, N-acetyl-5,6-dihydroxyindoline-2-carboxylic acid, 5-acetoxy-6-hydroxyindoline, 5 -acetoxy-6-hydroxyindoline-2-carboxylic acid and the like.

Salts of the compounds represented by formulas (1) and (2) include hydrochlorides, hydrobromides, sulfates, phosphates, acetates, propionates, lactates, citrates, and citrates of these compounds. and acid salts. Among these, hydrobromide is preferred from the viewpoint of availability.
When R ² is —COOH in the above formulas (1) and (2), the salts of the compounds represented by formulas (1) and (2) include carboxylates thereof (where R ² is —COO ⁻ ( X ⁿ⁺ ) _1/n (n is an integer of 1 or more, X ⁿ⁺ is an alkali metal ion such as K ⁺ , Na ⁺ , Li ^{+ ,} an alkaline earth metal ion such as Ca ²⁺ , Mg ²⁺ , an ammonium ion, etc. is a cation)). The alkali metal ion is preferably K ⁺ , Na ⁺ or Li ⁺ , more preferably K ⁺ or Na, from the viewpoint of water solubility of the salts of the compounds represented by the formulas (1) and (2). ⁺ , more preferably K ⁺ . From the same viewpoint, the alkaline earth metal ion is preferably Ca ²⁺ or Mg ²⁺ , more preferably Ca ²⁺ .

Among these, the nitrogen-containing polycyclic compound (A) is used from the viewpoint of homogenizing the target surface well, enhancing the modification effect imparted to the target surface, and improving the sustainability of the modification effect. , preferably at least one selected from the indole compounds represented by the formula (1) and salts thereof, more preferably 5,6-dihydroxyindole, 5,6-dihydroxyindole-2-carboxylic acid, and their at least one selected from salts of, more preferably at least one selected from 5,6-dihydroxyindole and 5,6-dihydroxyindole-2-carboxylic acid, still more preferably 5,6-dihydroxy is an indole.

The content or blending amount of the nitrogen-containing polycyclic compound (A) in the treatment agent I' according to the present invention is from the viewpoint of homogenizing the target surface well and enhancing the modification effect imparted to the target surface, From the viewpoint of improving the sustainability of the modification effect, it is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more. From the viewpoint of properties, the content is preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and even more preferably 1% by mass or less.

(other ingredients)
In addition to the nitrogen-containing polycyclic compound (A), the treatment agent I' according to the present invention may appropriately contain various additives within a range that does not impair the object of the present invention. Such additives include, for example, pH adjusters, anionic surfactants, nonionic surfactants, amphoteric surfactants, polymers, oils, preservatives, disinfectants, dyes, antidandruff agents, anti-inflammatory agents, Chelating agents, moisturizing agents, pearl agents, ceramides, fragrances, ultraviolet absorbers, and the like can be mentioned.

[Alkaline agent]
The processing agent I' according to the present invention preferably further contains an alkaline agent. The alkaline agent promotes the formation of a polymer of the compound (A) on the target surface, can homogenize the target surface well, improves the efficient adsorption of the compound (B), and the target The modification effect imparted to the surface can be enhanced.
Examples of alkaline agents include organic alkaline agents and inorganic alkaline agents.
Examples of organic alkaline agents include ammonia; monomethanolamine, dimethanolamine, trimethanolamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-amino-2- alkanolamines such as methylpropanol and 2-amino-2-hydroxymethyl-1,3-propanediol; alkylamines such as methylamine, dimethylamine, ethylamine, diethylamine, N-methylethylamine, propylamine and butylamine; benzylamine and the like aralkylamine; basic amino acids such as arginine, lysine and histidine;
Examples of inorganic alkaline agents include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and the like.
Alkaline agents can be used alone or in combination of two or more.
The carbon number of the alkanolamine, alkylamine, or aralkylamine is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less from the viewpoint of water solubility. Preferably, it is 2 or more.
The alkaline agent promotes the formation of a polymer of the compound (A) on the target surface, homogenizes the target surface well, and improves the efficient adsorption of the compound (B), so that the target From the viewpoint of enhancing the modification effect imparted to the surface and improving the durability of the modification effect, and from the viewpoint of resistance and skin irritation of the target surface, it is preferably an organic alkaline agent, more preferably ammonia and a carbon number. At least one selected from alkanolamines having 2 to 10 carbon atoms, more preferably alkanolamines having 2 to 10 carbon atoms, and still more preferably 2-amino-2-hydroxymethyl-1,3-propanediol is.

The content or blending amount of the alkali agent in the treatment agent I' according to the present invention promotes the formation of the polymer of the compound (A) on the target surface and homogenizes the target surface well, and From the viewpoint of improving the efficient adsorptivity of the compound (B), enhancing the modifying effect imparted to the target surface, and improving the sustainability of the modifying effect, it is preferably 0.01% by mass or more, more preferably is 0.1% by mass or more, more preferably 0.3% by mass or more, still more preferably 0.5% by mass or more, still more preferably 0.7% by mass or more, and even more preferably 1% by mass or more. And, from the viewpoint of resistance of the target surface and skin irritation, it is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, and even more preferably 2% by mass or less.

〔Oxidant〕
The treating agent I' according to the present invention may further contain an oxidizing agent from the viewpoint of promoting the polymerization of the compound (A) and promoting the formation of the polymer of the compound (A).
Examples of the oxidizing agent include hydrogen peroxide; alkali metal persulfates such as sodium persulfate and potassium persulfate; and ammonium persulfate.
In the present invention, the polymer of the nitrogen-containing polycyclic compound (A) in step 1 can be formed even under oxidizing conditions using oxygen without using an oxidizing agent. From the viewpoint of suppressing deterioration and contamination due to the oxidizing agent, the treating agent I' according to the present invention preferably does not contain an oxidizing agent.

(aqueous medium)
The treatment agent I' according to the invention preferably further contains an aqueous medium.
Examples of aqueous media include water; lower alcohols such as ethanol and isopropyl alcohol; low-molecular-weight diols and triols having 6 or less carbon atoms such as 1,3-butylene glycol, glycerin, ethylene glycol and propylene glycol.
As described above, when the polymer of the nitrogen-containing polycyclic compound (A) has a crosslinked structure and does not dissolve in the solvent that dissolves the compound (A), the aqueous medium of the treatment agent I′ is the compound A solvent that dissolves (A) and does not dissolve the polymer of compound (A) is preferred. As a result, in step 1, the polymer of compound (A) can be efficiently formed on the target surface, and it is considered that the target surface can be homogenized satisfactorily. Furthermore, in the subsequent step 2, the compound (B) having an amino group or a thiol group can be efficiently and strongly adsorbed onto the target surface via the polymer of the nitrogen-containing polycyclic compound (A), It is believed that the properties of the compound (B) having an amino group or a thiol group can enhance the modifying effect and improve the durability of the modifying effect. From this point of view, the aqueous medium is preferably at least one selected from water and lower alcohols, more preferably contains at least water, and still more preferably water.
The content or blending amount of the aqueous medium in the treatment agent I' according to the present invention is, when water is used as the aqueous medium, from the viewpoint of homogenizing the target surface well and enhancing the modification effect imparted to the target surface. , From the viewpoint of improving the sustainability of the modifying effect, and from the viewpoint of the adsorptivity of the compound (A), it is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more, and still more It is preferably 80% by mass or more, more preferably 85% by mass or more, still more preferably 90% by mass or more, still more preferably 95% by mass or more, and preferably 99% by mass or less.

The processing agent I' according to the present invention is prepared, for example, by blending the compound (A), an aqueous medium, and, if necessary, other components such as an alkali agent and an oxidizing agent, and mixing using a known stirring device or the like. It can be prepared by

The method of applying the treatment agent I' to the target surface in step 1 is not particularly limited, and examples thereof include the following methods (i-1) to (iii-1).
(i-1) A method of immersing the target surface in the treatment agent I' (ii-1) A method of spraying or coating the target surface with the treatment agent I' (iii-1) Using the treatment agent I' in a conventional manner Method of cleaning the surface The temperature of the surrounding environment when applying the treatment agent I' to the target surface is important from the viewpoint of homogenizing the target surface well, enhancing the modification effect imparted to the target surface, and maintaining the modification effect. From the viewpoint of improving the More preferably, it is 30° C. or less.
The immersion time in the method (i-1) is from the viewpoint of homogenizing the target surface well, enhancing the modification effect imparted to the target surface, improving the sustainability of the modification effect, and economic efficiency. From the viewpoint of, preferably 0.1 minutes or more, more preferably 0.3 minutes or more, still more preferably 0.5 minutes or more, still more preferably 1 minute or more, and preferably 48 hours or less, more preferably is less than or equal to 24 hours.
The method of spraying or coating in the method (ii-1) can be appropriately selected according to the width (area) of the target surface. Further, after spraying, a sponge or the like may be used to apply a thin layer.
The amount of treatment agent I' applied to the target surface in step 1 depends on the content or blending amount of compound (A) in treatment agent I', but is preferably 20 mL or more per 1 m ² of the target surface, for example. It is 300,000 mL or less, more preferably 100 mL or more and 200,000 mL or less, still more preferably 1,000 mL or more and 100,000 mL or less.

In step 1, formation of the polymer of the nitrogen-containing polycyclic compound (A) is not particularly limited as long as it is carried out under oxidative conditions with oxygen. For example, method (I) of polymerizing compound (A) under oxidative conditions due to oxygen dissolved in treating agent I′ during application of treating agent I′ to the target surface; Preferred is method (II) in which compound (A) is polymerized under oxidative conditions by exposure to air containing oxygen after application.
In the case of method (I), the method of applying the treatment agent I′ to the target surface in step 1 is preferably the method (i-1) above. In this case, the preferred range of the polymerization time of compound (A) in step 1 is the same as the above-mentioned preferred range of the immersion time from the viewpoint of efficiency of homogenization and modification treatment, and the polymerization temperature is the same as the above-mentioned It is the same as the preferred range of ambient temperature.
In the case of method (II), the method of applying the treatment agent I' to the target surface in step 1 may be any of the methods (i-1) to (iii-1). . In this case, the polymerization time of compound (A) after application of treatment agent I' to the target surface by exposure to air is not particularly limited, but is preferably 30 minutes or more and preferably 24 hours or less. .
Polymerization by air exposure of compound (A) after application of treatment agent I′ to the target surface is not particularly limited, but can be carried out at room temperature. That is, the polymerization of compound (A) is carried out at an ambient temperature of preferably 5°C or higher, more preferably 10°C or higher, still more preferably 15°C or higher, and preferably 50°C or lower, more preferably 40°C. It is preferable to carry out below, more preferably at 30° C. or lower.

In step 1, after the polymer of the nitrogen-containing polycyclic compound (A) is formed on the target surface, excess treatment agent I' on the surface to which treatment agent I' has been applied is removed using an aqueous medium. It is preferable to perform a process of removing the
There are no particular restrictions on the method for removing excess treatment agent I′, but examples include a method of immersing the surface to which treatment agent I′ has been applied in an aqueous medium, and spraying an aqueous medium onto the surface to which treatment agent I′ has been applied. Alternatively, a method of coating, and a method of rinsing the surface to which the treatment agent I' has been applied with an aqueous medium according to a conventional method can be used.
Water; lower alcohols such as ethanol and isopropyl alcohol; low molecular weight compounds having 6 or less carbon atoms such as 1,3-butylene glycol, glycerin, ethylene glycol and propylene glycol. Diols and triols are included. Among them, it is preferable to contain water.
The water used as the aqueous medium in the method for removing excess treating agent I′ is not particularly limited, and tap water, distilled water, ion-exchanged water, hard water, soft water, ultrapure water, etc. can be used.
The content of water in the aqueous medium used in the method for removing excess treating agent I′ is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass. % or more, and the upper limit is 100% by mass.

The contact angle of the surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed in step 1 is preferably 50° or more, more preferably 55° or more, still more preferably 55° or more, from the viewpoint of homogenization of the target surface. 60° or more and preferably 80° or less. The contact angle can be measured by the method described in Examples.
If the contact angle of the surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed in step 1 is within the range described above, the surface-modifying treatment agent to be used is selected according to the type and composition of the material of the target surface. can reduce the need to change

(Step 2)
In step 2, the nitrogen-containing polycyclic compound (A) containing a catechol structure on the target surface formed in step 1 is used from the viewpoint of enhancing the modification effect imparted to the target surface and improving the durability of the modification effect. is a step of applying a treatment agent I containing a compound (B) having an amino group or a thiol group to the polymer.

<Treatment agent I>
(Compound (B) having an amino group or a thiol group)
The compound (B) having an amino group or a thiol group is preferably a polymer having an amino group or a thiol group from the viewpoint of enhancing the modification effect imparted to the target surface and improving the durability of the modification effect.
Polymer skeletons of polymers having amino groups or thiol groups include polysiloxanes, polyacrylates, polymethacrylates, celluloses, polyethers, and the like.
The compound (B) having an amino group or a thiol group can be used singly or in combination of two or more.

Among these, the polymer having an amino group or a thiol group is preferably a modified silicone (B1) having an amino group or a thiol group (hereinafter also simply referred to as "modified silicone (B1)").
Modified silicone (B1) has an amino group or a thiol group on a side chain, one end, or both ends.
Amino groups and thiol groups are collectively referred to as "reactive groups", and groups containing reactive groups and other moieties are also referred to as "reactive group-containing groups".
By using the modified silicone (B1) having an amino group or a thiol group as the compound (B) having an amino group or a thiol group, a hydrophobic effect can be imparted to the target surface as a modification effect. From this point of view, it is preferable to use the modification method of the present invention as a surface hydrophobizing method.

〔式中、Ｒ¹¹は、それぞれ独立に、炭素数１以上６以下の炭化水素基であり、Ｒ¹²は、それぞれ独立に、炭素数１以上１０以下のアルキレン基であり、ａは１又は０であり、Ｘ¹は、それぞれ独立に、アミノ基又はチオール基を含む基であり、＊は結合部位である。〕で表される繰り返し単位、及び、式（１－２）：

〔式中、Ｒ¹¹は、それぞれ独立に、炭素数１以上６以下の炭化水素基であり、＊は結合部位である。〕で表される繰り返し単位を有する。
なお、シリコーンの末端は、式（１－３）：

〔式中、Ｒ¹³は、炭素数１以上１０以下の炭化水素基であり、＊は結合部位である。〕で表される基であってもよい。 [Modified silicone having a reactive group in the side chain]
The modified silicone having a reactive group in its side chain is preferably represented by formula (1-1):

[In the formula, R ¹¹ is each independently a hydrocarbon group having 1 to 6 carbon atoms, R ¹² is each independently an alkylene group having 1 to 10 carbon atoms, and a is 1 or 0 and each X ¹ is independently a group containing an amino group or a thiol group, and * is a binding site. ] and a repeating unit represented by formula (1-2):

[In the formula, each R ¹¹ is independently a hydrocarbon group having 1 to 6 carbon atoms, and * is a bonding site. ] has a repeating unit represented by
Note that the end of the silicone has the formula (1-3):

[In the formula, R ¹³ is a hydrocarbon group having 1 to 10 carbon atoms, and * is a bonding site. ] may be a group represented by

The number of carbon atoms in the hydrocarbon group for R ¹¹ is 6 or less, preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and even more preferably 1.
Hydrocarbon groups for R ¹¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and phenyl group. Among these, a methyl group is preferred.
The number of carbon atoms in the alkylene group of R ¹² is 10 or less, preferably 9 or less, and preferably 1 or more, more preferably 2 or more.
Examples of the alkylene group for R ¹² include methanediyl, ethane-1,2-diyl, ethane-1,1-diyl, n-propane-1,3-diyl, n-propane-1,2- diyl group, 1,4-n-butyl group, 1,2-tert-butyl group and 1,5-pentyl group.
The number of carbon atoms in the hydrocarbon group of R ¹³ is 10 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, even more preferably 3 or less, even more preferably 2 or less, and still more preferably 1 is.
Hydrocarbon groups for R ¹³ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and benzyl group. Among these, a methyl group is preferred.

Each X ¹ is independently a group containing an amino group or a thiol group. X ¹ is a reactive group or a group containing a reactive group.
In formula (1-1), when a is 1, X ¹ is a reactive group, and when a is 0, X ¹ is a reactive group-containing group.
When a is 0, X ¹ may have an ether bond and is a group in which a hydrocarbon group in which a part of the methylene groups are replaced with an ether bond is substituted with one or more reactive groups. may That is, X ¹ may be an aliphatic hydrocarbon group that may contain an ether bond, substituted with one or more amino groups or thiol groups, and the total number of carbon atoms in X ¹ is preferably 10 or less, more It is preferably 9 or less, and preferably 1 or more, more preferably 2 or more.
The aliphatic hydrocarbon group containing an ether bond means having an ether bond (--O--) between carbon-carbon bonds.

When the modified silicone (B1) is a silicone having an amino group on its side chain, X ¹ is a group containing an amino group. In this case, in formula (1-1), a is 1 or 0, X ¹ is each independently -NH ₂ or -R ¹⁴ -NH-R ¹⁴ -NH ₂ , and R ¹⁴ is each It is independently preferably an alkylene group having 1 to 5 carbon atoms, and when a is 1, X ¹ is —NH ₂ , and when a is 0, X is —R ¹⁴ —NH—R ¹⁴ — NH ₂ is more preferred, a is 1, X ¹ is —NH ₂ , R ¹² is more preferably an alkylene group having 1 to 10 carbon atoms, a is 1, X ¹ is —NH ₂ and R ¹² is more preferably an alkylene group having 1 to 3 carbon atoms.
When the modified silicone (B1) is a silicone having a thiol group on its side chain, X ¹ is a group containing a thiol group. In this case, in formula (1-1), a is 1, X ¹ is —SH, and R ¹² is preferably an alkylene group having 1 to 10 carbon atoms.

Examples of commercially available modified silicones having an amino group in the side chain include "KF-868", "KF-865", "KF-864", and "X-22-3939A" (manufactured by Shin-Etsu Chemical Co., Ltd.). mentioned.
Examples of commercially available modified silicones having a thiol group on the side chain include "KF-2001" and "KF-2004" (manufactured by Shin-Etsu Chemical Co., Ltd.).

〔式中、Ｒ²¹は、それぞれ独立に、炭素数１以上６以下の炭化水素基であり、Ｒ²²は、それぞれ独立に、炭素数１以上１０以下のアルキレン基であり、Ｒ²³は、それぞれ独立に、炭素数１以上１０以下の炭化水素基であり、Ｘ²は、それぞれ独立に、アミノ基又はチオール基であり、ｓは１以上３以下の整数であり、ｔは０以上３以下の整数であり、ｎは５以上３００以下の整数である。〕で表される変性シリコーンである。 [Modified Silicone Having Reactive Groups at One or Both Terminals]
The modified silicone having a reactive group at one end or both ends preferably has formula (2-1):

[In the formula, each R ²¹ is independently a hydrocarbon group having 1 to 6 carbon atoms, each R ²² is independently an alkylene group having 1 to 10 carbon atoms, and each R ²³ is independently a hydrocarbon group having 1 or more and 10 or less carbon atoms, X ² is each independently an amino group or a thiol group, s is an integer of 1 or more and 3 or less, and t is an integer of 0 or more and 3 or less It is an integer, and n is an integer of 5 or more and 300 or less. ] is a modified silicone represented by

The number of carbon atoms in the hydrocarbon group for R ²¹ is 6 or less, preferably 5 or less, more preferably 4 or less, still more preferably 3 or less, even more preferably 2 or less, and still more preferably 1.
Hydrocarbon groups for R ²¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and phenyl group. Among these, a methyl group is preferred.
The number of carbon atoms in the alkylene group of R ²² is 10 or less, preferably 8 or less, more preferably 5 or less, still more preferably 4 or less, still more preferably 3 or less, and preferably 1 or more, more preferably 2 or more. is.
Examples of the alkylene group for R ²² include methanediyl, ethane-1,2-diyl, ethane-1,1-diyl, n-propane-1,3-diyl, n-propane-1,2- diyl group, 2-methylethane-1,2-diyl group, 1,4-n-butyl group, 1,2-tert-butyl group and 1,5-pentyl group. Among these, ethane-1,2-diyl group, n-propane-1,3-diyl group and n-propane-1,2-diyl group are preferable, and n-propane-1,2-diyl group is more preferable. .
The number of carbon atoms in the hydrocarbon group of R ²³ is 10 or less, preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, still more preferably 3 or less, even more preferably 2 or less, and still more preferably 1 is.
Hydrocarbon groups for R ²³ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group and benzyl group. Among these, a methyl group is preferred.
^X2 is a group containing an amino group or a thiol group.
s is 3 or less, preferably 2 or less, more preferably 1;
t is 3 or less, preferably 2 or less, more preferably 0 or 1.
n is 300 or less, preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, and 5 or more, preferably 8 or more, more preferably 10 or more.

Modified silicones having amino groups at one or both ends include, for example, amino-modified silicones at both ends (commercially available products include "X-22-161A", "KF-8012", "KF-8008" (above , manufactured by Shin-Etsu Chemical Co., Ltd.)).
Examples of modified silicones having thiol groups at one or both ends include epoxy-modified silicones at both ends (commercially available products are "X-22-167B" and "X-22-167C" (Shin-Etsu Chemical Co., Ltd. manufactured by the company)).

Among these, the modified silicone (B1) improves the adsorptivity, enhances the modification effect imparted to the target surface, and improves the sustainability of the modification effect. It is a modified silicone having one end or both ends, more preferably a modified silicone having an amino group in a side chain.

The dynamic viscosity of the modified silicone (B1) at 25° C. is preferably 10 mm ² /s or more, more preferably 15 mm ² /s or more, still more preferably 20 mm ² /s or more, and preferably 20,000 mm ^{2 .} /s or less, more preferably 10,000 mm ² /s or less, still more preferably 5,000 mm ² /s or less, still more preferably 2,000 mm ² /s or less.
The kinematic viscosity of the modified silicone (B1) is measured at 25° C. using a fully automatic micro-kinematic viscometer (manufactured by Viscotec Co., Ltd.).
The functional group equivalent weight of the modified silicone (B1) is preferably 500 g/mol or more, more preferably 1,000 g/mol or more, still more preferably 2,000 g/mol or more, and preferably 50,000 g/mol or less. , more preferably 30,000 g/mol or less, still more preferably 20,000 g/mol or less, even more preferably 10,000 g/mol or less, and even more preferably 7,000 g/mol or less. Functional group equivalent means the mass of modified silicone per 1 mol of functional group.

The content or blending amount of the compound (B) in the treatment agent I according to the present invention enhances the modification effect imparted to the target surface, improves the durability of the modification effect, and the viewpoint of blending stability. Therefore, it is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, still more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 70% by mass. Above, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 100% by mass or less, more preferably 99.9% by mass or less, still more preferably 99.5% by mass or less , more preferably 99% by mass or less, even more preferably 98.5% by mass or less, and even more preferably 98% by mass or less.

(other ingredients)
The processing agent I according to the present invention may contain components other than the compound (B) as long as the effects of the present invention are not impaired. Other components, depending on the purpose of the modification effect, for example, aqueous medium, electrolyte, pH adjuster, anionic surfactant, nonionic surfactant, amphoteric surfactant, antioxidant, silicone, fragrance Group alcohols, polymers, oils, vitamins, bactericides, anti-inflammatory agents, anti-dandruff agents, preservatives, chelating agents, moisturizing agents, pearl agents, ceramides, fragrances, UV absorbers, etc. can be appropriately selected and used. can.
Examples of the aqueous medium include water; lower alcohols such as ethanol and isopropyl alcohol; and low-molecular-weight diols and triols having 6 or less carbon atoms such as 1,3-butylene glycol, glycerin, ethylene glycol and propylene glycol.
Examples of electrolytes include organic acids, inorganic acids, organic bases, inorganic bases, and compounds that undergo ion dissociation in water, such as salts thereof.

[Organic base compound]
The treatment agent I according to the invention preferably further contains an organic base compound. By further containing an organic base compound, the nucleophilicity of the amino group or thiol group of the compound (B) is enhanced, and the Schiff base reaction with the carbonyl group of the quinone structure of the polymer of the nitrogen-containing polycyclic compound (A) Alternatively, the nitrogen-containing polycyclic compound (A) promotes the Michael addition reaction with the quinone structure of the polymer, improves the adsorption of the compound (B) to the target surface, and improves the properties of the compound (B). The quality effect can be enhanced and the sustainability of the modification effect can be improved.
An organic base compound can be used individually by 1 type or in combination of 2 or more types.

Examples of organic base compounds include trialkylamines such as triethylamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; N-methylaminoethanol, N-methylaminopropanol, N-dimethylaminoethanol and N-dimethylaminopropanol. , N-methyldiethanolamine, N-methyldipropanolamine and other alkylalkanolamines.
The number of carbon atoms in the organic base compound increases the nucleophilicity of the amino group or thiol group of the compound (B), improves the adsorption of the compound (B) to the target surface, and improves the property of the compound (B). It is preferably 10 or less, more preferably 8 or less, still more preferably 6 or less from the viewpoint of enhancing the effect and improving the sustainability of the modification effect, and preferably 2 from the viewpoint of availability and economy. That's it.
Among these, the organic base compound is preferably an organic amine, more preferably at least one selected from trialkylamines, alkanolamines, and alkylalkanolamines, still more preferably trialkylamine, from the same viewpoint as described above. and alkylalkanolamine, more preferably trialkylamine, and still more preferably triethylamine.

The content or blending amount of the organic base compound in the treatment agent I according to the present invention increases the nucleophilicity of the amino group or thiol group of the compound (B), thereby increasing the adsorption of the compound (B) to the target surface. is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably from the viewpoint of improving the property of the compound (B) and improving the durability of the property of the compound (B). is 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more, and enhances the modification effect imparted to the target surface by the compound (B), and the modification effect From the viewpoint of improving the sustainability of the content, it is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 7% by mass or less, even more preferably 5% by mass or less, and even more preferably 4% by mass or less. be.

The processing agent I according to the present invention can be prepared, for example, by blending the compound (B) and, if necessary, other components such as an organic base compound, and mixing using a known stirring device or the like.

The method of applying the treatment agent I to the target surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed in step 2 is not particularly limited. mentioned.
(i) A method of immersing the surface of the object on which the polymer of the nitrogen-containing polycyclic compound (A) is formed in the treatment agent I. (ii) The object on which the polymer of the nitrogen-containing polycyclic compound (A) is formed. A method of spraying or applying the treatment agent I to the surface (iii) A method of washing the target surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed, using the treatment agent I in a conventional manner Treatment agent I is applied to the target surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed, the ambient temperature enhances the modification effect imparted to the target surface and improves the sustainability of the modification effect. and from the viewpoint of workability, the temperature is preferably 5°C or higher, more preferably 10°C or higher, still more preferably 20°C or higher, even more preferably 30°C or higher, and even more preferably 40°C or higher, and It is preferably 80° C. or lower, more preferably 70° C. or lower, and still more preferably 60° C. or lower.
The application time of the treatment agent I in step 2 is not particularly limited from the viewpoint of enhancing the modification effect imparted to the target surface, improving the durability of the modification effect, and from the viewpoint of economy, but is preferably 30 minutes. minutes or more, and preferably 24 hours or less, more preferably 18 hours or less, even more preferably 12 hours or less.
The method of spraying or coating in the method (ii) can be appropriately selected according to the width (area) of the surface to be treated. Further, after spraying, a sponge or the like may be used to apply a thin layer.
The amount of the treatment agent I applied to the target surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed in step 2 depends on the content or blending amount of the compound (B) in the treatment agent I. For example, it is preferably 20 mL or more and 50,000 mL or less, more preferably 100 mL or more and 40,000 mL or less, and still more preferably 1,000 mL or more and 30,000 mL or less per 1 m ² of the target surface.

In step 2, after applying the treating agent I to the target surface on which the polymer of the nitrogen-containing polycyclic compound (A) is formed, excess treating agent I on the surface to which the treating agent I has been applied is removed. You may perform processing to do.
There are no particular restrictions on the method for removing excess treatment agent I, but examples include a method of immersing the surface to which treatment agent I has been applied in a medium, a method of spraying or applying a medium to the surface to which treatment agent I has been applied, A method of rinsing the surface to which the treatment agent I has been applied with a medium according to a conventional method can be mentioned.
The medium used in the method for removing excess processing agent I is not particularly limited and can be appropriately selected depending on the purpose. Water; lower alcohols such as ethanol and isopropyl alcohol; 1,3-butylene glycol, glycerin, low-molecular-weight diols and triols having 6 or less carbon atoms such as ethylene glycol and propylene glycol; and hydrocarbons such as hexane.

The contact angle of the surface treated in step 2 is from the viewpoint of imparting a modification effect to the target surface when the compound (B) having an amino group or a thiol group has the function of imparting a hydrophobic effect, and the target From the viewpoint of imparting a hydrophobizing effect to the surface, the angle is preferably 80° or more, more preferably 85° or more, and still more preferably 90° or more, and the upper limit is not particularly limited, but is preferably 100° or less. . The contact angle can be measured by the method described in Examples.

(Method for surface modification of hair)
When the target surface is the surface of hair, the surface modification method of the present invention can well homogenize the surface of the hair, impart a high modification effect to the surface of the hair, and wash the hair. The modification effect can be maintained even afterward, and the feel of the hair can be improved.
In the present invention, when the target surface is the hair surface, the treating agent I' containing a nitrogen-containing polycyclic compound (A) containing a catechol structure and a compound (B) having an amino group or a thiol group are contained. The treatment agent I is preferably used as a hair treatment agent set.
Examples of the hair treating agents include hair cleansing agents such as shampoos; and hair cosmetics such as conditioners, treatments, and hair dyes. There are no particular restrictions on the dosage form of the hair treatment agent, and any dosage form such as liquid, foam, paste or cream may be used. Among these dosage forms, the hair treatment agent is preferably liquid.
The method of applying the treatment agent I' in step 1 and the treatment agent I in step 2 to the hair surface includes a method of applying, spraying or casting the treatment agent I' or the treatment agent I on the hair, and a method of applying the treatment agent I' or the treatment agent I to the hair. Alternatively, a method of immersing the hair in the treatment agent I may be used.
The hair can be dry or wet when each treatment is applied.
The ambient environmental temperature when applying each treatment agent is preferably 5 to 50° C., more preferably 15 to 45° C., from the viewpoint of efficient surface treatment.
The application time of each treatment agent is preferably 5 seconds to 60 minutes, more preferably 5 seconds to 20 minutes. The application time of each treatment agent means the time for applying, spraying or casting each treatment agent on the hair, or the time for immersing the hair in each treatment agent.

As a specific method for modifying the surface of hair, for example, when the treatment agent I′ is a hair cleansing agent such as shampoo and the treatment agent I is a hair cosmetic such as a conditioner, treatment, or hair dye. , After applying the treatment agent I' to the hair and lathering to wash the hair, applying the treatment agent I to the hair treated with the treatment agent I' and, if necessary, leaving it for about 1 to 180 minutes. A method of rinsing with water; when the treatment agent I' is a hair cosmetic such as a hair dye, and the treatment agent I is a hair cosmetic such as a conditioner or treatment, the treatment agent I' is applied to the hair, After leaving for about 1 to 180 minutes and then rinsing with water, the treatment agent I is applied to the hair treated with the treatment agent I', and if necessary, leaving for about 1 to 180 minutes and then rinsing off with water. method. By routinely repeating the steps described above, it is possible to easily improve the texture of the hair in a short period of time.

EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

The substrates used for the treatment are as follows.
Glass: manufactured by Akebono Trading Company PVC: Polyvinyl chloride (manufactured by Engineering Test Service Co., Ltd., trade name “test piece PVC”)
PP: Polypropylene (manufactured by Nippon Test Panel Co., Ltd., trade name “Standard test plate PP”)

(Preparation of treatment agent I')
Preparation Example 1-1
After preparing a 100 mM aqueous solution of 2-amino-2-hydroxymethyl-1,3-propanediol (TRIS) as an alkaline agent, a 1% by mass solution of 5,6-dihydroxyindole as compound (A) was mixed with the aqueous TRIS solution. The same mass was added to prepare a processing agent I'-1.

Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-3
A homogenization treatment was performed by the following method using the prepared treatment agent.
In Comparative Examples 1-1 to 1-3, water was used as the treatment agent I'-C1.
(Step 1)
Add 180 mL of the treatment agent I' shown in Table 1 to a dyeing vat with an internal capacity of about 200 mL, and the substrate shown in Table 1 (70 to 75 mm long x 25 mm wide x 1 mm thick) at room temperature (25 ° C.) for 90 minutes. Polymerization of the compound (A) was carried out by immersion to form a polymer of the compound (A) on the surface of the substrate. Next, the substrate was taken out of the treating agent I', rinsed with water for 20 seconds to remove excess treating agent I', and then dried by blowing nitrogen gas to obtain a homogenized substrate.

(Evaluation of homogenization effect)
Each substrate homogenized in Examples and Comparative Examples is placed on the stage of a fully automatic contact angle meter (manufactured by Kyowa Interface Science Co., Ltd. "DM-701"), and 1 μL of ultrapure water is attached. The value of the contact angle after seconds was determined by the θ/2 method. The higher the contact angle value, the higher the degree of hydrophobicity. Table 1 shows the results.

In Example 1-1, the value of the contact angle was 60° from 41° in Comparative Example 1-1, and in Example 1-2, it was 78° from 85° in Comparative Example 1-2. In Comparative Example 1-3, the angle changed from 100° to 70° in Comparative Example 1-3. The angle is in the range of 60 to 78°, indicating that the degree of hydrophilicity and hydrophobicity can be homogenized.

(Preparation of treatment agent I)
Preparation Example 2-1
According to the formulation shown in Table 2, side chain amino-modified silicone "KF-864" (manufactured by Shin-Etsu Chemical Co., Ltd., viscosity (25° C.): 1,700 mm ² /s, functional group equivalent: 3, 800 g/mol) and triethylamine as an organic base compound were blended and mixed to prepare treatment agent I-1.

Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2
Using the prepared treatment agents I'-1 and I-1, modification treatment was performed by the following method. In Comparative Examples 2-1 and 2-2, water was used as treatment agent I'-C1 and treatment agent I-C1.
(Step 1)
Add 180 mL of the treatment agent I' shown in Table 2 to a dyeing vat with a content of about 200 mL, and the substrate shown in Table 2 (70 to 75 mm long x 25 mm wide x 1 mm thick) at room temperature (25 ° C.) for 90 minutes. The compound (A) was polymerized by immersion to form a polymer of the compound (A) on the surface of the substrate. Next, the substrate was taken out of the treating agent I', rinsed with water for 20 seconds to remove excess treating agent I', and then dried by blowing nitrogen gas to obtain a homogenized substrate.
(Step 2)
Then, 80 mL of the treatment agent I shown in Table 2 was added to a petri dish having a content of 100 mL, the substrate obtained in step 1 was immersed at room temperature (25 ° C.) for 24 hours, and the compound of the substrate obtained in step 1 Treatment Agent I was applied to the polymer-formed surface of (A). Next, the substrate was taken out of the treatment agent I, rinsed with hexane for 60 seconds to remove excess treatment agent I, and then dried by blowing nitrogen gas to obtain a modified substrate.

(Evaluation of modification effect)
Each substrate that has been modified in Examples and Comparative Examples is placed on the stage of a fully automatic contact angle measurement meter ("DM-701" manufactured by Kyowa Interface Science Co., Ltd.), and 1 μL of ultrapure water is attached. The value of the contact angle after seconds was determined by the θ/2 method. The higher the contact angle value, the higher the degree of hydrophobicity. Table 2 shows the results.

(Evaluation of sustainability of modification effect)
After measuring the contact angle of each substrate modified in Examples and Comparative Examples, after washing 10 times with a plain shampoo having the following composition, the contact angle was measured in the same manner as in the evaluation of the modification effect described above, The amount of change in contact angle before and after washing was calculated from the following formula.
The cleaning using plain shampoo was carried out by applying the following plain shampoo to the modified substrate, rubbing the substrate for 1 minute, and then rinsing the substrate with water for 30 seconds, which was repeated 10 times.
The smaller the amount of change in contact angle, the better the durability of the modification effect. Table 2 shows the results.
Amount of change in contact angle before and after washing = | [Contact angle before washing (°)] - [Contact angle after washing (°)] |

<Composition of Plain Shampoo>
(Ingredients of plain shampoo) (% by mass)
Sodium polyoxyethylene lauryl ether sulfate (Emal E-27C (active ingredient 27% by mass), manufactured by Kao Corporation) 42
Coconut oil fatty acid N-methylethanolamide (Aminone C-11S, manufactured by Kao Corporation) 3
Citric acid 0.2
Methylparaben 0.3
Purified water Remainder
Total 100

From Table 2, it can be seen that Examples 2-1 and 2-2 have a larger contact angle value, a higher degree of hydrophobicity, and a higher modification effect than Comparative Examples 2-1 and 2-2. . Further, in Examples 2-1 and 2-2, even after washing 10 times, the amount of change in the contact angle is small, indicating that the durability of the modification effect is excellent.

Example 3-1 and Comparative Examples 3-1 to 3-2
Using the prepared treatment agents I'-1 and I-1, the hair surface was modified by the following method.
(Step 1)
100 mL of the treatment agent I′ shown in Table 3 was added to a beaker having a content of 200 mL, and 1 g of hair tress was immersed at room temperature (25° C.) for 90 minutes to polymerize compound (A). polymer was formed on the surface of the hair tress. Next, the hair tress was taken out from the treatment agent I', washed with tap water for 60 seconds to remove excess treatment agent I', and then dried with a hot air dryer to obtain a homogenized hair tress. .
(Step 2)
Next, 100 mL of the treatment agent I shown in Table 3 was applied to the surface of the hair tress obtained in step 1 on which the polymer of the compound (A) of the hair tress was formed, and allowed to stand at 50°C for 12 hours to remove the treatment agent I. applied to obtain a modified hair tress.

(Evaluation of sustainability of modification effect)
The hair tresses modified in Examples and Comparative Examples were washed with the plain shampoo for 15 minutes, and then rinsed with room temperature water for 30 seconds. Next, five panelists evaluated the texture of this hair tress while running their fingers through it, and the texture was scored according to the following criteria to evaluate the durability of the effect of modifying the hair surface. Table 3 shows the average scores of five panelists. The larger the average score, the better the feel of the hair after shampooing, and the longer the hair surface modification effect lasts.
Here, under the above-mentioned washing conditions using plain shampoo, since the washing time with shampoo in normal hair washing is about 1 minute, washing with shampoo for about 1 minute was performed 15 times. In order to evaluate the durability of the modification effect after washing, washing time with plain shampoo was set to 15 minutes.
[Score criteria]
Score 3: No creak when a finger is passed through.
Score 2: Slight creaking is felt when a finger is passed through.
Score 1: A creak is felt when a finger is put through.

From Table 3, it can be seen that Example 3-1 provides a better feel to the hair after shampooing than Comparative Examples 3-1 and 3-2, and the durability of the effect of modifying the hair surface is high.

According to the method of the present invention, the target surface can be homogenized satisfactorily, a high modification effect can be imparted to the target surface, and the durability of the modification effect can be improved. It is suitable as Therefore, the surface-modifying treatment agent set according to the present invention is useful, for example, as a surface-hydrophobicizing treatment agent set. In addition, the method of the present invention can impart a high modification effect to the hair surface and improve the durability of the modification effect. For example, it is possible to improve the feel of the hair after shampooing as the durability of the effect of modifying the surface of the hair. From this point of view, the surface-modifying treatment agent set according to the present invention is useful, for example, as a hair treatment agent set.

Claims (8)

A surface modification method for modifying a target surface,
Step 1 of applying a nitrogen-containing polycyclic compound (A) containing a catechol structure to a target surface, and then forming a polymer of the nitrogen-containing polycyclic compound (A);
A step 2 of applying a treatment agent I containing a compound (B) having an amino group or a thiol group to the polymer of the nitrogen-containing polycyclic compound (A) on the target surface formed in step 1,
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , surface modification methods.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ] 2. The surface modification method according to claim 1, wherein the nitrogen-containing polycyclic compound (A) containing a catechol structure is 5,6-dihydroxyindole. 3. The surface modification method according to claim 1, wherein the compound (B) having an amino group or a thiol group is a polymer having an amino group or a thiol group. The surface modification method according to claim 3, wherein the polymer having an amino group or a thiol group is a modified silicone (B1) having an amino group or a thiol group. The surface modification method according to any one of claims 1 to 4, wherein the surface modification method is a surface hydrophobizing method. The surface modification method according to any one of claims 1 to 5, wherein the surface modification method is a hair surface modification method. A treating agent I' containing a nitrogen-containing polycyclic compound (A) containing a catechol structure, and a treating agent I containing a compound (B) having an amino group or a thiol group,
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , treatment agent set for surface modification.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ] A surface homogenization method for homogenizing a target surface, comprising:
A step 1 of applying a nitrogen-containing polycyclic compound (A) containing a catechol structure to a target surface and then forming a polymer of the nitrogen-containing polycyclic compound (A);
The nitrogen-containing polycyclic compound (A) is at least one selected from indole compounds represented by the following formula (1) and salts thereof, and indoline compounds represented by the following formula (2) and salts thereof. , surface homogenization method.

[In the formula (1), R ¹ each independently represents a hydroxyl group or an acetoxy group, R ² represents a hydrogen atom or -COOR (R is a hydrogen atom, a methyl group or an ethyl group), R ³ represents a hydrogen indicates an atom, an acetyl group, a methyl group, or an ethyl group. ]

[In Formula (2), R ¹ to R ³ are the same as in Formula (1) above. ]