JP7195596B2 - Method for manufacturing covering - Google Patents

Description

The present invention relates to a method for manufacturing a coating. In particular, it relates to a method for producing a coated body in which a coating excellent in antifouling properties and the like is provided with excellent durability on at least part of the surface of a substrate.

Various techniques have been proposed for preventing the adhesion of dirt to the surface of a base material. For example, a method of making the surface of a base material hydrophilic is known as a technique for preventing dirt from adhering to the surface of the base material.

As a surface hydrophilization method, a technique is known in which the surface of a substrate is modified with a photocatalytic material such as titanium oxide, and the surface is highly hydrophilized in response to photoexcitation of the photocatalyst (see, for example, Patent Document 1). ).

However, in surface modification using such a photocatalyst, the binder that fixes the photocatalyst to the base material and the base material itself may decompose due to the photocatalyst function, and there is a problem in durability.

Methods for hydrophilizing the surface of the substrate include, for example, etching treatment and plasma treatment. Although these methods can make the surface of the base material highly hydrophilic, the effect is temporary and the hydrophilic state cannot be maintained for a long period of time. In addition, since general hydrophilic materials have ionic groups in their structures, they tend to adsorb contaminant components such as proteins.

There is also a method of coating a substrate with a predetermined hydrophilic polymer (see Patent Document 2), but it is difficult to achieve sufficiently excellent adhesion between the substrate and the hydrophilic polymer. It has been difficult to sufficiently improve the durability of the coating obtained by coating the above with a hydrophilic polymer. In addition, in Patent Document 2, it is also proposed to perform surface treatment such as plasma treatment on the substrate prior to imparting the hydrophilic polymer. It was difficult to make the adhesiveness to the polymer sufficiently excellent, and it was also difficult to make the coating formed by coating the base material with the hydrophilic polymer sufficiently excellent in durability.
Thus, conventionally, it has been difficult to achieve both antifouling properties and durability.

WO 1996/029375 Pamphlet WO 2018/008663 Pamphlet

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a coated body provided with a coating having excellent hydrophilicity and antifouling properties with excellent durability.

Such objects are achieved by the present invention described in [1] to [ 7 ] below.
[1] an ozone fine bubble treatment step of subjecting the substrate to ultrasonic treatment and ozone fine bubble treatment using ozone fine bubble water;
and a film forming step of forming a film using a polymer compound having a structure represented by the following formula (1) on the base material subjected to the ultrasonic treatment and the ozone fine bubble treatment. A method of manufacturing a covering body.

（式（１）中、Ｘ^１およびＸ^２は、それぞれ独立して、重合した状態の重合性原子団を表し；Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有していてもよいフェニル基、または、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－もしくは－Ｏ－で示される基を表し；Ｒ^３は、水素原子または炭素数が１以上３以下のアルキル基を表し；ｍおよびｎは、それぞれ独立して、１以上の整数を表し、ａおよびｂは、それぞれ独立して、２以上の整数を表し；Ｘ^１を含む構造単位およびＸ^２を含む構造単位はランダムな順序で結合している。）

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.)

（式（１）中、Ｘ ^１ およびＸ ^２ は、それぞれ独立して、重合した状態の重合性原子団を表し；Ｒ ^１ およびＲ ^２ は、それぞれ独立して、置換基を有していてもよいフェニル基、または、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－もしくは－Ｏ－で示される基を表し；Ｒ ^３ は、水素原子または炭素数が１以上３以下のアルキル基を表し；ｍおよびｎは、それぞれ独立して、１以上の整数を表し、ａおよびｂは、それぞれ独立して、２以上の整数を表し；Ｘ ^１ を含む構造単位およびＸ ^２ を含む構造単位はランダムな順序で結合している。）
［５］ 前記基材が中空部を有するものであり、前記超音波処理、前記オゾンファインバブル処理および前記被膜の形成を前記基材の前記中空部の内壁面に対して行う上記［１］ないし［４］のいずれかに記載の被覆体の製造方法。 [2] The method for producing a coated body according to [1] above, which includes an ultraviolet irradiation step of applying ultraviolet irradiation treatment to the base material prior to the film forming step.
[3] The method for producing a coated body according to [2] above, wherein the ultraviolet irradiation treatment is performed in the same step as the ozone fine bubble treatment.
[4] an ozone fine bubble treatment step of subjecting the substrate to ultrasonic treatment and ultraviolet irradiation treatment of irradiating ultraviolet rays, and performing ozone fine bubble treatment using ozone fine bubble water;
a coating forming step of forming a coating using a polymer compound having a structure represented by the following formula (1) on the substrate that has been subjected to the ultrasonic treatment, the ultraviolet irradiation treatment and the ozone fine bubble treatment; A method for producing a covering, comprising:

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.)
[ 5 ] The substrate has a hollow portion, and the ultrasonic treatment, the ozone fine bubble treatment, and the formation of the coating are performed on the inner wall surface of the hollow portion of the substrate [1] to [4] The method for producing the coated body according to any one of [4].

[ 6 ] The method for producing a coated body according to any one of [1] to [5] , wherein the base material has a portion where the film is formed is made of a metal material.

[ 7 ] The method for producing a coated body according to any one of [1] to [ 6 ] above, wherein the fine ozone bubbles have an average particle size of 0.08 μm or more and 0.50 μm or less.

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the coating with which the coating excellent in hydrophilicity and antifouling property was provided with excellent durability can be provided.

FIG. 1 is a vertical cross-sectional view schematically showing an example of the method for producing a covering according to the present invention. FIG. 2 is a photograph showing evaluation results of the antifouling property of the coating according to Example 1 and the untreated stainless steel plate made of SUS304.

Preferred embodiments of the present invention are described in detail below.
[Manufacturing method of covering]
First, a method for manufacturing a covering according to the present invention will be described.
FIG. 1 is a vertical cross-sectional view schematically showing an example of the method for producing a covering according to the present invention.

As shown in FIG. 1, the method for manufacturing the coated body 100 of the present embodiment includes a base material preparation step (1a) for preparing a base material 1, and a treatment of the base material 1 using ozone fine bubble water. and a coating of a polymer compound having a structure represented by the following formula (1) on the base material 1 subjected to the ozone fine bubble treatment: and a film forming step (1c) for forming 2.

（式（１）中、Ｘ^１およびＸ^２は、それぞれ独立して、重合した状態の重合性原子団を表し；Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有していてもよいフェニル基、または、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－もしくは－Ｏ－で示される基を表し；Ｒ^３は、水素原子または炭素数が１以上３以下のアルキル基を表し；ｍおよびｎは、それぞれ独立して、１以上の整数を表し、ａおよびｂは、それぞれ独立して、２以上の整数を表し；Ｘ^１を含む構造単位およびＸ^２を含む構造単位はランダムな順序で結合している。）

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.)

With such a configuration, the adhesive strength between each polymer compound forming the coating 2 and the substrate 1 can be made particularly excellent. For this reason, the coating 2 as a whole has excellent adhesion to the base material 1, and the resulting coating 100 is provided with the coating 2 having excellent hydrophilicity and antifouling properties with excellent durability. It will be the one that was given. In addition, it is possible to effectively prevent unintentional partial deterioration of the adhesion of the coating 2 . In addition, the coating 100 has excellent abrasion resistance of the coating 2 as well. In particular, even if the coating 2 has a small thickness such as a monomolecular film, the excellent effects as described above can be reliably obtained. Moreover, with the configuration as described above, the covering 100 also has excellent anti-fogging properties. Moreover, by adopting the ozone fine bubble treatment, it is possible to effectively prevent the substrate 1 from being unintentionally roughened.

It is believed that such excellent effects are obtained for the following reasons. That is, the polymer compound has excellent hydrophilicity, and when it is formed into a film, dirt does not readily adhere to the surface thereof, and even when dirt adheres, the dirt can be removed relatively easily. be. In addition, by performing ozone fine bubble treatment on the surface of the substrate 1 on which the coating 2 is to be formed prior to the formation of the coating 2, it is possible to effectively prevent denaturation and deterioration of the constituent materials of the substrate 1 in an undesirable form. Hydroxy groups can be uniformly, densely and efficiently introduced to the surface of the base material 1 while preventing it from becoming undesired. As a result, the phosphonic acid group (-P(=O)(OH) ₂ ) of the polymer compound and the hydroxyl group introduced to the surface of the base material 1 undergo a dehydration-condensation reaction to form a bond with the base material 1. A coating 2 having excellent adhesion can be formed. In particular, by densely introducing hydroxyl groups into the base material 1, it is possible to reduce the ratio of those that cannot react with the hydroxyl groups among the plurality of phosphonic acid groups that the polymer compound has in the molecule. , can form covalent bonds with the substrate at multiple points in the molecule of the polymer compound. In addition, it is possible to reduce the portion of the molecular chains of the polymer compound that are floating from the substrate 1 . As a result, the Van der Waals force between the base material 1 and the coating 2 can be increased even at the sites where covalent bonds are not formed.

In the following explanation, it is assumed that excellent effects are obtained by the presumed mechanism as described above.

The excellent effect as described above is obtained by combining ozone fine bubble treatment with a specific polymer compound (polymer compound represented by formula (1)). When the compound is used, when the polymer compound represented by the formula (1) is used but the ozone fine bubble treatment is not performed, or when other surface treatments are performed instead of the ozone fine bubble treatment, etc. No. More specifically, instead of ozone fine bubble treatment, for example, plasma treatment, UV/ozone cleaning, corona discharge treatment, flame treatment, ordinary general ozone water treatment (including relatively large ozone such as millibubbles Ozone water treatment), hydrogen peroxide water/Fenton reaction solution treatment, and other surface treatments do not provide the above-mentioned excellent effects.

《Base material preparation process》
In the base material preparing step, a base material 1 is prepared as an object to be processed which will be described in detail later (see FIG. 1(1a)).
The base material 1 normally constitutes the main part of the covering 100 .

The base material 1 may be made of any material, and the constituent material of the base material 1 includes, for example, various single metals such as Ti, Au, Cu, and Fe, and at least one of these. Metal materials such as alloys (various stainless steels, duralumin, etc.), carbon materials such as silicon, diamond, graphite, and diamond-like carbon, _{Al2O3 , TiO2} , ZrO2, silicon oxide _{( SiO2} ), _{Ta2O 5} , mica, hydroxyapatite, ZnO, ITO, metal compound materials such as IGZO, various glass materials, acrylic resins such as polymethyl (meth)acrylate, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polystyrene, Various thermoplastic elastomers such as polycarbonate polyvinylpyrrolidone and polyvinyl chloride thermoplastic elastomers, copolymers thereof, various plastic materials such as polymer blends, various rubber materials such as various silicone rubbers such as polydimethylsiloxane (PDMS), etc. and can be used alone or in combination of two or more selected from these. Further, the base material 1 may be a layered body having portions made of different constituent materials, for example, layers made of different materials. Moreover, the base material 1 may have a portion made of a gradient material whose composition changes in a gradient manner.

In particular, when at least the portion of the substrate 1 where the coating 2 is to be formed is made of a metal material, the adhesion between the substrate 1 and the coating 2, which will be described in detail later, is improved. , and the durability of the covering 100 can be improved.

Usually, the shape of the substrate 1 is determined by the covering 100 to be manufactured, and usually has substantially the same shape as the covering 100 to be manufactured. A plate-like shape such as a plate-like shape, a cylindrical shape, a porous shape, a granular shape, a fibrous shape, and the like can be mentioned. Further, the substrate 1 may be provided with, for example, holes, grooves, projections, and the like.

The ozone fine bubble treatment and the formation of the film 2, which will be described in detail later, are performed on at least part of the surface of the substrate 1. FIG.

For example, if the substrate 1 has a hollow portion, the ozone fine bubble treatment and the formation of the coating 2, which will be described in detail later, may be performed on at least the inner wall surface of the hollow portion of the substrate 1.

In the method according to the present invention, the inner wall surface of the hollow portion can also be suitably surface-treated (ozone fine-bubble treatment) and coated, and the effects described above can be reliably obtained. On the other hand, in the past, it was particularly difficult to form a film having excellent hydrophilicity and antifouling properties on the inner wall surface of the hollow portion. Therefore, when the substrate 1 has a hollow portion and the ozone fine bubble treatment and the formation of the coating 2, which will be described in detail later, are performed on at least the inner wall surface of the hollow portion of the substrate 1, the The effect is more pronounced.

For the base material 1, for example, pretreatment such as washing treatment may be performed before being subjected to the steps described later. More specifically, for example, washing with water, pickling, alkali washing, washing with a detergent such as a neutral detergent, washing with an organic solvent, etc. can be performed, but the surface of the base material 1 is contaminated. Even in such a case, the cleaning treatment can be omitted or the cleaning treatment conditions can be relaxed by adjusting the conditions of the ozone fine bubble treatment, which will be described in detail later.

《Ozone fine bubble treatment process》
In the ozone fine bubble treatment step, the base material 1 is subjected to ozone fine bubble treatment using ozone fine bubble water (see FIG. 1(1b)).

Ozone fine-bubble water is usually prepared by dissolving and dispersing ozone (O ₃ ) generated from oxygen gas (O ₂ ) in water.

Methods for generating ozone (O ₃ ) include, for example, a lamp method using a low-pressure mercury lamp, a silent discharge method, a creeping discharge method, an electrolysis method, and the like.

The fine ozone bubbles may have a particle size of 100 μm or less, but the average particle size of the ozone fine bubbles is preferably 0.08 μm or more and 0.50 μm or less, and more preferably 0.10 μm or more and 0.40 μm or less. more preferably 0.12 μm or more and 0.30 μm or less.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The number of fine bubbles having a particle size of 0.12 μm or more and 0.30 μm or less contained in the ozone fine bubble water per unit volume is 1.0×10 ⁷ /mL or more and 1.0×10 ¹⁰ /mL or less. is preferably 5.0 × 10 ⁷ /mL or more and 5.0 × 10 ⁹ /mL or less, more preferably 1.0 × 10 ⁸ /mL or more and 1.0 × 10 ⁹ /mL or less is more preferable.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The number of fine bubbles (ozone bubbles having a particle size of 100 μm or less) contained in the ozone fine bubble water per unit volume is 2.0×10 ⁷ /mL or more and 1.0×10 ¹¹ /mL or less. preferably 7.0 × 10 ⁷ / mL or more and 1.0 × 10 ¹⁰ /mL or less, more preferably 2.0 × 10 ⁸ /mL or more 5.0 × 10 ⁹ / It is more preferably no more than mL.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The number of fine bubbles contained in the fine bubble water can be measured, for example, with a particle size range of 1 μm or more and 10 μm or less using SALD7500 nano manufactured by Shimadzu Corporation. The diameter range can be determined using LM-10 manufactured by Nanosite Co., Ltd.

Further, the ozone concentration in the ozone fine bubble water is preferably 50 g/m ³ or more and 1000 g/m ³ or less, more preferably 100 g/m ³ or more and 700 g/m ³ or less, and 150 g/m ³ or more. More preferably, it is 500 g/m ³ or less.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

In consideration of the consumption of ozone, etc., this step is preferably carried out while fine bubbles of ozone are being supplied into the system.

The treatment time of the ozone fine bubble treatment is preferably 10 minutes or more and 600 minutes or less, more preferably 30 minutes or more and 300 minutes or less, and even more preferably 60 minutes or more and 150 minutes or less.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The treatment temperature of the ozone fine bubble treatment (temperature of fine bubble water) is preferably 0°C or higher and 60°C or lower, more preferably 4°C or higher and 40°C or lower, and 5°C or higher and 30°C or lower. is more preferred.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

《Ultrasonic treatment process》
An ultrasonic treatment step of applying ultrasonic treatment to the base material 1 may be included before the film forming step described later.

As a result, even if the treatment time of the ozone fine bubble treatment is shortened, the adhesion of the coating 2 to the substrate 1 can be sufficiently excellent, and the productivity of the coating 100 can be further enhanced. be able to. Moreover, the adhesion of the coating 2 to the substrate 1 can be improved, and the durability of the coating 100 can be improved.

The ultrasonic treatment can be performed before the film forming step described later, for example, it may be performed before the ozone fine bubble treatment or after the ozone fine bubble treatment. It is preferable to carry out in the same step as the treatment.

As a result, the adhesion of the coating 2 to the substrate 1 can be further improved, the durability of the coating 100 can be further improved, and the productivity of the coating 100 can be further improved. can be assumed.

The treatment time of the ultrasonic treatment may be the same as the treatment time of the ozone fine bubble treatment, may be shorter than the treatment time of the ozone fine bubble treatment, or may be longer than the treatment time of the ozone fine bubble treatment. .

The frequency of ultrasonic waves applied in the ultrasonic treatment is preferably 20 kHz or more and 100 MHz or less, more preferably 25 kHz or more and 50 MHz or less, and even more preferably 30 kHz or more and 150 kHz or less.

As a result, while effectively preventing ozone from being released into the atmosphere from the ozone fine bubble water, the surface of the base material 1 can be more efficiently prevented from unevenness in a shorter time. Hydroxyl groups can be introduced densely. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The treatment time of the ultrasonic treatment is preferably 1 minute or more and 600 minutes or less, more preferably 2 minutes or more and 300 minutes or less, and even more preferably 3 minutes or more and 150 minutes or less.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The treatment temperature of the ultrasonic treatment (the temperature of the substrate 1) is preferably 0° C. or higher and 60° C. or lower, more preferably 4° C. or higher and 40° C. or lower, and 5° C. or higher and 30° C. or lower. More preferred.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

《Ultraviolet irradiation process》
An ultraviolet irradiation step of applying an ultraviolet irradiation treatment for irradiating the substrate 1 with ultraviolet rays may be included prior to the film forming step described later.

As a result, even if the treatment time of the ozone fine bubble treatment is shortened, the adhesion of the coating 2 to the substrate 1 can be sufficiently excellent, and the productivity of the coating 100 can be further enhanced. be able to. Moreover, the adhesion of the coating 2 to the substrate 1 can be improved, and the durability of the coating 100 can be improved.

The ultraviolet irradiation treatment can be performed before the film forming step described later, for example, it may be performed before the ozone fine bubble treatment or after the ozone fine bubble treatment. It is preferable to carry out in the same step as the treatment.

As a result, the reactivity of the ozone fine bubbles can be more effectively increased, the adhesion of the coating 2 to the substrate 1 can be further improved, and the durability of the coating 100 can be further improved. and the productivity of the covering 100 can be improved.

Thereby, the adhesion of the coating 2 to the substrate 1 can be further improved, and the durability of the coating 100 can be further improved.

The peak wavelength of the ultraviolet rays used for the ultraviolet irradiation treatment may be 10 nm or more and 400 nm or less, preferably 15 nm or more and 350 nm or less, more preferably 20 nm or more and 300 nm or less, and further preferably 30 nm or more and 280 nm or less. preferable.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The treatment time of the ultraviolet irradiation treatment is preferably from 0.5 minutes to 10 minutes, more preferably from 1 minute to 7 minutes, and even more preferably from 2 minutes to 5 minutes.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

The treatment temperature of the ultraviolet irradiation treatment (the temperature of the substrate 1) is preferably 0° C. or higher and 60° C. or lower, more preferably 4° C. or higher and 40° C. or lower, and 5° C. or higher and 30° C. or lower. More preferred.

As a result, it is possible to efficiently introduce hydroxyl groups to the surface of the substrate 1 in a shorter time and more densely while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

<<Coating process>>
In the film forming step, the film 2 is formed on the base material 1 subjected to the ozone fine bubble treatment using a polymer compound having a structure represented by the following formula (1) (see FIG. 1(1c)).

（式（１）中、Ｘ^１およびＸ^２は、それぞれ独立して、重合した状態の重合性原子団を表し；Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有していてもよいフェニル基、または、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－もしくは－Ｏ－で示される基を表し；Ｒ^３は、水素原子または炭素数が１以上３以下のアルキル基を表し；ｍおよびｎは、それぞれ独立して、１以上の整数を表し、ａおよびｂは、それぞれ独立して、２以上の整数を表し；Ｘ^１を含む構造単位およびＸ^２を含む構造単位はランダムな順序で結合している。）

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.)

The polymer compound will be described later in detail.
The polymer compound can be applied to the base material 1 by various coating methods such as roll coating, bar coating, and spraying, various printing methods such as screen printing and inkjet, and various methods such as dipping. method.

A part of the base material 1 may be masked for the purpose of selectively applying the polymer compound to a predetermined portion of the base material 1 .

When the polymer compound is applied to the substrate 1 by an immersion method, the immersion time of the substrate 1 in the composition containing the polymer compound is not particularly limited, but is 1 minute or more and 60 minutes or less. is preferably 2 minutes or more and 30 minutes or less, and preferably 3 minutes or more and 15 minutes or less.

The amount of the polymer compound applied to the site to which the polymer compound is applied is preferably 0.01 mg/cm ² or more and 10 mg/cm ² or less, and more preferably 0.05 mg/cm ² or more and 5.0 mg/cm ² . It is more preferably 0.10 mg/cm ² or more and 1.0 mg/cm ² or less.

As a result, it is possible to form the film 2 of the polymer compound on the surface of the base material 1 more densely and efficiently in a shorter time while suppressing unevenness more efficiently. As a result, the hydrophilicity and antifouling properties of the coating 2 can be improved, and the durability of the coating 100 can be improved.

In this step, the surface of the substrate 1 that has been subjected to the ozone fine bubble treatment or the like as described above is treated with the polymer compound, and then heat treatment is usually performed.

By performing the heat treatment, the dehydration-condensation reaction described above can proceed more favorably, and the reliability and productivity of the covering 100 can be improved.

Prior to the heat treatment, the substrate 1 to which the polymer compound has been applied may be left for a predetermined period of time.

As a result, for example, when the polymer compound is applied to the base material 1 in the state of a composition containing a solvent, the base material 1 is effectively prevented from being excessively dried, and at least one of the solvent is The part can be removed by natural drying, the occurrence of bumping during heat treatment can be more suitably prevented, and the adhesion of the formed coating 2 to the base material 1 and the reliability of the coating 100 can be improved. can be excellent.

When the substrate 1 to which the polymer compound is applied is left for a predetermined time prior to the heat treatment, the standing time is preferably 0.5 minutes or more and 120 minutes or less, and 1 minute or more and 60 minutes or less. is more preferable, and more preferably 2 minutes or more and 10 minutes or less.

As a result, the productivity of the covering 100 can be improved, and the reliability and productivity of the covering 100 can be improved.

The treatment temperature of the heat treatment is preferably 60° C. or higher and 150° C. or lower, more preferably 70° C. or higher and 140° C. or lower, even more preferably 80° C. or higher and 130° C. or lower.

As a result, the productivity of the covering 100 can be improved, and the reliability and productivity of the covering 100 can be improved.

The treatment time of the heat treatment is preferably 30 minutes or more and 600 minutes or less, more preferably 45 minutes or more and 480 minutes or less, and even more preferably 60 minutes or more and 300 minutes or less.

As a result, the productivity of the covering 100 can be improved, and the reliability and productivity of the covering 100 can be improved.

Although the covering 100 can be obtained as described above, a post-treatment may be performed.
Examples of the post-treatment include cleaning treatment such as scrubbing and ultrasonic cleaning.

In particular, by rubbing, it is possible to suitably remove molecules that have not undergone a dehydration-condensation reaction with the constituent substances of the base material 1 among the polymer compounds that constitute the coating film 2, and the finally obtained coating 100 can be obtained. The wear resistance of the coating 2 in can be made more excellent.

For example, the scrubbing may be performed using running water, or the covering 100 may be immersed in water.

In addition, by performing ultrasonic cleaning, unnecessary substances adhering to the film 2 can be removed more effectively.
Ultrasonic cleaning can be performed, for example, in water.

After performing the cleaning treatment as described above, a drying treatment may be performed. In this case, the drying treatment may be performed, for example, by natural drying, by heating, or under a reduced pressure environment.

Although the thickness of the coating 2 in the finally obtained coating 100 is not particularly limited, it is preferably 0.03 μm or more and 10 μm or less, and more preferably 0.03 μm or more and 0.1 μm or less.

When the coating 2 is composed of a monomolecular film of the polymer compound, for example, the structure of the polymer compound (for example, the value of n in formula (1) and formula (2)) causes the coating 2 thickness can be suitably controlled.

The polymer compound used for forming the film 2 will be described in detail below.
The polymer compound used for forming the coating 2 is a polymer having a unit containing a phosphorylcholine group in its side chain and a unit containing a phosphonic acid group in its side chain, as represented by the above formula (1).

The phosphonic acid group contained in the side chain of the polymer compound enables fixation by chemical bonding to the surface of the base material 1 that has been subjected to ozone fine bubble treatment, and the adhesion of the coating 2 to the base material, the coating 100 durability can be improved.
Specifically, the phosphonic acid group undergoes a dehydration condensation reaction with a functional group (a functional group capable of interacting with the phosphonic acid group (for example, a hydroxyl group)) introduced on the surface of the base material 1 to form the base of the coating 2. Adhesion to the material and durability of the covering 100 can be improved.

The phosphorylcholine group contained in the side chain of the polymer compound has a zwitterionic structure.
Therefore, by including a phosphorylcholine group in a polymer compound, the polymer compound is excellent in hydrophilicity (wettability) and can effectively suppress non-specific adsorption to various molecules. As a result, an antifouling effect, a lubrication characteristic effect, a friction reduction effect, a self-cleaning effect, and the like can be exhibited. A phosphorylcholine group is a polar group having the same structure as the polar group of phospholipids (phosphatidylcholine), which is the main component of biological membranes. Therefore, the introduction of phosphorylcholine groups can impart very good biocompatibility, particularly non-adsorption and non-activation properties of biomolecules, to the surface of biological membranes.

In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently optionally have a substituent a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; m and n each independently represent an integer of ¹ or more, a and b each independently represent an integer of ² or more; Combined in order.

In formula (1), X ¹ and X ² are not particularly limited as long as they each independently represent a polymerizable atomic group in a polymerized state. groups, acetylene-based monomer residues, ester-based monomer residues, amide-based monomer residues, ether-based monomer residues, urethane-based monomer residues, etc., among which vinyl-based monomer residues are preferred.

In formula (1), R ¹ and R ² are each independently an optionally substituted phenyl group, or C(O)—, —C(O)O— or —O—. is preferably a group represented by -C(O)-, -C(O)O- or O-, more preferably a group represented by -C(O)O- .

Specific examples of substituents of the phenyl group in R ¹ and R ² include halogen atoms (F, Cl, Br, I), hydroxyl groups, thiol groups, nitro groups, cyano groups, formyl groups, carboxyl groups, and amino groups. , a silyl group, a methanesulfonyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, a cyclo having 3 to 8 carbon atoms Examples include an alkyl group, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an acyl group having 2 to 7 carbon atoms, and an alkoxycarbonyl group having 2 to 7 carbon atoms. be done.

R ¹ and R ² may be the same or different. In terms of polymerization reactivity, they are preferably the same, and more preferably both are groups represented by -C(O)O-.

In formula (1), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

As a result, the solubility in a solvent (especially, a polymerization solvent used when synthesizing (polymerizing) a polymer compound, a solvent used when applying a polymer compound to the substrate 1, etc.) can be made more excellent. can.

In formula (1), m represents an integer of 1 or more, preferably an integer of 1 or more and 12 or less, more preferably an integer of 1 or more and 4 or less, and still more preferably 2.

In formula (1), n represents an integer of 1 or more, preferably an integer of 1 or more and 12 or less, more preferably an integer of 1 or more and 6 or less, and still more preferably 1.

Specific examples of structural units containing X ¹ in formula (1) include 2-methacryloyloxyethylphosphorylcholine, 2-acryloyloxyethylphosphorylcholine, N-(2-methacrylamido)ethylphosphorylcholine, 4-methacryloyloxybutyl Structural units derived from phosphorylcholine, 6-methacryloyloxyhexylphosphorylcholine, 10-methacryloyloxydecylphosphorylcholine, ω-methacryloyldioxyethylenephosphorylcholine, 4-styryloxybutylphosphorylcholine and the like can be mentioned. Among them, structural units derived from 2-methacryloyloxyethylphosphorylcholine are particularly preferred. 2-Methacryloyloxyethylphosphorylcholine (MPC) and other phosphorylcholine compounds (monomeric compounds) may be commercially available products or can be easily prepared according to conventional methods.

Specific examples of the structural unit containing X ² in formula (1) include structural units derived from monomer compounds represented by formula (b1) and formula (b2) below.

（上記式（ｂ１）および上記式（ｂ２）中、ｎは１以上の整数を表す。）

(In the above formulas (b1) and (b2), n represents an integer of 1 or more.)

In the above formula (b1) and the above formula (b2), n may be an integer of 1 or more, preferably an integer of 1 or more and 12 or less, more preferably an integer of 1 or more and 6 or less, 1 is more preferred.

In particular, in formula ( ¹ ), the structural unit containing X2 is preferably derived from a monomer compound represented by formula (b1) and n=1.

^A monomer compound constituting a structural unit containing X2 can be synthesized by a conventional method based on the technical level of those skilled in the art. Further, for example, Phosmer M and Phosmer PP (compounds of n = 5 to 6 in the above formula (b2)), Phosmer PE (compounds where n = 4 to 5 in the above formula (b1)), and Phosmer M manufactured by Unichemical Co., Ltd. (Compound of n=1 in formula (b1) above), P-1M manufactured by Kyoeisha Chemical Co., Ltd. (compound of n=1 in formula (b1) above), and other commercially available products can also be used.

The polymer compound represented by formula ( ¹ ) may be a random polymer in which the structural unit containing X1 and the structural unit containing X2 ^are bonded in random order, or may be a block polymer. .

Moreover, as at ^{least one} of the structural unit containing X1 and the structural unit containing X2, a plurality of types of components may be used in combination.

A preferred specific example of the polymer compound having the structure represented by the general formula (1) is a polymer compound having the structure represented by the following general formula (2).

（式（２）中、Ｒ^３は、水素原子または炭素数が１以上３以下のアルキル基を表し、ａおよびｂは、それぞれ独立して２以上の整数を表し、ｎは１以上の整数を表し、各モノマーユニットはランダムな順序で結合している。）

(In formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a and b each independently represent an integer of 2 or more, and n represents an integer of 1 or more. , and each monomer unit is attached in a random order.)

In formula (2), a structural unit having a side chain containing a phosphorylcholine group (hereinafter also referred to as "MPC unit") and a structural unit having a side chain containing a phosphonic acid group (hereinafter also referred to as "PA unit") may be bonded in random order, as in formula (1), and is not limited.

In formula (2), R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

As a result, the solubility in a solvent (especially, a polymerization solvent used when synthesizing (polymerizing) a polymer compound, a solvent used when applying a polymer compound to the substrate 1, etc.) can be made more excellent. can.

In formula (2), n represents an integer of 1 or more, preferably an integer of 1 or more and 12 or less, more preferably an integer of 1 or more and 6 or less, and still more preferably 1.

In the polymer compounds represented by the above formulas (1) and (2), a and b may each independently be an integer of 2 or more, but the value of a/(a+b) is 0.0. It is preferably 10 or more and 0.99 or less, more preferably 0.30 or more and 0.99 or less, and even more preferably 0.60 or more and 0.95 or less.

The weight-average molecular weight of the polymer compound represented by formula (1) and formula (2) is not particularly limited, but is preferably 15,000 or more and 600,000 or less.

The weight average molecular weight of the polymer compound can be measured by a gel permeation chromatography (GPC) method.

The polymer compound having the structure represented by the above formula (1) and the above formula (2) may contain structural units derived from other monomers, if necessary. Generally, the proportion of structural units derived from other monomers is preferably 30 mol% or less, more preferably 10 mol% or less, relative to the total structural units (100 mol%) constituting the polymer compound. preferable.

A method for producing the polymer compound used for forming the film 2 will be described below.
Synthesis of the polymer compound represented by formula (1) or (2) above can generally be carried out by a conventional method based on the technical level of those skilled in the art. For example, a method of synthesizing the polymer compound includes a method of radically polymerizing a monomer including a monomer constituting an MPC unit and a monomer constituting a PA unit using a polymerization initiator. Examples of the radical polymerization method include a method using a redox polymerization initiator (Method 1) and a method using a radical polymerization initiator (Method 2).

(Method 1)
The polymer compound represented by the above formula (1) or the above formula (2) is preferably synthesized by redox polymerization using a redox polymerization initiator, especially by solution polymerization. is more preferred.

This makes it possible to more preferably obtain polymer compounds with various compositions while suppressing gelation and precipitation.

Since the polymer compound is water-soluble, for example, an aqueous solution of the polymer compound obtained after the redox polymerization may be used as it is for forming the film 2 .

This makes it possible to omit the removal of the polymerization solvent (for example, removal by freeze-drying), purification treatment of the polymer compound, and the like, which is advantageous from the viewpoint of energy saving and cost saving.

Also, the redox polymerization reaction can be performed at room temperature (10° C. or higher and 35° C. or lower). The reaction at room temperature does not require heating and is advantageous from the viewpoint of energy saving and cost saving.

Polymerization using an aqueous solution is also preferable from the viewpoint of avoiding the problem of volatile organic compounds (VOC).

A polymerization solvent used in synthesizing (polymerizing) a polymer compound is usually an aqueous solvent containing at least water.

As the aqueous solvent, water or a mixed solvent of water and an organic solvent can be used. Examples of the organic solvent include alcohols such as isopropyl alcohol and ketones such as acetone.

In particular, as the aqueous solvent used in the synthesis (polymerization) of the polymer compound, water or a mixed solvent of water and an alcohol solvent having an alcohol content of 70% by volume or less is preferable, and water alone is more preferable. preferable.

A redox polymerization initiator, which is a combination of an oxidizing agent and a reducing agent (polymerization accelerator), is used in the redox polymerization reaction.
As the redox polymerization initiator, a water-soluble redox polymerization initiator is preferred.

Examples of the oxidizing agent constituting the redox polymerization initiator include hydrogen peroxide, ammonium persulfate, potassium persulfate, sodium persulfate and the like, and one or more selected from these may be used in combination. can. Among them, at least one selected from the group consisting of ammonium persulfate, potassium persulfate and sodium persulfate is preferable, and ammonium persulfate is more preferable.

As a reducing agent that constitutes the redox polymerization initiator, for example, known reducing agents can be used. For example, metal ions such as iron, copper, silver, cerium, cobalt, nickel, hydroxymethanesulfinate, ethylenediaminetetraacetic acid (EDTA) or its salts, N,N,N',N'-tetramethylethylenediamine (TMEDA) , water-soluble thiosulfates, sulfites (eg, sodium sulfite), etc. Among them, amine compounds such as N,N,N',N'-tetramethylethylenediamine (TMEDA) are preferred.

Presumably, the presence of the amine neutralizes the monomer constituting the PA unit having a phosphonic acid group and forms a salt structure, thereby further suppressing gelation.

When an amine is used as the reducing agent, it is preferable to add an acid (for example, phosphoric acid) to the reaction solution after the polymerization to acidify the reaction solution, thereby desalting the polymer compound.
This further improves the adhesion of the coating 2 to the substrate 1 .

In one preferred form, phosphoric acid or the like is added to the reaction solution obtained after the polymerization to make it acidic, and ultrafiltration is performed.

As a result, the adhesion of the coating 2 to the substrate 1 is further improved, and the diamine desalted from the PA unit forms a salt with phosphoric acid, which can be easily removed.

A preferred combination of the oxidizing agent and reducing agent that constitute the redox polymerization initiator is a combination of ammonium persulfate and N,N,N',N'-tetramethylethylenediamine.

The amount of the oxidizing agent used is preferably 0.0001 parts by mass or more and 3 parts by mass or less, and 0.001 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the total monomers used for polymerization. is more preferable, and more preferably 0.05 parts by mass or more and 1 part by mass or less.

The amount of the reducing agent used is preferably 0.001 parts by mass or more and 15 parts by mass or less, and 0.01 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the total monomers used for polymerization. is more preferred.

The reaction temperature of the redox polymerization reaction is not particularly limited, but for example, it is preferably 0° C. or higher and 100° C. or lower, more preferably 10° C. or higher and 90° C. or lower, and 20° C. or higher and 40° C. or lower. More preferred. When the polymerization temperature is within this range, the polymerization rate is suitable and easy to control, and the productivity and stability of the polymer are excellent. The redox polymerization reaction is possible even at room temperature (10° C. or higher and 35° C. or lower). The reaction at room temperature is preferable because it does not require heating or the like and can reduce production costs.

The reaction is usually carried out in an aqueous solvent, but the monomer concentration is not particularly limited. The reaction time is not particularly limited, but can be, for example, 1 hour or more and 6 hours or less.

(Method 2)
The polymer compound can be synthesized by radical polymerization using a radical polymerization initiator under specific conditions. Specifically, the polymer compound can be preferably synthesized by radical polymerization in an organic solvent.

The radical polymerization initiator used for polymerization is not particularly limited, but examples include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2,4-dimethylvaleronitrile), 2, 2′-azobis(2-amidinopropane) dihydrochloride, 4,4′-azobis(4-cyanopentanoic acid), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile) and azo initiators such as benzoyl peroxide, t-butyl hydroperoxide, and potassium persulfate.

The amount of the radical polymerization initiator used can be adjusted according to the polymerizability of the monomer and the molecular weight of the required polymer. It is preferably from 0.01 part by mass to 3 parts by mass, and more preferably from 0.01 part by mass to 1 part by mass.

Examples of solvents used for radical polymerization include ester solvents such as ethyl acetate; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol; ketone solvents such as acetone; Ether solvents; Amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; Aromatic solvents such as benzene and toluene; Nitrile solvents such as acetonitrile; Halogenated solvents such as methylene chloride, chloroform and dichloroethane Solvents and the like can be mentioned, and one or more selected from these can be used in combination. Among them, alcoholic solvents such as methanol, ethanol, 1-propanol, 2-propanol and 1-butanol are preferred.

When the polymerization is performed by Method 2, the amount of the monomer having a phosphorylcholine group (the structural unit containing the MPC unit described above) is a [mol], and the amount of the monomer having a phosphonic acid group (the structural unit containing the PA unit described above) is When the amount used is b [mol], a/(a+b) is preferably 0.95 or more and 0.99 or less.

As a result, it is possible to more effectively prevent the occurrence of precipitation during radical polymerization, and it is possible to more preferably synthesize a polymer compound having a relatively large molecular weight.

The reaction temperature during the polymerization reaction can be appropriately set according to the molecular weight of the polymer compound to be synthesized, the type of the initiator, etc., but is preferably 30° C. or higher and 100° C. or lower.

After polymerization by Method 1, Method 2, or the like, the obtained polymer compound solution may be purified as necessary.

The purification method is not particularly limited, but it can be performed, for example, by ultrafiltration. In particular, when an amine is used as the reducing agent in the redox polymerization (Method 1 above), an acid (for example, phosphoric acid) is added to the polymer compound aqueous solution after polymerization to acidify it, and then ultrafiltration is performed. , the amine is desalted from the PA unit to form a salt with phosphoric acid and can be easily removed.

The purified solution may be used as it is for forming the coating 2, or may be further subjected to a freeze-drying treatment. Since the polymer compound after freeze-drying is water-soluble, it can be dissolved in an aqueous solvent and used to form the film 2, for example, when necessary.

As described above, in the method using a redox polymerization initiator (Method 1), the precipitation and gelation of the polymer are more effectively suppressed, and the resulting polymer compound is water-soluble. Coating 2 can be suitably performed as it is using the subsequent aqueous solution. This method 1 can be carried out at room temperature, and is more advantageous in terms of production cost than the method using a radical polymerization initiator (method 2), which is generally accompanied by heating.

At least the polymer compound described above may be used to form the coating 2, and for example, a composition containing components other than the polymer compound may be used.

Such components include, for example, various solvents, pigments, colorants such as dyes, various fillers, dispersants, ultraviolet absorbers, antioxidants, pH adjusters, preservatives/antifungal agents, rust preventives, and the like. mentioned.

Preferred examples of the solvent include water and a mixed solvent of water and alcohol, with water being more preferred.

Although the pH adjuster is not particularly limited, an inorganic salt is preferred. Examples of the inorganic salt include phosphates such as disodium hydrogen phosphate and sodium dihydrogen phosphate; carbonates such as sodium hydrogen carbonate and sodium carbonate; The above may be used in combination. Among them, phosphate is preferred, and disodium hydrogen phosphate dihydrate or disodium hydrogen phosphate dodecahydrate is more preferred.

Moreover, in order to adjust the pH to a desired value, for example, bases such as sodium hydroxide and potassium hydroxide; acids such as sulfuric acid, hydrochloric acid and nitric acid may be used.

In particular, it is preferable to use a solution of the polymer compound described above, and more preferably to use an aqueous solution, for forming the film 2 .

The content of the polymer compound in the composition used for forming the coating 2 is preferably 0.05% by mass or more and 5% by mass or less, and more preferably 0.1% by mass or more and 2% by mass or less. more preferred.

As a result, the viscosity of the composition used for forming the coating 2 can be set within a more suitable range, and the resulting coating 2 can be more effectively prevented from having undesired variations in thickness and composition. In addition, the coating 2 can be formed more efficiently.

When a liquid composition is used to form the coating 2, the pH of the composition (pH at 23° C.) is not particularly limited, but is preferably 3 or more and 11 or less, more preferably 3 or more and 7 or less. more preferred.

In the composition used for forming the coating 2, the polymer compound described above may be contained in a dissolved state, may be contained in a dispersed state, or may be contained in a molten state.

[Coating]
The coating 100 according to the present invention obtained as described above comprises a substrate 1 and a coating 2 . Moreover, the adhesiveness and durability between the substrate 1 and the coating 2 are excellent.

Applications of the covering 100 are not particularly limited, but for example, dental materials, dental instruments, various medical devices, contact lenses, artificial organs, biochips, biosensors, oxygen-enriched membranes, medical instruments such as cell storage instruments, Examples include automobile windshields and ship bottom paints. Examples of dental materials include dentures with dentures, bridge dentures, implant dentures, dental prostheses such as crowns, orthodontic materials, and denture lining materials.

0.011 g of vermillion oil (for example, clear vermillion ink, product number: SK-H manufactured by Sunby Corporation, product code: 3072030001) in the CIE 1976 L ^* a ^* b ^* color system for the portion of the covering 100 where the film 2 is provided. was applied at 0.011 g / cm ² , left to stand for 30 minutes in an environment of temperature: 25 ° C., humidity: 22% RH, and then washed with running water for 20 seconds. The color difference from the chromaticity at the site before application of oil and washing with water is preferably 5 or less, more preferably 3 or less, and even more preferably 1 or less.

Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these.

For example, the coating manufacturing method may have steps other than those described above. More specifically, for example, prior to the film forming step, the substrate is subjected to plasma treatment, corona discharge treatment, flame treatment, hydrogen peroxide solution/Fenton reaction solution treatment, treatment using a coupling agent, or the like. It may have a step of performing various treatments.

EXAMPLES The present invention will be described in detail below based on Examples and Comparative Examples, but the present invention is not limited thereto. It should be noted that the treatments and measurements for which no particular temperature condition is indicated were performed at 23°C.

<Synthesis of polymer compound>
(Synthesis Examples 1-6)
2-methacryloyloxyethylphosphorylcholine (MPC) (C ₁₁ H ₂₂ NO ₆ P Mw=295.27 CAS 67881-98-5) and Phosmer M (acid phosphoxy ethyl methacrylate) (C ₆ H ₁₁ O ₆ P Mw) as monomers = 210.12 CAS 24599-21-1), ammonium persulfate (APS) as redox polymerization initiator (oxidizing agent), N,N,N',N'-tetramethylethylenediamine as polymerization accelerator (reducing agent) (TMEDA) was used and dissolved in 15 mL of pure water as a reaction solvent with the formulation shown in Table 1 so that the monomer concentration was 0.5 mol / L, and then the solution was transferred to a test tube and argon was bubbled to The oxygen inside was degassed (20 minutes).

Next, the test tube was sealed with a gas burner and polymerized at room temperature (23° C.) for 24 hours.

After that, the test tube is opened, mixed with 600 mL of water, and subjected to continuous ultrafiltration using an ultrafiltration device (Gengoro manufactured by Technooffice Kaneko) to remove unreacted substances, collect them, and freeze-dry them. A polymer compound was obtained.
Table 1 summarizes the reaction conditions for each of the above synthesis examples.

<Production of covering>
(Example 1)
First, as a base material, a stainless steel plate made of SUS304 (manufactured by Nisshin Steel Co., Ltd., cold-rolled stainless steel (2B) was buffed with #800 to a mirror finish, cut into 45 mm × 80 mm, and 25 mm × 25 mm) was prepared.

This base material was subjected to ozone fine bubble treatment using ozone fine bubble water.

In the ozone fine bubble treatment, 60 L of water is placed in a water tank (width 600 mm x depth 300 mm x height 360 mm) in which a fine bubble generator (Microstar FS101-1 manufactured by Fuki Seisakusho Co., Ltd.) is installed. It was carried out in fine ozone bubble water prepared by supplying fine ozone bubbles generated from a bubble generator.

Ozone gas was supplied to the fine bubble generator from an ozone generator (ED-0G-R6 manufactured by Ecodesign Co., Ltd.) connected to an oxygen gas cylinder via a regulator.

As the oxygen gas cylinder, one with an oxygen purity of 99.5% was used, the regulator was set to a secondary pressure of 0.1 MPa, the oxygen gas flow rate to the ozone generator was set to 0.3 L/min, and the ozone generator was was set to 2.7A. The amount of ozone gas supplied from the ozone generator to the fine bubble generator was 4.64 g/hour. The ozone concentration in the ozone fine bubble water was 258 g/m ³ .

The ozone fine bubble treatment was performed by immersing the substrate in the ozone fine bubble water obtained as described above for 60 minutes.

Next, the substrate subjected to the ozone fine bubble treatment is taken out, washed with running water, and a 0.5% by mass aqueous solution of the polymer compound obtained in Synthesis Example 1 is applied to the surface of the substrate by an immersion method. Granted.

After that, heat treatment is performed at 100 ° C. for 2 hours, then the surface is scrubbed in water, ultrasonically cleaned for 5 minutes, dried naturally, and a coated body having a coating on one side of the substrate got The coating thickness was 30 nm. The thickness of the film was measured using OPTM-A1 manufactured by Otsuka Electronics Co., Ltd.

(Examples 2-6)
A coated body was produced in the same manner as in Example 1 except that the polymer compounds obtained in Synthesis Examples 2 to 6 were used instead of the polymer compound obtained in Synthesis Example 1.

(Examples 7-10)
A coated body was produced in the same manner as in Example 5 except that the treatment conditions of the ozone fine bubble treatment were changed as shown in Table 2.

(Example 11)
A coated body was produced in the same manner as in Example 5 except that ultrasonic treatment was performed while performing ozone fine bubble treatment.

The ultrasonic treatment was performed by applying ultrasonic vibration of 40 kHz for 60 minutes using YOUKAI-KUN USS-1 manufactured by Nippon Seiki Seisakusho.

(Example 12)
A coated body was produced in the same manner as in Example 5 except that the ultraviolet irradiation treatment was performed while performing the ozone fine bubble treatment.

The ultraviolet irradiation treatment was performed by irradiating the substrate surface with ultraviolet rays having a peak wavelength of 240 nm for 60 minutes using OPM2-502M manufactured by Ushio Inc. from a distance of 15 cm.

(Example 13)
A coated body was produced in the same manner as in Example 5 except that ultrasonic treatment and ultraviolet irradiation treatment were performed while performing ozone fine bubble treatment.

The ultrasonic treatment was performed by applying ultrasonic vibration of 40 kHz for 60 minutes using YOUKAI-KUN USS-1 manufactured by Nippon Seiki Seisakusho.

Further, the ultraviolet irradiation treatment was carried out by irradiating the substrate surface with ultraviolet rays having a peak wavelength of 300 nm for 60 minutes using OPM2-502M manufactured by Ushio Inc. from a distance of 15 cm.

(Comparative example 1)
A coated body was produced in the same manner as in Example 5 except that the ozone fine bubble treatment was omitted.

(Comparative example 2)
The fine bubble generator was removed, and the base material was treated with ozone water (not fine bubble water) containing bubbles of mm order, except that the treatment time was set to 2 hours. A coated body was produced in the same manner as in 5.

Table 2 summarizes the manufacturing conditions of the coated bodies of the above Examples and Comparative Examples. In Table 2, the ozone fine bubble is shown as "FB", and the ozone fine bubble water is shown as "FB water". The particle size of ozone bubbles is measured using SALD7500nano manufactured by Shimadzu Corporation for the particle size range of 1 μm to 10 μm, and LM manufactured by Nanosite Co., Ltd. for the particle size range of 0.08 μm to 1 μm. -10 was used. In Comparative Example 2, since the treatment was performed using ozonated water containing millibubbles without containing fine bubbles, the conditions for fine bubbles (FB) are shown in the item showing the conditions for fine bubbles.

Elemental analysis of the surface of the coated body of each example was performed using an XPS (X-ray photoelectron spectroscopy) measurement device (Kuratos, Shimadzu Corporation).

As a result, peaks of P near 133 eV and quaternary ammonium N near 403 eV, which do not exist in the untreated base material (SUS304), were confirmed. All of them are peaks derived from the polymer compound, and indicate that a film of the polymer compound is formed on the substrate surface.

<Evaluation>
(1) Friction coefficient HHS2000 (Shinto Kagaku Co., Ltd.) was used to measure the dynamic friction coefficient in water and evaluated according to the following criteria. The measurement conditions were load: 29 g, speed: 3.3 mm/sec, distance: 10 mm, and temperature: 23°C. HHS2000 (manufactured by Shinto Kagaku Co., Ltd.) was used with a steel wool holder (contact surface: 27 mm). Suprale (manufactured by Idemitsu Techno Fine Co., Ltd.) was used as a rubbing object. The measurement was carried out by immersing in water while controlling the temperature at 23° C. in a low-temperature constant temperature water bath (LBX-300, manufactured by AS ONE) using a liquid receiving vat.

A: The dynamic friction coefficient is less than 0.10.
B: The coefficient of dynamic friction is 0.10 or more and less than 0.20.
C: The coefficient of dynamic friction is 0.20 or more and less than 0.30.
D: Dynamic friction coefficient of 0.30 or more and less than 0.50.
E: The coefficient of dynamic friction is 0.50 or more.

(2) Antifouling property (self-cleaning effect, visual observation)
Regarding the untreated SUS304 stainless steel plate (25 mm × 25 mm) and the coverings (25 mm × 25 mm size) of each of the above examples and comparative examples, the area near the center of one of these surfaces (1 cm ² ), 0.011 g of vermillion oil (manufactured by Sunby, clear vermilion pad, product number: SK-H, product code: 3072030001) was applied at 0.011 g/cm ² in an environment of temperature: 25°C and humidity: 22% RH. It was left to stand for 30 minutes under a low temperature environment and then washed with running water for 20 seconds. The condition was visually observed and evaluated according to the following criteria.

A: No residue of vermillion oil is observed.
B: Remaining vermilion oil is hardly observed.
C: A small amount of vermillion oil remains.
D: Residual vermilion oil is clearly recognized.
E: Residual vermilion oil is remarkably observed.

(3) Antifouling property (self-cleaning effect, color difference)
Using a chromaticity meter (CM-3700A, manufactured by Konica Minolta Co., Ltd.), the coated body (25 mm × 25 mm size) of each of the above examples and comparative examples was measured before applying vermilion oil, and , 0.011 g of vermillion oil (manufactured by Sunby, clear vermillion ink pad product code: 3072030001) was applied at 0.011 g/cm ² to an area (1 cm ² ) near the center of one side, and the temperature : 25 ° C., humidity: 22% ^RH , after standing for 30 minutes, the ^chromaticity of the state after washing with running water for 20 seconds was measured ^. The color difference at the site to which vermilion oil was applied in the color system was determined and evaluated according to the following criteria.

A: The color difference is 1 or less.
B: The color difference is more than 1 and 3 or less.
C: The color difference is more than 3 and 5 or less.
D: The color difference is more than 5 and 10 or less.
E: The color difference is more than 10.

(4) Surface energy Untreated SUS304 stainless steel plate (25 mm × 25 mm) and coatings (25 mm × 25 mm size) of each of the above examples and comparative examples were checked for wettability by Arcotest. Using a dyne pen (test pen for surface energy value evaluation), the surface energy of the portion provided with the film was determined and evaluated according to the following criteria.

A: The surface energy is over 90 mN/m.
B: The surface energy is more than 84 mN/m and 90 mN/m or less.
C: The surface energy is more than 70 mN/m and 84 mN/m or less.
D: The surface energy is more than 50 mN/m and 70 mN/m or less.
E: The surface energy is 50 mN/m or less.

(5) Durability HHS2000 (Shinto Kagaku (manufactured by Co., Ltd.), the dynamic friction coefficient was measured at 3000 reciprocations in water, and evaluated according to the following criteria. The measurement conditions were load: 29 g, speed: 3.3 mm/sec, distance: 10 mm, and temperature: 23°C. HHS2000 (manufactured by Shinto Kagaku Co., Ltd.) was used with a steel wool holder (contact surface: 27 mm). Suprale (manufactured by Idemitsu Techno Fine Co., Ltd.) was used as a rubbing object. The measurement was carried out by immersing in water while controlling the temperature at 23° C. in a low-temperature constant temperature water bath (LBX-300, manufactured by AS ONE) using a liquid receiving vat.

A: The dynamic friction coefficient at the 3000th reciprocation was less than 0.5.
B: The dynamic friction coefficient reached 0.5 at 2000 or more and 3000 or less reciprocations.
C: The dynamic friction coefficient reached 0.5 at 1000 or more and less than 2000 reciprocations.
D: The dynamic friction coefficient reached 0.5 at 500 or more and less than 1000 reciprocations.
E: The coefficient of dynamic friction reached 0.5 when reciprocating 0 times or more and less than 500 times.

These results are summarized in Table 3. In Table 3, Comparative Example 3 shows an untreated SUS304 stainless steel plate which was neither surface-treated nor coated. In addition, FIG. 2 shows photographs of evaluation results of the antifouling properties of the coating according to Example 1 and the untreated SUS304 stainless steel plate.

As is clear from Table 3, excellent results were obtained for all the coatings according to the present invention. On the other hand, in each comparative example, satisfactory results were not obtained.

In addition, except that the base material was changed from SUS304 to glass, titanium, aluminum, or duralumin, the coating was produced in the same manner as in the above examples and comparative examples, When the same evaluation as described above was performed, the same tendency as described above was confirmed.

In addition, instead of a stainless steel plate as a base material, a stainless steel pipe made of SUS304 (with an outer diameter of 5 mm and a thickness of 0.5 mm whose inner and outer surfaces were polished to #150 to #400) was used, and a liquid feed pump (Cole Parmer Co., Ltd., MASTER FLEX (registered trademark) L / S), fine ozone bubble water is sent and circulated in the hollow part of the steel pipe, and selectively applied to the inner wall surface of the hollow part of the base material. Ozone fine bubble treatment is applied, and then a 0.5% by mass aqueous solution of the polymer compound obtained in each synthesis example is introduced into the hollow portion, heat treatment is performed at 100 ° C. for 2 hours, and then the hollow portion is Washed with running water, further ultrasonically washed using YOUKAI-KUN USS-1 manufactured by Nippon Seiki Seisakusho Co., Ltd. for 5 minutes, dried naturally, and a coating having a coating on the inner wall surface of the hollow part. Obtained. The coating had a coating selectively formed only on the inner wall surface of the hollow portion, and had no coating formed on the outer surface. When the coating was evaluated in the same manner as described above, the same tendency as described above was confirmed.

The method for producing a coated body of the present invention comprises an ozone fine-bubble treatment step of subjecting a substrate to ozone fine-bubble treatment using ozone fine-bubble water; and a film forming step of forming a film using a polymer compound having a structure represented by the following formula (1).

（式（１）中、Ｘ^１およびＸ^２は、それぞれ独立して、重合した状態の重合性原子団を表し；Ｒ^１およびＲ^２は、それぞれ独立して、置換基を有していてもよいフェニル基、または、－Ｃ（Ｏ）－、－Ｃ（Ｏ）Ｏ－もしくは－Ｏ－で示される基を表し；Ｒ^３は、水素原子または炭素数が１以上３以下のアルキル基を表し；ｍおよびｎは、それぞれ独立して、１以上の整数を表し、ａおよびｂは、それぞれ独立して、２以上の整数を表し；Ｘ^１を含む構造単位およびＸ^２を含む構造単位はランダムな順序で結合している。）

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.)

Therefore, it is possible to provide a method for producing a coated body in which a coating having excellent hydrophilicity and antifouling properties is provided with excellent durability. Therefore, the method for producing a coated body of the present invention has industrial applicability.

DESCRIPTION OF SYMBOLS 100... Coating 1... Base material 2... Coating

Claims (7)

an ozone fine bubble treatment step of subjecting the substrate to ultrasonic treatment and ozone fine bubble treatment using ozone fine bubble water;
and a film forming step of forming a film using a polymer compound having a structure represented by the following formula (1) on the base material subjected to the ultrasonic treatment and the ozone fine bubble treatment. A method of manufacturing a covering body.

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.) 2. The method of manufacturing a coated body according to claim 1 , further comprising an ultraviolet irradiation step of applying an ultraviolet irradiation treatment for irradiating the base material with ultraviolet rays before the film forming step. 3. The method of manufacturing a coated body according to claim 2 , wherein the ultraviolet irradiation treatment is performed in the same step as the ozone fine bubble treatment. an ozone fine bubble treatment step of subjecting the substrate to ultrasonic treatment and ultraviolet irradiation treatment of irradiating ultraviolet rays, and performing ozone fine bubble treatment using ozone fine bubble water;
a coating forming step of forming a coating using a polymer compound having a structure represented by the following formula (1) on the substrate that has been subjected to the ultrasonic treatment, the ultraviolet irradiation treatment and the ozone fine bubble treatment; A method for producing a covering, comprising:

(In formula (1), X ¹ and X ² each independently represent a polymerizable atomic group in a polymerized state; R ¹ and R ² each independently have a substituent, a phenyl group, or a group represented by -C(O)-, -C(O)O- or -O-; R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms m and n each independently represent an integer of 1 or more, a and b each independently represent an integer of 2 or more; the structural unit containing X ¹ and the structural unit containing X ² are random are combined in the correct order.) 5. The substrate according to any one of claims 1 to 4, wherein the substrate has a hollow portion, and the ultrasonic treatment, the ozone fine bubble treatment and the formation of the coating are performed on the inner wall surface of the hollow portion of the substrate. 2. A method for producing the covering according to item 1 . 6. The method of manufacturing a coated body according to claim 1, wherein the base material has a portion on which the film is formed is made of a metal material. 7. The method for producing a coated body according to claim 1 , wherein the fine bubbles of ozone have an average particle size of 0.08 [mu]m or more and 0.50 [mu]m or less.

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