WO2023176900A1

WO2023176900A1 - Member

Info

Publication number: WO2023176900A1
Application number: PCT/JP2023/010157
Authority: WO
Inventors: 弘優徳留; 拓真川崎; 寿明鴨志田; 綾子角崎; 萌美小柳; 恭子片岡
Original assignee: Toto株式会社
Priority date: 2022-03-16
Filing date: 2023-03-15
Publication date: 2023-09-21

Abstract

Disclosed is a member capable of suppressing adhesion of contaminating materials such as limescale and protein. This member is used in an environment in which is repeated a cycle wherein water and contaminating materials including an organic component and/or an inorganic component are attached onto a surface and the water is dried off in a state in which the water is mixed with the contaminating materials on the surface. The member is characterized by including a base material and a surface layer and in that the surface layer includes a certain sulfobetaine structure and a certain hydrophilic and nonionic structure.

Description

Element

The present invention relates to a member. Specifically, in an environment where water and contaminants containing organic and/or inorganic components adhere to a surface, and the water dries with water and contaminants mixed on the surface, a cycle is repeated. Related to members for use in.

When tap water adheres to the surface of a member used in an environment where water can be splashed and dries, limescale is formed due to the adhesion of inorganic components contained in the tap water. Typical inorganic components include silicate ions (SiO ₃ ²⁻ ) and calcium ions (Ca ²⁺ ). Silicate ions (SiO ₃ ^2- ) are polymerized by dehydration condensation, and calcium ions react with CO ₂ in the air or water and become densely crystallized as calcium carbonate as water evaporates. It adheres to the surface of the component and forms limescale. When a large amount of water adheres to the surface of a component, or when water adheres to the surface of the component and dries repeatedly, the amount and frequency of adhesion of silicate ions and calcium ions on the surface of the component increases, causing water scale to build up. The formation is accelerated, resulting in a state in which water scale is strongly adhered to the surface of the member, that is, a state in which water scale is firmly adhered to the surface of the member.

In addition, various contaminants adhere to the surface of components, including not only water but also the inorganic components (silicate ions, calcium ions, etc.) and organic components (sebum, soap scum, rinse, protein, etc.) listed above. . These contaminants remain on the surface of the component when the water dries. In many cases, at least one type of these contaminants adheres to the surface of the component, so that a mixture of limescale and contaminants is formed on the surface of the component after drying. In order to suppress the adhesion of such dirt and to improve the cleanability of the adhered dirt, techniques have been proposed for modifying the surface of the member.

For example, JP-A-2008-239949 (Patent Document 1) discloses a hydrophilic member having a surface with excellent antifouling properties, antifogging properties, and abrasion resistance. Specifically, a zwitterionic low-molecular compound having a betaine structure is bonded to a hydrophilic polymer having a silane coupling group at the terminal or side chain by silane coupling, and inorganic components such as Si, Ti, Zr, and Al are bonded to the hydrophilic polymer having a silane coupling group at the terminal or side chain. A member is disclosed in which a hydrophilic film introduced and densified is formed on a base material.

Furthermore, WO2017/018146 (Patent Document 2) discloses a member in which a coating formed on a base material by curing a curable composition containing a polyfunctional (meth)acrylamide monomer and a betaine monomer of acrylic or acrylamide is disclosed. is disclosed. This member is said to be able to exhibit excellent antifogging properties, and has excellent antifogging durability while maintaining high hardness.

Furthermore, JP-A-5-179155 (Patent Document 3) discloses a coating film obtained by curing a composition containing a polyfunctional (meth)acryloyl monomer and a sulfobetaine type monomer containing a (meth)acryloyl group. Disclosed is a member formed on a methacrylic resin plate. This member is said to have excellent scratch resistance, abrasion resistance, antistatic properties, and antifogging properties.

Japanese Patent Application Publication No. 2008-239949 WO2017/018146 publication Japanese Patent Application Publication No. 5-179155

The present inventors proposed an environment in which a cycle in which water and contaminants containing organic and/or inorganic components adhere to a surface, and then the water dries with water and contaminants mixed on the surface is repeated. Among the various contaminants present on the surface of the parts used below, we focused on the fact that protein is present at a high rate. For example, a typical protein generated in the bathroom environment is human-derived keratin. Proteins have a hydrophobic region, a positively charged region, and a negatively charged region in their molecules, so they cannot be attached to inorganic materials such as glass and ceramics, resin materials, or metal materials that are commonly used as plumbing materials. It can also be attached to objects by hydrophobic action, electrostatic action, etc. Therefore, proteins were considered as the main contaminant. This led to the idea that it is important to suppress the adhesion of proteins, which are major contaminants, to the surfaces of components. First, we confirmed that protein adhesion could be suppressed by including a betaine structure on the surface of the member. However, by including a betaine structure on the surface of the component, water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries while water and contaminants are mixed on the surface. It has been discovered that specific problems arise with parts used in environments where this cycle is repeated. That is, a novel problem has been discovered in that the formation of water scale is promoted by including a betaine structure on the surface of the member. Therefore, we have found that by including a hydrophilic nonionic structure in addition to the betaine structure on the surface of the member, it is possible to suppress the adhesion of proteins and at the same time suppress the formation of water scale, thereby solving the above problem. The present invention is based on these findings.

The member according to the invention comprises:
Components used in environments where water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries in a state where water and contaminants coexist on the surface, a cycle repeated. And,
The member includes a base material and a surface layer,
The surface layer includes a structure represented by the following formula (A1) and a structure represented by the following formula (A2),

In formula (A1),
L ₁ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
X ₁ is a functional group represented by the following formula (B),

In formula (B),
R ₂ and R ₅ are each independently a hydrocarbon group represented by -(CH ₂ ) _l - (l is a natural number from 1 to 10),
R ₃ and R ₄ are each independently an organic group containing C and H as essential components, O as an optional component, and not containing N and S,
In formula (A2),
L ₂ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
X ₂ is a functional group represented by the following formula (C),

In formula (C),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
a is a natural number,
R ₆ has any structure selected from the group consisting of H, CH ₃ , C ₂ H ₅ , the following formula (D1), the following formula (D2), the following formula (D3), and the following formula (D4). including,

In formula (D1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
In formula (D2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X ₃ is a structure represented by the following formula (E1),

In formula (E1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
a is a natural number,
In formula (D3),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X ₃ is a structure represented by the above formula (E1),
In formula (D4),
X ₄ is a structure represented by the following formula (E2),

In formula (E2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
A is characterized in that a is a natural number.

According to the present invention, an environment in which a cycle is repeated in which water and contaminants containing organic and/or inorganic components adhere to a surface, and the water dries while water and contaminants are mixed on the surface. Below, a member is provided which is able to suppress the adhesion or adhesion of dirt, in particular limescale and proteins, to the surface, and which can furthermore allow the adhering dirt to be removed easily, ie with a low cleaning load.

FIG. 1 is a schematic cross-sectional view of an example of a member according to the present invention. 3 is a microscopic photograph of a member sample of Example 1. 3 is a micrograph of a member sample of Comparative Example 2.

Figure 1 shows a structure in which water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries with the water and contaminants mixed on the surface, according to the present invention. FIG. 2 is a schematic cross-sectional view of an example of a member (hereinafter also simply referred to as "member") used in an environment where the vehicle is used. The member 10 according to the present invention comprises a base material 1 . The member 10 further includes a surface layer 2. Preferably, the surface layer 2 is on the outermost surface of the member 10. The member 10 may further include an intermediate layer 3 and/or a primer layer 4, which will be described later. The member 10 may further include layers (not shown) other than those described above, as long as the effects of the present invention can be achieved. Note that it can be confirmed that the member 10 includes the surface layer 2 by observing a cross section of the member 10 using an electron microscope and separating the layers.

Applications The member according to the present invention can be applied to all members used around water. Examples of water areas include bathrooms, toilets, washrooms, and kitchens. Specific examples of water-related members include floors, bathtubs, walls, ceilings, counters, aprons, drains, mirrors, etc. for bathrooms. Examples of toilets include toilet bowls, tanks, toilet lids, toilet seats, and Washlets (registered trademark). For washrooms, examples include washbowls, washstand counters, mirrors, lighting, faucet fittings, drains, cabinets, washing machine pans, etc. For the kitchen, examples include sinks, counters, faucet fittings, drains, dishwashers, dish dryers, cooking ranges, kitchen hoods, ventilation fans, etc.

The member according to the present invention can be used in an environment where a cycle is repeated in which water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries while water and contaminants are mixed on the surface. This is the member used below. For example, parts are used in environments where water, components that make up limescale (silicate ions, calcium ions, etc.) and proteins adhere to the surface of the component, and a cycle of water drying in a mixed state is repeated. It is a member that Further, the present invention is applicable to any situation where the above cycle is repeated. For example, if the component is a bathtub, the filled condition (a condition in which water and contaminants adhere to the surface) and the drained condition (a condition in which water dries with water and contaminants mixed together) are one. There may also be situations where a state is held for a long time and then transitions to another state, or where two states exist unevenly, but the present invention is applicable even in such cases. The member according to the present invention can effectively suppress not only protein adhesion but also limescale adhesion under such an environment. Here, contaminants refer to all the dirt that adheres to the surfaces of parts used in environments where water adhesion and drying occur repeatedly, and more specifically, silicate ions, calcium ions, sebum, soap scum, etc. , rinse, and protein. In addition, the member according to the present invention can be made from any base material that is commonly used in an environment where a cycle of adhesion of water and contaminants and drying of water in a state where these are mixed is repeated. The above-mentioned effects can be achieved on various substrates.

Surface Layer In the present invention, the surface layer includes a structure represented by the following formula (A1) and a structure represented by the following formula (A2).

In formula (B),
R ₂ and R ₅ are each independently a hydrocarbon group represented by -(CH ₂ ) _l - (l is a natural number from 1 to 10),
R ₃ and R ₄ are each independently an organic group containing C and H as essential components, O as an optional component, and not containing N or S.

In formula (A2),
L ₂ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
X ₂ is a functional group represented by the following formula (C),

In formula (C),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
a is a natural number,
R ₆ has any structure selected from the group consisting of H, CH ₃ , C ₂ H ₅ , the following formula (D1), the following formula (D2), the following formula (D3), and the following formula (D4). It is characterized by containing.

In formula (D1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
_R1 is H or _CH3 .

In formula (D2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X ₃ has a structure represented by the following formula (E1).

In formula (E1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ a is a natural number.

In formula (D3),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X ₃ is a structure represented by the above formula (E1).

In formula (D4),
X ₄ has a structure represented by the following formula (E2).

In formula (E2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ a is a natural number.

By including the structure represented by formula (A1) and the structure represented by formula (A2) in the surface layer, the member according to the present invention can suppress adhesion of various contaminants to the surface. In particular, it is possible to suppress both protein adhesion and limescale adhesion. These suppressing mechanisms are thought to be as follows, but these are only hypotheses, and the present invention is not limited by this hypothesis in any way. The structure represented by formula (A1) is a betaine structure as described later, and has antifouling ability (protein adsorption suppressing ability). This performance makes it possible to suppress the adhesion of proteins to the surface of the member. On the other hand, there is a possibility that silicate ions may be electrostatically adsorbed to the N ⁺ site in the structure represented by formula (A1). In this case, the amount of silicate ions attached increases. That is, the adhesion density of silicate ions increases. This induces or promotes polymerization through dehydration condensation between silicate ions, and when the adhesion density of silicate ions further increases in this state, the generated polymer becomes denser, which accelerates the adhesion of limescale. There is a risk of causing Furthermore, there is a possibility that calcium ions may be electrostatically adsorbed to the SO ₃ ^- site in the structure represented by formula (A1). In this case, the amount of calcium ions adsorbed increases. That is, the adsorption density of calcium ions increases. This induces or promotes crystallization of calcium carbonate, and if the adsorption density of calcium ions further increases in this state, the generated crystals become denser, which may accelerate the fixation of limescale. However, since the surface layer of the member according to the present invention includes the structure represented by formula (A2) as well as the structure represented by formula (A1), polymerization of silicate ions and/or crystallization of calcium carbonate, and further formation of It is possible to suppress the densification of the polymer and/or crystals. That is, the structure represented by formula (A2) is a structure that is hydrophilic and nonionic, as described below, so silicate ions and /or Calcium ions cannot be electrostatically adsorbed. In the surface layer of the member according to the present invention, a hydrophilic and nonionic structure represented by formula (A2) and a betaine structure represented by formula (A1) coexist (for example, both are randomly distributed). Existing). Therefore, even if there is a site where a silicate ion is attached to N ⁺ in the structure represented by formula (A1) and/or a site where calcium ion is adsorbed to SO ₃ ^- in the same structure, it is hydrophilic and There are also sites where adsorption of silicate ions and/or calcium ions is inhibited due to the nonionic structure. Therefore, polymerization of silicate ions and/or crystallization of calcium carbonate as well as densification of the produced polymer and/or crystals can be blocked at this site, and the adhesion of scale can be suppressed. As described above, by including the structure represented by formula (A1) and the structure represented by formula (A2), the member according to the present invention can simultaneously suppress not only protein adhesion but also limescale adhesion. .
In the present invention, the expression that the surface layer includes a structure represented by formula (A1) refers to that the surface layer contains one or more of a specific number of structures represented by formula (A1), The expression that the surface layer includes a structure represented by formula (A2) refers to that the surface layer contains one or more types of a specific number of structures represented by formula (A2).

In the present invention, the surface layer is preferably a layer containing only the structure represented by formula (A1) and the structure represented by formula (A2).

In the present invention, the surface layer is preferably a polymer layer. The polymer layer is a layer containing a polymer compound. In the present invention, the surface layer preferably contains a polymer compound having a structure represented by formula (A1) and a structure represented by formula (A2). It is further preferable that the surface layer contains a polymer compound containing only the structure represented by formula (A1) and the structure represented by formula (A2). In this case, it is preferable that the structure represented by formula (A1) and the structure represented by formula (A2) are randomly bonded.

The structure represented by formula (A1) and the structure represented by formula (A2) will be further explained.

In structural formula (A1) represented by formula (A1), L ₁ is preferably -COO-. Thereby, adhesion of proteins and adhesion of scale can be further suppressed.

In formula (A1), X ₁ , that is, in formula (B), R ₂ and R ₅ are preferably 1 to 6, more preferably 1 to 5, and preferably 1 to 3. Even more preferred. This makes it possible to minimize the adsorption of anionic silicate ions to cationic N ⁺ sites and/or adsorption of cationic calcium ions to anionic SO ₃ ^- sites. can. Thereby, the structure represented by formula (A1) can constitute a stable molecule. That is, since the distance between the cationic N ⁺ site and the anionic SO ₃ ^- site at the end of the structure represented by formula (A1) does not become too large, the anionic silicate ion and/or cation It is possible to suppress the easy approach of chemical calcium ions to the structure represented by formula (A1) (that is, the surface layer), and to suppress the adsorption of anionic silicate ions and/or cationic calcium ions.

In structural formula (A2) represented by formula (A2), L ₂ is preferably -COO-. Thereby, adhesion of proteins and adhesion of scale can be further suppressed.

In X ₂ of formula (A2), that is, formula (C), R ₆ preferably contains any one of H, CH ₃ , C ₂ H ₅ , or a structure represented by formula (D1). Here, when R ₆ is H, CH ₃ or C ₂ H ₅ , these are monovalent functional groups. This can enhance the effect of preventing attachment of various contaminants including proteins. More preferably, R ₆ is H or CH ₃ . As a result, the proportion of the hydrophilic moiety (-YO- repeating structure) in formula (A2) can be increased, so that the hydrophilicity of the surface layer can be increased. As a result, it becomes possible to further enhance the effect of preventing the adhesion of contaminants. On the other hand, R ₆ preferably includes any one of formula (D1), formula (D2), formula (D3), or formula (D4). Here, the structure represented by formula (D1) is a divalent functional group, the structures represented by formulas (D2) and (D3) are trivalent functional groups, and the structure represented by formula (D4) is a tetravalent functional group. This makes it possible to improve durability such as sliding durability and abrasion resistance. More preferably, R ₆ is formula (D2), formula (D3), or formula (D4). This makes it possible to increase the crosslinking density in the surface structure, making it possible to further improve durability.

In any case where R ₆ has a valence of 2 to 4, Y is preferably a linear hydrocarbon group having 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Preferably, the number of carbon atoms is 1 to 3, even more preferably. This also increases the hydrophilicity of the surface layer, making it possible to prevent attachment of various contaminants including proteins.

In the present invention, it can be specified by the following method that the surface layer contains the structure represented by formula (A1) and the structure represented by formula (A2).

(Infrared spectroscopy (IR))
By measuring the infrared light absorption spectrum near the surface of the surface layer using infrared spectroscopy, it is possible to estimate the functional groups contained in the surface layer. For example, it is possible to identify the presence of -C=O and -C-O- in an ester bond (-COO-) from the absorption wave number. Methods for measuring the infrared absorption spectrum near the surface of the surface layer include collecting the powder by scraping off the surface layer and measuring the powder using a transmission method, and simpler methods such as the single-reflection ATR method and microscopy. Examples include the ATR method.

(Time-of-flight secondary ion mass spectrometry (TOF-SIMS))
By TOF-SIMS, structural information on organic substances present on the surface of the surface layer can be obtained. By evaluating the surface layer by TOF-SIMS, it is possible to identify the partial structure from the fragment peak specific to the structure represented by formula (A1) or the structure represented by formula (A2). For example, if the structure represented by formula (A1) is the structure represented by formula (A1-1) below, unique fragment peaks at m/z = 279.11 and m/z = 421.26 can be detected. I can do it. Furthermore, when the structure represented by formula (A2) is the structure represented by formula (A2-1) below, a unique fragment peak at m/z=88.99 can be detected. When measuring with TOF-SIMS, in order to remove dirt from the surface of the sample to be measured, the sample surface is sputtered several nm thick with an ion source such as GCIB as a pretreatment, and then irradiated with a primary ion source such as Bi ₃ ²⁺ . and measure the fragments.

(X-ray photoelectron spectroscopy (XPS))
By XPS, it is possible to specify the composition ratio and chemical bonding state of C, N, O, and S contained in the molecules constituting the surface layer. For example, the XPS spectrum (N1s orbital) of the N atom derived from the sulfobetaine structure as shown in formula (A1-1) has a peak position with a binding energy of 401.2 eV. On the other hand, the structure represented by formula (A1) is the structure shown in the following formula (A3) (a structure containing a cationic ammonium moiety), or the structure represented by the formula (A3) and the following formula (A4) (anionic In the case of a mixture of structures containing sulfonic acid moieties), the peak positions are 402.0 eV and 401.8 eV, respectively. In this way, it is possible to identify whether an N atom is derived from sulfobetaine based on the difference in peak position. Similarly, it is possible to identify whether or not the S atom originates from sulfobetaine from the peak position. The energy is 166.2 eV, whereas in the case of the structure shown in formula (A4) (anionic sulfonic acid) or a mixture of formula (A3) and formula (A4), the peak position is 167.5 eV. , 167.1 eV. Note that all these peak positions are obtained by correcting the peak position of the C1s orbit at 284.5 [eV].

(Nuclear magnetic resonance measurement (NMR))
By NMR, information regarding the bonding states of H, C, and N contained in the molecules constituting the surface layer and interactions with neighboring atoms can be obtained by chemical shifts compared with standard samples. Thereby, the molecular structure constituting the surface layer can be specified in detail.

Static contact angle of surface layer In the present invention, the static contact angle of water with respect to the surface of the surface layer is preferably as low as possible. Specifically, the angle is preferably 30° or less, more preferably 25° or less, and even more preferably 15° or less. This increases hydrophilicity, making it possible to prevent attachment of various contaminants including proteins.

The static contact angle of water with respect to the surface of the surface layer is measured, for example, using the following apparatus and software under the following measurement conditions.
Equipment: SA-301 (manufactured by Kyowa Interface Science Co., Ltd.)
Software: Interface measurement/analysis integrated system FAMAS
Version: 5.0.16
Measurement method: Droplet method Droplet volume: 2.0μL
Waiting time: 1000ms
Analysis method: θ/2 method

Existence ratio of the structure represented by formula (A1) (betaine structure) in the surface layer In the present invention, the abundance ratio (SB ratio) of the structure represented by formula (A1) (sulfobetaine structure) in the surface layer is 14 It is preferable that %<SB ratio<92%, and it is preferable that 22%<SB ratio<75%. Thereby, adhesion of proteins and adhesion of scale can be suppressed well.

<How to calculate the SB ratio>
As described later, the SB ratio can be calculated from the S atom concentration obtained by XPS measurement of the surface layer. The S atom concentration obtained by XPS measurement of a surface layer consisting only of a compound having a sulfobetaine structure, and the S atom concentration obtained by XPS measurement of a surface layer that does not have a sulfobetaine structure (does not contain S atoms). By normalizing the S atom concentration obtained by XPS measurement of the surface of each sample using , it is possible to estimate the proportion of sulfobetaine structures present on the surface of each sample.

More specifically, the S atom concentration of a member sample containing only a compound having a sulfobetaine structure as a component of the surface layer is 100%, and the sample contains only a nonionic monomer (does not contain a compound having a sulfobetaine structure). The S atom concentration of the member sample is normalized as 0%. By using the linear regression line obtained from these two points, a normalized value for each component sample is calculated from the S concentration value obtained by the XPS measurement, and this value is taken as the SB ratio of each component sample.

<XPS measurement>
- Preparation of measurement sample A measurement sample can be obtained by cutting an area of an appropriate size from a plate-shaped member sample. Note that it is preferable to wash the surface of the measurement sample before measurement. For example, it is more preferable to wash the surface of the measurement sample using a neutral detergent and a sponge, and then rinse thoroughly with ultrapure water.
- XPS measurement device K-alpha (manufactured by ThermoFisher Scientific) can be used as the XPS measurement device.
・XPS measurement conditions X-ray conditions: Monochromatic AlKα ray, 72W-12KV
Photoelectron extraction angle: 90°
Analysis area: 400μmφ
Neutralization gun conditions: 200μA
Ion gun conditions: 10mA
(survey)
Time per step: 10ms
Energy step size: 1.000eV
Sweep: 2 times Pass energy: 200eV
Scanning range: -10 to 1350eV
(Narrow)
Time per step: 50ms
Energy step size: 0.100eV
Sweep: 5 times Pass energy: 50eV
Scanning range: C1s peak 279.000eV to 298.000eV, O1s peak 525.000eV to 545.000eV, N1s peak 392.000eV to 410.000eV, S2p peak 157.000eV to 175.000eV, Si2p peak 95.000eV to 11 0 .000eV, P2p peak 124.000eV to 144.000eV

<Calculation of each atomic concentration (S, N, Si, P)>
The concentration of the detected atoms can be calculated from the obtained spectrum using, for example, data analysis software Thermo Avantage (version 5.9916, manufactured by ThermoFisher Scientific). Charge correction is performed on the spectrum obtained by narrow analysis by setting the C1s peak to 284.5 eV. After that, the background is removed using the Shirley method for the peak based on the electron orbit of each measured atom, and then the peak area intensity is calculated and divided by the device-specific sensitivity coefficient preset in the data analysis software. The process is performed, and the concentration of each atom is calculated when the total of C atoms , O atoms, N atoms, S atoms, Si atoms, and P atoms is taken as 100%.

Concentration of Si atoms In the present invention, it is preferable that the concentration of Si atoms obtained by XPS measurement of the surface of the member is 1.0% or less. Since the concentration of Si atoms contained in the surface of the member is low, formation and adsorption of water scale can be suppressed. More preferably, the concentration of Si atoms is 0.4% or less.

Concentration of S atoms In the present invention, it is preferable that the concentration of S atoms obtained by XPS measurement of the surface of the member is 0.5% or more. Thereby, protein adsorption can be suppressed. The concentration of S atoms is preferably 0.7% or more. Note that the concentration of S atoms is considered to be the concentration due to S in the sulfobetaine structure existing on the surface.

N atom concentration/S atom concentration In the present invention, it is preferable that the N atom concentration/S atom concentration obtained by XPS measurement of the surface of the member is 0.5 or more and 2.5 or less. Thereby, protein adsorption and scale formation and adsorption can be effectively suppressed. The ratio of N atom concentration/S atom concentration is more preferably 0.6 or more and 2.0 or less.

In the present invention, the surface layer may be provided on the base material. The surface layer may be provided on the surface of the base material. That is, the surface layer may be formed directly on the surface of the base material without including any other layer between the base material and the surface layer. When the surface layer is provided on the surface of the base material, the surface layer is preferably a gradient film having a gradient composition. Specifically, the surface side of the surface layer includes a structure represented by formula (A1) and a structure represented by formula (A2), and the base material side of the surface layer includes, for example, a main chain described below. A gradient film containing a large amount of acrylic resin or polyvinyl resin is preferable. This makes it possible to ensure close contact with the base material while suppressing protein adsorption and scale formation and adsorption.

Composition for Forming Surface Layer In the present invention, the surface layer is preferably formed by curing the composition for forming surface layer. In the present invention, the composition for forming a surface layer may contain a compound having a betaine structure, a nonionic monomer, a polymerization initiator, and a solvent as an optional component.

Compound Having Betaine Structure In the present invention, the composition for forming a surface layer may contain a compound having a betaine structure. This allows the surface layer obtained by curing the surface layer forming composition to include the structure represented by formula (A1). In the present invention, a compound having a betaine structure means a compound having at least one cation, anion, and an ethylenically unsaturated group in the same molecule. In the present invention, examples of the cation include cations such as quaternary ammonium, sulfonium, and phosphonium. Examples of anions include anions such as -COO ^- , -PO ₄ ^2- , -HPO ₄ ^- , and -SO ₃ ^- .

In the present invention, as a compound having a betaine structure, sulfobetaine containing quaternary ammonium as a cation and -SO ₃ ^- as an anion in the molecule is preferred. Sulfobetaine having a (meth)acrylic skeleton in the molecule is more preferred.

In the present invention, Compound 1 represented by the following formula (F1) can be mentioned as a compound having a betaine structure.
Compound 1:

In compound 1,
L ₁ includes any one of -COO-, -CONH-, -(CH ₂ )m- (m is a natural number),
R ₁ is H or CH ₃ ;
R ₂ and R ₅ are each independently a hydrocarbon group represented by -(CH ₂ ) _l - (l is a natural number from 1 to 10),
R ₃ , R ₄ and R ₇ are each independently an organic group containing C and H as essential components, O as an optional component, and not containing N and S,
A is PO ₄ ⁻ ;
B is N ⁺ , S ⁺ or P ⁺ .
Note that it can be specified from the above-mentioned IR that L ₁ includes -CO-.

In the present invention, Compound 2 represented by the following formula (F2) can be mentioned as a compound having a betaine structure.
Compound 2:

In compound 2,
L ₁ includes any one of -COO-, -CONH-, -(CH ₂ )m- (m is a natural number),
R ₁ is H or CH ₃ ;
R ₂ and R ₅ are each independently a hydrocarbon group represented by -(CH ₂ ) _l - (l is a natural number from 1 to 10),
R ₃ and R ₄ are each independently an organic group containing C and H as essential components, O as an optional component, and not containing N and S,
A is COO ⁻ , PO ₄ ²⁻ , HPO ₄ ⁻ or SO ₃ ⁻ ,
B is N ⁺ , S ⁺ or P ⁺ .

In the present invention, specific examples of compounds having a betaine structure include 3-[[2-(acryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid, 3-[[2-(methacryloyloxy)ethyl]dimethyl ammonio]propane-1-sulfonic acid, 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1-sulfonic acid, 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propionate, 2 -[[2-(methacryloyloxy)ethyl]dimethylammonio]acetic acid, 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate], 4-[[2-(methacryloyloxy)ethyl]dimethylammonio] o]butane-1-sulfonic acid, 3-[(3-acrylamidopropyl)dimethylammonio]propanoate, 3-[(3-acrylamidopropyl)dimethylammonio]propane-1-sulfonic acid, 3-[(3- Methacrylamide propyl)dimethylammonio]propane-1-sulfonic acid is mentioned. Among these, 3-[[2-(acryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid, 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid , [3-(methacryloylamino)propyl]dimethyl(3-sulfobutyl)ammonium hydroxide is preferred.

Nonionic Monomer In the present invention, the composition for forming a surface layer may contain a nonionic monomer. This allows the surface layer obtained by curing the surface layer forming composition to include the structure represented by formula (A2). In the present invention, a nonionic monomer means a monomer having one or more ethylenically unsaturated groups and oxyalkylene in the molecule. Nonionic monomers are hydrophilic. The nonionic monomer is more preferably a monomer having a (meth)acrylic skeleton and an oxyalkylene group in the molecule.

In the present invention, examples of the nonionic monomer include monofunctional nonionic monomers represented by the following formula (G1).

In formula (G1),
L ₂ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
_R8 is H or _CH3 or _C2H5 _,
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
a is a natural number.

In the present invention, examples of the nonionic monomer include a bifunctional nonionic monomer represented by the following formula (G2).

In formula (G2),
L ₂ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
a is a natural number.

In the present invention, trifunctional nonionic monomer 1 represented by the following formula (G3) can be mentioned as a nonionic monomer.

In formula (G3),
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
Y is a linear or cyclic hydrocarbon group having 1 to 10 carbon atoms,
b, c, and d are each independent natural numbers.

In the present invention, trifunctional nonionic monomer 2 represented by the following formula (G4) can be mentioned as a nonionic monomer.

In the above formula,
L ₃ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
Y is a linear or cyclic hydrocarbon group having 1 to 10 carbon atoms,
b, c, and d are each independent natural numbers.

In the present invention, examples of the nonionic monomer include a tetrafunctional nonionic monomer represented by the following formula (G5).

In formula (G5),
L ₁ includes any one of -COO-, -CONH-, -(CH ₂ ) _m - (m is a natural number),
L ₂ includes any one of -OCO-, -NHCO-, -(CH ₂ ) _m - (m is a natural number),
R ₁ is H or CH ₃ ;
Y is a linear or cyclic hydrocarbon group having 1 to 10 carbon atoms, and b, c, d, and e are each independent natural numbers.

In the present invention, specific examples of nonionic monomers include 4-hydroxybutyl acrylate, 2-methoxyethyl acrylate (2-methoxyethyl acrylate), 2-[2-(2-methoxyethoxy)ethoxy]ethyl acrylate, -Hydroxyethyl methacrylate (2-hydroxyethyl methacrylate (HEMA)), 2-methoxyethyl methacrylate, diethylene glycol monomethyl ether methacrylate, hydroxypropyl methacrylate, N-(hydroxymethyl)acrylamide, N-(2-hydroxyethyl)acrylamide, N -(methoxymethyl)acrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)methacrylamide, methoxydiethylene glycol methacrylate, methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, methoxypolyethylene glycol acrylate, polyethylene glycol methacrylate, N -(4-hydroxyphenyl)methacrylamide, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, alkoxylated trimethylolpropane acrylate, alkoxylated trimethylolpropane methacrylate, alkoxylated glycerin acrylate, alkoxy Examples include glycerol methacrylate, alkoxylated pentaerythritol tetraacrylate, and alkoxylated pentaerythritol tetramethacrylate. Among these, 2-hydroxyethyl methacrylate (HEMA), methoxytetraethylene glycol methacrylate, methoxypolyethylene glycol methacrylate, 2-methoxyethyl acrylate, and diethylene glycol dimethacrylate are preferred. More preferred are 2-hydroxyethyl methacrylate (HEMA) and methoxypolyethylene glycol methacrylate.

(solvent)
In the present invention, the composition for forming a surface layer may contain a solvent. Thereby, the wettability to the base material can be improved and the viscosity of the composition for forming a surface layer can be adjusted. Examples of solvents include alcohols such as methanol, ethanol, IPA (isopropanol), and n-butanol, cellosolves such as 2-methoxyethanol and methoxypropanol, ketones such as acetone, DMF (N,N'-dimethylformamide), Water and the like can be used, but are not limited to these. Further, a plurality of types of solvents may be mixed and used as necessary. Note that the solvent can also be used when preparing the composition for forming a primer layer and the composition for forming an intermediate layer, which will be described later.

(Polymerization initiator)
It is preferable that the composition for forming a surface layer contains a polymerization initiator. As the polymerization initiator, known ones can be used, such as photopolymerization initiators and thermal polymerization initiators.

Preferred examples of the photopolymerization initiator include IRGACURE 651, IRGACURE 184, IRGACURE 500, IRGACURE 2959, IRGACURE 127, IRGACURE 907, IRGACURE 369, IRGACURE 1300, and IRGACURE 819 provided by BASF. , Irgacure 1800, Irgacure OXE01, Irgacure OXE02, Darocure 1173, Darocure TPO, Darocure 4265, and the like.

As preferred examples of the thermal polymerization initiator, thermal radical generators such as peroxides, persulfates, and azo compounds are preferably used.

In addition to the above, the composition for forming a surface layer may contain known additives such as a surfactant depending on the purpose, as long as the surface function is not impaired.

It is preferable that the composition for forming a surface layer does not contain a compound containing a sulfur atom other than a compound containing a betaine structure. It is thought that protein adhesion increases because the surface layer contains a large amount of sulfur atoms. In the present invention, the composition for forming a surface layer contains only a compound containing a betaine structure as a compound containing a sulfur atom, so that protein adsorption can be suppressed in the surface layer obtained by curing the composition. .

Intermediate layer In the present invention, an intermediate layer 3 may be formed between the base material 1 and the surface layer 2 in order to further strengthen the adhesion between the base material 1 and the surface layer 2. In order to obtain strong adhesion with the surface layer 2, which is an organic film, the intermediate layer 3 contains an acrylic resin (polyacrylic copolymer) or a polyvinyl copolymer containing vinyl alcohol in its main chain. It is preferable.

Composition for Forming an Intermediate Layer In the present invention, the intermediate layer 3 is preferably formed by curing a composition for forming an intermediate layer. The intermediate layer forming composition preferably contains a monomer capable of forming a polyacrylic or polyvinyl copolymer. It is preferable that the composition for forming an intermediate layer also contains the above-mentioned solvent and polymerization initiator.

(polyfunctional acrylate)
A polyfunctional acrylate can be suitably used as a monomer constituting the polyacrylic copolymer. In the present invention, polyfunctional acrylate means a monomer having at least two ethylenically unsaturated groups in the molecule. Specific examples of polyfunctional acrylates include 2-hydroxy-3-acryloyloxypropyl methacrylate, propoxylated ethoxylated bisphenol A diacrylate, ethoxylated bisphenol A diacrylate, 9,9-bis[4-(2-acryloyloxyethoxy) phenyl]fluorene, propoxylated bisphenol A diacrylate, tricyclodecanedimethanol diacrylate, 1,10-decanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate Acrylate, tripropylene glycol diacrylate, ethoxylated isocyanuric acid triacrylate, ε-caprolactone modified tris-(2-acryloxyethyl) isocyanurate, pentaerythritol triacrylate, trimethylolpropane triacrylate, ditrimethylolpropane trimethacrylate, ethoxy glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 2,2 bis[4 -(Methacryloxyethoxy)phenyl]propane, tricyclodecane dimethanol dimethacrylate, 1,10-decanediol dimethacrylate, 1,6-hexanediol methacrylate, 1,9-nonanediol methacrylate, neopentyl glycol methacrylate, glycerin dimethacrylate Methacrylate, trimethylolpropane trimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, polytetramethylene glycol diacrylate, glycerin triacrylate ethoxylate, dipentaerythritol polyacrylate, ethoxylated polypropylene glycol dimethacrylate, polypropylene Examples include dimethacrylate.

Examples of polyfunctional acrylates include urethane (meth)acrylate oligomers (polymers) having two or more ethylenically unsaturated groups. For example, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, phenyl glycidyl ether acrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate Examples include urethane prepolymers, dipentaerythritol pentaacrylate hexamethylene diisocyanate urethane prepolymers, oligourethane acrylates, and carboxylic acid-containing urethane acrylate oligomers.

Examples of polyfunctional acrylates include epoxy (meth)acrylate oligomers (polymers) having two or more ethylenically unsaturated groups. Examples include cresol novolac type epoxy acrylate, carboxylic anhydride-modified epoxy acrylate, and the like.

In the present invention, as a specific example of a preferable polyfunctional acrylate, one in which the functional group equivalent of an ethylenically unsaturated group is 200 g/eq or less is preferable. This makes it possible to obtain a highly durable primer layer. Further, the functional group equivalent of the ethylenically unsaturated group is preferably 150 g/eq or less, more preferably 27 g/eq or more and 150 g/eq or less. Thereby, a more durable primer layer can be obtained. Here, the functional group equivalent represents the molecular weight of a compound per functional group. That is, it is the value obtained by dividing the molecular weight of the polyfunctional acrylate by the number of ethylenically unsaturated groups. Specifically, (meth)acrylate monomers (oligomers) as polyfunctional acrylates, urethane (meth)acrylate monomers (oligomers) that are urethane modified products thereof, and epoxy (meth)acrylate monomers (oligomers) that are epoxy modified products thereof. ) divided by the number of (meth)acryloyl groups, which are ethylenically unsaturated groups. Compounds that satisfy such functional group equivalents include pentaerythritol tetraacrylate (88 g/eq), dipentaerythritol tetraacrylate (105 g/eq), dipentaerythritol hexaacrylate (96 g/eq), and trimethylolpropane triacrylate ( 99g/eq), trimethylolpropane tetraacrylate (117g/eq), 1,3,5-tris(2,2-diacryloyloxymethyl-3-(2,2,2-triacryloyloxymethylethoxy)propylhexyl) carbamate) isocyanurate (153 g/eq), ethoxylated dipentaerythritol hexaacrylate (185 g/eq), and the like.

Among these, those having 6 or more functional groups in one molecule are particularly preferred in order to further enhance the durability of the intermediate layer, such as dipentaerythritol hexaacrylate (6 functional), ethoxylated dipentaerythritol hexaacrylate ( (6 functional), 1,3,5-tris(2,2-diacryloyloxymethyl-3-(2,2,2-triacryloyloxymethylethoxy)propylhexylcarbamate)isocyanurate (15 functional).

(Polyfunctional vinyl compound)
A polyfunctional vinyl compound can be suitably used as a monomer constituting the polyvinyl copolymer. In the present invention, the polyfunctional vinyl compound means a monomer having at least two ethylenically unsaturated groups in the molecule. Specific examples of polyfunctional vinyl compounds include diallyl ether, diethylene glycol divinyl ether, 1,3-diallyloxy-2-propanol, 1,2,3-triallyloxy-2-propanol, 2,2bisallyloxymethyl-1 -Propanol, 2,2 bisallyloxyethyl-1-butanol, 2,2 bisallyloxymethyl-1-hexanol, 3,3 bisallyloxyethyl-1-butanol, 3,3 bisallyloxyethyl-1-hexanol , 2,2,2 triallyloxymethyl-1-ethanol, 2,2,2 triallyloxymethyl-1-propanol, 2,2,2 triallyloxymethyl-1-butanol, 2,2,2 triallyl Oxymethyl-1-hexanol, 1,5-hexadiene-3,4-diol, diallyl isophthalate, 1,5-hexanediene, tetraallyloxyethane, tetraallyloxypropane, tetraallyloxybutane, triallyl citrate, adipine divinyl acid, etc.

In the present invention, by using a composition in which a composition for forming a surface layer and a composition for forming an intermediate layer are mixed, the surface layer and the intermediate layer can be formed at the same time. At that time, it is necessary to form a film so that the structure represented by formula (A1) and the structure represented by formula (A2) are sufficiently included in the surface layer. For example, by adding an additive such as a surfactant to the composition, it is possible to cause the structure represented by formula (A1) and the structure represented by formula (A2) to be gradient segregated on the surface. Here, the surfactant preferably has a hydrophilic part and a hydrophobic part consisting of an organic residue, and has a molecular weight of less than 10,000.

Primer Layer In the present invention, when the base material 1 is an inorganic material such as glass, ceramic, or metal, a primer layer 4 may be formed to strengthen the adhesion between the surface layer 2 and the inorganic material. The primer layer 4 is preferably formed between the inorganic material that is the base material 1 (hereinafter referred to as "inorganic base material") and the surface layer 2. The primer layer 4 needs to be bonded to both the inorganic base material and the surface layer 2 in order to increase adhesion. For this reason, the primer layer 4 is preferably a layer containing silicon atoms.

Primer layer forming composition The primer layer 4 is preferably a cured primer layer forming composition. The composition for forming the primer layer may contain a commonly used silane-based or phosphoric acid-based coupling agent. Further, these coupling agents preferably contain an ethylenically unsaturated group such as an acryloyl group or a methacryloyl group in order to further strengthen the adhesion with the surface layer.

(silane compound)
A silane compound can be suitably used as the silane coupling agent. In the present invention, the silane compound refers to a hydrolyzable Si-OR group (reactive silyl group, OR may be a hydroxyl group or a hydrolyzable group. The hydrolyzable group is, for example, an alkoxy group, It means an organic compound having a halogeno group (specifically, -OCH ₃ , -OCH ₂ CH ₃ , and -Cl). Specific examples of silane compounds include tetraethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane. Roxymethyltriethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxymethyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltrimethoxysilane Ethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3 -glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, Tris- (trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-trimethoxysilylpropylsuccinic anhydride Examples include things.

In the present invention, specific examples of preferred silane compounds include those having three or more hydrolyzable Si-OR groups for adhesion to an inorganic base material, and acrylic or methacrylic polymerizable functionalities for adhesion to a surface layer that is an organic film. Compounds having groups are preferred. Examples of such silane compounds include 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 8-methacryloxyoctyltrimethoxysilane, and 3-methacryloxymethyltriethoxysilane. Examples include silane, 3-methacryloxypropyltriethoxysilane, and 3-methacryloxymethyltrimethoxysilane.

(phosphoric acid compound)
A phosphoric acid compound can be suitably used as the phosphoric acid coupling agent. In the present invention, the phosphoric acid compound refers to a covalent P(OH) _n group (adsorptive phosphoric acid group, n is any one of 1 to 3, and the OH group is a base substitute thereof, ONa, OK, ONH ₄ , etc.). The phosphoric acid compound preferably contains in its molecule phosphoric acid or phosphate as an adsorptive functional group, and an acrylic group, methacrylic group, or vinyl group as a polymerizable functional group. Specific examples include 2-acryloxyethyl phosphoric acid, 2-acryloxyethyl phosphoric acid, 2-methacryloxyethyl phosphoric acid, 2-methacryloxyethyl phosphoric acid, 2-acryloxypropyl phosphoric acid, 2-acryloxypropyl phosphate, 2-methacryloxypropyl phosphate, 2-methacryloxypropyl phosphate vinyl phosphate, 2-acryloxybutyl phosphate, 2-acryloxybutyl phosphate, 2-meta Chloroxybutyl phosphoric acid, 2-methacloroxybutyl phosphoric acid, vinyl phosphoric acid, or their phosphates are used.

Substrate In the present invention, the substrate is not particularly limited. As the material for the base material, any material that is generally used as a plumbing member, such as resin, metal, or inorganic material (glass, ceramic, etc.), can be used. Further, the shape of the base material can be a general shape of plumbing parts. For example, it may be a flat plate or may have a complicated shape.

Method for manufacturing member The member according to the present invention can be manufactured, for example, by the following method.

<Preparation of base material>
Prepare the base material. In the present invention, it is preferable to pre-treat the substrate. For example, it is preferable to wash the substrate with a neutral detergent and rinse with ion-exchanged water or ultrapure water. It is preferable to dry the water droplets remaining on the surface of the base material using an air blower or a dryer.

<Preparation of composition for forming surface layer>
A compound containing the structure represented by formula (A1) (compound having a betaine structure), a compound containing the structure represented by formula (A2) (nonionic monomer), and other components are mixed in any ratio. , dissolved in a solvent. A polymerization initiator is subsequently added to this solution and stirred to obtain a composition for forming a surface layer. The total weight concentration of the compound containing the structure represented by formula (A1) and the compound containing the structure represented by formula (A2) is preferably from 0.5% to 20%, and the weight in each composition Preferably, the concentration ratio is from 90:10 to 5:95.

<Application of surface layer forming composition>
A composition for forming a surface layer is applied onto a substrate. As a coating method, a known method may be used. For example, the coating can be applied by a common method such as brush coating, spray coating, dip coating, spin coating, curtain coating, or bar coating.

<Drying>
The surface layer forming composition applied onto the substrate is dried. In the present invention, when the composition for forming a surface layer contains a solvent (solvent), in order to dry the solvent, it is preferable to apply the composition for forming a surface layer onto a substrate and then dry it. Furthermore, in view of the productivity of the member, drying by heating can be suitably used.

<Curing>
The surface layer forming composition applied onto the base material is cured. Examples of the curing means include thermosetting, active energy ray curing, or a combination of thermosetting and active energy ray curing. When thermal curing is performed, a known thermal polymerization initiator can be used as the polymerization initiator, and a known method of heating with infrared rays, hot air, etc. can be used. Furthermore, in the case of active energy ray curing, examples of the radiation include visible light of 400 to 800 nm, ultraviolet rays of 400 nm or less, or electron beams. Usually, ultraviolet rays or visible rays, which are relatively inexpensive, are preferably used rather than electron beams, which require expensive equipment. When performing active energy ray curing using ultraviolet rays or visible rays, a known photopolymerization initiator can be used. When using ultraviolet light, examples of sources of ultraviolet light include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, ultraviolet lasers, and ultraviolet light from sunlight. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon.

<Formation of intermediate layer>
In the present invention, the intermediate layer 3 may be formed on the base material 1 before the surface layer 2 is formed on the base material 1. Thereby, the adhesion between the base material 1 and the surface layer 2 can be made stronger. The composition for forming an intermediate layer can be prepared by, for example, adding a polymerization initiator to a solution in which the above-mentioned monomer capable of forming a polyacrylic or polyvinyl copolymer and a solvent are dissolved in an arbitrary weight ratio, and stirring the mixture. It can be prepared by Thereafter, the intermediate layer 3 can be formed by applying the prepared composition for forming an intermediate layer onto the base material 1, drying it, and curing it.

<Formation of primer layer>
In the present invention, when the base material 1 is an inorganic material such as glass, ceramic, metal, etc., the primer layer 4 may be formed on the inorganic base material before forming the intermediate layer 3 on the inorganic base material. Thereby, the adhesion between the inorganic base material and the surface layer 2 can be made stronger. The composition for forming a primer layer can be prepared, for example, by dissolving the above-mentioned coupling agent, a solvent, and, if necessary, a catalyst for promoting a hydrolysis reaction in any weight ratio, and stirring the mixture. Thereafter, the primer layer 4 can be formed by applying the prepared composition for forming a primer layer onto an inorganic base material and drying it.

The present invention will be explained in further detail with the following examples. Note that the present invention is not limited to these examples.

1. preparation
1-1. Base materials The following five types of base materials were prepared.
・Acrylic board: Acrylite EX (manufactured by Mitsubishi Rayon)
・PET film: Lumirror film T60 (manufactured by As One)
・Glass: Borosilicate glass ・Ceramics: Sanitary ware with a glaze layer on the surface ・Metal: Brass plate with a nickel-chromium plating layer on the surface

1-2. Reagents The following reagents were prepared.

<Multifunctional acrylate>
dipentaerythritol polyacrylate

<Polymerization initiator>
A mixture of 1-hydroxycyclohexyl phenyl ketone and benzophenone in a weight ratio of 1:1.

<Solvent>
2-methoxyethanol

<Compound with betaine structure>
・Compound 1: 3-[[2-(methacryloyloxy)ethyl]dimethylammonio]propane-1-sulfonic acid ・Compound 2: 4-[(3-methacrylamidopropyl)dimethylammonio]butane-1-sulfonic acid

<Nonionic monomer>
・Nonionic monomer 1: 2-hydroxyethyl methacrylate (HEMA)
・Nonionic monomer 2: Methoxytetraethylene glycol methacrylate ・Nonionic monomer 3: Methoxypolyethylene glycol methacrylate ・Nonionic monomer 4: 2-methoxyethyl acrylate ・Nonionic monomer 5: Diethylene glycol dimethacrylate

<Silane compound>
- Silane compound 1: 3-acryloxypropyltrimethoxysilane - Silane compound 2: 3-methacryloxypropyltrimethoxysilane - Silane compound 3: Tetraethoxysilane

<Surfactant>
・Sodium di-2-ethylhexyl sulfosuccinate (aerosol OT) (standard content was 75% by weight).

2. Preparation of component samples
Examples 1 to 13, 19
(Preprocessing)
The surface of the acrylic board, which is the base material, was cleaned with a neutral detergent and rinsed with ion-exchanged water or ultrapure water. Water droplets on the surface of the substrate were blown off with air, and the substrate was dried at 60° C. for 30 minutes in a dryer.

(middle class)
A polymerization initiator was added at a weight concentration of 0.6% to a solution of polyfunctional acrylate:solvent=33:67 (weight ratio), and the mixture was stirred with a stirrer for 1 hour to prepare a composition for forming an intermediate layer. This composition was applied to the pretreated substrate by spin coating (1500 rpm, 15 seconds) or bar coating (#10) as shown in Table 1. Immediately after coating, it was placed in a hot air drying oven and left to stand at 60°C for 10 minutes. Thereafter, the coated surface was exposed to UV light using an ultraviolet irradiation device (MDB15001N-01, manufactured by Sun Energy Co., Ltd.) so that the cumulative light intensity was 1000 mJ/cm ² (measured with an ultraviolet integrated light meter, C9536-254, manufactured by Hamamatsu Photonics Co., Ltd.). Irradiated and cured.

(Surface layer)
A compound having a betaine structure shown in Table 1 and a nonionic monomer were mixed in an arbitrary ratio and dissolved in a solvent so that the total weight concentration was 10%. To this solution, a polymerization initiator was added at a weight concentration of 0.2%, and the mixture was stirred with a stirrer for 1 hour to prepare a composition for forming a surface layer. This composition was applied to the intermediate layer by spin coating (1500 rpm, 15 seconds) or bar coating (#10) as shown in Table 1. Immediately after coating, it was placed in a hot air drying oven and left to stand at 60°C for 10 minutes. After that, the coated surface was heated using an ultraviolet irradiation device (MDB15001N-01, manufactured by Sun Energy Co., Ltd.) so that the cumulative light intensity was 3 J/cm ² (measured with an ultraviolet integrated light meter, C9536-254, manufactured by Hamamatsu Photonics Co., Ltd.). It was cured by UV irradiation.
In order to remove uncured components, it was washed with a neutral detergent, rinsed with ion-exchanged water or ultrapure water, and left to dry at room temperature to obtain a member sample.

Example 14
A member sample was obtained in the same manner as in Example 1 except that the acrylic plate was replaced with a PET film as the base material.

Examples 15-17
(Preprocessing)
As the base material, the inorganic base material shown in Table 1 was used, and in the same pretreatment as in Example 1, after drying, the surface of the base material was activated by UV ozone treatment. In the UV ozone treatment, UV ozone was irradiated for 10 minutes using a UV ozone irradiation device (manufactured by Asumi Giken Co., Ltd.).

(Primer layer)
A mixed solution of silane compound (1 or 2): 10 wt % acetic acid aqueous solution: ethanol = 0.5:2:97.5 (weight ratio) was stirred with a stirrer at room temperature for 1 hour to prepare a composition for forming a primer layer. Thereafter, this composition was coated on the surface of the inorganic substrate with a bar coat (#10) as shown in Table 1, and dried in a dryer at 50°C for 5 minutes and then at 120°C for 30 minutes to form a primer layer. was formed. Thereafter, an intermediate layer and a surface layer were produced in this order by the same manufacturing method as in Example 1 to obtain a member sample.

Example 18
In the manufacturing method of Example 1, in addition to compound 1 having a betaine structure and nonionic monomer 1, a polyfunctional acrylate was further added to the surface layer forming composition so that the total weight concentration was 10%. Dissolved in a solvent. To this solution, a polymerization initiator was added at a weight concentration of 0.2%, and the mixture was stirred with a stirrer for 1 hour to prepare a composition for forming a surface layer. After this, a member sample was obtained by the same manufacturing method as in Example 1.

Example 20
In the manufacturing method of Example 1, in addition to compound 1 having a betaine structure and nonionic monomer 1, silane compound 3 (tetraethoxysilane) was further added to the surface layer forming composition, and the total weight concentration was It was dissolved in a solvent to a concentration of 10%. To this solution, a polymerization initiator was added at a weight concentration of 0.2%, and the mixture was stirred with a stirrer for 1 hour to prepare a composition for forming a surface layer. After this, a member sample was obtained by the same manufacturing method as in Example 1.

Example 21
Each weight concentration is 1% of compound 1 having a betaine structure, 0.5% of nonionic monomer 3, 30% of polyfunctional acrylate, 0.75% of polymerization initiator, and 0.1% of surfactant. % in a solvent, stirred with a stirrer for 1 hour, and coated on a substrate with a bar coat (#24). Immediately after coating, it was placed in a hot air drying oven and left to stand at 60°C for 10 minutes. Then, using an ultraviolet irradiation device (MDB15001N- ⁰¹ , manufactured by Sun Energy Co., Ltd.), the applied surface was It was irradiated with UV and cured to obtain a member sample.

Example 22
The respective weight concentrations are 0.5% of compound 1 having a betaine structure, 10% of nonionic monomer 1, 1.5% of nonionic monomer 3, 30% of polyfunctional acrylate, and 0.0% of polymerization initiator. 75% and 0.025% of the surfactant were dissolved in the solvent and stirred with a stirrer for 1 hour. Thereafter, a member sample was obtained by the same manufacturing method as in Example 21.

Comparative example 1
A member sample was obtained in the same manner as in Example 1 except that only Compound 1 having a betaine structure was used as the surface layer forming composition.

Comparative example 2
A member sample was obtained in the same manner as in Example 1 except that only nonionic monomer 1 was used as the surface layer forming composition.

Comparative example 3
A member sample was obtained in the same manner as in Example 1 except that only nonionic monomer 5 was used as the surface layer forming composition.

Comparative example 4
The acrylic plate as the base material was used as a member sample.

3. Evaluation and results
3-1. XPS evaluation <Preparation of evaluation sample>
A measurement sample was obtained by cutting a region approximately 1 cm square in size from a plate-shaped member sample. Before measurement, the surface of the measurement sample was washed to sufficiently remove dirt adhering to the surface. Specifically, it was cleaned by sliding with a sponge using a neutral detergent, and then thoroughly rinsed with ultrapure water.

<XPS measurement>
- An XPS measuring device K-alpha (manufactured by ThermoFisher Scientific) was used.
・XPS measurement conditions X-ray conditions: Monochromatic AlKα ray, 72W-12KV
Photoelectron extraction angle: 90°
Analysis area: 400μmφ
Neutralization gun conditions: 200μA
Ion gun conditions: 10mA
(survey)
Time per step: 10ms
Energy step size: 1.000eV
Sweep: 2 times Pass energy: 200eV
Scanning range: -10 to 1350eV
(Narrow)
Time per step: 50ms
Energy step size: 0.100eV
Sweep: 5 times Pass energy: 50eV
Scanning range: C1s peak 279.000eV to 298.000eV, O1s peak 525.000eV to 545.000eV, N1s peak 392.000eV to 410.000eV, S2p peak 157.000eV to 175.000eV, Si2p peak 95.000eV to 11 0 .000eV, P2p peak 124.000eV to 144.000eV

<Each atomic concentration (S, N, Si, P)>
The concentration of the detected atoms was calculated from the obtained spectrum using data analysis software Thermo Avantage (version 5.9916, manufactured by ThermoFisher Scientific). After performing charge correction on the spectrum obtained by narrow analysis by setting the C1s peak at 284.5 eV, the peak area intensity was calculated after removing the background using the Shirley method for the peak based on the measured electron orbit of each atom. Then, an analysis process is performed to divide by the device-specific sensitivity coefficient preset in the data analysis software, and the total of C atoms , O atoms, N atoms, S atoms, Si atoms, and P atoms is taken as 100%. The concentration of each atom was calculated. The results are shown in Table 1.

<SB ratio>
The SB ratio was calculated from the S atom concentration obtained by the above XPS measurement. The SB ratio can be calculated using the S atom concentration obtained from XPS measurement. S atom concentration obtained by XPS measurement of a surface layer consisting only of a compound with a sulfobetaine structure and S atom concentration obtained by XPS measurement of a surface layer without a sulfobetaine structure (film containing no S atoms) By normalizing the S atom concentration obtained by XPS measurement on the surface of each sample using , it can be used to estimate the abundance ratio of the sulfobetaine structure present on the surface of each sample. In addition, although the analysis depth by XPS is approximately 10 nm, in the manufacturing method of the member samples of Examples and Comparative Examples, a sufficient amount of the composition to form a layer thickness of 10 nm is applied and cured. The layer thickness is sufficiently thicker than the analysis depth by XPS. Therefore, analysis by XPS can analyze surface layer components without being influenced by the base material. Furthermore, the surface to be coated can be covered by spin coating or bar coating, and the base material is not exposed. From the above, XPS allows analysis of surface layer components without being affected by the base material.

(Calculation method)
The S concentration of the sample cut out from the member sample of Comparative Example 1 containing only Compound 1 having a betaine structure as a component of the surface layer = 2.9% is taken as 100%, and Comparative Example 2 containing only Nonionic Monomer 1 The S concentration of the sample cut out from the member sample of 0.1% was normalized as 0%. By using the linear regression line obtained from these two points, a normalized value for each member sample was calculated from the S concentration value obtained by the XPS measurement, and this value was taken as the SB ratio of each member sample. The obtained values are shown in Table 1.

3-2. Contact angle The static contact angle of water on the surface of the surface layer was measured using the following equipment and software under the following measurement conditions. The results are shown in Table 1.
Equipment: SA-301 (manufactured by Kyowa Interface Science Co., Ltd.)
Software: Interface measurement/analysis integrated system FAMAS
Version: 5.0.16
Measurement method: Droplet method Droplet volume: 2.0μL
Waiting time: 1000ms
Analysis method: θ/2 method

3-3. Water scale cleaning performance evaluation <Lake scale preparation 1>
20μL of tap water (Chigasaki City) was dropped onto the surface of each component sample with a micropipette, placed in a constant temperature bath (manufactured by ESPEC), and left to stand at 25℃ and 75% relative humidity for 24 hours to remove water scales. I got it.

<Preparation of limescale 2>
In the above "Preparation of water scale 1", instead of tap water, 0.1 wt% of wool keratin (Tokyo Kasei Kogyo Co., Ltd.) was mixed with tap water, and the suspension was obtained by ultrasonication for 10 minutes to disperse the mixture. A sample with water scale formed was obtained by the same method except that .

<Cleanability evaluation>
The resulting samples were evaluated for their limescale cleaning performance using the following method. Using a sliding machine (manufactured by Tester Sangyo Co., Ltd.), the sliding load was increased in stages, and the surface on which water scale was formed was slid at the following levels. Thereafter, the surface of the sample was visually observed, and the level at which limescale was no longer visible was evaluated as the scale cleaning performance of the sample. The results are shown in Table 1.

・Level 5: Wet a commercially available urethane sponge (Scotch Brite Bath Shine, manufactured by 3M Japan) with water and make 5 reciprocations with a load of 50 [g/cm2] ・Level 4: Commercially available urethane sponge (Scotch Brite Bath Shine, 3M Japan Co., Ltd.) Japan Co., Ltd.) mixed with water and a neutral detergent (Bath Magic Clean, Kao) at a weight ratio of 90:10, and 5 reciprocations at a load of 25 [g/cm2]. Level 3: Commercially available urethane sponge (Scotch Brite). Bath Shine, manufactured by 3M Japan Co., Ltd.) was mixed with water and a neutral detergent (Bath Magic Clean, Kao) in the same proportion as Level 4, and the load was 50 [g/cm2] for 5 cycles. Level 2: Commercially available A urethane sponge (Scotch Brite Bath Shine, manufactured by 3M Japan Co., Ltd.) is soaked in water and a neutral detergent (Bath Magic Clean, Kao) mixed in the same proportion as Level 4, and the load is 50 [g/cm2] for 30 reciprocations. Level 1: A commercially available urethane sponge (Scotch Brite Bath Shine, manufactured by 3M Japan) is soaked in water and an abrasive cleaner (Kiraria, manufactured by TOTO), and a load of 50 [g/cm2] is used for 5 reciprocations, level 0. :Can't get it even at level 1

3-4. Evaluation of protein adsorption amount <Preparation of suspension containing protein>
2 g of commercially available wool keratin (manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a protein was mixed and suspended in 100 mL of ion-exchanged water, and 0. .2 g was added and subjected to ultrasonication for 10 minutes to obtain a suspension.

<Protein attachment and cleaning>
After the component sample was immersed in the suspension for 5 minutes, the component sample was taken out from the suspension. Thereafter, the surface of the member sample was washed with 0.4 [mL/cm ² ] of ultrapure water using a dropper. Thereafter, the member sample was dried in a dryer at 60° C. for 10 minutes to accelerate the fixation of keratin. This procedure was repeated three times to obtain a member sample to which keratin was attached.

<Surface observation of component sample with protein attached>
Using a laser microscope LEXT OLS5000 (manufactured by Olympus), magnification: 467 times, standard mode (pitch 1.2 μm) was selected, and images of 645 μm×645 μm per field of view were photographed. The specs of the above microscope are as follows.
Equipment: OLS5000
Product version: 1.2.1.4807
Light source: 405nm semiconductor laser Detection system: Photomultiplier Objective lens: OLYMPUS MPlan APO N 20X/0.60 LEXT

The captured images are shown in FIGS. 2 and 3. FIG. 2 is an image of a member sample of Example 1, and FIG. 3 is an image of a member sample of Comparative Example 2. The black particles seen in the image are attached proteins. The protein adhesion area ratio can be calculated by the method shown below.

<Calculation of protein adhesion area ratio>
The protein adhesion area ratio was calculated for the obtained image using image processing software "WinROOF2018" (manufactured by Mitani Shoji, software version: 3.10.0). First, images were taken with a laser microscope, imported into the software, subjected to monochrome image processing, and then binarized. The setting of the threshold value for the binarization process was adjusted as appropriate so that the attached proteins were selected. Next, ``filling processing'' was selected from ``processing of shape features'', and the total area ratio was calculated. This total area ratio was defined as the protein adhesion area ratio. The results are shown in Table 1.

<Sliding durability evaluation>
A sliding durability test was conducted on the member sample of Example 5 using a sliding machine (manufactured by Tester Sangyo Co., Ltd.).
A commercially available urethane sponge (Scotch Brite Bath Shine, manufactured by 3M Japan) was soaked in water and a neutral detergent (Bath Magic Clean, Kao) mixed at a weight ratio of 90:10, and the sample was washed under a load of 25 [g/cm2]. The surface was moved back and forth 5,000 times. After washing the sample with running water, it was dried, and the contact angle was measured using the method described above. Sliding durability was judged based on the following criteria.
〇: Contact angle after sliding test is 30 degrees or less ×: Contact angle after sliding test is greater than 30 degrees

As a result, the contact angle of the member sample of Example 5 after the sliding durability test was 7.0 degrees, and the evaluation was 0.

10 Member 1 Base material 2 Surface layer 3 Intermediate layer 4 Primer layer

Claims

A member,
The member includes a base material and a surface layer,
The surface layer includes a structure represented by the following formula (A1) and a structure represented by the following formula (A2),

In formula (A1),
L 1 includes any one of -COO-, -CONH-, -(CH 2 ) m - (m is a natural number),
R 1 is H or CH 3 ;
X 1 is a functional group represented by the following formula (B),

In formula (B),
R 2 and R 5 are each independently a hydrocarbon group represented by -(CH 2 ) l - (l is a natural number from 1 to 10),
R 3 and R 4 are each independently an organic group containing C and H as essential components, O as an optional component, and not containing N and S,
In formula (A2),
L 2 includes any one of -COO-, -CONH-, -(CH 2 ) m - (m is a natural number),
R 1 is H or CH 3 ;
X 2 is a functional group represented by the following formula (C),

In formula (C),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
a is a natural number,
R 6 includes any structure selected from the group consisting of H, CH 3 , C 2 H 5 , the following formula (D1), the following formula (D2), the following formula (D3), and the following formula (D4) ,

In formula (D1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L 3 includes any one of -OCO-, -NHCO-, -(CH 2 ) m - (m is a natural number),
R 1 is H or CH 3 ;
In formula (D2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X 3 is a structure represented by the following formula (E1),

In formula (E1),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L 3 includes any one of -OCO-, -NHCO-, -(CH 2 ) m - (m is a natural number),
R 1 is H or CH 3 ;
a is a natural number,
In formula (D3),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
X 3 is a structure represented by the above formula (E1),
In formula (D4),
X 4 is a structure represented by the following formula (E2),

In formula (E2),
Y is a straight chain, branched or cyclic hydrocarbon group having 1 to 10 carbon atoms,
L 3 includes any one of -OCO-, -NHCO-, -(CH 2 ) m - (m is a natural number),
R 1 is H or CH 3 ;
a is a natural number,
The above-mentioned member is used in an environment where water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries while water and contaminants are mixed on the surface. A member characterized in that it is used.
The member according to claim 1 , wherein in the formula (C), R6 is H, CH3 or C2H5 .
The member according to claim 1 or 2, wherein the static contact angle of water with the surface is 30° or less.
The member according to any one of claims 1 to 3, wherein in the formulas (A1) and (A2), L 1 and L 2 are -COO-.
The member according to any one of claims 1 to 4, wherein the concentration of Si atoms obtained by measuring the surface of the member by X-ray photoelectron spectroscopy (XPS) is 1.0% or less.
The member according to any one of claims 1 to 5, wherein the concentration of S atoms obtained by measuring the surface of the member by X-ray photoelectron spectroscopy (XPS) is 0.5% or more.
Any one of claims 1 to 6, wherein the concentration of N atoms/concentration of S atoms obtained by measuring the surface of the member by X-ray photoelectron spectroscopy (XPS) is 0.5 or more and 2.5 or less. Components listed in section.
The member according to any one of claims 1 to 7, wherein the base material is made of resin, inorganic material, or metal.
A method of using the member according to any one of claims 1 to 8, comprising:
The member is placed in an environment where water and contaminants containing organic and/or inorganic components adhere to the surface, and the water dries in a state where water and contaminants are mixed on the surface, and a cycle is repeated. How to use it, including using it.