JP2020147034A - Active energy ray-curable resin composition for wet area, antifouling laminate for wet area, and method for manufacturing the same, and article for wet area - Google Patents

Abstract

To provide an antifouling laminate for wet area which is excellent in all of water scale removability, sebum dirt removability, oil-based ink removability and chemical resistance.SOLUTION: An antifouling laminate for wet area has a base material for wet area and an antifouling resin layer on the base material for wet area, in which a water falling angle of the antifouling resin layer is less than 40°, surface energy of the antifouling resin layer is 25 mJ/m2 or less, the antifouling resin layer is a cured product of the active energy ray-curable resin composition, and the active energy ray-curable resin composition contains 55-80 mass% of urethane (meth)acrylate (excluding urethane (meth)acrylate having polysiloxane-derived structure) with respect to the total amount of a monomer in the active energy ray-curable resin composition.SELECTED DRAWING: Figure 1

Description

The present invention relates to an antifouling laminate that can be used around water, a method for producing the same, an active energy ray-curable resin composition applicable to the formation of an antifouling resin layer of the antifouling laminate, and an article.

In parts used around water such as bathrooms, washrooms, toilets, and kitchens, oil stains such as tap water, soap, skin oil, and oil-based ink are repeatedly attached and the deposits are dried. Water stains, soap scum, sebum stains, and oil-based ink stick to the surface. Further, if a chemical used around water such as a hair dye adheres to the member, the member will be dyed. These are difficult to remove with normal cleaning and impair appearance and hygiene.

Therefore, in order to prevent dirt from remaining on the surface of the water-related member, a device for imparting antifouling property to the surface of the water-related member has been proposed (see, for example, Patent Documents 1 to 4).
However, these proposed techniques have a problem that it is difficult to achieve both the removability of water stains, the removability of sebum stains, the removability of oil-based inks, and the chemical resistance.

Japanese Unexamined Patent Publication No. 2012-144695 Japanese Patent No. 613022 Japanese Unexamined Patent Publication No. 2016-172923 JP-A-2009-2432333

An object of the present invention is to solve the above-mentioned problems in the past and to achieve the following object. That is, the present invention provides an antifouling laminate for water circulation, which is excellent in removing water stains, removing sebum stains, removing oil-based ink, and chemical resistance, a method for producing the same, and the antifouling property for water circulation. It is an object of the present invention to provide an article for water circulation provided with a laminate, and an active energy ray-curable resin composition for water circulation that can be applied to form an antifouling resin layer of the antifouling laminate for water circulation.

The means for solving the above-mentioned problems are as follows. That is,
<1> A base material for water circulation and an antifouling resin layer on the base material for water circulation.
The water fall angle of the antifouling resin layer is less than 40 °.
The surface energy of the antifouling resin layer is 25 mJ / m ² or less.
The antifouling resin layer is a cured product of the active energy ray-curable resin composition.
The active energy ray-curable resin composition contains urethane (meth) acrylate (excluding urethane (meth) aclate having a structure derived from polysiloxane) in the total amount of the monomers in the active energy ray-curable resin composition. On the other hand, it is an antifouling laminate for water circulation, which is characterized by containing 55% by mass to 80% by mass.
<2> The antifouling laminate for water circulation according to <1>, wherein the antifouling resin layer has a water-repellent molecular structure.
<3> The antifouling laminate for water circulation according to <2>, wherein the water-repellent molecular structure is a perfluoropolyether structure.
<4> The active energy ray-curable resin composition contains a water-repellent monomer having a water-repellent molecular structure in an amount of 0.01% by mass to 5.% by mass based on the total amount of the monomers in the active energy ray-curable resin composition. The antifouling laminate for water circulation according to any one of <1> to <3>, which contains 0% by mass.
<5> The antifouling laminate for water circulation according to <4>, wherein the water-repellent monomer is a (meth) acrylate having a perfluoropolyether structure.
<6> The antifouling laminate for water circulation according to any one of <1> to <5>, wherein the antifouling resin layer has a Martens hardness of 200 N / mm ² or more.
<7> The antifouling laminate for water circulation according to any one of <1> to <6>, wherein the dynamic friction coefficient of the antifouling resin layer is 0.40 or less.
<8> The antifouling laminate for water circulation according to any one of <1> to <7>, which has a primer layer between the base material for water circulation and the antifouling resin layer.
<9> An article for water circulation, which comprises the antifouling laminate for water circulation according to any one of <1> to <8>.
<10> A method for producing an antifouling laminate for water supply according to any one of <1> to <8> above, wherein the antifouling laminate for water supply is produced.
The uncured layer formed from the active energy ray-curable resin composition is irradiated with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume, and includes a step of forming the antifouling resin layer. This is a method for manufacturing an antifouling laminate for water circulation, which is characterized by this.
<11> An active energy ray-curable resin composition for water circulation.
Contains a water-repellent monomer having a water-repellent molecular structure,
Urethane (meth) acrylate (excluding urethane (meth) aclate having a structure derived from polysiloxane) is 55% by mass or more based on the total amount of monomers in the active energy ray-curable resin composition for water circulation. Contains 80% by mass,
The antifouling resin layer when the active energy ray-curable resin composition for water circulation is cured by irradiating the active energy ray-curable resin composition with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume to prepare an antifouling resin layer. This is an active energy ray-curable resin composition for water circulation, characterized in that the water fall angle is less than 40 ° and the surface energy is 25 mJ / mm ² or less.
<12> The active energy ray-curable resin composition for water circulation according to <11>, wherein the water-repellent molecular structure is a perfluoropolyether structure.
<13> The active energy ray-curable resin composition for water circulation according to any one of <11> to <12>, wherein the water-repellent monomer is a (meth) acrylate having a perfluoropolyether structure.
<14> The above <11> to <13> containing the water-repellent monomer in an amount of 0.01% by mass to 5.0% by mass with respect to the total amount of the monomers in the active energy ray-curable resin composition for water circulation. The active energy ray-curable resin composition for water circulation according to any one of the above.

According to the present invention, water which can solve the above-mentioned problems in the past and achieve the above object, and is excellent in all of water stain removability, sebum stain removability, oil-based ink removability, and chemical resistance. Antifouling laminate for water and its manufacturing method, articles provided with the antifouling laminate for water, and active energy for water that can be applied to form an antifouling resin layer of the antifouling laminate for water. A linear curable resin composition can be provided.

FIG. 1 is a schematic cross-sectional view of an example of the antifouling laminate for water circulation of the present invention. FIG. 2 is a schematic cross-sectional view of another example of the antifouling laminate for water circulation of the present invention.

(Anti-fouling laminate for water supply)
The antifouling laminate for water circulation of the present invention has at least a base material for water circulation and an antifouling resin layer, and further has other members such as a primer layer, if necessary.

<Characteristics of antifouling laminate for water supply>
The antifouling laminate for water circulation has the following features.
The water fall angle of the antifouling resin layer is less than 40 °.
The surface energy of the antifouling resin layer is 25 mJ / m ² or less.
The antifouling resin layer is a cured product of an active energy ray-curable resin composition.
The active energy ray-curable resin composition may be referred to as urethane (meth) acrylate (excluding urethane (meth) acrylate having a structure derived from polysiloxane) (hereinafter, referred to as "urethane (meth) acrylate". ) Is contained in an amount of 55% by mass to 80% by mass based on the total amount of the monomers in the active energy ray-curable resin composition.

If the water roll angle of the antifouling resin layer is small, even if tap water hits the surface of the antifouling resin layer, the tap water rolls down, so that the amount of water stains attached can be suppressed.
Further, if the surface energy of the antifouling resin layer is small, even if dirt remains on the surface of the antifouling resin layer, it is difficult to adhere and easy to remove. Therefore, it can be easily removed by cleaning with a cloth or sponge using tap water. In addition, when the water fall angle is small, the adhering oil stains can be removed by a shower, and the cleanability is remarkably excellent.
In addition, the antifouling resin layer is a cured product of an active energy ray-curable resin composition, and the active energy ray-curable resin composition is a urethane (meth) acrylate and the active energy ray-curable product. When it is contained in an amount of 55% by mass to 80% by mass with respect to the total amount of the monomers in the sex resin composition, it has excellent chemical resistance, and for example, it does not dye even if a hair dye adheres to the surface. Further, when the active energy ray-curable resin composition contains urethane (meth) acrylate in an amount of 55% by mass to 80% by mass with respect to the total amount of the monomers in the active energy ray-curable resin composition, scratch resistance is obtained. It tends to increase. If the surface is scratched by repeated wiping, the dye will soak into it and it will not be wiped off, resulting in reduced chemical resistance. In that respect, it is preferable that the scratch resistance is increased.
Therefore, the antifouling laminate for water circulation is excellent in all of the above-mentioned characteristics, such as water stain removal property, sebum stain removal property, oil-based ink removal property, and chemical resistance.

<Base material for water circulation>
The base material for water circulation is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a resin base material and an inorganic base material.
The base material for water circulation is a base material used for water circulation. The water-related equipment in which the water-related base material is used is a device having a water supply function, a drainage function, a water supply / drainage function, and the like, and is required to be maintained in hygiene, for example. Examples include flush toilets, dishwashers, washing machines, kitchen sinks, hand wash basins, wash basins, and bathtubs.

<< Inorganic base material >>
Examples of the inorganic base material include a metal base material, a glass base material, a ceramic base material, and the like.

Examples of the metal of the metal base material include copper, copper alloys, zinc, steel and the like.

The glass base material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silicate glass (silicate glass), soda-lime glass and potash glass.
Further, the glass base material may be tempered glass, laminated glass, heat-resistant glass or the like.
The shape of the glass base material is usually plate-like, but it may be any shape such as sheet-like or curved.

<< Resin base material >>
The material of the resin base material is not particularly limited and may be appropriately selected depending on the intended purpose. For example, acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), polypropylene methacrylate (PMMA), polystyrene. (PS), polypropylene (PP), modified polyphenylene ether (m-PPE), PC / ABS alloy and the like.

The shape of the base material for water circulation is not particularly limited and may be appropriately selected depending on the intended purpose.

The surface of the water-related base material (the surface on the antifouling resin layer side) may have gloss.
Further, the surface of the water-related base material may be provided with a satin pattern, a hairline, a spin, or a diamond cut.
Further, the surface of the water-related base material may be plated. Examples of the plating include nickel plating, chrome plating, tin plating, tin alloy plating, zinc plating, copper plating, gold plating, silver plating and the like. These may be provided in a single layer or may be provided in combination of a plurality of layers.

<Primer layer>
In order to improve the adhesion between the antifouling resin layer and the water-related base material, the primer layer may be provided between the water-related base material and the antifouling resin layer.

If the primer layer is thin, the effect of improving adhesion is insufficient. Therefore, the average thickness of the primer layer is preferably 0.5 μm or more, more preferably 1 μm to 20 μm, further preferably 1 μm to 10 μm, and 2 μm. ~ 5 μm is particularly preferable.
When the average thickness of the primer layer is within the above preferable range, even if it is exposed to high temperature steam (for example, 60 ° C. or higher), thermal shock (for example, a rapid change from -20 ° C. to 80 ° C.), or an alkaline detergent. Adhesion does not easily decrease and the antifouling resin layer can be prevented from peeling off.

The average thickness is determined by the following method.
The thickness of the primer layer is measured at any 10 points with an F20 film thickness measuring system manufactured by Filmmetrics Co., Ltd. The average value is taken as the average film thickness.

The primer layer can be formed, for example, by applying an active energy ray-curable resin composition. That is, the primer layer is, for example, a cured product obtained by curing the active energy ray-curable resin composition with active energy rays. The active energy ray-curable resin composition contains, for example, urethane (meth) acrylate and a photopolymerization initiator, and if necessary, other components such as a solvent. Examples thereof include a sex resin composition.

The urethane (meth) acrylate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate. Among these, aliphatic urethane (meth) acrylate is preferable.
Specific examples of the photopolymerization initiator include, for example, specific examples of the photopolymerization initiator exemplified in the description of the antifouling resin layer described later.
Specific examples of the solvent include, for example, specific examples of the solvent exemplified in the description of the antifouling resin layer described later.

The active energy ray-curable resin composition preferably further contains a trifunctional or higher functional (meth) acrylate. Examples of the trifunctional or higher functional (meth) acrylate include pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, and glycerin ethoxytri (meth) acrylate. , Glycerin propoxytri (meth) acrylate, ethoxytri (meth) acrylate of isocyanurate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) Examples include acrylate.
Here, examples of the alkoxy include ethoxy, propoxy and the like.

The coating method is not particularly limited and may be appropriately selected depending on the intended purpose. For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, and gravure coating. , Microgravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.

<Anti-fouling resin layer>
The water fall angle of the antifouling resin layer is less than 40 °.
The surface energy of the antifouling resin layer is 25 mJ / m ² or less.
The Martens hardness of the antifouling resin layer is preferably 200 N / mm ² or more.
The coefficient of kinetic friction of the antifouling resin layer is preferably 0.40 or less.
The antifouling resin layer is a cured product of an active energy ray-curable resin composition.
The antifouling resin layer preferably has a water-repellent molecular structure. Examples of the water-repellent molecular structure include a perfluoropolyether structure.

<< Water fall angle >>
The water fall angle of the antifouling resin layer is less than 40 °, for example, 5 ° to 30 °, and 10 ° to 25 °. When the water fall angle is 40 ° or more, the removability of sebum stains is lowered.
The water fall angle of the antifouling resin layer is preferably 30 ° or less, more preferably 25 ° or less.

The water fall angle can be measured by, for example, the following method.
The water fall angle is measured under the following conditions using an automatic contact angle meter DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.
Amount of distilled water dropped = 20 μL
Measurement temperature = 25 ° C
Water is dropped on the test piece, and after 5 seconds, the test piece is continuously tilted and the angle at which the water drops start to fall is measured. Measure at any 10 points on the test piece, and use the average value as the water fall angle.

<< Surface energy >>
Surface energy of the antifouling resin layer is 25 mJ / ^{m 2} or less, for ^example, a ^{5mJ / m 2 ~20mJ / m 2} , is ^{10mJ / m 2 ~20mJ / m 2} . When the surface energy exceeds 25 mJ / m ² , the removability of the oil-based ink is lowered.
The surface energy of the antifouling resin layer is preferably 20 mJ / m ² or less.

The surface energy can be measured by, for example, the following method.
The surface energy is calculated by the Kaelble-Uy method by measuring the contact angle between water and hexadecane using an automatic contact angle meter DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.
<<< Water contact angle >>>
The water contact angle is measured under the following conditions.
Amount of distilled water dropped = 2 μL
Measurement temperature = 25 ° C
The contact angle after 5 seconds have passed since the water was dropped was measured at any 10 points on the test piece, and the average value was taken as the water contact angle.
<<< Hexadecane contact angle >>>
The hexadecane contact angle is measured under the following conditions.
Hexadecane dropping amount = 1 μL
Measurement temperature = 25 ° C
The contact angle 20 seconds after dropping hexadecane is measured at any 10 points on the test piece, and the average value is taken as the hexadecane contact angle.

Kaelble-Uy's theoretical formula is a method for quantitatively determining the surface energy γ of a solid.

In the Kaelble-Uy theoretical formula, it is assumed that the surface energy γ is composed of the dispersion component γ ^d and the polar component γ ^p , and the total surface free energy γ is expressed by the following formula (1).
γ = γ ^d + γ ^p ... Equation (1)

Further, when the surface energy of the surface of the liquid is expressed by γ _L , the surface energy of the solid is expressed by γ _S , and the contact angle is expressed by θ, the following equation (2) holds.
γ _L (1 + cosθ) = 2√γ _S ^d γ _L ^d + 2√γ _S ^p γ _L ^p ... Equation (2)

Therefore, the θ respective contact angles were measured using two liquid components of gamma ^L is ^known, γ _{S d,} γ _S is obtained by solving the simultaneous equations for gamma _S ^p.

<< Martens hardness >>
The Martens hardness of the antifouling resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 200 N / mm ² or more, for ^example, it is 200N / mm ² ~300N / mm 2 ..

The Martens hardness of the antifouling resin layer can be measured by, for example, the following method.
The Martens hardness of the antifouling resin layer in the antifouling laminate for water circulation is measured using PICODENTOR HM500 manufactured by Fisher Instruments Co., Ltd. under the following conditions.
Load = 1mN / 20s
Needle = diamond cone with face angle of 136 ° Measure at any 10 points and use the average value as the Martens hardness.

<< Dynamic friction coefficient >>
The dynamic friction coefficient of the antifouling resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.40 or less, for example, 0.10 to 0.40, 0.20 to 0. Examples thereof include 0.35 and 0.25 to 0.30.

The dynamic friction coefficient of the antifouling resin layer can be measured by, for example, the following method.
The measurement is performed using a Tribotter TS501 manufactured by Kyowa Interface Science Co., Ltd. Asahi Kasei Corp. BEMCOT the surface contacts (TM) M-3II paste measured by a double-sided tape load 50 g / cm ^2, measuring speed 1.7 mm / s, measured 12 times as the measured distance 20mm dynamic friction and the average value Let it be a coefficient.

In the antifouling resin layer, when the Martens hardness is 200 N / mm ² or more and the dynamic friction coefficient is 0.40 or less, the antifouling resin layer is not easily damaged. Therefore, even if it is repeatedly cleaned for a long period of time, it is hard to be scratched or traced, and it has high antifouling property and high durability without changing its appearance. As a result, the scratch resistance is excellent and the stains on the hair dye are less likely to adhere.

<< Active energy ray-curable resin composition >>
The antifouling resin layer is a cured product of an active energy ray-curable resin composition.
The active energy ray-curable resin composition contains urethane (meth) acrylate (excluding urethane (meth) aclate having a structure derived from polysiloxane).
The active energy ray-curable resin composition preferably contains a water-repellent monomer having a water-repellent molecular structure, and further contains other monomers, a polymerization initiator, a solvent and the like, if necessary.

<<< Urethane (meth) acrylate >>>
Examples of the urethane (meth) acrylate include aliphatic urethane (meth) acrylate and aromatic urethane (meth) acrylate.
The urethane (meth) acrylate does not have a structure derived from polysiloxane.

The urethane (meth) acrylate refers to a material having a urethane bond and a (meth) acryloyl group in one molecule, and such a material can be used without particular limitation.

The urethane (meth) acrylate is obtained, for example, by reacting a hydroxy compound having at least one (meth) acryloyl group with an isocyanate.
Examples of the isocyanate include polyisocyanate.

The aliphatic urethane (meth) acrylate is obtained, for example, by reacting a hydroxy compound having at least one (meth) acryloyl group with an aliphatic isocyanate. Examples of the aliphatic isocyanate include aliphatic diisocyanates and aliphatic triisocyanates.
The aromatic urethane (meth) acrylate is obtained, for example, by reacting a hydroxy compound having at least one (meth) acryloyl group with an aromatic isocyanate. Examples of the aromatic isocyanate include aromatic diisocyanate and aromatic triisocyanate.

The content of the urethane (meth) acrylate in the active energy ray-curable resin composition is 55% by mass to 80% by mass, 55% by mass, based on the total amount of the monomers in the active energy ray-curable resin composition. It is preferably from% to 70% by mass.

<<< Water-repellent monomer >>>
The water-repellent monomer has a water-repellent molecular structure. Examples of the water-repellent molecular structure in the present invention include a structure having fluorine or silicon, and examples thereof include a fluoroalkyl structure, a perfluoropolyether structure, and a dimethylsiloxane structure. Among these, the perfluoropolyether structure is preferable in that the water rolling angle and the dynamic friction coefficient can be lowered. Among the water-repellent monomers, the water-repellent monomer having the perfluoropolyether structure is preferable in that not only the surface energy can be lowered, but also the water rolling angle and the dynamic friction coefficient can be lowered because the molecular chain is flexible and easy to move.
The urethane (meth) acclate having a structure derived from polysiloxane belongs to the water-repellent monomer among the urethane (meth) acrylate and the water-repellent monomer.

The water-repellent monomer is, for example, (meth) acrylate. That is, the water-repellent monomer is, for example, a (meth) acrylate having a water-repellent molecular structure.

The water-repellent monomer is preferably a (meth) acrylate containing a perfluoropolyether group, and the perfluoropolyether group is-(O-CF ₂ CF ₂ )-,-(O-CF ₂ CF ₂ CF _2). )-Or-(O-CF ₂ C (CF ₃ ) F)-repeated structure is preferred. Examples of commercially available products include DAC-HP manufactured by Daikin Industries, Ltd., Fluorolink AD1700 manufactured by Solvay Specialty Polymers, Fluorolink MD700 manufactured by Solvay Specialty Polymers, CN4000 manufactured by Sartmer, and KY-1203 manufactured by Shin-Etsu Chemical Co., Ltd. ..

The content of the water-repellent monomer in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but the total amount of the monomers in the active energy ray-curable resin composition. On the other hand, 0.001% by mass to 10% by mass is preferable, 0.001% by mass to 5.0% by mass is more preferable, and 0.01% by mass to 5.0% by mass is particularly preferable. If the content is less than 0.001% by mass, the water roll angle and surface energy may not be easily lowered, and the dynamic friction coefficient may not be lowered. The higher the content, the higher the antifouling property and the durability, but it peaks at a certain point and does not need to be contained any more. However, if the content exceeds 5.0% by mass, the antifouling resin layer tends to whiten and the appearance is impaired, or the Martens hardness is out of the preferable range and scratches and traces are formed by repeated cleaning for durability. May be inadequate.

<<< Other Monomers >>>
The other monomer is not particularly limited as long as it is a monomer other than the water-repellent monomer, and can be appropriately selected depending on the intended purpose. It may be a monofunctional monomer or a polyfunctional monomer. May be good.

In addition, examples of the other monomer include trifunctional or higher functional (meth) acrylates. The trifunctional or higher functional (meth) acrylate is a cross-linking agent and can increase the cross-linking density of the cured product. Examples of the trifunctional or higher functional (meth) acrylate include dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethoxytri (meth) acrylate, and glycerin ethoxytri (meth) acrylate. , Glycerin propoxytri (meth) acrylate, ethoxytri (meth) acrylate of isocyanurate, pentaerythritol tetra (meth) acrylate, pentaerythritol alkoxytetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) Examples include acrylate.
Here, examples of the alkoxy include ethoxy, propoxy and the like.

The content of the trifunctional or higher functional (meth) acrylate in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. It is preferably 20% by mass to 45% by mass, more preferably 30% by mass to 40% by mass, based on the total amount of the monomers in the composition. However, the total amount of monomers in the active energy ray-curable resin composition does not exceed 100% by mass.

<<< Photopolymerization Initiator >>>
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, a bisazido compound, hexamethoxymethylmelamine, tetramethoxyglycoyl and the like.
The photoradical polymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include the following compounds.
1-Hydroxy-cyclohexyl-phenyl-ketone ・ 2-Hyrodoxy-1- {4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one ・2,2-Dimethoxy-1,2-diphenylethane-1-one ・ 2-hydroxy-2-methyl-1-phenyl-propane-1-one ・ 1- [4- (2-hydroxyethoxy) -phenyl]- 2-Hydroxy-2-methyl-1-propane-1-one-oxyphenylacetic acid, 2- [2-oxo-2-phenylacetoxyethoxy] ethyl ester and oxyphenylacetic acid, 2- (2-hydroxyethoxy) ethyl Ester mixture ・ 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide ・ 2-Methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one ・ Etanone, 1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime)

The photopolymerization initiator preferably does not contain a nitrogen atom as a constituent element from the viewpoint of preventing yellowing in appearance.
On the other hand, the photopolymerization initiator may contain only C, H, and O as constituent elements, or only C, H, P, and O as constituent elements from the viewpoint of preventing yellowing in appearance. preferable.

The content of the photopolymerization initiator in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1% by mass to 10% by mass. 0.1% by mass to 5% by mass is more preferable, and 1% by mass to 5% by mass is particularly preferable.

<<< Solvent >>>
The solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include organic solvents.
Examples of the organic solvent include aromatic solvents, alcohol solvents, ester solvents, ketone solvents, glycol ether solvents, glycol ether ester solvents, chlorine solvents, ether solvents, N-methylpyrrolidone, and dimethyl. Examples include formamide, dimethylsulfoxide, dimethylacetamide and the like.

As the solvent, a solvent having a boiling point of 80 ° C. or higher is preferable from the viewpoint of obtaining an antifouling resin layer having a better appearance.
Examples of the solvent having a boiling point of 80 ° C. or higher include propylene glycol monomethyl ether and the like.

The content of the solvent in the active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose.

The active energy ray-curable resin composition is cured by being irradiated with active energy rays. The active energy ray is not particularly limited and may be appropriately selected depending on the intended purpose. For example, electron beam, ultraviolet ray, infrared ray, laser beam, visible ray, ionizing radiation (X-ray, α ray, β ray, γ ray). Lines, etc.), microwaves, high frequencies, etc.

<< Average thickness >>
The average thickness of the antifouling resin layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 μm or more, and more preferably 1 μm or more and 15 μm or less.

The average thickness is determined by the following method.
The thickness of the antifouling resin layer is measured at any 10 points with an F20 film thickness measuring system manufactured by Filmometrics Co., Ltd. The average value is taken as the average film thickness.

Here, an example of the antifouling laminate for water circulation will be described.
FIG. 1 is a schematic cross-sectional view of an example of the antifouling laminate for water circulation of the present invention.
The antifouling laminate for water circulation in FIG. 1 has a base material 1 for water circulation and an antifouling resin layer 3.
FIG. 2 is a schematic cross-sectional view of another example of the antifouling laminate for water circulation of the present invention.
The antifouling laminate for water circulation in FIG. 2 has a base material 1 for water circulation, a primer layer 2, and an antifouling resin layer 3.

(Manufacturing method of antifouling laminate for water supply)
The method for producing an antifouling laminate for water circulation of the present invention includes at least an antifouling resin layer forming step, preferably includes a primer layer forming step, and further includes other steps, if necessary.

The method for producing the antifouling laminate for water circulation is a preferred method for producing the antifouling laminate for water circulation of the present invention.

<Primer layer forming process>
The primer layer forming step is not particularly limited as long as it is a step of forming the primer layer, and can be appropriately selected depending on the intended purpose. For example, for forming a primer layer on the water-related base material. Examples thereof include a step of applying an active energy ray-curable resin composition and irradiating with ultraviolet rays to form the primer layer.

<Antifouling resin layer forming process>
In the antifouling resin layer forming step, the oxygen concentration is 1% by volume with respect to the uncured layer formed from the active energy ray-curable resin composition on the water-related base material or the primer layer. The step of forming the antifouling resin layer by irradiating with active energy rays in an atmosphere less than that is not particularly limited, and can be appropriately selected depending on the intended purpose.
When the antifouling resin layer is formed, by irradiating with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume, inhibition of surface hardening is suppressed, resulting in excellent curability, resulting in antifouling property. , Durability is increased.
Examples of the atmosphere having an oxygen concentration of less than 1% by volume include an inert gas atmosphere such as a nitrogen atmosphere.

(Active energy ray-curable resin composition for water circulation)
The active energy ray-curable resin composition for water circulation of the present invention contains at least a water-repellent monomer having a water-repellent molecular structure and urethane (meth) acrylate, and if necessary, other monomers and a polymerization initiator. , Contains other components such as solvents.
The antifouling resin layer when the active energy ray-curable resin composition for water circulation is cured by irradiating with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume to prepare an antifouling resin layer. The water fall angle is less than 40 °, and the surface energy is 25 mJ / mm ² or less.
The active energy ray-curable resin composition for water circulation contains the urethane (meth) acrylate in an amount of 55% by mass to 80% by mass with respect to the total amount of the monomers in the active energy ray-curable resin composition for water circulation. To do.

Details of the water-repellent monomer, the urethane (meth) acrylate, the other monomer, the photopolymerization initiator, and the solvent are described in the description of the antifouling resin layer of the antifouling laminate for water circulation. The details are the same as those of the aqueous monomer, the urethane (meth) acrylate, the other monomer, the photopolymerization initiator, and the solvent, and the preferred embodiments are also the same.

The details of the water fall angle and the preferred embodiment are the same as the details of the water fall angle and the preferred embodiment of the antifouling resin layer of the antifouling laminate for water circulation of the present invention.

The details of the surface energy and the preferred embodiment are the same as the details of the surface energy and the preferred embodiment of the antifouling resin layer of the antifouling laminate for water circulation of the present invention.

(Articles for water supply)
The article for water circulation of the present invention has the antifouling laminate for water circulation of the present invention, and further has other members, if necessary.
The article for water circulation is not particularly limited and may be appropriately selected depending on the intended purpose, but it is preferable that the antifouling laminate for water circulation of the present invention is a water circulation device capable of exerting its effect. .. The water-related equipment includes a water supply function, a drainage function, a water supply / drainage function, and the like, and is required to be maintained in hygiene. For example, a flush toilet, a dishwasher, a washing machine, a kitchen sink, and the like. Examples include hand wash basins, wash basins, and bathtubs.

The antifouling laminate for water circulation may be formed on a part of the article for water circulation, or may be formed on the entire surface.

Examples of the present invention will be described below, but the present invention is not limited to these examples.

<Average thickness>
The film thicknesses of the antifouling resin layer and the primer layer were measured at arbitrary 10 points by the F20 film thickness measuring system manufactured by Filmometrics Co., Ltd. The average value was taken as the average film thickness of each.

<Adhesion>
A cross-cut test was conducted in accordance with JIS K5400. The number remaining without peeling out in 100 squares was counted.
The case where it cannot be peeled off (100 squares out of 100 squares remain) is expressed as "100/100", and the case where all the cells are peeled off (no 1 square out of 100 squares remains) is expressed as "0/100".

<Water fall angle>
The water fall angle was measured under the following conditions using an automatic contact angle meter DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.
Amount of distilled water dropped = 20 μL
Measurement temperature = 25 ° C
Water was dropped on the test piece, and after 5 seconds had passed, the test piece was continuously tilted and the angle at which the water droplets began to fall was measured. The measurement was performed at any 10 points on the test piece, and the average value was taken as the water fall angle.

<Surface energy>
The surface energy was calculated by the Kaelble-Uy method by measuring the contact angle between water and hexadecane using an automatic contact angle meter DM-501 manufactured by Kyowa Surface Chemistry Co., Ltd.
<< Water contact angle >>
The water contact angle was measured under the following conditions.
Amount of distilled water dropped = 2 μL
Measurement temperature = 25 ° C
The contact angle after 5 seconds after dropping water was measured at any 10 points on the test piece, and the average value was taken as the water contact angle.
<< Hexadecane contact angle >>
The hexadecane contact angle was measured under the following conditions.
Hexadecane dropping amount = 1 μL
Measurement temperature = 25 ° C
The contact angle 20 seconds after dropping hexadecane was measured at any 10 points on the test piece, and the average value was taken as the hexadecane contact angle.

<Martens hardness>
The Martens hardness of the test piece was measured using PICODENTOR HM500 manufactured by Fisher Instruments Co., Ltd. under the following conditions.
Load = 1mN / 20s
Needle = diamond cone with face angle of 136 ° Measured at any 10 points, and the average value was taken as the Martens hardness.

<Dynamic friction coefficient>
The measurement was performed using a Tribotter TS501 manufactured by Kyowa Interface Science Co., Ltd. BEMCOT (registered trademark) M-3II manufactured by Asahi Kasei Co., Ltd. is attached to the surface contactor with double-sided tape. Measured load 50 g / cm ² , measurement speed 1.7 mm / s, measurement distance 20 mm, measured 12 times, and the average value is dynamic friction. It was used as a coefficient.

<Removability of scale>
The process of spraying tap water on the test piece and drying it at 50 ° C. was repeated 60 times. After wiping with a clean cloth, it was visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: Water stain could be removed cleanly. There were no scratches.
×: Water stains remained or were scratched.

<Removability of oil-based magic>
Specimens were soiled with Sharpie PROFESSIONAL (black oil-based magic, trade name, manufactured by Newell Rubbermaid). This was wiped dry with tissue paper (manufactured by Daio Paper Corporation, Eliere) 10 times in a circular motion, and then visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: The magic ink was well repelled and the stain was removed by wiping it 2 to 5 times.
Δ: Weakly repels Magic ink. The dirt was removed by wiping 6 to 10 times.
X: Dirt remained even after wiping 10 times without repelling Magic ink.

<Removability of sebum>
The sebum was pressed against the leaning test piece with a finger. After tapping tap water with a dropper, it was visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: The sebum was gone.
X: Sebum remained.

<Scratch resistance>
The test piece was rubbed with a melamine sponge (Lec Co., Ltd. Drama Ochi-kun) under a load of 300 gf / 4 cm ² for 500 reciprocations, and then visually observed and evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◯: No change.
×: I have been hurt.

<Hair dye resistance>
The test piece was rubbed with a melamine sponge (Lec Co., Ltd. Drama Ochi-kun) under a load of 300 gf / 4 cm ² for 500 reciprocations, and then Hoyu Co., Ltd. Men's Bigen Speedy IIS was applied and left for 24 hours. After washing with water, it was wiped with a clean cloth and visually observed for evaluation according to the following evaluation criteria.
〔Evaluation criteria〕
◯: No change.
×: The color has been dyed.

(Example 1)
<Base material for water circulation>
As the base material for water circulation, a PS plate with grain (thickness = 3 mm) (base material No. A) used for the bathroom door surface material was used.

<Formation of antifouling resin layer>
The active energy ray-curable resin composition having the following composition was applied onto a substrate for water circulation so that the average thickness after drying and curing was 2 μm. After application, it was dried in an oven at 80 ° C. for 2 minutes. An antifouling laminate was obtained by irradiating ultraviolet rays at an irradiation amount of 500 mJ / cm ² in a nitrogen atmosphere using a metal halide lamp to cure the antifouling resin layer.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.13 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-1.

(Comparative Example 1)
The textured PS plate (thickness = 3 mm) (base material No. A) of the bathroom door surface material used in Example 1 was evaluated without forming an antifouling resin layer. The results are shown in Table 1-1.

(Example 2)
<Base material for water circulation>
A nickel-chrome-plated ABS plate (thickness = 3 mm) (base material No. B) used for washing metal fittings was used as the base material for water circulation.

<Formation of primer layer>
In order to improve the adhesion of the antifouling resin layer, a primer layer was provided between the water-related base material and the antifouling resin layer. Specifically, the primer layer was provided by the following method.
The active energy ray-curable resin composition having the following composition was applied onto a substrate for water circulation so that the average thickness after drying and curing was 2 μm. After application, it was dried in an oven at 80 ° C. for 2 minutes. A primer layer was formed by irradiating ultraviolet rays with an irradiation amount of 500 mJ / cm ² in an air atmosphere using a metal halide lamp.

-Active energy ray-curable resin composition-
・ UT5181 (manufactured by Nippon Synthetic Co., Ltd.) 65 parts by mass ・ A-TMM-3L (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacure 184 (manufactured by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

<Formation of antifouling resin layer>
The active energy ray-curable resin composition having the following composition was applied onto the primer layer so that the average thickness after drying and curing was 2 μm. After application, it was dried in an oven at 80 ° C. for 2 minutes. An antifouling laminate was obtained by irradiating ultraviolet rays at an irradiation amount of 500 mJ / cm ² in a nitrogen atmosphere using a metal halide lamp to cure the antifouling resin layer.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.13 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacure 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-1.

(Comparative Example 2)
The nickel-chrome-plated ABS plate (thickness = 3 mm) (base material No. B) of the water-washing metal fitting used in Example 2 was evaluated without forming a primer layer and an antifouling resin layer. The results are shown in Table 1-1.

(Example 3)
An antifouling laminate was obtained in the same manner as in Example 1 except that the base material for water circulation was replaced with an ABS plate (thickness = 3 mm) (base material No. C) used for the toilet seat member in Example 1. ..
The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-1.

(Comparative Example 3)
A PP plate (thickness = 3 mm) (base material No. D) to which water-repellent particles used for the toilet seat member were added was evaluated. The results are shown in Table 1-1.

(Comparative Example 4)
The glass (thickness = 5 mm) coated with DLC (diamond-like carbon) used in the bathroom was evaluated (base material No. E). The results are shown in Table 1-1.

(Example 4)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.5 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Example 5)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 1.5 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Example 6)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.05 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Example 7)
In the formation of the antifouling resin layer of Example 1, the same as in Example 1 except that the active energy ray-curable resin composition having the following composition was used and applied so that the average thickness after drying and curing was 10 μm. Then, an antifouling laminate was obtained.

-Active energy ray-curable resin composition-
・ Optool DAC-HP (manufactured by Daikin Industries, Ltd.) 0.01 parts by mass ・ KRM8200 (manufactured by Daisel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Example 8)
An antifouling laminate was obtained in the same manner as in Example 7 except that the average thickness of the antifouling resin layer was changed to 5 μm in Example 7.
The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Example 9)
In Example 1, the antifouling laminate was carried out in the same manner as in Example 1 except that the active energy curable resin composition for forming the antifouling resin layer was changed to the following active energy ray curable resin composition. I got a body.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.13 parts by mass ・ KRM8200 (manufactured by Daicel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-2.

(Comparative Example 5)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KRM8200 (manufactured by Daicel Ornex Co., Ltd.) 65 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 35 parts by mass ・ Irgacure 184 (manufactured by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Comparative Example 6)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that ultraviolet rays were irradiated in an air atmosphere.
The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Example 10)
In the formation of the antifouling resin layer of Example 3, an antifouling laminate was obtained in the same manner as in Example 3 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.10 parts by mass ・ KRM8200 (manufactured by Daicel Ornex Co., Ltd.) 55 parts by mass ・ A-DPHA (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 45 parts by mass ・ Irgacare 184 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) Made by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Example 11)
In the formation of the antifouling resin layer of Example 3, an antifouling laminate was obtained in the same manner as in Example 3 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.20 parts by mass ・ MU9500 (manufactured by Miwon Specialty Chemical Co., Ltd.)
80 parts by mass ・ EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 20 parts by mass ・ Irgacare 184 (manufactured by BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Example 12)
In the formation of the antifouling resin layer of Example 3, an antifouling laminate was obtained in the same manner as in Example 3 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shinetsu Chemical Industry Co., Ltd.) 0.10 parts by mass ・ CN975 (manufactured by Sartmer Co., Ltd.) 70 parts by mass ・ A-TMM-3 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 30 parts by mass ・ Irgacure 184 (BASF) 3 parts by mass ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Comparative Example 7)
In the formation of the antifouling resin layer of Example 2, an antifouling laminate was obtained in the same manner as in Example 2 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.10 parts by mass ・ EBECRYL 40 (manufactured by Daicel Ornex Co., Ltd.) 20 parts by mass ・ SR9035 (manufactured by Sartmer) 80 parts by mass ・ Irgacure 184 (manufactured by BASF) 3 Parts by mass-Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

(Comparative Example 8)
In the formation of the antifouling resin layer of Example 1, an antifouling laminate was obtained in the same manner as in Example 1 except that the active energy ray-curable resin composition having the following composition was used.

-Active energy ray-curable resin composition-
・ KY-1203 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.10 parts by mass ・ KRM8200 (manufactured by Daicel Ornex Co., Ltd.) 20 parts by mass ・ SR9035 (manufactured by Sartmer) 80 parts by mass ・ Irgacure 184 (manufactured by BASF) 3 masses Parts ・ Propylene glycol monomethyl ether 200 parts by mass

The prepared antifouling laminate was subjected to the above-mentioned evaluation. The results are shown in Table 1-3.

In Tables 1-1 to 1-3, the water-repellent monomer content (% by mass) is the water-repellent monomer content based on the total amount of the monomers in the active energy ray-curable resin composition in the active energy ray-curable resin composition. The content (% by mass). The urethane (meth) acrylate content (% by mass) is the content (% by mass) of the urethane (meth) acrylate in the active energy ray-curable resin composition with respect to the total amount of the monomers in the active energy ray-curable resin composition. is there.

The details of the base material for water circulation are as follows.
・ Base material for water circulation No. A: PS plate with grain used for bathroom door surface material (thickness = 3 mm)
・ Base material for water circulation No. B: Nickel chrome plated ABS plate used for flush fittings (thickness = 3 mm)
・ Base material for water circulation No. C: ABS plate used for toilet seat member (thickness = 3 mm)
・ Base material for water circulation No. D: PP plate (thickness = 3 mm) to which water-repellent particles used for the toilet seat member are added.
・ Base material for water circulation No. E: DLC (diamond-like carbon) coated glass used in the bathroom (thickness = 5 mm)

Details of the materials shown in Tables 1-1 to 1-3 are as follows.

<Antifouling resin layer material>
-Optur DAC-HP: Daikin Industries, Ltd., (meth) acrylic group-containing perfluoropolyether (PFPE)
KY-1203: (Meta) acrylic group-containing perfluoropolyether (PFPE) manufactured by Shin-Etsu Chemical Co., Ltd.
・ KRM8200: Daicel Ornex Co., Ltd., aliphatic urethane acrylate ・ MU9500: Miwon Specialty Chemical Co., Ltd., aliphatic urethane acrylate ・ CN975: Sartmer Co., Ltd., aromatic urethane acrylate ・ A-DPHA: Shin-Nakamura Chemical Industry Co., Ltd. , Dipentaerythritol hexaacrylate ・ EBECRYL 40: Daicel Ornex Co., Ltd., tetrafunctional acrylate monomer ・ A-TMM-3: Shin-Nakamura Chemical Industry Co., Ltd., trifunctional acrylate monomer ・ SR9035: Sartmer, ethoxylated tri Methylol propantri (meth) acrylate ・ Irgacure 184: BASF, photoinitiator, 1-hydroxy-cyclohexyl-phenyl-ketone ・ PGME: propylene glycol monomethyl ether

<Primer layer material>
-UT5181: Urethane acrylate manufactured by Nippon Synthetic Co., Ltd.-A-TMM-3L: Pentaerythritol triacrylate (triester approx. 55%) manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
-Irgacure 184: BASF, photoinitiator, 1-hydroxy-cyclohexyl-phenyl-ketone-PGME: propylene glycol monomethyl ether

The antifouling laminates of Examples 1 to 12 were excellent in all of water stain removing property, sebum stain removing property, oil-based ink removing property, and chemical resistance (hair dye resistance). Furthermore, it was also excellent in scratch resistance.
Compared with Example 8, in Examples 1 to 7 and 9 to 12, the water roll angle and surface energy of the antifouling resin layer were smaller, the water fall angle was 30 ° or less, and the surface energy was 20 mJ / m ² or less. Therefore, the removability of the oil-based ink was more excellent.

On the other hand, Comparative Examples 1 and 3 were inferior in all of the removability of water stains, the removability of sebum stains, the removability of oil-based inks, the scratch resistance, and the chemical resistance (hair dye resistance).
In Comparative Example 2, although it was excellent in scratch resistance and chemical resistance (hair dye resistance), it was inferior in water stain removal property, sebum stain removal property, and oil-based ink removal property.
In Comparative Examples 4 and 5, although the water stain removal property, the scratch resistance, and the chemical resistance (hair dye resistance) were excellent, the sebum stain removal property and the oil-based ink removal property were inferior.
In Comparative Example 6, although it was excellent in water stain removal property, sebum stain removal property, scratch resistance, and chemical resistance (hair dye resistance), the oil-based ink removal property was inferior.
In Comparative Examples 7 and 8, although they were excellent in water stain removal property, sebum stain removal property, oil-based ink removal property, and scratch resistance, they were inferior in chemical resistance (hair dye resistance).

The antifouling laminate for water around the present invention is a water wash basin and toilet seat member (toilet seat, toilet lid, nozzle, nozzle cover) which are water around (washroom, bathroom, kitchen, toilet, kitchen, food factory, etc.) equipment. , Dishwasher, washing machine, kitchen sink, kitchen hood parts, work table, hand wash basin, wash basin, bath body, bath apron, window material, partition, wall material, floor material, faucet fitting, curan, shower head , Showers, hoses, racks, holders, handrails, window sashes, door sashes, drainage fittings, drainage ports, mirrors, etc.

1 Base material for water circulation 2 Primer layer 3 Antifouling resin layer

Claims (14)

It has a base material for water circulation and an antifouling resin layer on the base material for water circulation.
The water fall angle of the antifouling resin layer is less than 40 °.
The surface energy of the antifouling resin layer is 25 mJ / m ² or less.
The antifouling resin layer is a cured product of the active energy ray-curable resin composition.
The active energy ray-curable resin composition contains urethane (meth) acrylate (excluding urethane (meth) aclate having a structure derived from polysiloxane) in the total amount of the monomers in the active energy ray-curable resin composition. On the other hand, an antifouling laminate for water circulation, which is characterized by containing 55% by mass to 80% by mass. The antifouling laminate for water circulation according to claim 1, wherein the antifouling resin layer has a water-repellent molecular structure. The antifouling laminate for water circulation according to claim 2, wherein the water-repellent molecular structure is a perfluoropolyether structure. The active energy ray-curable resin composition contains a water-repellent monomer having a water-repellent molecular structure in an amount of 0.01% by mass to 5.0% by mass based on the total amount of the monomers in the active energy ray-curable resin composition. The antifouling laminate for water circulation according to any one of claims 1 to 3 contained. The antifouling laminate for water circulation according to claim 4, wherein the water-repellent monomer is a (meth) acrylate having a perfluoropolyether structure. The antifouling laminate for water circulation according to any one of claims 1 to 5, wherein the maltensity hardness of the antifouling resin layer is 200 N / mm ² or more. The antifouling laminate for water circulation according to any one of claims 1 to 6, wherein the dynamic friction coefficient of the antifouling resin layer is 0.40 or less. The antifouling laminate for water circulation according to any one of claims 1 to 7, which has a primer layer between the base material for water circulation and the antifouling resin layer. An article for water circulation, which comprises the antifouling laminate for water circulation according to any one of claims 1 to 8. A method for producing an antifouling laminate for water supply according to any one of claims 1 to 8, wherein the antifouling laminate for water supply is produced.
The uncured layer formed from the active energy ray-curable resin composition is irradiated with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume, and includes a step of forming the antifouling resin layer. A method for manufacturing an antifouling laminate for water circulation, which is characterized by this. An active energy ray-curable resin composition for water circulation.
Contains a water-repellent monomer having a water-repellent molecular structure,
Urethane (meth) acrylate (excluding urethane (meth) aclate having a structure derived from polysiloxane) is 55% by mass or more based on the total amount of monomers in the active energy ray-curable resin composition for water circulation. Contains 80% by mass,
The antifouling resin layer when the active energy ray-curable resin composition for water circulation is cured by irradiating the active energy ray-curable resin composition with active energy rays in an atmosphere having an oxygen concentration of less than 1% by volume to prepare an antifouling resin layer. An active energy ray-curable resin composition for water circulation, wherein the water roll angle is less than 40 ° and the surface energy is 25 mJ / mm ² or less. The active energy ray-curable resin composition for water circulation according to claim 11, wherein the water-repellent molecular structure is a perfluoropolyether structure. The active energy ray-curable resin composition for water circulation according to any one of claims 11 to 12, wherein the water-repellent monomer is a (meth) acrylate having a perfluoropolyether structure. The method according to any one of claims 11 to 13, wherein the water-repellent monomer is contained in an amount of 0.01% by mass to 5.0% by mass with respect to the total amount of the monomers in the active energy ray-curable resin composition for water circulation. Active energy ray-curable resin composition for water circulation.