JP6393479B2 - Hydrophilic laminate, method for producing the same, article, and method for producing the same - Google Patents

Description

  The present invention uses hydrophilic laminates that have hydrophilicity and can be used in a wide range of architectural uses, industrial uses, automobile uses, optical uses, solar battery panels, and the like, and methods for producing the same, and the hydrophilic laminates described above. The present invention relates to an article and a manufacturing method thereof.

In order to decorate and protect the surface of various articles, a resin film, glass, or the like is attached to the surface.
However, the visibility and aesthetics of the article may deteriorate due to fogging of the resin film, glass, etc. that decorates and protects the surface of the article.
Therefore, in order to prevent the visibility and aesthetics of such articles from deteriorating, the resin film and glass are subjected to an antifogging treatment.

As an anti-fogging technique, for example, a technique in which water droplets are not formed by a water-absorbing layer formed by combining various crosslinking agents with a hydrophilic resin such as a hydrophilic acrylic resin, polyvinyl alcohol, or polyalkyleneimine is known. .
However, in the case of this technology, the thickness of the water absorption layer is about 3 μm to 60 μm, so there is a limit to the amount of moisture to be absorbed. If water droplets adhere one after another, the water cannot be absorbed into the water absorption layer and reaches the moisture absorption saturation point. Then, there is a problem that water droplets are formed on the surface and become cloudy. In addition, the amount of water that can be absorbed decreases at low temperatures, making it more likely to be cloudy. (Specific examples of “at low temperatures” are used on the inner surface of ski goggles and on the surfaces of glass windows that are in contact with refrigerators or freezers. If you want, etc.) there is a problem. In addition, excessive absorption of water may cause deformation (rippling, drooping, pulling, etc.), water droplet contamination (water droplets may be caused by dissolution when water droplets are formed), and stickiness. There is a problem. Further, since it absorbs moisture and swells, it has a problem that mechanical strength is reduced (it is easily damaged by abrasion or scratching) and chemical resistance is reduced.

In view of this, a technique has been proposed in which the surface layer is provided with a concavo-convex structure so that the surface can be easily wetted and the antifogging property is improved (see, for example, Patent Document 1). A technique for providing a concavo-convex structure on the surface has been conventionally performed in order to provide an antireflection function for light. In the concavo-convex structure, since it becomes difficult to remove the dirt when the surface becomes dirty, the technique for improving the hydrophilicity of the surface layer for the purpose of improving the antifouling property and the like, as in the technique proposed above. Have been proposed (see, for example, Patent Documents 2 to 9).
However, these proposed techniques do not take into account a decrease in antifogging property over time, and there is a problem that the antifogging property is reduced due to deterioration of the concavo-convex structure due to physical contact over time.

  Therefore, in a hydrophilic laminate having a concavo-convex structure, a hydrophilic laminate excellent in antifogging properties and excellent in anti-fogging stability over time, a method for producing the same, and an article using the hydrophilic laminate, In addition, there is a demand for providing a manufacturing method thereof.

JP 2009-271298 A Japanese Patent No. 4687718 Japanese Patent No. 479659 JP 2007-187868 A JP 2008-158293 A Japanese Patent Application Laid-Open No. 2011-169961 JP2012-242525A Japanese Patent No. 5260790 JP 2013-182007 A

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention relates to a hydrophilic laminate having a concavo-convex structure, an excellent antifogging property and an antifogging property with respect to time stability, a method for producing the same, and the hydrophilic laminate. It is an object of the present invention to provide an article used and a manufacturing method thereof.

Means for solving the problems are as follows. That is,
<1> Having a base material and a hydrophilic layer on the base material,
The hydrophilic layer has either a fine convex part or a concave part on the surface,
The pure water contact angle on the surface of the hydrophilic layer is 50 ° or less,
Either of the average height of the said convex part and the average depth of the said recessed part is 100 nm or less, It is a hydrophilic laminated body characterized by the above-mentioned.
<2> The hydrophilic laminate according to <1>, wherein the elongation percentage is 40% or more.
<3> The hydrophilic laminate according to any one of <1> to <2>, wherein an average surface area ratio of the hydrophilic layer is 1.10 or more.
<4> The hydrophilic laminate according to any one of <1> to <3>, wherein either the average height of the protrusions or the average depth of the recesses is 60 nm or less.
<5> The hydrophilic laminate according to any one of <1> to <4>, wherein the substrate is any one of a resin substrate and a glass substrate.
<6> The method for producing a hydrophilic laminate according to any one of <1> to <5>,
An uncured resin layer forming step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a substrate;
Adhering a transfer master having either a fine convex part or a concave to the uncured resin layer, irradiating the uncured resin layer to which the transfer master is in contact with an active energy ray to cure the uncured resin layer And a hydrophilic layer forming step of forming a hydrophilic layer by transferring one of the fine convex portions and concave portions.
<7> The hydrophilicity according to <6>, wherein any one of the fine convex portion and the concave portion of the transfer master is formed by etching the surface of the transfer master using a photoresist having a predetermined pattern shape as a protective film. Is a method for producing a conductive laminate.
<8> The hydrophilic laminate according to <6>, wherein any one of the fine convex portion and the concave portion of the transfer master is formed by irradiating the surface of the transfer master with laser processing of the transfer master. It is a manufacturing method of a body.
<9> An article having the hydrophilic laminate according to any one of <1> to <5> on a surface thereof.
<10> The method for producing an article according to <9>,
A heating step for heating the hydrophilic laminate,
A hydrophilic laminate forming step of forming the heated hydrophilic laminate into a desired shape;
An injection molding step of injecting a molding material onto the substrate side of the hydrophilic laminate formed into a desired shape, and molding the molding material.
<11> The method for manufacturing an article according to <10>, wherein the heating in the heating step is performed by infrared heating.

  According to the present invention, the conventional problems can be solved and the object can be achieved. In the hydrophilic laminate having a concavo-convex structure, the antifogging property is excellent and the antifogging property is stable over time. An excellent hydrophilic laminate, a method for producing the same, an article using the hydrophilic laminate, and a method for producing the same can be provided.

FIG. 1A is an atomic force microscope (AFM) image showing an example of the surface of a hydrophilic layer having convex portions. 1B is a cross-sectional view taken along the line aa in FIG. 1A. FIG. 2A is an AFM image showing an example of the surface of a hydrophilic layer having a recess. 2B is a cross-sectional view taken along line aa in FIG. 2A. FIG. 3A is a perspective view illustrating an example of a configuration of a roll master that is a transfer master. 3B is an enlarged plan view showing a part of the roll master shown in FIG. 3A. 3C is a cross-sectional view of the track T in FIG. 3B. FIG. 4 is a schematic diagram showing an example of the configuration of a roll master exposure apparatus for producing a roll master. FIG. 5A is a process diagram for explaining an example of a process for producing a roll master. FIG. 5B is a process diagram for explaining an example of a process for producing a roll master. FIG. 5C is a process diagram for explaining an example of a process for producing a roll master. FIG. 5D is a process diagram for explaining an example of a process for producing a roll master. FIG. 5E is a process diagram for explaining an example of a process for producing a roll master. FIG. 6A is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions by a roll master. FIG. 6B is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a roll master. FIG. 6C is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a roll master. FIG. 7A is a plan view illustrating an example of a configuration of a plate-shaped master that is a transfer master. FIG. 7B is a cross-sectional view taken along the line aa shown in FIG. 7A. FIG. 7C is an enlarged cross-sectional view of a part of FIG. 7B. FIG. 8 is a schematic diagram showing an example of the configuration of a laser processing apparatus for producing a plate-shaped master. FIG. 9A is a process diagram for explaining an example of a process for producing a plate-shaped master. FIG. 9B is a process diagram for explaining an example of a process for producing a plate-shaped master. FIG. 9C is a process diagram for explaining an example of a process for producing a plate-shaped master. FIG. 10A is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions with a plate-shaped master. FIG. 10B is a process diagram for explaining an example of a process of transferring fine convex portions or concave portions by a plate-shaped master. FIG. 10C is a process diagram for explaining an example of a process of transferring a fine convex portion or a concave portion with a plate-shaped master. FIG. 11A is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding. FIG. 11B is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding. FIG. 11C is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding. FIG. 11D is a process diagram for explaining an example of producing the article of the present invention by in-mold molding. FIG. 11E is a process diagram for explaining an example of producing the article of the present invention by in-mold molding. FIG. 11F is a process diagram for explaining an example of manufacturing the article of the present invention by in-mold molding. 12A is an AFM image of the surface of the hydrophilic resin layer of the hydrophilic laminate of Example 1. FIG. 12B is a cross-sectional view taken along line aa in FIG. 12A. 13A is an AFM image of the surface of the hydrophilic resin layer of the hydrophilic laminate of Example 2. FIG. 13B is a cross-sectional view taken along the line aa in FIG. 13A. 14A is an AFM image of the surface of the hydrophilic resin layer of the hydrophilic laminate of Example 3. FIG. 14B is a cross-sectional view taken along line aa in FIG. 14A. FIG. 15A is an AFM image of the surface of the hydrophilic resin layer of the hydrophilic laminate of Comparative Example 1. 15B is a cross-sectional view taken along line aa in FIG. 15A.

(Hydrophilic laminate)
The hydrophilic laminated body of this invention has a base material and a hydrophilic layer at least, and also has another member as needed.

<Base material>
There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, a resin-made base material, an inorganic base material, etc. are mentioned. Examples of the inorganic substrate include a glass substrate, a quartz substrate, and a sapphire substrate.

  There is no restriction | limiting in particular as a material of the said resin-made base materials, According to the objective, it can select suitably, For example, a triacetyl cellulose (TAC), polyester (TPEE), a polyethylene terephthalate (PET), a polyethylene naphthalate ( PEN), polyimide (PI), polyamide (PA), aramid, polyethylene (PE), polyacrylate, polyether sulfone, polysulfone, polypropylene (PP), polystyrene, diacetyl cellulose, polyvinyl chloride, acrylic resin (PMMA), Polycarbonate (PC), epoxy resin, urea resin, urethane resin, melamine resin, phenol resin, acrylonitrile-butadiene-styrene copolymer, cycloolefin polymer (COP), cycloolefin copolymer (CO ), PC / PMMA laminate, such as rubber additives PMMA and the like.

  The base material preferably has transparency.

There is no restriction | limiting in particular as a shape of the said base material, According to the objective, it can select suitably, For example, film shape, plate shape, block shape etc. are mentioned.
When the substrate is in the form of a film, the average thickness of the substrate is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of productivity, 5 μm to 1,000 μm is preferable, and 5 μm. ˜500 μm is more preferable, and 50 μm to 500 μm is particularly preferable.

  Characters, patterns, images, etc. may be printed on the surface of the substrate.

  The base material may have a curved surface.

  On the surface of the base material, in order to increase the adhesion between the base material and the molding material at the time of molding the hydrophilic laminate, or from the flow pressure of the molding material at the time of molding processing, the letters, the pattern, and In order to protect the image, a binder layer may be provided. As the material of the binder layer, various adhesives can be used in addition to various binders such as acrylic, urethane, polyester, polyamide, ethylene butyl alcohol, and ethylene vinyl acetate copolymer systems. Two or more binder layers may be provided. As the binder to be used, one having heat sensitivity and pressure sensitivity suitable for the molding material can be selected.

<Hydrophilic layer>
The hydrophilic layer has either a fine convex part or a concave part on the surface.
The pure water contact angle on the surface of the hydrophilic layer is 50 ° or less.
The hydrophilic layer is formed on the substrate.
One of the average height of the convex part and the average depth of the concave part is 100 nm or less.

  The hydrophilic layer is preferably a resinous hydrophilic layer (hereinafter sometimes referred to as “hydrophilic resin layer”) from the viewpoint of excellent molding processability.

  There is no restriction | limiting in particular as a material of the said hydrophilic layer, According to the objective, it can select suitably, For example, an organic material, an inorganic material, an organic-inorganic hybrid material etc. are mentioned. Examples of the organic material include a thermoplastic resin, a cured product of a thermosetting resin, a cured product of an active energy ray curable resin composition, and the like. Examples of the inorganic material include metals and metalloid oxides (silica, titania, zirconia, alumina, etc.). Examples of the organic-inorganic hybrid material include a mixture of particles made of the inorganic material and the organic material, and a hydrolysis / polycondensation product of a metal alkoxide and / or a semimetal alkoxide.

-Fine convex portions and fine concave portions-
The hydrophilic layer has either a fine convex part or a concave part on its surface.
Either the fine convex part or the concave part is formed on the surface opposite to the substrate side in the hydrophilic layer.

Here, the fine convex portion means that the average distance between adjacent convex portions on the surface of the hydrophilic layer is 1,000 nm or less.
Here, the fine recess means that the average distance between adjacent recesses on the surface of the hydrophilic layer is 1,000 nm or less.

  The shape of the convex portion and the concave portion is not particularly limited and can be appropriately selected depending on the purpose. For example, a cone shape, a column shape, a needle shape, or a partial shape of a sphere (for example, a hemisphere) Shape), a partial shape of an ellipsoid (for example, a semi-ellipsoidal shape), and a polygonal shape. These shapes need not be mathematically defined complete shapes, and may have some distortion.

  The convex portion or the concave portion is two-dimensionally arranged on the surface of the hydrophilic layer. The arrangement may be a regular arrangement or a random arrangement. The regular arrangement is preferably a close-packed structure from the viewpoint of the filling rate.

There is no restriction | limiting in particular as an average distance of the said adjacent convex part, Although it can select suitably according to the objective, 5 nm-1,000 nm are preferable, 10 nm-500 nm are more preferable, 50 nm-300 nm are especially preferable.
There is no restriction | limiting in particular as an average distance of the said adjacent recessed part, Although it can select suitably according to the objective, 5 nm-1,000 nm are preferable, 10 nm-500 nm are more preferable, 50 nm-300 nm are especially preferable.
When the average distance between the adjacent convex portions and the average distance between the adjacent concave portions are within the preferable range, the hydrophilic component attached to the hydrophilic layer effectively wets and spreads. When the average distance is within the particularly preferable range, the effect of spreading the hydrophilic component becomes remarkable.

The average height of the convex portions is 100 nm or less, preferably 80 nm or less, and more preferably 60 nm or less. There is no restriction | limiting in particular as a lower limit of the average height of the said convex part, Although it can select suitably according to the objective, 30 nm is preferable.
The average depth of the recess is 100 nm or less, preferably 80 nm or less, and more preferably 60 nm or less. There is no restriction | limiting in particular as a lower limit of the average depth of the said recessed part, Although it can select suitably according to the objective, 30 nm is preferable.
When the average height of the convex portions and the average depth of the concave portions exceed 100 nm or less, the abrasion resistance is insufficient, and the hydrophilic laminate has insufficient antifogging stability over time.

As the average aspect ratio of the convex part (average height of the convex part / average distance of the adjacent convex part) and the average aspect ratio of the concave part (average depth of the concave part / average distance of the adjacent concave part) There is no particular limitation, and it can be appropriately selected according to the purpose. However, 0.001 to 1,000 is preferable, 0.10 to 10 is more preferable, 0.10 to 1.0 is still more preferable, and 0.0. 20 to 0.50 is particularly preferable.
When the average aspect ratio of the convex portions and the average aspect ratio of the concave portions are within the preferable range, the hydrophilic component attached to the hydrophilic layer effectively wets and spreads. When the aspect ratio is in the particularly preferable range, the effect of spreading the hydrophilic component becomes remarkable.

Here, the average distance (Pm) of the convex part or the concave part, and the average height of the convex part or the average depth (Hm) of the concave part can be measured as follows.
First, the surface S of the hydrophilic layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM), and the pitch of the convex portion or the concave portion, the height of the convex portion or Find the depth of the recess. This is repeated at 10 locations randomly selected from the surface of the hydrophilic layer, and the pitches P1, P2,..., P10 and the heights or depths H1, H2,. Ask.
Here, the pitch of the convex portions is a distance between the vertices of the convex portions. The pitch of the recesses is the distance between the deepest portions of the recesses. The height of the convex portion is the height of the convex portion based on the lowest point of the valley between the convex portions. The depth of the recess is the depth of the recess based on the highest point of the peak between the recesses.
Next, these pitches P1, P2,..., P10 and the heights or depths H1, H2,..., H10 are simply averaged (arithmetic average), and the average distance between the convex portions or the concave portions is calculated. (Pm) and the average height of the convex portions or the average depth (Hm) of the concave portions are obtained.
In addition, when the pitch of the said convex part or a recessed part has in-plane anisotropy, the said Pm shall be calculated | required using the pitch of the direction where a pitch becomes the maximum. Further, when the height of the convex portion or the depth of the concave portion has in-plane anisotropy, the height or depth in the direction in which the height or depth is maximum is used. Is to be sought.
Moreover, when the said convex part or a recessed part is rod-shaped, the pitch of a short-axis direction is measured as said pitch.
In the AFM observation, the cross-sectional profile is a measurement target so that the convex vertex or concave base of the cross-sectional profile matches the vertex of the solid convex portion or the deepest portion of the concave portion. It cuts out so that it may become a cross section which passes through the top of a convex part of a solid shape, or the deepest part of a concave part of a solid shape.

Here, whether the fine shape formed on the surface of the hydrophilic layer is a convex portion or a concave portion can be determined as follows.
The surface S of the hydrophilic layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM) to obtain a cross section and an AFM image of the surface S.
When the AFM image of the surface is a bright image on the outermost surface side and a dark image on the deep side, when the bright image is formed in an island shape in the dark image, the surface has a convex portion. Shall.
On the other hand, when a dark image is formed in an island shape in a bright image, the surface thereof has a recess.
For example, the surface of the hydrophilic layer having the AFM image of the surface and cross section shown in FIGS. 1A and 1B has a convex portion. The surface of the hydrophilic layer having the AFM image of the surface and cross section shown in FIGS. 2A and 2B has a recess.

The average surface area ratio of the surface of the hydrophilic layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1.10 or more, more preferably 1.20 or more, and 1.30 or more. Particularly preferred. The surface area ratio is a ratio (surface area / area) between the surface area generated by the surface shape of the object in a specified area and the area of the specified area. When the average surface area ratio is less than 1.10, the hydrophilic component attached to the hydrophilic layer is insufficiently wetted and the antifogging property may be difficult to obtain. When the average surface area ratio is within the preferable range, the hydrophilic component attached to the hydrophilic layer is effectively spread by wetting. When the average surface area ratio is within the particularly preferable range, the effect of spreading the hydrophilic component becomes remarkable.
Here, the average surface area ratio of the surface of the hydrophilic layer can be measured as follows.
The surface S of the hydrophilic layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM) to obtain an AFM image of the surface S. This is repeated at 10 locations randomly selected from the surface of the hydrophilic layer to determine the surface areas S1, S2,. Next, the ratio (surface area / area) SR1, SR2,..., SR10 of these surface areas S1, S2,..., S10 and the area of each observation region is simply averaged (arithmetic average). The average surface area ratio SRm of the surface of the hydrophilic layer is obtained.

−Pure water contact angle−
The pure water contact angle on the surface of the hydrophilic layer is 50 ° or less, preferably 40 ° or less, and more preferably 10 ° or less. There is no restriction | limiting in particular as a lower limit of the said pure water contact angle, According to the objective, it can select suitably, For example, 2 degrees etc. are mentioned.
The pure water contact angle can be measured by, for example, a sliding method under the following conditions using PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.).
-Put distilled water in a plastic syringe, attach a stainless steel needle to the tip, and drop it onto the evaluation surface. After dropping, the contact angle after 5 seconds is measured at any 10 locations on the evaluation surface, and the average value is defined as the pure water contact angle.
・ Drip amount of water: 2μL
・ Measurement temperature: 25 ℃

The method for obtaining the pure water contact angle is not particularly limited and may be appropriately selected depending on the purpose. For example, when the hydrophilic layer is made of a smooth film, the pure water contact angle is 70 °. For example, the following materials may be used. When the material of the hydrophilic layer is a smooth film, when the contact angle of pure water exceeds 70 °, water tends to be unable to penetrate to the bottom of the concavo-convex structure. As a result, air is trapped, and the pure water contact angle on the surface of the hydrophilic layer is higher than the pure water contact angle value of the smooth film, so that the antifogging property may not be obtained.
The pure water contact angle of the smooth film is obtained by, for example, applying the material forming the hydrophilic layer dissolved in a solvent on a resin base material such as polyethylene terephthalate with a coil bar, an applicator, etc., and removing the solvent by drying. Thus, a smooth film can be obtained, and the pure water contact angle can be determined by measuring the pure water contact angle by the method described above. When the hydrophilic layer is obtained through a curing process, the same curing process is performed when the smooth film is obtained.

-Active energy ray-curable resin composition-
The active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it contains at least a hydrophilic monomer and a photopolymerization initiator, and further if necessary. And active energy ray-curable resin compositions containing other components.

--Hydrophilic monomer--
Examples of the hydrophilic monomer include polyoxyalkyl-containing (meth) acrylate, quaternary ammonium salt-containing (meth) acrylate, tertiary amino group-containing (meth) acrylate, sulfonic acid group-containing monomer, carboxylic acid group-containing monomer, Examples thereof include phosphoric acid group-containing monomers and phosphonic acid group-containing monomers.
Here, in the present invention, (meth) acrylate means acrylate or methacrylate. The same applies to (meth) acryloyl and (meth) acryl.

The polyoxyalkyl-containing (meth) acrylate is obtained, for example, by a reaction between a polyhydric alcohol (polyol or polyhydroxy-containing compound) and a compound selected from the group consisting of acrylic acid, methacrylic acid and derivatives thereof. Mono or polyacrylate, mono or polymethacrylate, etc. may be mentioned. Examples of the polyhydric alcohol include divalent alcohol, trivalent alcohol, and tetravalent or higher alcohol. Examples of the divalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a number average molecular weight of 300 to 1,000, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2,2′-thiodiethanol, 1,4-cyclohexanedi For example, methanol. Examples of the trivalent alcohol include trimethylolethane, trimethylolpropane, pentaglycerol, glycerol, 1,2,4-butanetriol, 1,2,6-hexanetriol, and the like. Examples of the tetravalent or higher alcohol include pentaerythritol, diglycerol, and dipentaerythritol.
Examples of the polyoxyalkyl-containing (meth) acrylate include polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate. Examples of the polyethylene glycol (meth) acrylate include methoxypolyethylene glycol (meth) acrylate. There is no restriction | limiting in particular as the molecular weight of the polyethyleneglycol unit in the said polyethyleneglycol (meth) acrylate, According to the objective, it can select suitably, For example, 300-1,000 etc. are mentioned. A commercial item can be used as said methoxypolyethyleneglycol (meth) acrylate. As said commercial item, MEPM-1000 (made by Daiichi Kogyo Seiyaku Co., Ltd.) etc. are mentioned, for example.
Among these, polyethylene glycol (meth) acrylate is preferable, and methoxypolyethylene glycol (meth) acrylate is more preferable.

  Examples of the quaternary ammonium salt-containing (meth) acrylate include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethyldimethylglycidylammonium chloride, (meth) Acryloyloxyethyltrimethylammonium methylsulfate, (meth) acryloyloxydimethylethylammonium ethylsulfate, (meth) acryloyloxyethyltrimethylammonium-p-toluenesulfonate, (meth) acrylamidopropyltrimethylammonium chloride, (meth) acrylamidopropyldimethyl Benzyl ammonium chloride, (meth) acrylamide pro Le dimethyl glycidyl chloride, (meth) acrylamide trimethyl ammonium methyl sulfate, (meth) acrylamide dimethyl ethyl ammonium ethylsulfate, and (meth) acrylamide trimethylammonium -p- toluenesulfonate.

  Examples of the tertiary amino group-containing (meth) acrylate include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, Examples include 2,6,6-pentamethylpiperidyl (meth) acrylate and 2,2,6,6-tetramethylpiperidyl (meth) acrylate.

  Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, styrene sulfonic acid, and sulfonic acid group-containing (meth) acrylate. Examples of the sulfonic acid group-containing (meth) acrylate include, for example, sulfoethyl (meth) acrylate, sulfopropyl (meth) acrylate, 2-acrylamido-2-methylpropanesulfonic acid, and terminal sulfonic acid-modified polyethylene glycol mono (meth). Examples include chlorate. These may form a salt. Examples of the salt include sodium salt, potassium salt, ammonium salt and the like.

  Examples of the carboxylic acid group-containing monomer include acrylic acid and methacrylic acid.

  Examples of the phosphate group-containing monomer include (meth) acrylate having a phosphate ester.

  The hydrophilic monomer is preferably a monofunctional hydrophilic monomer.

  There is no restriction | limiting in particular as molecular weight of the said hydrophilic monomer, Although it can select suitably according to the objective, 200 or more are preferable.

  There is no restriction | limiting in particular as content of the said hydrophilic monomer in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 15 mass%-99.9 mass% are preferable, 20 The mass% is more preferably 90% by mass, and particularly preferably 25% by mass to 50% by mass.

  Instead of the hydrophilic monomer, a photosensitive group containing at least one selected from an azide group, phenyl azide group, quinone azide group, stilbene group, chalcone group, diazonium base, cinnamic acid group, acrylic acid group and the like was introduced. A polymer may be used. Examples of the polymer include polyvinyl alcohol, polyvinyl butyral, polyvinyl pyrrolidone, polyacrylamide, polyvinyl acetate, polyoxyalkylene, and the like.

-Photopolymerization initiator-
Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photoacid generator, a bisazide compound, hexamethoxymethylmelamine, and tetramethoxyglycolyl.
The radical photopolymerization initiator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethoxyphenyl (2,4,6-trimethylbenzoyl) phosphine oxide and bis (2,6-dimethylbenzoyl). ) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,6-dichlorobenzoyl) -2 , 4,4-trimethylpentylphosphine oxide, 1-phenyl 2-hydroxy-2methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane -1-one, 1,2-diphenylethanedione, methylphenylglycone Kishireto and the like.

  There is no restriction | limiting in particular as content of the said photoinitiator in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 0.1 mass%-10 mass% are preferable, 0.5 mass%-8 mass% are more preferable, and 1 mass%-5 mass% are especially preferable.

-Other ingredients-
There is no restriction | limiting in particular as said other component, According to the objective, it can select suitably, For example, urethane (meth) acrylate, isocyanuric acid group containing (meth) acrylate, a filler, etc. are mentioned.
These may be used to adjust the elongation, hardness, etc. of the hydrophilic layer (the hydrophilic resin layer).

  There is no restriction | limiting in particular as said urethane (meth) acrylate, According to the objective, it can select suitably, For example, aliphatic urethane (meth) acrylate, aromatic urethane (meth) acrylate, etc. are mentioned. Among these, aliphatic urethane (meth) acrylate is preferable.

There is no restriction | limiting in particular as content of the said urethane (meth) acrylate in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 10 mass%-45 mass% are preferable, 15 More preferred is 40% by weight, and especially preferred is 20% to 35% by weight.
There is no restriction | limiting in particular as said isocyanuric acid group containing (meth) acrylate, According to the objective, it can select suitably, For example, ethoxylated isocyanuric acid (meth) acrylate etc. are mentioned. Among these, ethoxylated isocyanuric acid (meth) acrylate is preferable.

  There is no restriction | limiting in particular as content of the said isocyanuric acid group containing (meth) acrylate in the said active energy ray curable resin composition, Although it can select suitably according to the objective, 10 mass%-45 mass% are Preferably, 15 mass%-40 mass% are more preferable, and 20 mass%-35 mass% are especially preferable.

  The filler is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include silica, zirconia, titania, tin oxide, indium tin oxide, antimony-doped tin oxide, and antimony pentoxide. Examples of the silica include solid silica and hollow silica.

  The active energy ray-curable resin composition can be diluted with an organic solvent when used. 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, dimethyl sulfoxide, dimethylacetamide, and the like.

  The active energy ray-curable resin composition is cured when irradiated with active energy rays. There is no restriction | limiting in particular as said active energy ray, According to the objective, it can select suitably, For example, an electron beam, an ultraviolet-ray, infrared rays, a laser beam, visible light, ionizing radiation (X ray, alpha ray, beta ray, gamma) Wire, etc.), microwave, high frequency and the like.

The Martens hardness of the hydrophilic layer is not particularly limited and may be appropriately selected depending on the intended ^purpose, but is preferably ^{50N / mm 2 ~300N / mm 2} , 50N / mm 2 ~290N / mm 2 Gayori 50 N / mm ^{2 to} 280 N / mm ² is particularly preferable. When the hydrophilic laminate is molded, for example, during injection molding of polycarbonate, the hydrophilic laminate is heated and pressurized at 290 ° C. and 200 MPa. At this time, either the fine convex part or the concave part on the surface of the hydrophilic layer may be deformed. Examples of the deformation include a decrease in the height of the fine convex portion and a decrease in the depth of the fine concave portion. Although it may be deformed as long as it does not affect the antifogging performance, if it is deformed too much, the contact angle of pure water is increased and the antifogging performance is deteriorated. When the Martens hardness is less than 50 N / mm ² , when forming the hydrophilic laminate, any one of the fine convex portions and concave portions on the surface of the hydrophilic layer is deformed excessively, and pure water The contact angle is increased and anti-fogging performance is deteriorated, and the hydrophilic layer is scratched by surface cleaning during normal use, such as handling and surface cleaning when manufacturing or molding the hydrophilic laminate. When it exceeds 300 N / mm ² , cracks may be generated in the hydrophilic layer or the hydrophilic layer may be peeled off during punching, bending or molding. When the Martens hardness is within the particularly preferable range, the hydrophilic laminate is variously three-dimensional without deteriorating antifogging performance and without causing defects such as scratches, cracks, and peeling. This is advantageous in that it can be easily formed into a shape.
In addition, after molding the hydrophilic laminate, high temperature and high pressure are applied to the hydrophilic layer in an injection molding process, so that the Martens hardness of the hydrophilic layer may be higher than before the molding process.
Moreover, when compared by the average height of the same convex part (or average depth of a recessed part), it exists in the tendency for abrasion resistance to be excellent, so that the Martens hardness of the said hydrophilic layer is high.
The Martens hardness can be measured by using, for example, PICODETOR HM500 (trade name; manufactured by Fisher Instruments). The load is 1 mN / 20 s, a diamond cone is used as the needle, and the surface angle is 136 °.

There is no restriction | limiting in particular as pencil hardness of the said hydrophilic layer, Although it can select suitably according to the objective, B-4H is preferable, HB-4H is more preferable, F-4H is especially preferable. If the pencil hardness is less than B (softer than B), the hydrophilic layer is scratched by surface cleaning during normal use, such as handling and surface cleaning when manufacturing or molding the hydrophilic laminate. Is easy to enter. In addition, when forming the hydrophilic laminate, either the fine convex portion or the concave portion on the surface of the hydrophilic layer is deformed excessively, resulting in a high pure water contact angle and deterioration of the anti-fogging performance. There is. When the pencil hardness exceeds 4H (harder than 4H), cracks may occur in the hydrophilic layer or the hydrophilic layer may peel off during molding. When the pencil hardness is within the particularly preferable range, the hydrophilic laminate is variously three-dimensional without deteriorating antifogging performance and without causing defects such as scratches, cracks, and peeling. This is advantageous in that it can be easily formed into a shape.
In addition, since high temperature and high pressure are applied to the hydrophilic layer in the injection molding process after molding the hydrophilic laminate, the pencil hardness of the hydrophilic layer may be higher than before the molding process.
The pencil hardness is measured according to JIS K 5600-5-4.

  There is no restriction | limiting in particular as average thickness of the said hydrophilic layer, Although it can select suitably according to the objective, 0.01 micrometer-100 micrometers are preferable, 0.05 micrometer-50 micrometers are more preferable, 0.1 micrometer-30 micrometers are Particularly preferred.

<Other members>
Examples of the other members include an anchor layer.

-Anchor layer-
The anchor layer is a layer provided between the base material and the hydrophilic layer.
By providing the anchor layer, the adhesion between the substrate and the hydrophilic layer can be improved.
The anchor layer preferably has a refractive index close to that of the hydrophilic layer in order to prevent interference unevenness. Therefore, the refractive index of the anchor layer is preferably within ± 0.10 of the refractive index of the hydrophilic layer, and more preferably within ± 0.05. Or it is preferable that the refractive index of the said anchor layer is between the refractive index of the said hydrophilic layer and the refractive index of the said base material.

  The anchor layer can be formed, for example, by applying an active energy ray curable resin composition. As the active energy ray-curable resin composition, for example, an active energy ray-curable resin composition containing at least urethane (meth) acrylate and a photopolymerization initiator, and further containing other components as necessary. Such as things. Examples of the urethane (meth) acrylate and the photopolymerization initiator include the urethane (meth) acrylate and the photopolymerization initiator exemplified in the description of the hydrophilic layer. There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.

  There is no restriction | limiting in particular as average thickness of the said anchor layer, Although it can select suitably according to the objective, 0.01 micrometer-10 micrometers are preferable, 0.1 micrometer-5 micrometers are more preferable, 0.3 micrometer-3 micrometers are especially preferable.

  Note that the anchor layer may be provided with a function of reducing reflectance or preventing static electricity.

There is no restriction | limiting in particular as elongation rate of the said hydrophilic laminated body, Although it can select suitably according to the objective, 10% or more is preferable, 40% or more is preferable, 40%-200% are more preferable, 40 % To 150% is particularly preferred. If the elongation is less than 10%, molding may be difficult. When the elongation percentage is within the particularly preferable range, it is advantageous in that the moldability is excellent.
The said elongation rate can be calculated | required with the following method, for example.
The hydrophilic laminate is formed into a strip having a length of 10.5 cm and a width of 2.5 cm, and used as a measurement sample. The tensile elongation of the obtained measurement sample is measured with a tensile tester (Autograph AG-5kNXplus, manufactured by Shimadzu Corporation) (measurement condition: tensile speed = 100 mm / min; distance between chucks = 8 cm). In the measurement of the elongation percentage, the measurement temperature varies depending on the type of the base material, and the elongation percentage is measured at a temperature near or above the softening point of the base material. Specifically, it is between 10 ° C and 250 ° C. For example, when the substrate is a polycarbonate or PC / PMMA laminate, it is preferable to measure at 190 ° C.

  When applying the said hydrophilic laminated body to insert molding, overlay molding, etc., it is preferable to use the said resin-made base material for the said base material, and the elongation rate of the said hydrophilic laminated body is 10% or more. Examples of the overlay molding include a TOM method (Three-dimension over-lay method).

  The hydrophilic laminate preferably has a smaller difference in heat shrinkage between the X direction and the Y direction in the plane of the hydrophilic laminate. The X direction and the Y direction of the hydrophilic laminate correspond to, for example, the longitudinal direction and the width direction of the roll when the hydrophilic laminate is in a roll shape. The difference between the heat shrinkage rate in the X direction and the heat shrinkage rate in the Y direction in the hydrophilic laminate is preferably within 5% at the heating temperature used in the heating step during molding. If it is out of this range, the hydrophilic layer may be peeled or cracked during the molding process, or the characters, the pattern, the image, etc. printed on the surface of the substrate may be deformed or misaligned. Molding may be difficult.

  The hydrophilic laminate is particularly suitable for in-mold molding films, insert molding films, and overlay molding films.

  There is no restriction | limiting in particular as a manufacturing method of the said hydrophilic laminated body, Although it can select suitably according to the objective, The manufacturing method of the hydrophilic laminated body of this invention mentioned later is preferable.

(Method for producing hydrophilic laminate)
The manufacturing method of the hydrophilic laminated body of this invention contains an uncured resin layer formation process and a hydrophilic layer formation process at least, and also includes another process as needed.
The method for producing the hydrophilic laminate is a method for producing the hydrophilic laminate of the present invention.

<Uncured resin layer forming step>
The uncured resin layer forming step is not particularly limited as long as it is a step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a substrate, and is appropriately selected according to the purpose. be able to.

There is no restriction | limiting in particular as said base material, According to the objective, it can select suitably, For example, the said base material etc. which were illustrated in description of the said hydrophilic laminated body of this invention are mentioned.
The active energy ray-curable resin composition is not particularly limited and may be appropriately selected depending on the purpose. For example, the activity exemplified in the description of the hydrophilic layer of the hydrophilic laminate of the present invention. Examples include an energy ray curable resin composition.

  The uncured resin layer is formed by applying the active energy ray-curable resin composition on the substrate and drying it as necessary. The uncured resin layer may be a solid film or a film having fluidity due to a low molecular weight curable component contained in the active energy ray curable resin composition.

  There is no restriction | limiting in particular as said application | coating method, According to the objective, it can select suitably, For example, wire bar coating, blade coating, spin coating, reverse roll coating, die coating, spray coating, roll coating, gravure coating , Micro gravure coating, lip coating, air knife coating, curtain coating, comma coating method, dipping method and the like.

  The uncured resin layer is not cured because it is not irradiated with active energy rays.

In the uncured resin layer forming step, the uncured resin layer may be formed by applying the active energy ray-curable resin composition onto the anchor layer of the base material on which the anchor layer is formed.
There is no restriction | limiting in particular as said anchor layer, According to the objective, it can select suitably, For example, the said anchor layer etc. which were illustrated in description of the said hydrophilic laminated body of this invention are mentioned.

<Hydrophilic layer forming step>
In the hydrophilic layer forming step, the uncured resin layer is brought into close contact with a transfer master having either a fine convex portion or a recess, and the uncured resin layer to which the transfer master is in close contact is irradiated with active energy rays. There is no particular limitation as long as the hydrophilic layer is formed by curing the uncured resin layer and transferring one of the fine convex portions and concave portions, and can be appropriately selected according to the purpose. .

-Transcription master-
The transfer master has either a fine convex part or a concave part.
There is no restriction | limiting in particular as a material of the said transfer original disc, a magnitude | size, and a structure, According to the objective, it can select suitably.
There is no particular limitation on the method for forming any of the fine convex portions and concave portions of the transfer master, and it can be selected as appropriate according to the purpose. However, the transfer using a photoresist having a predetermined pattern shape as a protective film is possible. It is preferably formed by etching the surface of the master. Further, it is preferable to form the transfer master by irradiating the surface of the transfer master with a laser.

-Active energy rays-
The active energy ray is not particularly limited as long as it is an active energy ray that cures the uncured resin layer, and can be appropriately selected according to the purpose. For example, the description of the hydrophilic laminate of the present invention. And the active energy rays exemplified in 1.

  Here, a specific example of the hydrophilic layer forming step will be described with reference to the drawings.

[First Embodiment]
In the first embodiment, the hydrophilic layer is formed by using a transfer master in which either a fine convex portion or a concave portion is formed by etching the surface of the transfer master using a photoresist having a predetermined pattern shape as a protective film. It is an example of a formation process.

  First, the transfer master and its manufacturing method will be described.

[Configuration of the transfer master]
FIG. 3A is a perspective view illustrating an example of a configuration of a roll master that is a transfer master. 3B is an enlarged plan view showing a part of the roll master shown in FIG. 3A. 3C is a cross-sectional view of the track T in FIG. 3B. The roll master 231 is a transfer master for producing a hydrophilic laminate having the above-described configuration, more specifically, a master for forming a plurality of convex portions or concave portions on the surface of the hydrophilic tree layer. . The roll master 231 has, for example, a columnar or cylindrical shape, and the columnar surface or cylindrical surface is a molding surface for molding a plurality of convex portions or concave portions on the surface of the hydrophilic layer. For example, a plurality of structures 232 are two-dimensionally arranged on the molding surface. In FIG. 3C, the structure 232 has a concave shape with respect to the molding surface. As a material of the roll master 231, for example, glass can be used, but it is not particularly limited to this material.

  The plurality of structures 232 disposed on the molding surface of the roll master 231 and the plurality of protrusions or recesses disposed on the surface of the hydrophilic layer are in an inverted uneven relationship. That is, the arrangement, size, shape, arrangement pitch, height or depth, aspect ratio, and the like of the structures 232 of the roll master 231 are the same as the convex portions or concave portions of the hydrophilic layer.

[Roll master exposure equipment]
FIG. 4 is a schematic diagram showing an example of the configuration of a roll master exposure apparatus for producing a roll master. This roll master exposure apparatus is configured based on an optical disk recording apparatus.

  The laser light source 241 is a light source for exposing the resist deposited on the surface of the roll master 231 as a recording medium, and oscillates a recording laser beam 234 having a wavelength λ = 266 nm, for example. The laser light 234 emitted from the laser light source 241 travels straight as a parallel beam and enters an electro-optic element (EOM: Electro Optical Modulator) 242. The laser beam 234 that has passed through the electro-optical element 242 is reflected by the mirror 243 and guided to the modulation optical system 245.

  The mirror 243 is composed of a polarization beam splitter and has a function of reflecting one polarization component and transmitting the other polarization component. The polarization component transmitted through the mirror 243 is received by the photodiode 244, and the electro-optic element 242 is controlled based on the received light signal to perform phase modulation of the laser beam 234.

In the modulation optical system 245, the laser beam 234 is collected by an acousto-optic modulator (AOM) 247 made of glass (SiO ₂ ) or the like by a condenser lens 246. The laser beam 234 is intensity-modulated by the acousto-optic element 247 and diverges, and then converted into a parallel beam by the lens 248. The laser beam 234 emitted from the modulation optical system 245 is reflected by the mirror 251 and guided horizontally and parallel on the moving optical table 252.

  The moving optical table 252 includes a beam expander 253 and an objective lens 254. The laser beam 234 guided to the moving optical table 252 is shaped into a desired beam shape by the beam expander 253 and then irradiated to the resist layer on the roll master 231 through the objective lens 254. The roll master 231 is placed on a turntable 256 connected to a spindle motor 255. Then, while rotating the roll master 231 and moving the laser beam 234 in the height direction of the roll master 231, the laser light 234 is intermittently applied to the resist layer formed on the peripheral side surface of the roll master 231. Then, a resist layer exposure step is performed. The formed latent image has a substantially elliptical shape having a major axis in the circumferential direction. The laser beam 234 is moved by moving the moving optical table 252 in the arrow R direction.

  The exposure apparatus includes a control mechanism 257 for forming a latent image corresponding to the two-dimensional pattern of the plurality of convex portions or concave portions described above on the resist layer. The control mechanism 257 includes a formatter 249 and a driver 250. The formatter 249 includes a polarity reversal unit, and this polarity reversal unit controls the irradiation timing of the laser beam 234 on the resist layer. The driver 250 receives the output from the polarity inversion unit and controls the acoustooptic device 247.

  In this roll master exposure apparatus, the polarity inversion formatter signal and the rotation controller are synchronized for each track so that the two-dimensional pattern is spatially linked, and the intensity is modulated by the acousto-optic element 247. A two-dimensional pattern such as a hexagonal lattice pattern can be recorded by patterning with a constant angular velocity (CAV) and an appropriate rotational speed, an appropriate modulation frequency, and an appropriate feed pitch.

[Resist film formation process]
First, as shown in the cross-sectional view of FIG. 5A, a columnar or cylindrical roll master 231 is prepared. The roll master 231 is, for example, a glass master. Next, as shown in the cross-sectional view of FIG. 5B, a resist layer (for example, a photoresist) 233 is formed on the surface of the roll master 231. Examples of the material for the resist layer 233 include organic resists and inorganic resists. Examples of the organic resist include novolak resist and chemically amplified resist. Examples of the inorganic resist include metal compounds.

[Exposure process]
Next, as shown in the cross-sectional view of FIG. 5C, the resist layer 233 formed on the surface of the roll master 231 is irradiated with laser light (exposure beam) 234. Specifically, the roll master 231 is placed on the turntable 256 of the roll master exposure apparatus shown in FIG. 4, the roll master 231 is rotated, and the resist layer 233 is irradiated with a laser beam (exposure beam) 234. . At this time, the laser beam 234 is intermittently irradiated while moving the laser beam 234 in the height direction of the roll master 231 (a direction parallel to the central axis of the columnar or cylindrical roll master 231). Layer 233 is exposed over the entire surface. Thereby, a latent image 235 corresponding to the locus of the laser beam 234 is formed over the entire surface of the resist layer 233.

  For example, the latent image 235 is arranged to form a plurality of rows of tracks T on the surface of the roll master, and is formed with a regular periodic pattern of a predetermined unit cell Uc. The latent image 235 has, for example, a circular shape or an elliptical shape. When the latent image 235 has an elliptical shape, the elliptical shape preferably has a major axis direction in the extending direction of the track T.

[Development process]
Next, for example, while rotating the roll master 231, a developing solution is dropped on the resist layer 233 to develop the resist layer 233. As a result, a plurality of openings are formed in the resist layer 233 as shown in the cross-sectional view of FIG. 5D. When the resist layer 233 is formed of a positive type resist, the exposed portion exposed with the laser beam 234 has a higher dissolution rate in the developer than the non-exposed portion, and as shown in the sectional view of FIG. 5D. A pattern corresponding to the latent image (exposed portion) 235 is formed on the resist layer 233. The pattern of the opening is, for example, a regular periodic pattern of a predetermined unit cell Uc.

[Etching process]
Next, the surface of the roll master 231 is etched using the pattern (resist pattern) of the resist layer 233 formed on the roll master 231 as a mask. Thereby, as shown to sectional drawing of FIG. 5E, the structure (recessed part) 232 which has a cone shape can be obtained. The cone shape is preferably, for example, an elliptical cone shape or an elliptical truncated cone shape having a major axis direction in the extending direction of the track T. As the etching, for example, dry etching or wet etching can be used. At this time, by alternately performing the etching process and the ashing process, for example, a pattern of the cone-shaped structure 232 can be formed. Thus, the intended roll master 231 is obtained.

[Transfer processing]
A base material 211 on which an uncured resin layer 236 as shown in the sectional view of FIG. 6A is formed is prepared.
Next, as shown in the cross-sectional view of FIG. 6B, the roll master 231 and the uncured resin layer 236 formed on the base material 211 are brought into close contact with each other, and the active energy ray 237 is irradiated to the uncured resin layer 236. The cured resin layer 236 is cured to transfer any of the fine convex portions and concave portions, thereby obtaining the hydrophilic layer 212 in which any one of the fine convex portions and concave portions 212a is formed.
Finally, the obtained hydrophilic layer 212 is peeled from the roll master 231 to obtain a hydrophilic laminate (FIG. 6C).
In addition, when the base material 211 is comprised with the material which does not permeate | transmit active energy rays, such as an ultraviolet-ray, the roll original recording 231 is comprised with the material (for example, quartz) which can permeate | transmit active energy rays, You may make it irradiate an active energy ray with respect to the uncured resin layer 236 from the inside. The transfer master is not limited to the roll master 231 described above, and a flat master may be used. However, from the viewpoint of improving mass productivity, it is preferable to use the roll master 231 described above as the transfer master.

[Second Embodiment]
In the second embodiment, the hydrophilic layer forming step is performed using a transfer master in which either a fine convex portion or a concave portion is formed by irradiating the surface of the transfer master with a laser to laser-process the transfer master. It is an example.

  First, the transfer master and its manufacturing method will be described.

[Configuration of the transfer master]
FIG. 7A is a plan view showing an example of the configuration of a plate-shaped master. FIG. 7B is a cross-sectional view taken along the line aa shown in FIG. 7A. FIG. 7C is an enlarged cross-sectional view of a part of FIG. 7B. The plate-shaped master 331 is a master for producing a hydrophilic laminate having the above-described configuration, more specifically, a master for forming a plurality of convex portions or concave portions on the surface of the hydrophilic layer. . The plate-shaped master 331 has, for example, a surface provided with a fine concavo-convex structure, and the surface is a molding surface for molding a plurality of convex portions or concave portions on the surface of the hydrophilic layer. For example, a plurality of structures 332 are provided on the molding surface. The structure 332 illustrated in FIG. 7C has a concave shape with respect to the molding surface. As a material of the plate-shaped master 331, for example, a metal material can be used. As the metal material, for example, Ni, NiP, Cr, Cu, Al, Fe, and alloys thereof can be used. The alloy is preferably stainless steel (SUS). Examples of the stainless steel (SUS) include, but are not limited to, SUS304, SUS420J2, and the like.

  The plurality of structures 332 provided on the molding surface of the plate-shaped master 331 and the plurality of protrusions or recesses provided on the surface of the hydrophilic layer have an inverted uneven relationship. That is, the arrangement, size, shape, arrangement pitch, height, depth, and the like of the structures 332 of the plate-like master 331 are the same as the convex portions or concave portions of the hydrophilic layer.

[Configuration of laser processing equipment]
FIG. 8 is a schematic diagram showing an example of the configuration of a laser processing apparatus for producing a plate-shaped master. The laser body 340 is, for example, IFRIT (trade name) manufactured by Cyber Laser Corporation. The wavelength of the laser used for laser processing is, for example, 800 nm. However, the wavelength of the laser used for laser processing may be 400 nm or 266 nm. The repetition frequency is preferably larger in consideration of the processing time and the narrow pitch of the concave portions or convex portions to be formed, and is preferably 1,000 Hz or more. The laser pulse width is preferably shorter, and is preferably about 200 femtoseconds ( ^10-15 seconds) to 1 picosecond ( ^10-12 seconds).

  The laser body 340 emits laser light linearly polarized in the vertical direction. Therefore, in this apparatus, linear polarization or circular polarization in a desired direction is obtained by rotating the polarization direction using a wave plate 341 (for example, a λ / 2 wave plate). Further, in this apparatus, a part of the laser light is extracted using an aperture 342 having a square opening. This is because the intensity distribution of the laser beam is a Gaussian distribution, so that only the center vicinity is used to obtain a laser beam having a uniform in-plane intensity distribution. Further, in this apparatus, the laser beam is focused using two orthogonal cylindrical lenses 343 so that a desired beam size is obtained. When processing the plate-shaped master 331, the linear stage 344 is moved at a constant speed.

  The beam spot of the laser irradiated on the plate-shaped master 331 is preferably rectangular. The beam spot can be shaped by using, for example, an aperture or a cylindrical lens. Further, the intensity distribution of the beam spot is preferably as uniform as possible. This is because it is preferable to make the in-plane distribution such as the depth of the unevenness formed in the mold as uniform as possible. In general, since the size of the beam spot is smaller than the area to be processed, it is necessary to give an uneven shape to all the areas to be processed by scanning the beam.

The master (form) used for forming the surface of the hydrophilic layer is, for example, a substrate of a metal such as SUS, NiP, Cu, Al, Fe or the like with a pulse width of 1 picosecond ( ^10-12 seconds) or less. It is formed by drawing a pattern using an ultrashort pulse laser, so-called femtosecond laser. The polarization of the laser light may be linearly polarized light, circularly polarized light, or elliptically polarized light. At this time, a pattern having desired irregularities can be formed by appropriately setting the laser wavelength, repetition frequency, pulse width, beam spot shape, polarization, laser intensity applied to the sample, laser scanning speed, and the like.

The parameters that can be changed to obtain the desired shape include the following. The fluence is an energy density (J / cm ² ) per pulse, and is obtained by the following equation.
F = P / (fREPT × S)
S = Lx × Ly
F: fluence P: laser power fREPT: laser repetition frequency S: area at the laser irradiation position Lx × Ly: beam size Note that the number of pulses N is the number of pulses irradiated at one place, and It is calculated by the formula.
N = fREPT × Ly / v
Ly: Beam size in laser scanning direction v: Laser scanning speed

  Further, the material of the plate-shaped master 331 may be changed in order to obtain a desired shape. The shape of laser processing varies depending on the material of the plate-shaped master 331. In addition to using metals such as SUS, NiP, Cu, Al, and Fe, the surface of the master may be coated with a semiconductor material such as DLC (diamond-like carbon). Examples of the method for coating the surface of the master with the semiconductor material include plasma CVD and sputtering. As the semiconductor material to be coated, in addition to DLC, for example, DLC mixed with fluorine (F), titanium nitride, chromium nitride, or the like can be used. The average thickness of the coating obtained by coating may be about 1 μm, for example.

[Laser processing process]
First, as shown in FIG. 9A, a plate-shaped master 331 is prepared. A surface 331A that is a surface to be processed of the plate-like master 331 is in a mirror state, for example. The surface 331A may not be in a mirror state. For example, the surface 331A may have irregularities finer than the transfer pattern, or may be equivalent to the transfer pattern. Rougher irregularities may be formed.

Next, the surface 331A of the plate-shaped master 331 is laser-processed as follows using the laser processing apparatus shown in FIG. First, a pattern is drawn on the surface 331A of the plate-shaped master 331 using an ultrashort pulse laser having a pulse width of 1 picosecond (10 ⁻¹² seconds) or less, so-called femtosecond laser. For example, as shown in FIG. 9B, the surface 331A of the plate-shaped master 331 is irradiated with femtosecond laser light Lf, and the irradiation spot is scanned with respect to the surface 331A.

  At this time, the laser wavelength, the repetition frequency, the pulse width, the beam spot shape, the polarization, the intensity of the laser applied to the surface 331A, the laser scanning speed, etc. are appropriately set, as shown in FIG. A plurality of structures 332 having the structure is formed.

[Transfer processing]
A base material 311 having an uncured resin layer 333 as shown in the cross-sectional view of FIG. 10A is prepared.
Next, as shown in the cross-sectional view of FIG. 10B, the plate-shaped master 331 and the uncured resin layer 333 formed on the base material 311 are brought into close contact with each other, and the active energy ray 334 is irradiated to the uncured resin layer 333. Then, the uncured resin layer 333 is cured, and any one of the fine convex portions and concave portions of the plate-shaped master 331 is transferred to obtain the hydrophilic layer 312 in which any one of the fine convex portions and concave portions is formed.
Finally, the obtained hydrophilic layer 312 is peeled from the plate-shaped master 331 to obtain a hydrophilic laminate (FIG. 10C).
When the base material 311 is made of a material that does not transmit active energy rays such as ultraviolet rays, the plate-shaped master 331 is made of a material that can transmit active energy rays (for example, quartz), and the plate An active energy ray may be applied to the uncured resin layer 333 from the back surface (surface opposite to the molding surface) of the master 331.

(Other manufacturing methods for hydrophilic laminates)
There is no restriction | limiting in particular as a method of manufacturing the said hydrophilic laminated body of this invention other than the manufacturing method of the said hydrophilic laminated body of this invention, According to the objective, it can select suitably, For example, uneven structure is used. Examples thereof include a method of forming the hydrophilic layer having either a fine convex portion or a concave portion on the surface thereof. There is no restriction | limiting in particular as a preparation method of the base material which has the said uneven structure, According to the objective, it can select suitably. There is no restriction | limiting in particular as a formation method of the said hydrophilic layer, According to the objective, it can select suitably, For example, (1) An active energy ray curable resin composition is formed on the base material which has the said uneven structure. Examples thereof include a method of coating to form an uncured resin layer, irradiating the uncured resin layer with active energy rays to cure the uncured resin layer, and (2) a vacuum forming method. By doing so, the uneven structure of the substrate is reflected in the surface shape of the hydrophilic layer, and the hydrophilic laminate can be produced.

  The substrate, the active energy ray curable resin composition, the application method of the active energy ray curable resin composition, and the active energy ray are not particularly limited and may be appropriately selected depending on the purpose. For example, what was illustrated in description of the said hydrophilic laminated body of this invention and description of the manufacturing method of the said hydrophilic laminated body of this invention is mentioned.

  Examples of the vacuum forming method include vapor deposition, sputtering, and CVD (Chemical Vapor Deposition).

(Goods)
The article of the present invention has the hydrophilic laminate of the present invention on the surface, and further includes other members as necessary.
The article is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include glass windows, refrigerated / frozen showcases, window materials such as automobile windows, bathroom mirrors, automobile side mirrors, and the like. Examples include covers for instruments mounted on mirrors, automobiles, motorcycles, construction machinery, ships, bathroom floors and walls, solar panels, security surveillance cameras, and the like.
The article may be glasses, goggles, a helmet, a lens, a microlens array, a cover for an instrument, a headlight cover for an automobile, a front panel, a side panel, a rear panel, and the like. These are preferably formed by in-mold molding, insert molding, or overlay molding.

  The hydrophilic laminate may be formed on a part of the surface of the article or may be formed on the entire surface.

  There is no restriction | limiting in particular as a manufacturing method of the said article | item, Although it can select suitably according to the objective, The manufacturing method of the article | item of this invention mentioned later is preferable.

(Product manufacturing method)
The method for producing an article of the present invention includes at least a heating step, a hydrophilic laminate molding step, and an injection molding step, and further includes other steps as necessary.
The manufacturing method of the article is the manufacturing method of the article of the present invention.

<Heating process>
The heating step is not particularly limited as long as it is a step of heating the hydrophilic laminate, and can be appropriately selected according to the purpose.
The hydrophilic laminate is the hydrophilic laminate of the present invention.

There is no restriction | limiting in particular as said heating, Although it can select suitably according to the objective, It is preferable that it is infrared heating.
There is no restriction | limiting in particular as the temperature of the said heating, Although it can select suitably according to the objective, It is preferable that it is the glass transition temperature vicinity of the said base material or more than a glass transition temperature.
There is no restriction | limiting in particular as time of the said heating, According to the objective, it can select suitably.

<Hydrophilic laminate molding process>
The hydrophilic laminate forming step is not particularly limited as long as it is a step of forming the heated hydrophilic laminate into a desired shape, and can be appropriately selected according to the purpose. The process etc. which make it closely_contact | adhere to a metal mold | die and shape | mold into a desired shape with an air pressure are mentioned.

<Injection molding process>
The injection molding step is not particularly limited as long as it is a step of injecting a molding material onto the substrate side of the hydrophilic laminate molded into a desired shape, and molding the molding material, depending on the purpose. It can be selected appropriately.

  Examples of the molding material include a resin. Examples of the resin include olefin resins, styrene resins, ABS resins (acrylonitrile-butadiene-styrene copolymers), AS resins (acrylonitrile-styrene copolymers), acrylic resins, urethane resins, unsaturated polyesters. Resin, epoxy resin, polyphenylene oxide / polystyrene resin, polycarbonate, polycarbonate modified polyphenylene ether, polyethylene terephthalate, polysulfone, polyphenylene sulfide, polyphenylene oxide, polyether imide, polyimide, liquid crystal polyester, polyallyl heat resistant resin, various composite resins, various modified resins Resin etc. are mentioned.

  The injection method is not particularly limited and may be appropriately selected depending on the purpose. For example, the molten molding material is applied to the base of the hydrophilic laminate that is in close contact with a predetermined mold. The method of pouring etc. is mentioned.

  The article manufacturing method is preferably performed using an in-mold molding apparatus, an insert molding apparatus, and an overlay molding apparatus.

Here, an example of a method for manufacturing an article of the present invention will be described with reference to the drawings. This manufacturing method is a manufacturing method using an in-mold molding apparatus.
First, the hydrophilic laminate 500 is heated. Heating is preferably infrared heating.
Subsequently, as shown in FIG. 11A, the heated hydrophilic laminate 500 is disposed at a predetermined position between the first mold 501 and the second mold 502. At this time, it arrange | positions so that the resin-made base materials of the hydrophilic laminated body 500 may face the 1st metal mold | die 501 and a hydrophilic resin layer may face the 2nd metal mold | die 502. FIG. In FIG. 11A, the first mold 501 is a fixed mold, and the second mold 502 is a movable mold.

After the hydrophilic laminate 500 is disposed between the first mold 501 and the second mold 502, the first mold 501 and the second mold 502 are clamped. Subsequently, the hydrophilic laminate 500 is sucked through the suction holes 504 opened in the cavity surface of the second mold 502, and the hydrophilic laminate 500 is mounted on the cavity surface of the second mold 502. By doing so, the cavity surface is shaped with the hydrophilic laminate 500. At this time, the outer periphery of the hydrophilic laminate 500 may be fixed and positioned by a film pressing mechanism (not shown). Thereafter, unnecessary portions of the hydrophilic laminate 500 are trimmed (FIG. 11B).
If the second mold 502 does not have the suction hole 504 and the first mold 501 has a pressurized hole (not shown), the pressurized hole of the first mold 501 can be used to enter the hydrophilic laminate 500. By sending the compressed air, the hydrophilic laminate 500 is mounted on the cavity surface of the second mold 502.

  Subsequently, the molten molding material 506 is injected from the gate 505 of the first mold 501 toward the resin base material of the hydrophilic laminate 500, and the first mold 501 and the second mold 502 are clamped. Then, it is injected into the cavity formed (FIG. 11C). Thereby, the molten molding material 506 is filled in the cavity (FIG. 11D). Further, after the filling of the molten molding material 506 is completed, the molten molding material 506 is cooled to a predetermined temperature and solidified.

Thereafter, the second mold 502 is moved to open the first mold 501 and the second mold 502 (FIG. 11E). By doing so, the article 507 in which the hydrophilic laminate 500 is formed on the surface of the molding material 506 and in-molded into a desired shape is obtained.
Finally, the protruding pin 508 is pushed out from the first mold 501 and the obtained article 507 is taken out.

A manufacturing method in the case of using the overlay molding apparatus is as follows. This is a process of directly decorating the hydrophilic laminate on the surface of the molding material, and an example thereof is a TOM (Three Dimension Overlay Method) method. An example of a method for producing the article of the present invention using the TOM method will be described below.
First, air is sucked with a vacuum pump or the like in both spaces in the apparatus divided by the hydrophilic laminate fixed to the fixed frame, and the spaces are evacuated.
At this time, a molding material that has been injection molded in advance is placed in a space on one side. At the same time, it is heated with an infrared heater until a predetermined temperature at which the hydrophilic laminate is softened. At the timing when the hydrophilic laminate is heated and softened, the hydrophilic laminate is firmly adhered to the three-dimensional shape of the molding material in a vacuum atmosphere by sending air to the side of the apparatus space where there is no molding material. If necessary, compressed air pressing from the side where the atmosphere is sent may be used in combination. After the hydrophilic laminate is in close contact with the molded body, the obtained decorative molded product is removed from the fixed frame. Vacuum forming is usually performed at 80 ° C to 200 ° C, preferably about 110 ° C to 160 ° C.

  In overlay molding, an adhesive layer may be provided on the surface opposite to the hydrophilic surface of the hydrophilic laminate in order to bond the hydrophilic laminate and the molding material. There is no restriction | limiting in particular as said adhesion layer, According to the objective, it can select suitably, For example, an acrylic adhesive, a hot-melt-adhesive etc. are mentioned. There is no restriction | limiting in particular as a formation method of the said adhesion layer, According to the objective, it can select suitably, For example, after forming the said hydrophilic resin layer on the said base material, the said hydrophilic property of the said resin-made base materials Examples include a method of forming the adhesive layer by applying an adhesive layer coating solution on the side opposite to the resin layer side. Also, after the adhesive layer coating liquid is applied on the release sheet to form the adhesive layer, the resin base material and the adhesive layer on the release sheet are laminated, and the resin base material is laminated. The adhesive layer may be laminated on top.

  Moreover, the said article | item of this invention may laminate | stack the hydrophilic laminated body by the vacuum forming method on the following things instead of a molding material. For example, plate materials such as flat plates and curved plates of various materials, three-dimensional articles, sheets (or films), and the like. Examples of the various materials include wood fiber boards, metal materials, glass, ceramics, ceramic materials, non-ceramic ceramic materials, and resin materials. Examples of the wood fiber board include a wood veneer, a wood plywood, a particle board, and an MDF (medium density fiber board). Examples of the metal material include iron and aluminum. Examples of the ceramic include ceramics. Examples of the non-cement ceramic material include gypsum. Examples of the non-ceramic ceramic material include ALC (lightweight cellular concrete). Examples of the resin material include rubber.

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

<Average distance of convex part, average distance of concave part, average height of convex part, average depth of concave part, average aspect ratio, and average surface area ratio>
In the following examples, the average distance of the convex portions, the average distance of the concave portions, the average height of the convex portions, the average depth of the concave portions, and the average aspect ratio were determined as follows.
First, the surface of the hydrophilic resin layer having a convex portion or a concave portion is observed with an atomic force microscope (AFM), and the pitch of the convex portion or the concave portion, the height of the convex portion or the concave portion is determined from the cross-sectional profile of the AFM. Sought the depth of. This is repeated at 10 locations randomly selected from the surface of the hydrophilic resin layer, and pitches P1, P2,..., P10 and heights or depths H1, H2,. Asked.
Here, the pitch of the convex portions is a distance between the vertices of the convex portions. The pitch of the recesses is the distance between the deepest portions of the recesses. The height of the convex portion is the height of the convex portion based on the lowest point of the valley between the convex portions. The depth of the recess is the depth of the recess based on the highest point of the peak between the recesses.
Next, these pitches P1, P2,..., P10 and the heights or depths H1, H2,..., H10 are simply averaged (arithmetic average), and the average distance between the convex portions or the concave portions is calculated. (Pm) and the average height of the convex portions or the average depth (Hm) of the concave portions were determined.
An average aspect ratio (Hm / Pm) was determined from the Pm and the Hm.
AFM images were repeatedly obtained at 10 locations randomly selected from the surface of the hydrophilic resin layer having convex portions or concave portions, and surface areas S1, S2,. Next, the ratio (surface area / area) SR1, SR2,..., SR10 of these surface areas S1, S2,..., S10 and the area of each observation region is simply averaged (arithmetic average). The average surface area ratio SRm of the surface of the hydrophilic resin layer was determined.

<Anti-fogging property>
<< Pure water contact angle >>
The pure water contact angle was measured by a sliding method using PCA-1 (manufactured by Kyowa Interface Chemical Co., Ltd.) under the following conditions.
-Distilled water was put into a plastic syringe, and a stainless steel needle was attached to the tip thereof and dropped onto the evaluation surface. After dropping, the contact angle after 5 seconds was measured at any 10 locations on the evaluation surface, and the average value was defined as the pure water contact angle.
・ Drip amount of water: 2μL
・ Measurement temperature: 25 ℃

<< Breath test >>
In an environment of 25 ° C. and 50% RH, breathe out once from the surface of the hydrophilic resin layer of the hydrophilic laminate at a distance of 5 cm in the normal direction from the surface and evaluate according to the following evaluation criteria. did.
〔Evaluation criteria〕
A: The appearance of the hydrophilic laminate was not changed at all.
○: Although the hydrophilic laminate was not cloudy white, it was confirmed that a water film was formed on the surface of the hydrophilic resin layer.
X: The hydrophilic laminate was cloudy white.

<< Abrasion resistance >>
After placing Zabina MX (KB Selen Co., Ltd.) on the surface of the hydrophilic resin layer and sliding back and forth 10,000 times at a load of 75 gf / diameter of 13 mm (sliding stroke: 3 cm, sliding frequency: 60 Hz), pure water Contact angle, breath test, and appearance were evaluated. The evaluation method for the pure water contact angle and breath test is the same as above. The appearance was evaluated according to the following evaluation criteria.
[Evaluation criteria for appearance]
○: No change in appearance.
X: At least one of damage and cloudiness was confirmed.

<< Water resistance >>
The hydrophilic laminate was immersed in water at 40 ° C. for 24 hours, and immediately after removal, the water was wiped off with a tissue (Erière, manufactured by Daio Paper Co., Ltd.). Thereafter, the breath test, appearance, and pencil hardness were evaluated and judged according to the following evaluation criteria.
〔Evaluation criteria〕
○: No whitening due to exhalation, no change in appearance, and a decrease in pencil hardness (softening) within 1 rank.
×: Corresponds to one or more of the following. (1) Whitening occurs due to exhalation, (2) Appearance changes, (3) Pencil hardness reduction (softening) is 2 ranks or more.

<< Low temperature resistance test >>
After holding the hydrophilic laminate in a refrigerator set at 5 ° C. for 30 minutes, the cloudiness when taken out in an environment of 25 ° C. and 50% RH was evaluated, and judged according to the following evaluation criteria.
〔Evaluation criteria〕
A: There was no cloudiness.
◯: Although white and not cloudy, it was confirmed that a water film was formed on the surface of the hydrophilic resin layer.
×: White and cloudy.

<Martens hardness>
The Martens hardness of the hydrophilic resin layer was measured using PICODERTOR HM500 (trade name; manufactured by Fisher Instruments). The load was 1 mN / 20 s, a diamond cone was used as the needle, and the surface angle was 136 °.

<Pencil hardness>
The pencil hardness of the hydrophilic resin layer was measured according to JIS K 5600-5-4.

<Elongation>
The elongation rate was determined by the following method.
The hydrophilic laminate was formed into a strip shape having a length of 10.5 cm and a width of 2.5 cm to obtain a measurement sample. The tensile elongation of the obtained measurement sample was measured with a tensile tester (Autograph AG-5kNXplus, manufactured by Shimadzu Corporation) (measurement condition: tensile speed = 100 mm / min; distance between chucks = 8 cm; measurement temperature = 190 ° C.) )did.

<Total light transmittance>
The total light transmittance of the hydrophilic laminate was evaluated using HM-150 (trade name; manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 7361.

<Haze>
The haze of the hydrophilic laminate was evaluated using HM-150 (trade name; manufactured by Murakami Color Research Laboratory Co., Ltd.) according to JIS K 7136.

<Adhesion>
The adhesiveness of the hydrophilic resin layer was evaluated by a peel test (cross cut (1 mm interval × 100 mass) cellophane tape (manufactured by Nichiban Co., Ltd., CT24)) according to JIS K 5400.

<Heat shrinkage difference>
The difference in the heat shrinkage rate of the hydrophilic laminate was determined by the following method.
First, a square test piece having a size of 100 mm × 100 mm was cut out. At this time, it cut out so that the vertical direction and horizontal direction of this test piece might correspond with the longitudinal direction and width direction of a resin-made base material, respectively. Next, this was heated in an oven at 190 ° C. for 30 minutes. After taking out from the oven and naturally cooling to room temperature, the length in the vertical direction and the horizontal direction were each measured with a ruler. The rate of change from the length before heating (= 100 mm) was calculated for both directions, and the absolute value of the difference was obtained. This was calculated | required with the test piece of N = 10 piece, and those arithmetic mean values were made into the heat contraction rate difference of a hydrophilic laminated body.

<Molding processability 1>
An adhesive layer is provided on the side of the hydrophilic laminate opposite to the side on which the hydrophilic resin layer is formed, and this is integrated with the concave side of a polycarbonate 4-curve lens by the TOM method (Three-dimension Over-lay Method). I let you. Thereafter, the breath test and appearance were evaluated, and the following evaluation criteria were used.
〔Evaluation criteria〕
○: No whitening due to exhalation, no change in appearance.
×: Corresponds to one or more of the following. (1) Whitening occurs due to exhalation, (2) Appearance changes (cracks, peeling, wrinkles).

<Molding processability 2>
An adhesive layer is provided on the side of the hydrophilic laminate opposite to the side where the hydrophilic resin layer is formed, and this is integrated with polycarbonate by film insert molding, and a 4-curve lens provided with a hydrophilic resin layer on the concave side Produced. Thereafter, the breath test and appearance were evaluated, and the following evaluation criteria were used.
〔Evaluation criteria〕
○: No whitening due to exhalation, no change in appearance.
×: Corresponds to one or more of the following. (1) Whitening occurs due to exhalation, (2) Appearance changes (cracks, peeling, wrinkles).

Example 1
<Preparation of transfer master (glass roll master) having either fine convex part or concave part>
First, a glass roll master having an outer diameter of 126 mm was prepared, and a resist layer was formed on the surface of the glass roll master as follows. That is, the photoresist was diluted to 1/10 by weight with a thinner, and this diluted resist was applied to the average thickness of about 70 nm on the cylindrical surface of the glass roll master by dipping, thereby forming a resist layer. Next, the glass roll master is transported to the roll master exposure apparatus shown in FIG. 4, and the resist layer is exposed to form a hexagonal lattice pattern between three adjacent tracks while being continuous in one spiral. The latent image was patterned on the resist layer. Specifically, a hexagonal lattice-shaped exposure pattern was formed by irradiating a region where a hexagonal lattice-shaped exposure pattern was to be formed with 0.50 mW / m of laser light.

  Next, the resist layer on the glass roll master was subjected to development treatment, and the exposed resist layer was dissolved and developed. Specifically, an undeveloped glass roll master is placed on a turntable of a developing machine (not shown), and a developer is dropped on the surface of the glass roll master while rotating the entire turntable to develop the resist layer on the surface. did. Thereby, a resist glass master having a resist layer opened in a hexagonal lattice pattern was obtained.

Next, plasma etching was performed in a CHF ₃ gas atmosphere using a roll etching apparatus. As a result, only the hexagonal lattice pattern exposed from the resist layer is etched on the surface of the glass roll master, and the resist layer is used as a mask for the other regions and etching is not performed. Formed on the master. At this time, the etching amount (depth) was adjusted by the etching time. Finally, the resist layer was completely removed by O ₂ ashing to obtain a glass roll master having a concave hexagonal lattice pattern.

<Preparation of hydrophilic laminate>
Next, a hydrophilic laminate was produced by UV imprinting using the roll master obtained as described above. Specifically, it was performed as follows.
DF02U (PMMA / PC laminate) (average thickness 125 μm) manufactured by Mitsubishi Gas Chemical Co., Ltd. was used as the resin base material.
The UV curable resin composition for anchor layer having the following composition was applied on the surface of PMMA of the resin base material so that the average thickness after drying and curing was 0.7 μm.

-UV curable resin composition for anchor layer-
CN985B88 (aliphatic urethane acrylate, manufactured by Sartomer) 20 parts by mass A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.) 20 parts by mass butyl acetate 56 parts by mass Irgacure 907 (manufactured by BASF) 1 part by mass・ Irgacure 184 (manufactured by BASF) 3 parts by mass

After drying, the uncured anchor layer was irradiated with ultraviolet rays at a dose of 500 mJ / cm ² using a metal halide to obtain an ultraviolet-cured resin base material with an anchor layer.

The ultraviolet curable resin composition for a hydrophilic resin layer having the following composition was applied on the anchor layer of the resin base material with an anchor layer so that the resulting hydrophilic resin layer had an average thickness of 3.2 μm. The resin base material with an anchor layer coated with the ultraviolet curable resin composition for the hydrophilic resin layer and the roll master obtained as described above are in close contact with each other, using a metal halide lamp, and the resin base material side Then, the hydrophilic resin layer was cured by irradiating with ultraviolet rays at an irradiation amount of 1,500 mJ / cm ² . Thereafter, the hydrophilic resin layer and the roll master were peeled off.

-UV curable resin composition for hydrophilic resin layer-
SR203 (tetrahydrofurfuryl methacrylate, manufactured by Sartomer) 16 parts by mass M-215 (isocyanuric acid EO modified diacrylate, manufactured by Toagosei Co., Ltd.) 80 parts by mass Lucirin TPO (manufactured by BASF) 4 parts by mass

  As described above, a hydrophilic laminate having fine convex portions on the surface of the hydrophilic resin layer was obtained. FIG. 12A shows an AFM image of the surface of the hydrophilic resin layer of the obtained hydrophilic laminate. A cross-sectional view taken along line aa in FIG. 12A is shown in FIG. 12B.

  About the obtained hydrophilic laminated body, by the above-mentioned method, the average distance (or average distance of a recessed part) (Pm), the average height (or average depth of a recessed part) (Hm), average aspect of a convex part Ratio (Hm / Pm), anti-fogging property (pure water contact angle, breath test, abrasion resistance, water resistance, low temperature environment test), Martens hardness, pencil hardness, elongation, total light transmittance, haze, adhesion The difference in heat shrinkage and the moldability were measured. The results are shown in Table 1.

(Example 2)
In Example 1, the hydrophilic laminated body was produced like Example 1 except having changed the exposure pattern of the resist layer at the time of producing a glass roll original disc.
FIG. 13A shows an AFM image of the surface of the hydrophilic resin layer of the obtained hydrophilic laminate. A cross-sectional view taken along line aa in FIG. 13A is shown in FIG. 13B.
About the produced hydrophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Example 3)
In Example 1, except that the exposure pattern of the resist layer at the time of producing the glass roll master was changed and the ultraviolet curable resin composition for the hydrophilic resin layer was changed to the following composition, the same as in Example 1, A hydrophilic laminate was prepared.

-UV curable resin composition for hydrophilic resin layer-
CN985B88 (aliphatic urethane acrylate, manufactured by Sartomer) 32 parts by mass A-9300 (ethoxylated isocyanuric acid triacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.) 32 parts by mass MPEM-1000 (methoxypolyethylene glycol methacrylate, first (Manufactured by Kogyo Seiyaku Co., Ltd.) 32 parts by mass ・ Lucirin TPO (manufactured by BASF) 4 parts by mass

FIG. 14A shows an AFM image of the surface of the hydrophilic resin layer of the obtained hydrophilic laminate. A cross-sectional view taken along line aa in FIG. 14A is shown in FIG. 14B.
About the produced hydrophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Example 4)
In Example 2, a hydrophilic laminate was produced in the same manner as in Example 2 except that the UV curable resin composition for anchor layer and the UV curable resin composition for hydrophilic resin layer were changed to the following compositions. did.

-UV curable resin composition for anchor layer-
・ 8BR-500 45 parts by mass (urethane acrylate polymer, Taisei Fine Chemical Co., Ltd.)
-UV-7550 (urethane acrylate, manufactured by Nippon Synthetic Industry Co., Ltd.) 15 parts by mass-38.8 parts by mass of butyl acetate-Irgacure 184 (manufactured by BASF) 0.6 parts by mass-Irgacure 907 (manufactured by BASF) 0.6 Parts by mass · KP323 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.003 parts by mass

-UV curable resin composition for hydrophilic resin layer-
・ A-600 33 parts by mass (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-M-215 (isocyanuric acid diacrylate, manufactured by Toagosei Co., Ltd.) 43 parts by mass-Light ester THF (1000) 20 parts by mass (THF-modified methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)
・ Lucirin TPO (manufactured by BASF) 4 parts by mass

  About the produced hydrophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Example 5)
In Example 2, a hydrophilic laminate was produced in the same manner as in Example 2 except that the UV curable resin composition for anchor layer and the UV curable resin composition for hydrophilic resin layer were changed to the following compositions. did.

-UV curable resin composition for anchor layer-
・ 8BR-500 45 parts by mass (urethane acrylate polymer, Taisei Fine Chemical Co., Ltd.)
・ UV-7550 (urethane acrylate, manufactured by Nihon Gosei Co., Ltd.) 15 mass parts ・ Butyl acetate 38.8 mass parts ・ Irgacure 184 (manufactured by BASF) 0.6 mass parts ・ Irgacure 907 (manufactured by BASF) 0.6 mass・ KP323 (Shin-Etsu Chemical Co., Ltd.) 0.003 parts by mass

-UV curable resin composition for hydrophilic resin layer-
A-600 48 parts by mass (polyethylene glycol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.)
-M-215 (isocyanuric acid diacrylate, manufactured by Toagosei Co., Ltd.) 28 parts by mass-Light ester THF (1000) 20 parts by mass (THF-modified methacrylate, manufactured by Kyoeisha Chemical Co., Ltd.)
・ Lucirin TPO (manufactured by BASF) 4 parts by mass

  About the produced hydrophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Comparative Example 1)
In Example 1, the laminated body was produced like Example 1 except having changed the exposure pattern of the resist layer at the time of producing a glass roll original disc.
About the produced laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Comparative Example 2)
In Example 1, a laminate was obtained in the same manner as in Example 1 except that the roll master was not adhered to the anchor-coated resin base material coated with the ultraviolet curable resin composition for the hydrophilic resin layer. It was.
About the produced laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Comparative Example 3)
In Comparative Example 2, a laminate was obtained in the same manner as in Comparative Example 2, except that the ultraviolet curable resin composition for the hydrophilic resin layer was changed to the following composition.

-UV curable resin composition for hydrophilic resin layer-
-CN985B88 (aliphatic urethane acrylate, manufactured by Sartomer) 95 parts by mass-Lucirin TPO (manufactured by BASF) 5 parts by mass

  About the produced laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Comparative Example 4)
In Example 2, the laminated body was obtained like Example 2 except having changed the ultraviolet curable resin composition for hydrophilic resin layers into the following composition.

-UV curable resin composition for hydrophilic resin layer-
-CN985B88 (aliphatic urethane acrylate, manufactured by Sartomer) 95 parts by mass-Lucirin TPO (manufactured by BASF) 5 parts by mass

  About the produced laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

(Comparative Example 5)
In Comparative Example 1, a laminate was obtained in the same manner as in Comparative Example 1 except that the ultraviolet curable resin composition for the hydrophilic resin layer was changed to the following composition.

-UV curable resin composition for hydrophilic resin layer-
-CN985B88 (aliphatic urethane acrylate, manufactured by Sartomer) 95 parts by mass-Lucirin TPO (manufactured by BASF) 5 parts by mass

  About the produced hydrophilic laminated body, evaluation similar to Example 1 was performed. The results are shown in Tables 1 and 2.

Example 1, Example 2, Example 3, Example 4, and Example 5 were excellent in antifogging properties such as wear resistance, water resistance, and low temperature resistance. Moreover, the moldability was also excellent.
In particular, in Example 4 and Example 5, an adhesive layer is provided on the side opposite to the side on which the hydrophilic resin layer of the hydrophilic laminate is formed, and this is applied by a TOM method (Three-dimension Over-lay Method). Even when integrated on the concave side of the polycarbonate 8-curve lens, there was no whitening due to exhalation and no change in appearance. In Example 4 and Example 5, an adhesive layer is provided on the opposite side of the hydrophilic laminate from the side on which the hydrophilic resin layer is formed, and this is integrated with polycarbonate by film insert molding, and the concave side Even when an 8-curve lens provided with a hydrophilic resin layer was produced, whitening due to exhalation did not occur and the appearance did not change.

In Comparative Example 1, the height of the protrusion (convex portion) was higher than 100 nm, and in the wear resistance test, after reciprocating 2,000 times, the protrusion was broken and the pure water contact angle was increased. . Further, after 2,000 reciprocating slides, the pure water contact angle was 33 °, but it was scratched and clouded by exhalation.
In Comparative Example 2, since the pure water contact angle exceeded 50 °, the breath test was “x”.
From Comparative Example 3, Comparative Example 4, and Comparative Example 5, when the pure water contact angle of the solid film (smooth film) of the hydrophilic resin layer exceeds 70 °, the pure water contact angle is provided even if a nano uneven structure is provided on the surface. Was not less than 50 °, and no antifogging property was obtained.

  Use of the hydrophilic laminate of the present invention is repeatedly wiped with cloth on the inside of a lens window such as glasses and goggles, a door such as a refrigerator compartment, a freezer compartment, a glass window built into the door, etc. And is particularly suitable for applications used in low temperature environments.

211 Base material 212 Hydrophilic layer 231 Roll master 232 Structure 236 Uncured resin layer 237 Active energy ray 311 Base material 312 Hydrophilic layer 331 Plate master 332 Structure 333 Uncured resin layer 334 Active energy ray

Claims (11)

A substrate and a hydrophilic layer on the substrate;
The hydrophilic layer has either a fine convex part or a concave part on the surface,
The pure water contact angle on the surface of the hydrophilic layer is 50 ° or less,
The hydrophilic layer is a cured product of the active energy ray-curable resin composition,
Either of the average height of the convex part and the average depth of the concave part is 100 nm or less,
Either of the average aspect ratio of the convex part (average height of the convex part / average distance of the adjacent convex part) and the average aspect ratio of the concave part (average depth of the concave part / average distance of the adjacent concave part) The hydrophilic laminate is characterized by having 0.001 to 0.50.   The hydrophilic laminate according to claim 1, wherein the elongation is 40% or more.   The hydrophilic laminate according to claim 1, wherein the hydrophilic layer has an average surface area ratio of 1.10 or more.   Either of the average height of a convex part and the average depth of a recessed part is 60 nm or less, The hydrophilic laminated body in any one of Claim 1 to 3.   The hydrophilic laminate according to any one of claims 1 to 4, wherein the substrate is any one of a resin substrate and a glass substrate. A method for producing a hydrophilic laminate according to any one of claims 1 to 5,
An uncured resin layer forming step of forming an uncured resin layer by applying an active energy ray-curable resin composition on a substrate;
A transfer master having any one of a fine convex part and a concave part is brought into close contact with the uncured resin layer, and the uncured resin layer is cured by irradiating active energy rays to the uncured resin layer to which the transfer master is in close contact. And a hydrophilic layer forming step of forming a hydrophilic layer by transferring any one of the fine convex portions and concave portions. The hydrophilic laminate according to claim 6, wherein any one of the fine convex portions and concave portions of the transfer master is formed by etching the surface of the transfer master using a photoresist having a predetermined pattern shape as a protective film. Production method. 7. The method for producing a hydrophilic laminate according to claim 6, wherein any one of the fine convex portion and the concave portion of the transfer master is formed by irradiating the surface of the transfer master with laser to process the transfer master. . An article having the hydrophilic laminate according to any one of claims 1 to 5 on a surface thereof. A method of manufacturing an article according to claim 9,
A heating step for heating the hydrophilic laminate,
A hydrophilic laminate forming step of forming the heated hydrophilic laminate into a desired shape;
A method for producing an article, comprising: an injection molding step of injecting a molding material onto a substrate side of the hydrophilic laminate formed into a desired shape, and molding the molding material. The method for manufacturing an article according to claim 10, wherein the heating in the heating step is performed by infrared heating.