JP2014001106A - Antifogging glass article and method for manufacturing the same, and article for transportation equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an antifogging glass article having both of a black ceramic layer and a water-absorbing antifogging film and a method for manufacturing the antifogging glass article, which has good appearance and visibility, excellent antifogging property, excellent durability such as chemical resistance of the water-absorbing antifogging film, in particular, durability such as chemical resistance of the water-absorbing antifogging film formed on the black ceramic layer, and to provide an article for transportation equipment having the above antifogging glass article.SOLUTION: The antifogging glass article includes: a glass substrate; a black ceramic layer formed in a peripheral edge part on at least one main surface of the glass substrate; a water-absorbing antifogging film formed on the main surface in such a manner that a laminate region overlapping with the black ceramic layer is present; and an adhesive layer formed between the water-absorbing antifogging film and the black ceramic layer in at least the laminate region on the main surface. The region where the adhesive layer is formed does not exceed a region comprising the laminate region and its neighboring region.

Description

  The present invention relates to an antifogging glass article, a method for producing the same, and an article for transportation equipment including the antifogging glass article.

Transparent substrates such as glass and plastic have a so-called “cloudy” state when the substrate surface falls below the dew point temperature because fine water droplets adhere to the surface and scatter transmitted light. . Various proposals have been made as a means for preventing fogging.
Specifically, a method of providing a water-absorbing resin layer on the substrate surface and absorbing and removing minute water droplets formed on the substrate surface, or reducing the atmospheric humidity on the substrate surface, and the like are known.

  As an anti-fogging technique using such a water-absorbing compound layer, specifically, an anti-fogging article having an anti-fogging film including a water-absorbing crosslinked resin layer obtained from polyepoxides (see Patent Document 1), etc. Has been proposed.

  Here, the antifogging article is expected to be used as an antifogging glass article for window glass for transportation equipment, for example, windshield of automobiles. In many cases, the window glass of a transportation device has a dark color region composed of a black ceramic layer at the peripheral edge of the inner surface of the vehicle. When a window glass having such a dark color area is used in combination with an antifogging film, the antifogging film is also provided on the vehicle interior side, but when the end of the antifogging film is provided in the dark color area without being overlapped, If there is a problem such as deterioration of the appearance or visibility outside the vehicle, and if an anti-fogging film is provided so as to cover the end of the window glass so as to cover the entire dark area, the window glass In some cases, it may become an obstacle when adhering to the vehicle body.

Therefore, Patent Document 2 discloses a technology for an antifogging glass for a vehicle window in which an antifogging film is formed on a vehicle windowglass having a dark color area at the peripheral edge of the surface on the inner side of the vehicle so that the end portion exists in the dark color area. Is described.
However, when a water-absorptive anti-fogging film is used, when the anti-fogging film absorbs water on a dark color region composed of a black ceramic layer, especially when alkaline or acidic water is absorbed, the anti-fogging film expands from the substrate. Resistance to the phenomenon of peeling, in other words, chemical resistance, has been a problem.

International Publication No. 2007/052710 Pamphlet International Publication No. 2008/069186 Pamphlet

  The present invention provides an anti-fogging glass article having both a black ceramic layer and a water-absorptive anti-fogging film, has good appearance and visibility, excellent anti-fog property, and durability such as chemical resistance in the water-absorptive anti-fog film. In particular, an anti-fogging glass article having excellent durability such as chemical resistance in a water-absorbing anti-fogging film formed on a black ceramic layer, a method for producing the same, and an article for transport equipment comprising the anti-fogging glass article The purpose is to provide.

The present invention provides an antifogging glass article having the following configuration, a method for producing the same, and an article for transport equipment including the antifogging glass article.
[1] It is formed on the main surface so that there is a glass substrate, a black ceramic layer formed on a peripheral portion on at least one main surface of the glass substrate, and a laminated region overlapping on the black ceramic layer. An anti-fogging glass article comprising: a water-absorbing anti-fogging film; and an adhesive layer formed between the water-absorbing anti-fogging film and the black ceramic layer in at least the laminated region on the main surface, The area where the adhesive layer is formed is an antifogging glass article that does not exceed the area composed of the laminated area and its vicinity.
[2] The adhesive layer is a layer mainly composed of a metal oxide or an organic group-containing metal oxide formed by a sol-gel method using a hydrolyzable metal compound, wherein the metal of the hydrolyzable metal compound is The antifogging glass article according to [1], which is at least one selected from silicon, aluminum, titanium, and zirconium.
[3] The hydrolyzable metal compound is at least one selected from the group consisting of a trifunctional or tetrafunctional hydrolyzable titanium compound and a trifunctional or tetrafunctional hydrolyzable silicon compound. Antifogging glass article.
[4] The antifogging glass article according to [2] or [3], wherein the hydrolyzable metal compound is a tetrafunctional hydrolyzable silicon compound.

[5] The antifogging glass article according to any one of [1] to [4], wherein the adhesive layer has a thickness of 1 to 500 nm.
[6] The antifogging glass article according to any one of [1] to [5], wherein the water absorbing antifogging film has a water absorbing layer mainly composed of a water-absorbing crosslinked resin.
[7] The antifogging glass article according to [6], wherein the water-absorbing crosslinked resin is selected from a curable epoxy resin, a urethane resin, and a crosslinked acrylic resin.
[8] In the water-absorbing anti-fogging film, the water-absorbing layer is a layer mainly composed of a water-absorbing curable epoxy resin, and is further on the glass substrate side than the water-absorbing layer and has a lower water absorption than the water-absorbing curable epoxy resin The antifogging glass article according to [6] or [7], which has a base layer mainly composed of a curable epoxy resin.
[9] The antifogging glass article according to any one of [6] to [8], wherein the layer closest to the glass substrate of the antifogging film is a raw material component of a crosslinked resin that is a main component of the layer. , At least one selected from a silane coupling agent, a titanium coupling agent and a zirconium coupling agent having a functional group and a hydrolyzable group reactive to the reactive group of the raw material component The antifogging glass article which is a layer formed using the composition to contain.

[10] The antifogging property according to any one of [6] to [9], wherein the water absorbing layer has a thickness of 5 to 50 μm, and the base layer has a thickness of 1 to 20 μm when the base layer is provided. Glass article.
[11] An article for transportation equipment comprising the antifogging glass article according to any one of [1] to [10].
[12] A method for producing an antifogging glass article according to any one of the above [2] to [10], comprising the following steps (1) to (3).
(1) A step of forming a black ceramic layer on a peripheral edge portion on at least one main surface of the glass substrate;
(2) forming an adhesive layer using an adhesive layer forming composition containing a hydrolyzable metal compound and a solvent in a formation region of the adhesive layer including the laminated region on the black ceramic layer;
(3) The process of forming a water absorption anti-fogging film in the predetermined area | region of the said glass substrate after the process of said (2).

  According to the present invention, in the antifogging glass article having both the black ceramic layer and the water absorption antifogging film, the appearance and visibility are good, the antifogging property is excellent, and the chemical resistance in the water absorption antifogging film is Anti-fogging glass article excellent in durability, in particular, durability such as chemical resistance in a water-absorbing anti-fogging film formed on a black ceramic layer, and a method for producing the same, and for transport equipment comprising the anti-fogging glass article Articles can be provided.

It is a front view of an example of an embodiment of an antifogging glass article of the present invention. It is a figure which expand | deploys and shows the anti-fogging glass article shown in FIG. 1 for every structural layer. It is the elements on larger scale of the black ceramic layer (frame shape concealment part) in the anti-fogging glass article shown in FIG. It is sectional drawing in the XX line of the anti-fogging glass article shown in FIG. It is sectional drawing in the YY line of the anti-fogging glass article shown in FIG.

  Hereinafter, embodiments of the present invention will be described. Note that the present invention is not limited to these embodiments, and these embodiments can be changed or modified without departing from the spirit and scope of the present invention.

[Anti-fogging glass article]
The anti-fogging glass article of the present invention has a glass substrate, a black ceramic layer formed on a peripheral edge portion on at least one main surface of the glass substrate, and a laminated region overlapping on the black ceramic layer. A water-absorbing anti-fogging film formed on the main surface; and an adhesive layer formed between the water-absorbing anti-fogging film and the black ceramic layer in at least the laminated region on the main surface. The formation region is an antifogging glass article that does not exceed the region composed of the laminated region and its vicinity. That is, the formation region of the adhesive layer includes at least the entire area of the laminated area, and is an area obtained by adding the vicinity to the laminated area at the maximum.

  In the present invention, an antifogging glass article having a black ceramic layer at the peripheral edge on at least one main surface of a glass substrate and having an antifogging film on the same main surface is antifogged on the black ceramic layer. By forming the anti-fogging film so that there is a laminated region in which the films are stacked, the appearance and visibility are improved. Further, by providing an adhesive layer between the black ceramic layer and the antifogging film in the laminated region, durability such as chemical resistance in the antifogging film formed on the black ceramic layer is improved. In the present invention, thereby, durability such as chemical resistance of the antifogging film is improved in the entire antifogging glass article, and an antifogging glass article excellent in antifogging property can be provided.

  The antifogging glass article of the present invention having both a black ceramic layer and an antifogging film is a glass article used for applications requiring antifogging properties as well as concealing properties and decorative properties by the black ceramic layer.

  In the antifogging glass article of the present invention, the black ceramic layer is formed on the peripheral edge portion on at least one main surface of the glass substrate for the purpose of imparting concealability and decorative properties to the antifogging glass article. The region on the glass substrate on which the black ceramic layer is formed is not necessarily limited to the peripheral portion. In addition to the peripheral portion, a region in which the black ceramic layer is formed may be provided on a glass substrate other than the peripheral portion for the purpose of imparting concealability and decorative properties. Moreover, it is not necessary that the peripheral portion is the entire peripheral portion, and an embodiment in which a black ceramic layer is formed on a part of the peripheral portion is also included in the present invention. The black ceramic layer is usually formed only on the peripheral portion on one main surface of the glass substrate, or on the peripheral portion and a region in the vicinity thereof.

  Specifically, as such a black ceramic layer, for the black ceramic layer formed on the peripheral portion, for example, a part of the peripheral portion or the like is concealed in order to conceal the adhesive portion when the glass substrate is attached to another member as a window. A black ceramic layer formed in a band shape or a frame shape is cited as an example. In addition, the black ceramic layer formed in the vicinity of the peripheral portion on the glass substrate is a black ceramic layer provided in the vicinity of the peripheral portion as characters or marks, and is positioned in the vicinity of the peripheral portion when a vehicle window glass is used. In order to conceal the attachment part of various sensors to be performed, a black ceramic layer or the like formed on the entire attachment part including the vicinity thereof may be used.

  As a method for forming the black ceramic layer on the glass substrate, a conventionally known method can be applied. Specifically, a black ceramic paste in which a heat-resistant black pigment powder such as metal oxide, which is an inorganic component, and a low-melting glass frit powder and optional components added as necessary are kneaded in addition to a resin and a solvent To prepare. Next, the obtained black ceramic paste is applied to a predetermined position and region on at least one main surface of the glass substrate by screen printing or the like, dried as necessary, and then heated and baked to produce black ceramics. A layer is formed.

  The black pigment, low-melting glass, resin and solvent, and other optional components used for the preparation of the black ceramic paste are usually restricted by the same materials as the black ceramic paste used to form the black ceramic layer on the glass substrate. It is usable without. Moreover, a commercial item can be used for a black ceramic paste. Examples of commercially available products include black ceramic paste N9-104 (trade name, manufactured by Fellow), black ceramic paste AP51330 (trade name, manufactured by Asahi Glass), and the like.

  In addition, the baking condition after coating on the glass substrate is not particularly limited as long as the black ceramic paste coating film is degreased and fired to become a black ceramic layer. For example, in black ceramic paste N9-104 (trade name, manufactured by Fellow Corporation) and black ceramic paste AP51330 (trade name, manufactured by Asahi Glass Co., Ltd.), a baking treatment at 600 to 750 ° C. for 3 to 15 minutes can be mentioned.

  Furthermore, in the formation of the glass substrate used in the present invention, for example, in the case of having a heating bending process for forming an automobile window glass or the like, a black ceramic paste is applied before the heating bending process. You may form a black ceramic layer by performing degreasing and baking of a paste coating film simultaneously with the said heating bending process.

The “black color” of the black ceramic layer may be adjusted so as not to transmit visible light to such an extent that at least a portion required to be concealed can be concealed. From this viewpoint, the black pigment to be used includes a combination of pigments that become black by a combination of a plurality of colored pigments.
Further, from the same viewpoint, the black ceramic layer may be configured as an integrated film in which the entire layer is continuous, or may be configured by a dot pattern or the like that is an aggregate of fine dots.

  The shape of the dots is not limited to a circle, and may be an ellipse, a rectangle, a polygon, a star, or the like. Moreover, the dot part can be made transparent and the other part can be made into a dot pattern which is a black ceramic layer. Further, the dots may be formed by changing the size or interval in the formation region of the black ceramic layer. For example, when a black ceramic layer is formed by a dot pattern on the peripheral part of the antifogging glass article, by decreasing the dot size toward the inner side (inner peripheral direction) or by increasing the interval between dots, The area ratio of a transparent part can be enlarged, so that it becomes the inner side of an antifogging glass article. Further, the black ceramic layer may have various patterns such as a stripe pattern by parallel lines, a corrugated pattern, a serpentine pattern, a lattice pattern, a checkered pattern, and an annual ring pattern.

  The thickness of the black ceramic layer is not particularly limited as long as the visibility and the adhesion of the water absorption antifogging film formed thereon are not problematic. The black ceramic layer is preferably formed with a thickness of about 8 to 20 μm, and more preferably 10 to 15 μm.

  The material of the glass substrate used for the antifogging glass article of the present invention is not particularly limited, and examples thereof include ordinary soda lime glass, borosilicate glass, alkali-free glass, and quartz glass. Moreover, it is also possible to use the glass substrate which absorbs an ultraviolet-ray or infrared rays as a glass substrate of the anti-fogging glass article of this invention. Moreover, the laminated glass laminated | stacked using the resin intermediate film can also be used.

  The shape, size, and thickness of the glass substrate used for the antifogging glass article of the present invention are not particularly limited. The shape of the glass substrate may be a flat plate, or the entire surface or a part thereof may have a curvature. About the thickness of a glass substrate, when using for the window for motor vehicles or the window for construction, the thickness of about 0.5-10 mm is mentioned, for example.

  Note that the antifogging glass article of the present invention is preferably applied to applications in which antifogging properties and durability thereof are particularly required as well as appearance and visibility, specifically for automobile windows, in particular. For windshields and sliding windows. Therefore, as the glass substrate, a glass substrate having a material, a size, and a shape usually used for such applications is preferably used.

Hereinafter, embodiments of the antifogging glass article of the present invention will be described with reference to the drawings, taking an automobile windshield as an example. FIG. 1 is a front view of an example of an embodiment of an anti-fogging glass article of the present invention as an automotive windshield, and FIG. 2 is an exploded view of the anti-fogging glass article shown in FIG. ) To FIG. 2 (c) are shown.
FIG. 2A is a front view showing the shape and region of the black ceramic layer 3 formed on the main surface of the glass substrate 2 that is the vehicle interior side.
FIG. 2B is a front view showing the shape and region of the adhesive layer 4 formed in a region partially including the surface of the black ceramic layer 3 on the main surface which is the vehicle interior side of the glass substrate 2.
FIG. 2 (c) shows the shape and region of the water-absorbing anti-fogging film 5 formed in a region partially including the surfaces of the black ceramic layer 3 and the adhesive layer 4 on the main surface that is the vehicle interior side of the glass substrate 2. It is a front view.
In addition, the notations of “upper” and “lower” used in the following description indicate upper and lower when the antifogging glass article is mounted on an automobile as an automobile windshield, respectively.

  The antifogging glass article 1 is composed of a glass substrate 2 and a black ceramic layer 3 formed in a predetermined shape and region in order from the glass substrate 2 side on the main surface which is the inside of the vehicle when used. It has the adhesive layer 4 and the water absorption anti-fogging film 5.

  As shown in FIG. 2 (a), the antifogging glass article 1 is a black ceramic layer 3 for concealing the attachment portion to the vehicle opening flange around the entire peripheral edge on the main surface of the glass substrate 2 on the vehicle interior side. The frame-shaped concealing portion 31 is formed in a substantially frame shape. Further, the antifogging glass article 1 has a character display part 32 as a black ceramic layer 3 on the same main surface of the glass substrate 2 and inside the lower left frame-like concealing part 31. The width W of the frame-shaped concealing portion 3 is formed wider on the lower side than the other three sides in order to conceal the wiper storage portion, for example. In addition, there is a wide portion in the substantially central portion on the upper side for the purpose of concealing the presence of the indoor mirror and various sensors.

  In the anti-fogging glass article 1 of the present embodiment, the width W of the frame-shaped concealing portion 31 is not particularly limited as long as the attachment portion to the vehicle opening flange is concealed, and at the central portion and the lower side of the upper side. Is preferably 10 to 300 mm, more preferably 30 to 200 mm. 10-100 mm is preferable and, as for the width W of the frame shape concealing part 31 in a part other than that, 20-50 mm is more preferable. Note that the width W of the frame concealment 31 improves the design of the antifogging glass article 1 and can be changed depending on the size and shape of the antifogging glass article 1.

  FIG. 3 shows a partially enlarged view of the P portion surrounded by the dotted line of the frame-shaped concealing portion 31 in the black ceramic layer 3 shown in FIG. The frame-shaped concealing portion 31 is formed in an outer edge region 33 formed as an integrated layer from the outer side toward the center from the outer periphery of the glass substrate 2 and a circular dot pattern toward the center with the inner edge of the outer edge region 33 as the outer edge. A dot pattern area 34 is formed. The width W of the frame-shaped concealing portion 3 is a width obtained by combining the width w1 of the outer edge region 33 and the width w2 of the dot pattern region 34.

  In the dot pattern region 34, the dot size can be set as appropriate, and for example, the diameter is preferably 0.001 to 10 mm. In the dot pattern region 34, the ratio of the area of the dot formation portion to the entire area of the dot pattern region can be 1 to 99%, preferably 10 to 90%, more preferably 30 to 80%, and particularly Preferably, it can be 30 to 70%.

  In the antifogging glass article 1 of the present embodiment, the dot size in the dot pattern region 34 is formed so as to decrease from the outer edge side to the inner edge side along the width direction of the dot pattern area 34. It is comprised so that the area ratio of a transparent part may become large so that it may become inside. In the dot pattern region 34, a change in transmittance does not occur abruptly at the boundary between the outer edge region 33 composed entirely of a black ceramic monolithic layer and the transparent region at the center of the antifogging glass article 1. It has the function to do. If the dot size in the dot pattern region 34 or the ratio of the area of the dot formation portion to the entire area of the dot pattern region is within the above range, it is preferable for designability, visibility of the driver or the like outside the vehicle, and the like. From this point of view, as in the antifogging glass article 1, in the dot pattern region 34, the ratio of the area of the dot formation portion to the area of the entire dot pattern region gradually decreases from the outer edge side to the inner edge side. It is more preferable to do.

  The width w2 of the dot pattern region 34 is preferably 0.5 to 100 mm, more preferably 1 to 50 mm, and particularly preferably 2 to 30 mm. The width w1 of the outer edge region 33 can be a value obtained by subtracting the width w2 of the dot pattern region 34 from the width W of the frame-shaped concealing portion 3. However, the width w1 of the outer edge region 33 is preferably at least 20 mm or more, and more preferably 30 mm or more.

  As shown in FIG. 2 (b), the adhesive layer 4 is formed in a region covering the entire portion where the width of the substantially central portion of the upper side of the frame-shaped concealing portion 31 is wide, and a region including the vicinity of the glass substrate. ing. Further, the adhesive layer 4 is also formed in a region covering the entire lower side of the frame-shaped concealing portion 31 and a lower portion of the side and the region including the glass substrate in the vicinity thereof. Furthermore, the adhesive layer 4 is formed so as to cover the entire character display portion 32. In this case, in the frame-shaped concealing portion 31, one end of the adhesive layer 4 coincides with the outer edge, and the other end is 5 to 10 mm from the inner edge of the frame-shaped concealing portion 31 toward the center side of the glass substrate 2. Preferably in the region. In the character display part 32, it is preferable to exist in the area | region of 5-10 mm toward the outer side from the outer periphery.

In the antifogging glass article 1 of the present embodiment, as described above, the adhesive layer 4 is formed at least when the following water absorption antifogging film 5 is formed on the glass substrate 2 with the black ceramic layer 3. It includes the entire laminated region where the antifogging film 5 and the black ceramic layer 3 overlap. The adhesive layer 4 may be formed only over the entire laminated region, but as shown in FIG. 2 (b), the adhesive layer 4 may be formed over the region up to the vicinity thereof to ensure adhesion to the entire laminated region. It is preferable at the point which can form a layer. Here, in this specification, the vicinity of the laminated region refers to a region of 0.1 to 50 mm outward from the end of the laminated region.
When water absorption, particularly alkaline or acidic water is absorbed, the water absorption and antifogging film tends to swell and peel off from the black ceramic layer. By forming the adhesive layer 4 in such a region, antifogging is achieved. It is possible to efficiently improve the durability such as the chemical resistance in the antifogging film of the porous glass article, particularly the durability such as the chemical resistance in the antifogging film formed on the black ceramic layer.

  Here, the antifogging glass article of the present invention does not have an adhesive layer beyond the vicinity of the laminated region. The water-absorbing anti-fogging film has sufficient adhesion to the glass substrate in a region where the black ceramic layer is not present, and therefore it is not necessary to provide an adhesive layer in such a region. Therefore, from the viewpoints of economy and work efficiency, the region where the adhesive layer is formed is a region consisting of the laminated region and its vicinity at most, and the other regions do not have the adhesive layer.

  The adhesive layer sufficiently bonds the black ceramic layer and the water-absorbing anti-fogging film. When the water-absorbing and anti-fogging film absorbs water, especially when alkaline or acidic water is absorbed, the water-absorbing and anti-fogging film expands and the The layer is not particularly limited as long as it is a layer that can impart resistance to the phenomenon of peeling, in other words, chemical resistance.

  Specifically, a substantially transparent layer mainly composed of a metal oxide or an organic group-containing metal oxide formed by a sol-gel method using a hydrolyzable metal compound is preferable as the adhesive layer. The hydrolyzable metal compound used for forming the adhesive layer is preferably a hydrolyzable metal compound in which a hydrolyzable functional group or atom is bonded to a metal such as silicon, aluminum, titanium, or zirconium, and is trifunctional or tetrafunctional. At least one selected from the group consisting of a hydrolyzable titanium compound and a trifunctional or tetrafunctional hydrolyzable silicon compound is more preferred, and a tetrafunctional hydrolyzable silicon compound is particularly preferred.

The trifunctional or tetrafunctional hydrolyzable titanium compound is a compound in which three or four hydrolyzable functional groups or atoms are bonded to titanium or silicon.
Examples of the hydrolyzable functional group or atom bonded to titanium or silicon include an alkoxy group, an acyloxy group, a ketoxime group, an alkenyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen atom.

  Among these, as the hydrolyzable functional group or atom bonded to silicon, an alkoxy group, an isocyanate group and a halogen atom are preferable from the viewpoint of the balance between the stability of the resulting compound and the ease of hydrolysis. As the halogen atom, a chlorine atom is preferable. As an alkoxy group, a C1-C4 alkoxy group is preferable and a methoxy group or an ethoxy group is more preferable. As the hydrolyzable functional group or atom bonded to silicon, an isocyanate group, a chlorine atom, a methoxy group, or an ethoxy group is more preferable, and an isocyanate group is particularly preferable.

The hydrolyzable functional group or atom bonded to titanium is preferably an alkoxy group, an acyloxy group, etc. from the viewpoint of the balance between the stability of the resulting compound and the ease of hydrolysis, and the compound is also a chelate compound. preferable. As an alkoxy group, a C1-C4 alkoxy group is preferable and an isopropoxy group or normal butoxy group is more preferable. As the hydrolyzable functional group or atom bonded to titanium, an isopropoxy group or a normal butoxy group is particularly preferable.
The hydrolyzable functional groups or atoms present in the hydrolyzable titanium compound or hydrolyzable silicon compound may be the same or different, and all three or four may be the same. The same is preferable in terms of availability.

  When the hydrolyzable titanium compound or hydrolyzable silicon compound is trifunctional, there is one group or atom other than the hydrolyzable functional group or atom bonded to titanium or silicon. In this case, the group or atom other than the hydrolyzable functional group or atom is preferably, for example, an alkenyl group having an addition polymerizable unsaturated group or an alkyl group having a reactive group. The alkyl group having a reactive group may be an alkyl group substituted with an organic group having a reactive group. As for carbon number of such an alkyl group, 1-4 are preferable. As a reactive group, an epoxy group, an amino group, a mercapto group, a ureido group, a hydroxyl group, a carboxy group, a (meth) acryloyloxy group (hereinafter, “(meth) acryloxy” is used in the notation of a compound as necessary. ), A functional group such as an isocyanate group, and a chlorine atom. Examples of the organic group having such a reactive group include a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted amino group. Among these, an alkyl group having an epoxy group, an amino group, a mercapto group, or a ureido group as a reactive group is preferable.

When a trifunctional hydrolyzable metal compound having a reactive group as described above is used, the functional group possessed by the component constituting the water-absorbing antifogging film formed on the adhesive layer and the reactive group possessed by the compound In the case of reactivity, it is considered that the adhesion is improved by combining these.
In addition, when a tetrafunctional hydrolyzable metal compound is used, the metal oxide matrix can be strengthened by adding the hydrolyzable metal compound to the components constituting the water-absorbing antifogging film formed on the adhesive layer. Bonds are formed, and the adhesion is further improved. Therefore, as the hydrolyzable metal compound used for forming the adhesive layer, a tetrafunctional hydrolyzable metal compound is preferable, and a tetrafunctional hydrolyzable silicon compound is particularly preferable from the viewpoint of durability to chemicals.

  Specific examples of the trifunctional hydrolyzable titanium compound include triisopropoxyisopropyl titanium, trinormal butoxy normal butyl titanium, and trinormal butoxy titanium monostearate. Specific examples of the tetrafunctional hydrolyzable titanium compound include tetraisopropoxy titanium and tetranormal butoxy titanium.

  Specific examples of the trifunctional hydrolyzable silicon compound include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2 -Aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl- 3- Mino propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyl trimethoxysilane.

Specific examples of the tetrafunctional hydrolyzable silicon compound include tetraisocyanate silane, tetrachlorosilane, tetramethoxysilane, tetraethoxysilane, tetranormalpropoxysilane, and tetranormalbutoxysilane.
In the present invention, among these hydrolyzable metal compounds, tetraisocyanate silane and tetrachlorosilane are particularly preferable.

  As a method of forming an adhesive layer by a sol-gel method using a hydrolyzable metal compound, a conventionally known method is used. Specifically, after preparing a composition for forming an adhesive layer containing a hydrolyzable metal compound and a solvent as essential components and other optional components such as an organic polymer, inorganic fine particles, and an acid as a hydrolysis promoting compound. The composition may be applied to the surface to be formed, dried and cured. Here, specific methods, such as application | coating, drying, hardening, are demonstrated in the below-mentioned manufacturing method.

  The solvent used in the composition for forming an adhesive layer is a solvent having good solubility with respect to the above-mentioned hydrolyzable metal compound and other optional ingredients, and an inert solvent for these ingredients. If it is, it will not specifically limit, Specifically, alcohol, acetate ester, ethers, ketones, water etc. are mentioned. As a ratio of the solvent and the hydrolyzable metal compound used in the composition for forming an adhesive layer, the hydrolyzable metal compound is 0.1 to 10% by mass with respect to 100% by mass of the total amount of the solvent and the hydrolyzable metal compound. The ratio which becomes is more preferable, and 0.5-5 mass% is more preferable.

  1-500 nm is preferable and, as for the thickness of the contact bonding layer formed using the composition for contact bonding layer formation, 10-50 nm is more preferable. If the thickness of the adhesive layer is within this range, the adhesive layer itself deteriorates the appearance quality such as cracks while providing sufficient chemical resistance for adhesion between the black ceramic layer and the water-absorbing anti-fogging film. This is preferable because it does not occur.

  In the antifogging glass article 1 of the present embodiment, as shown in FIG. 2 (c), the water absorption antifogging film 5 is formed on the inner surface of the antifogging glass article 1 and its end is a glass substrate. 2 is preferably formed so as to be entirely present in the frame-shaped concealing portion 31 formed on the surface 2. About the position of the edge part of the water absorption anti-fogging film 5, sectional drawing in the XX line of the anti-fogging glass article 1 shown in FIG. 4 and sectional drawing in the YY line of the anti-fogging glass 1 shown in FIG. It explains using.

  The cross-sectional view shown in FIG. 4 is a cross-sectional view in which the upper side of the antifogging glass article 1 is located on the left side. On the upper side of the antifogging glass article 1, a frame-like concealing portion 31 composed of an outer edge region 33 and a dot pattern region 34 is formed as a black ceramic layer 3 on the inner periphery of the glass substrate 2. In the position shown in the figure, an adhesive layer 4 is formed in a region covering the whole and a region including the glass substrate 2 in the vicinity thereof. The position of the end portion of the water-absorbing anti-fogging film 5 is set to an inner position within the outer edge region 33 so as not to hinder attachment to the vehicle opening flange. Specifically, when the distance from the outer edge of the glass substrate 2 to the end of the water-absorbing anti-fogging film 5 is w3, w3 is assumed to be present in the outer edge region 33, assuming that the end exists in the outer edge region 33. 10-30 mm is preferable on the upper side of the porous glass article 1, and 15-25 mm is more preferable. Moreover, 10-300 mm is preferable in the lower side, and 50-200 mm is more preferable. In addition, as above-mentioned, the distance L from the inner edge of the frame-shaped concealment part 31 shown in FIG. 4 to the inner edge of the contact bonding layer 4 is 5-10 mm as above-mentioned.

  FIG. 5 is a cross-sectional view mainly showing cross sections of both side portions of the antifogging glass 1. The frame-shaped concealing portion 31 as the black ceramic layer 3, the adhesive layer 4, and the water-absorptive anti-fogging film 5, which is composed of the glass substrate 2, the outer edge region 33, and the dot pattern region 34 on both sides of the antifogging glass 1 The stacking relationship is the same as the stacking relationship in the central portion on the upper side and the lower side shown in FIG. As for the formation region of each layer on the glass substrate 2 shown in FIG. 5, the width W of the frame-shaped concealing portion 31 is set smaller on both the left and right sides than the center and lower sides on the upper side as shown in FIG. Is formed. As shown in FIG. 4, the adhesive layer 4 is formed so as to cover the entire frame-shaped concealing portion 31 and reach the inside from the inner edge of the frame-shaped concealing portion 31 by a distance L. The distance L can be the same as described in FIG. The water-absorbing anti-fogging film 5 is formed so that the ends thereof are located in the dot pattern region 34 of the frame-shaped concealing portion 31 on both the left and right sides of the anti-fogging glass 1. The distance w3 from the outer edge of the glass substrate 2 to the end of the water-absorbing and anti-fogging film 5 is the same on both the left and right sides, preferably 10 to 30 mm, which is the same as the upper side of the antifogging glass 1, and 15 to 25 mm. More preferred.

  5 shows an example in which the end portions of the water-absorbing and anti-fogging film 5 are formed so as to be located in the dot pattern region 34 on both sides of the anti-fogging glass 1. 1, the water-absorbing and anti-fogging film 5 may be formed so that the end portions reach the outer edge region 33 in both side portions as in the case shown in FIG. 4.

  Here, the portion other than the central portion on the upper side of the antifogging glass article 1 has the same width W of the frame-shaped concealing portion 31 as that of the side, and in this portion, the frame-shaped concealing portion 31, the adhesive layer 4 and About the lamination | stacking relationship and formation area of the water absorption anti-fogging film | membrane 5, it is preferable that it is the same structure as the side side shown in FIG. That is, it is preferable that the end portion of the water-absorbing and antifogging film 5 is present in the same dot pattern region 34 as that on the side of the antifogging glass article 1 except for the central portion on the upper side of the antifogging glass article 1. . In addition, about the material and formation method which comprise the water absorption anti-fogging film | membrane 5, the below-mentioned material and formation method are applicable.

  On the frame concealing part 31 as the black ceramic layer 3 through the adhesive layer 4, the end of the water-absorbing anti-fogging film 5 is located at a position as shown in FIG. The antifogging glass article 1 is obtained which is free from distortion of the visual field due to the influence of the edge of the water-absorbing antifogging film 5 in a transparent region where the ceramic layer 3 is not formed, and has good appearance and visibility. Furthermore, the problem about adhesion | attachment with the vehicle opening part flange of the anti-fogging glass article 1 is also eliminated. Further, by causing the end of the water-absorbing anti-fogging film 5 to exist at a position as shown in FIG. 5, there is little deterioration in the appearance due to the difference in gloss of the frame-shaped concealing portion 31 depending on the presence or absence of the water-absorbing anti-fogging film 5, The visual influence on the driver and the like is further reduced, and improvement effects such as ease of seeing outside the vehicle and eye fatigue are increased.

  The water-absorbing and anti-fogging film of the anti-fogging glass article of the present embodiment is substantially transparent with anti-fogging property that prevents the fogging by removing fine water droplets adhering to the glass substrate surface by having water absorption. If it is a film | membrane, it will not restrict | limit in particular. Specific examples of the water-absorbing anti-fogging film include a water-absorbing anti-fogging film having a water-absorbing layer mainly composed of a water-absorbing crosslinked resin. The water-absorbing anti-fogging film may be composed of only the water-absorbing layer, and may further have various functional layers on the glass substrate side or the vehicle interior side in addition to the water-absorbing layer. The water-absorptive antifogging film preferably has a lower water-absorbing base layer than the water-absorbing layer on the glass substrate side of the water-absorbing layer. If the water-absorbing anti-fogging film has a low water-absorbing base layer, the difference in the degree of expansion / contraction at the bonding interface between the glass substrate and the water-absorbing anti-fog film, in fact, the glass substrate and the base layer is reduced. The peel resistance in can be improved.

  Here, the water absorption of the water absorbing layer and the base layer mainly depends on the properties of the materials constituting each layer. That is, the material constituting the water-absorbing layer (hereinafter referred to as the water-absorbing material) has a high water absorption sufficient for the water-absorbing and anti-fogging film to exhibit sufficient anti-fogging properties, and the material constituting the base layer (hereinafter referred to as the base material). ) Is preferably less water-absorbing than water-absorbing materials. In addition, the water absorption is relative, and “high water absorption” and “low water absorption” in the water absorption of both materials do not mean high or low with a threshold, but the water absorption of each material is For example, “saturated water absorption” measured by the following method can be shown as an index.

  A soda lime glass substrate having a predetermined shape and size, for example, 3 cm × 4 cm × thickness 2 mm, is provided with a layer of a material to be a specimen (hereinafter referred to as “material layer”), and this is placed at 10 ° C. and 95 to 99% RH environment. The moisture content (I) of the whole substrate with the material layer is measured using a trace moisture meter after leaving it in a constant temperature and humidity chamber for 2 hours. Further, the moisture content (II) is measured for the substrate only by the same procedure. A value obtained by subtracting the amount of water (II) from the amount of water (I) and dividing the volume by the volume of the material layer is defined as a saturated water absorption amount. The moisture content is measured as follows using a trace moisture meter FM-300 (trade name, manufactured by Kett Science Laboratory Co., Ltd.). The measurement sample is heated at 120 ° C., the moisture released from the sample is adsorbed to the molecular sieve in the micro moisture meter, and the mass change of the molecular sieve is measured as the moisture content. The end point of the measurement is the time when the mass change per 25 seconds becomes 0.05 mg or less.

Further, as an index indicating water absorption, in addition to the saturated water absorption, which is an index indicating the water absorption of the material constituting each layer, the water absorption of the layer itself by the material constituting each layer and the thickness of the layer is shown below. You may use "water absorption anti-fogging property" to define.
The water absorption and anti-fogging property is the same as described above, and a soda lime glass substrate having a predetermined shape and size, for example, 3 cm × 4 cm × 2 mm thickness, is provided with a material layer serving as a specimen, and this is formed at 20 ° C. and 50% relative humidity. The surface of the material layer after being left in the environment for 1 hour is placed on a 40 ° C. hot water bath, and is indicated by the antifogging time (seconds) until fogging is visually observed.

In the water-absorbing layer having water absorption antifogging saturated water amount of the water-absorbing material constituting the layer is, 50 mg / cm ³ or more preferably, 70 mg / cm ³ or more, more preferably, 100 mg / cm ³ or more is particularly preferable. When the saturated water absorption amount of the water absorbing material takes the above value, sufficient antifogging property can be secured. On the other hand, from the viewpoint of preventing the durability of the water antifogging decreases, the saturated water absorption amount of the water-absorbing material, preferably 900 mg / cm ³ or less, 500 mg / cm ³ or less is more preferable. Further, regarding the water absorption of the water absorbing layer, if water absorbing antifogging property is indicated as an index, the water absorbing antifogging property of the water absorbing layer is preferably 50 seconds or longer, more preferably 60 seconds or longer, and particularly preferably 70 seconds or longer.

  From the relationship between the saturated water absorption amount of the water-absorbing material constituting the water-absorbing layer shown above and the water-absorbing antifogging property of the water-absorbing layer, the thickness of the water-absorbing layer is preferably 5 μm or more and more preferably 10 μm or more. Thereby, it becomes easy to ensure the necessary saturated water absorption amount for the entire water absorption anti-fogging film. On the other hand, from the viewpoint of preventing the durability of the water-absorbing antifogging film from being lowered, the thickness of the water-absorbing layer is preferably 50 μm or less, and more preferably 40 μm or less.

In addition, when a water absorption anti-fogging film | membrane has a base layer, 30 mg / cm < ³ > or less is preferable from the said viewpoint, and the saturated water absorption amount of the base material which comprises this layer has more preferable 20 mg / cm < ³ > or less. On the other hand, from the viewpoint of reducing the degree difference of the expansion and contraction of the base layer and the water-absorbing layer in water antifogging film, the saturated water absorption of the base material, 1 mg / cm ³ or more, more is 3 mg / cm ³ or more preferable. Moreover, if water absorption anti-fogging property is shown as a parameter | index about the water absorption of a base layer, 10 seconds or less are preferable and the water absorption anti-fog property of a base layer has more preferable 7 seconds or less. From the same viewpoint as the saturated water absorption amount, the water absorption and antifogging property of the base layer is preferably 1 second or longer, and more preferably 2 seconds or longer.

From the relationship between the saturated water absorption amount of the base material constituting the base layer and the water absorption and antifogging property of the base layer, the thickness of the base layer is preferably 1 μm or more, more preferably 3 μm or more, and particularly preferably 5 μm or more. If the thickness of the underlayer is 1 μm or more, the peel resistance of the water-absorbing antifogging film can be improved. Furthermore, the thickness of the underlayer is more preferably 3 μm or more, and particularly preferably 5 μm or more, because the stress generated at the interface due to the expansion / contraction of the water absorption layer is relaxed. In addition, the thickness of the underlayer is preferably 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less from the viewpoint of reducing material costs and improving the yield rate.
The water absorption and antifogging property as the water absorption and antifogging film in the case of having a base layer is preferably 50 seconds or more, more preferably 60 seconds or more, and particularly preferably 70 seconds or more, similarly to the water absorption antifogging property of the water absorption layer. preferable.
Here, since the anti-fogging performance required of the anti-fogging glass article varies depending on the application, the design of each layer may be appropriately changed in accordance with the required performance.

Hereinafter, the water-absorbing material constituting the water-absorbing layer having the water-absorbing performance shown above and the base material constituting the base layer will be described.
(Water absorption layer and water absorption material)
The water-absorbing layer of the water-absorbing antifogging film according to the present invention is composed of a water-absorbing material mainly composed of a water-absorbing crosslinked resin. The water-absorbing material is highly water-absorbing enough to obtain anti-fogging performance, preferably a material that has a saturated water absorption of 50 mg / cm ³ or more, and may be composed of a crosslinked resin alone. The solid component may be included. The cross-linked resin may be a cross-linked resin obtained by reacting a cross-linkable component and a curing agent, or a cross-linked resin obtained by reacting a composition containing a reactive component in addition to the cross-linkable component and the hardener. May be. In the case where the water-absorbing anti-fogging film has an underlayer, in order to distinguish between the crosslinked resin constituting the water-absorbing layer and the crosslinked resin constituting the underlayer, hereinafter, the crosslinked resin constituting the water-absorbing layer is referred to as the first crosslinked resin. The cross-linked resin that constitutes the base layer is referred to as a second cross-linked resin.

  In this specification, the cross-linked resin refers to a cross-linked resin obtained from a composition containing a cross-linkable component and a curing agent as main raw material components in a maximum proportion in all reactive components. In addition, in this specification, the catalyst which concerns on a crosslinkable component is classified into a hardening | curing agent as a reactive component. Furthermore, when the reactive component is a component whose chemical composition obtained after the reaction is significantly different from that of the raw material, such as a tetrafunctional hydrolyzable silicon compound, the blending amount in the composition is obtained after the reaction. In consideration of the chemical structure, for example, the tetrafunctional hydrolyzable silicon compound is calculated in terms of oxide.

Examples of the first cross-linked resin include a first cured epoxy resin, a first urethane resin, and a first cross-linked acrylic resin. These may be used alone or in combination of two or more. In the following description, in the first cross-linked resin, the cross-linking component and the curing agent are all referred to as “first ...”.
The first cured epoxy resin is obtained by reaction of a composition containing a first polyepoxide component and a first curing agent. The first urethane resin is obtained by the reaction of a composition containing the first polyisocyanate and the first polyol. The first cross-linked acrylic resin is obtained by reaction of a composition containing the first cross-linkable (meth) acrylic polymer and the first curing agent for acrylic resin.

In this specification, polyepoxide refers to a compound having two or more epoxy groups in one molecule. Polyepoxide includes low molecular weight compounds, oligomers, and polymers. The polyepoxide component is a component composed of at least one polyepoxide, and may be hereinafter referred to as a main agent as necessary.
Further, the curing agent is a compound having two or more reactive groups in one molecule that react with the epoxy group of the polyepoxide, and is a polyaddition type curing agent that polyadds to the polyepoxide by reaction, and the polyepoxide by reaction. It is used as a term encompassing a condensation type curing agent that is polycondensed with a catalyst and a reaction type catalyst such as a Lewis acid that catalyzes a polymerization reaction between polyepoxides. The catalyst-type curing agent includes a thermosetting type and a photo-curing type, and these are collectively referred to as a catalyst-type curing agent.
Further, the cured epoxy resin refers to a cured product obtained by a crosslinking reaction between the main agent and the curing agent. The cured epoxy resin has a structure in which polyepoxide is cross-linked by a polyaddition type curing agent or the like to form a three-dimensional structure and / or a structure in which polyepoxides are linearly or three-dimensionally polymerized.

  In this specification, polyisocyanate refers to a compound having two or more isocyanate groups in one molecule. Polyisocyanates include low molecular compounds, oligomers and polymers. Polyol refers to a polymer compound having an active hydrogen group such as two or more alcoholic hydroxyl groups in one molecule and a molecular weight of approximately 200 or more. The urethane resin refers to a cured product obtained by crosslinking reaction of the polyisocyanate and the polyol. The urethane resin has a structure in which a polyol is cross-linked with a polyisocyanate to form a three-dimensional structure.

  In this specification, the crosslinkable (meth) acrylic polymer is a (co) polymer obtained by (co) polymerizing a (meth) acrylic acid compound selected from acrylic acid, methacrylic acid, and esters thereof. And a compound having two or more crosslinkable groups in one molecule. The crosslinkable (meth) acrylic polymer may contain a polymer unit derived from a monomer other than the (meth) acrylic acid compound in an amount of less than 100 mol% with respect to all the polymerized units. The curing agent for acrylic resin refers to a compound having two or more functional groups having reactivity with the crosslinkable group of the crosslinkable (meth) acrylic polymer. The cross-linked acrylic resin refers to a cured product obtained by a cross-linking reaction between the cross-linkable (meth) acrylic polymer and the acrylic resin curing agent. Here, the “polymerization unit” refers to the minimum repeating unit formed by a polymerization reaction of a monomer that is a compound having a polymerizable reactive group.

In addition, in the crosslinked acrylic resin, a reactive component other than the crosslinkable (meth) acrylic polymer and the acrylic resin curing agent is partly formed in a crosslinked structure formed by the crosslinkable (meth) acrylic polymer and the acrylic resin curing agent. In which a cured product is formed by mechanically bonding. The cross-linked acrylic resin has a three-dimensional structure in which a cross-linkable (meth) acrylic polymer is cross-linked with a curing agent for acrylic resin.
"(Meth) acrylic ..." in this specification is a general term for "methacrylic ..." and "acrylic ...". The same applies to (meth) acryloyl.

The first cured epoxy resin used in the present invention is a cross-linked resin obtained by the reaction of the composition containing the first polyepoxide component and the first curing agent, and when it is a water-absorbing material mainly composed of it, It is a cross-linked resin having a high water absorption to such an extent that anti-fogging performance is obtained, and preferably a saturated water absorption amount of 50 mg / cm ³ or more.

  For example, the water absorption evaluated by the saturated water absorption of the cured epoxy resin mainly depends on the abundance of hydrophilic groups such as hydroxyl groups and hydrophilic chains (polyoxyethylene groups and the like) derived from the main agent. The water absorption also depends on the degree of crosslinking in the cured epoxy resin. If the number of cross-linking points contained in the cured epoxy resin per unit amount is large, the cured epoxy resin has a dense three-dimensional network structure, and it is considered that the water absorption becomes low because the space for water retention becomes small. On the other hand, if the number of cross-linking points contained per unit amount is small, it is considered that the space for water retention becomes large and the water absorption becomes high. The glass transition point of the cured epoxy resin is closely related to the number of crosslinking points in the cured epoxy resin. In general, a resin having a high glass transition point is considered to have a large number of crosslinking points per unit amount.

  Accordingly, it is generally preferable to control the glass transition point of the cured epoxy resin low to increase the water absorption, and to control the glass transition point of the cured epoxy resin high to increase the scratch resistance. In consideration of these, the glass transition point of the first water-absorbing layer-containing first cured epoxy resin is preferably −20 to 60 ° C., although it depends on the type of the cured epoxy resin. More preferably, it is 40 degreeC.

  The glass transition point is a value measured according to JIS K 7121. Specifically, it is a value measured using a differential scanning calorimeter after providing a resin layer as a specimen on a substrate and leaving it in an environment of 20 ° C. and 50% relative humidity for 1 hour. However, the heating rate at the time of measurement shall be 10 degrees C / min.

  The first cured epoxy resin having the water absorption property used in the present invention is a composition for forming a water absorption layer comprising a first polyepoxide component, a first polyaddition type curing agent, and a first catalyst type curing agent described below. It is preferably a resin obtained by reacting a product.

  As the polyepoxide constituting the first polyepoxide component, the glycidyl ether polyepoxide, glycidyl ester polyepoxide, glycidylamine polyepoxide, cycloaliphatic polyepoxide, etc., which are used as raw material components of ordinary cured epoxy resins, have the molecular weight described above. It can adjust and use so that it may become a range. The number of epoxy groups per molecule of polyepoxide in the first polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, more preferably 2 to 7 3 to 5 are particularly preferable.

  The glycidyl ether-based polyepoxide is a polyepoxide having a structure in which a glycidyloxy group is substituted for a phenolic hydroxyl group of a polyphenol having two or more phenolic hydroxyl groups or an alcoholic hydroxyl group of a polyol having two or more alcoholic hydroxyl groups. Polyepoxide oligomer). The glycidyl ester polyepoxide is a polyepoxide having a structure in which the carboxy group of a polycarboxylic acid having two or more carboxy groups is substituted with a glycidyloxycarbonyl group, and the glycidylamine polyepoxide has two or more hydrogen atoms bonded to a nitrogen atom. It is a polyepoxide having a structure in which a hydrogen atom bonded to a nitrogen atom of an amine is substituted with a glycidyl group. The cycloaliphatic polyepoxide is a polyepoxide having an alicyclic hydrocarbon group (such as a 2,3-epoxycyclohexyl group) in which an oxygen atom is bonded between adjacent carbon atoms of the ring.

  Among such various polyepoxides, as the polyepoxide constituting the first polyepoxide component, a polyepoxide having no aromatic ring is preferable from the viewpoint of obtaining high water absorption in the obtained cured epoxy resin. A cured epoxy resin obtained using a polyepoxide having an aromatic ring, for example, a glycidyl ether-based polyepoxide derived from polyphenols, is difficult to incorporate moisture into the three-dimensional network structure due to the hard aromatic ring, It is thought that water absorption is low.

  Specific examples of the polyepoxide having no aromatic ring include glycidyl ether-based polyepoxides derived from polyols, glycidyl ester-based polyepoxides, glycidylamine-based polyepoxides, and polyepoxides having no aromatic ring among cyclic aliphatic polyepoxides. Of these, glycidyl ether polyepoxides derived from polyols having no aromatic ring are particularly preferred in the invention.

  As a raw material polyol of glycidyl ether-based polyepoxide derived from polyols having no aromatic ring, there are polyols having no aromatic ring such as aliphatic polyols and alicyclic polyols, and the number of hydroxyl groups per molecule is 2 to 10 The number is preferable, 2 to 8 is more preferable, and 3 to 5 is particularly preferable. Hereinafter, such a polyol having no aromatic ring is referred to as an aliphatic / alicyclic polyol. Examples of the aliphatic / alicyclic polyol include alkane polyol, etheric oxygen atom-containing polyol, sugar alcohol, polyoxyalkylene polyol, and polyester polyol. The polyoxyalkylene polyol is obtained by ring-opening addition polymerization of a monoepoxide such as propylene oxide or ethylene oxide to a relatively low molecular weight polyol such as an alkane polyol, an etheric oxygen atom-containing polyol or a sugar alcohol. The polyester polyol includes a compound having a structure in which an aliphatic diol and an aliphatic dicarboxylic acid are condensed, a compound having a structure in which a cyclic ester is ring-opening polymerized, and the like.

  Specific examples of the glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols preferably used in the present invention include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, neopentyl glycol. Diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol poly Glycidyl ether, polyethylene glycol diglycidyl ether, polyoxypropylene diol diglycidyl ether Polyoxypropylene triol triglycidyl ether, poly (oxypropylene-oxyethylene) triol triglycidyl ether and the like.

  Among these, the glycidyl ether-based polyepoxide derived from aliphatic / alicyclic polyols that are preferably used preferably has an average number of glycidyloxy groups per molecule of preferably 2 to 10, more preferably 2 to 8. And particularly preferably 3 to 5 polyepoxides.

  Such polyepoxides include, for example, triol triglycidyl ether, tetraol tetraglycidyl ether, a mixture of triol triglycidyl ether and the same triol diglycidyl ether, tetraol tetraglycidyl ether, triglycidyl ether and diol. Examples thereof include a mixture of glycidyl ether, a mixture of triglycidyl ether of triol and diglycidyl ether of diol, and the like. More specifically, the average number of glycidyloxy groups per molecule is preferably 2-10, more preferably 2-8, particularly preferably 3-5, glycerol polyglycidyl ether, di- Examples thereof include glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, and sorbitol polyglycidyl ether.

  The polyepoxide having no aromatic ring other than the glycidyl ether-based polyepoxide derived from the above aliphatic / alicyclic polyols is a cycloaliphatic polyepoxide, 3,4-epoxycyclohexylmethyl-3 ′, 4′- Examples thereof include epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.

  Among these, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, polyethylene glycol polyglycidyl ether, polyethylene glycol sorbitol polyglycidyl ether, which are glycidyl ether-based polyepoxides derived from aliphatic / alicyclic polyols Polysorbitol polyglycidyl ether and the like are particularly preferably used in the present invention.

The molecular weight of the polyepoxide constituting the first polyepoxide component is preferably from 100 to 3000, more preferably from 300 to 2000, from the viewpoints of durability, thermosetting property of the coating film, and handling property at the time of adjusting the coating liquid. ˜1800 is particularly preferred. The epoxy equivalent of the polyepoxide (gram number of resin containing 1 gram equivalent of epoxy group [g / eq]) is preferably 120 to 200 g / eq, and more preferably 150 to 180 g / eq.
In the present specification, molecular weight refers to mass average molecular weight (Mw) unless otherwise specified. Moreover, the mass average molecular weight (Mw) in this specification means the mass average molecular weight which uses polystyrene as a standard measured by gel permeation chromatography (GPC).

As a 1st polyepoxide component, 1 type of the said polyepoxide may be used independently, and 2 or more types may be used together.
Moreover, as a polyepoxide which can comprise the said 1st polyepoxide component, it is possible to use a commercial item.
As such a commercially available product, specifically, Denacol EX-313 (molecular weight (Mw): 383, average number of epoxy groups: 2.0) which is a glycerol polyglycidyl ether under the trade name manufactured by Nagase ChemteX Corporation. Per molecule), Denacol EX-314 (molecular weight (Mw): 454, average number of epoxy groups: 2.3 per molecule), polyglycerol polyglycidyl ether, Denacol EX-512 (molecular weight (Mw): 630, average) Epoxy group number: 4.1 / molecule).

Furthermore, Denacol EX-1410 (molecular weight (Mw): 988, average number of epoxy groups: 3.5 / molecule), Denacol EX-1610 (molecular weight (Mw): 1130, average number of epoxy groups: aliphatic polyglycidyl ether: 4.5 / molecule), Denacol EX-610U (molecular weight (Mw): 1408, average number of epoxy groups: 4.5 / molecule), polyglycerol polyglycidyl ether, Denacol EX-521 (molecular weight (Mw): 1294, average number of epoxy groups: 6.3 / molecule).
Examples of sorbitol polyglycidyl ether include Denacol EX-622 (molecular weight (Mw): 930, average number of epoxy groups: 4.9 / molecule).

The first cured epoxy resin that mainly constitutes the water absorption layer is a first cured epoxy resin obtained by reacting the first polyepoxide component with a first curing agent, and the first polyepoxide component The first cured epoxy resin obtained by reacting the first polyaddition type curing agent with the first catalytic type curing agent is preferable.
The first polyaddition type curing agent is a compound having two or more reactive groups that react with the epoxy group of the polyepoxide, and is not particularly limited as long as it is a type of curing agent that polyadds to the polyepoxide by reaction.

  Examples of the reactive group that reacts with the epoxy group in the first polyaddition type curing agent include an amino group having active hydrogen, a carboxy group, and a thiol group. That is, the first polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxy groups, or a compound having two or more thiol groups, More preferably, an amino compound having the above active hydrogen is used. Specific examples of such a compound having two or more reactive groups include polyamines, polycarboxylic acid anhydrides, polyamides, polythiols and the like. In the present invention, polyamines and polycarboxylic acid anhydrides are exemplified. The product is preferably used. As a 1st polyaddition type hardening | curing agent, these 1 type may be used independently and 2 or more types may be used together.

As described above, the first polyepoxide component used in the first cured epoxy resin that is the main component of the water absorbing layer in the present invention is preferably a polyepoxide having no aromatic ring from the viewpoint of obtaining high water absorption. Similarly, the polyaddition type curing agent which is one of the reactive raw materials of the first cured epoxy resin is also preferably a compound having no aromatic ring from the viewpoint of obtaining high water absorption.
That is, even if the first polyepoxide component is composed of an aliphatic polyepoxide, if the first polyaddition type curing agent to be used has an aromatic ring, a cured epoxy resin obtained by reacting these, It becomes a cured epoxy resin having a relatively large number of aromatic rings, which may result in insufficient water absorption.

  Accordingly, the first polyaddition type curing agent is preferably a polyamine or polycarboxylic anhydride having no aromatic ring, and particularly preferably a polyamine having no aromatic ring. Polyamines having 2 to 4 amino groups having active hydrogen are preferable as polyamines, and dicarboxylic acid anhydrides, tricarboxylic acid anhydrides, and tetracarboxylic acid anhydrides are preferable as polycarboxylic acid anhydrides.

  Examples of polyamines having no aromatic ring include aliphatic polyamine compounds and alicyclic polyamine compounds. Specific examples of these polyamines include ethylenediamine, triethylenediamine, triethylenetetramine, tetraethylenepentamine, hexamethylenediamine, polyoxyalkylenepolyamine, isophoronediamine, mensendiamine, 3,9-bis (3-amino Propyl) -2,4,8,10-tetraoxaspiro (5,5) undecane and the like.

The polyoxyalkylene polyamine is a polyamine having a structure in which the hydroxyl group of the polyoxyalkylene polyol is substituted with an amino group. For example, the hydroxyl group of the polyoxypropylene polyol having 2 to 4 hydroxyl groups is converted to an amino group having active hydrogen. There are compounds having 2 to 4 amino groups having a structure substituted on the group. The molecular weight per amino group is preferably 1000 or less, and particularly preferably 500 or less.
Examples of the polycarboxylic acid anhydride having no aromatic ring include succinic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and the like.

  A commercial item can also be used for the first polyaddition type curing agent. As such a commercial product, specifically, as polyoxyalkylene triamine, Jeffamine T403 (trade name, manufactured by Huntsman, molecular weight (Mw): 480) and the like are used as polysulfide polymers which are crosslinking accelerators, and polythiol QE340M. (Trade name, manufactured by Toray Fine Chemical Co., Ltd.).

  The blending ratio of the first polyepoxide component, which is the raw material component of the first cured epoxy resin used in the present invention, and the first polyaddition type curing agent is the first weight to the epoxy group derived from the first polyepoxide component. The ratio of the reactive group equivalent group of the addition-type curing agent is preferably 0.8 to 1.2, and more preferably 1.0 to 1.1. If the equivalent ratio of the reactive group of the first polyaddition type curing agent to the epoxy group derived from the first polyepoxide component is in the above range, the water absorption is achieved without lowering the durability such as wear resistance. Thus, a cured epoxy resin having a suitably crosslinked three-dimensional network structure is obtained.

  In the present invention, when an amino compound having active hydrogen is used as the first polyaddition type curing agent, the equivalent ratio of amine active hydrogen to epoxy group derived from the first polyepoxide component is 0.6 to 0.8. It is preferable to use so that it may become a ratio. Similarly to the above, when the equivalent ratio of the amine active hydrogen to the epoxy group is in the above range, a cured epoxy resin having a three-dimensional network structure that is appropriately cross-linked so as to have the above-mentioned water absorption without significant yellowing can be obtained.

  Here, if the mass ratio of the first polyaddition type curing agent to the first polyepoxide component is too large, the physical properties of the first cured epoxy resin obtained may be insufficient. It is preferable that the ratio of the 1st polyaddition type hardening | curing agent with respect to a component is 40 mass% or less.

  When the first polyepoxide component and the first polyaddition type curing agent are used in combination when obtaining the first cured epoxy resin used in the present invention, in addition to these, the first catalytic type curing agent is used. It is preferable to use both. By using the first catalyst type curing agent, the effect of accelerating the crosslinking rate by the polyaddition reaction between the first polyepoxide component and the first polyaddition type curing agent, and the first polyepoxide component and the first weight This is because it is possible to obtain an effect of reducing problems occurring at the cross-linked site formed by the addition type curing agent. An example of a defect in the cross-linked site is the color development of the cured epoxy resin due to the alteration of the cross-linked site due to heat load.

  Further, the first cured epoxy resin used in the present invention may be a cured epoxy resin obtained by crosslinking reaction of the first polyepoxide component in the presence of the first catalytic curing agent. The first catalyst-type curing agent is a reaction catalyst such as a Lewis acid and is a catalyst-type curing agent that catalyzes a polymerization reaction between polyepoxides and / or a polyaddition reaction between a polyepoxide and a polyaddition-type curing agent. Can be used without any particular restrictions.

  Specific examples of the first catalyst-type curing agent include curing catalysts such as tertiary amines, imidazoles, Lewis acids, onium salts, dicyandiamides, organic acid dihydrazides, and phosphines. More specifically, 2-methylimidazole, 2-ethyl-4-methylimidazole, tris (dimethylaminomethyl) phenol, boron trifluoride-amine complex, dicyandiamide, diphenyliodonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate Etc. As a 1st catalyst type hardening | curing agent, these 1 type may be used independently and 2 or more types may be used together.

  Here, as explained below, the first catalyst-type curing agent gives the water absorption of the cured epoxy resin obtained even if it is a compound having an aromatic ring, due to the small amount of the first polyepoxide component used. There is almost no impact. Therefore, you may use the compound which has an aromatic ring as a 1st catalyst type hardening | curing agent as needed. The onium salts exemplified above, such as diphenyliodonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate, are catalytic curing agents that generate a Lewis acid catalyst by being decomposed by light such as ultraviolet rays, and are usually photocured. It is used as a catalyst-type curing agent for the cured epoxy resin.

  Among such first catalyst type curing agents, the first polyaddition type curing agent in the present invention, preferably the first catalyst type curing agent used together with polyamines having no aromatic ring, is 2-methyl. Imidazole compounds such as imidazole and 2-ethyl-4-methylimidazole are preferred.

  A commercial item can also be used for the 1st catalyst type hardening agent. Examples of such commercially available products include Adekaoptomer SP152 (trade name, manufactured by Adeka) as a triarylsulfonium salt that is a photocurable catalyst-type curing agent.

  The amount of the first catalytic curing agent used in the case of using the first catalytic curing agent in addition to the first polyaddition curing agent is 1.0 to 20 with respect to 100% by mass of the first polyepoxide component. % By mass is preferable, 1 to 10% by mass is more preferable, and 1 to 5% by mass is particularly preferable. When the amount of the first catalyst-type curing agent used is 100% by mass or more with respect to 100% by mass of the first polyepoxide component, the reaction proceeds sufficiently and sufficient water absorption is obtained in the obtained first cured epoxy resin. And durability. Moreover, if the usage-amount of the 1st catalyst type hardening | curing agent with respect to 100 mass% of 1st polyepoxide components is 20 mass% or less, the residue of a 1st catalyst type hardening | curing agent will be in the obtained 1st hardening epoxy resin. It is easy to suppress the appearance problems such as yellowing of the cured epoxy resin.

  Moreover, when using a 1st catalyst type hardening | curing agent independently as a 1st hardening | curing agent when obtaining a 1st hardening epoxy resin, the usage-amount of the 1st catalyst type hardening | curing agent is the 1st polyepoxide component 100. 1-20 mass% is preferable with respect to mass%, and 1-10 mass% is more preferable.

  When the first catalyst type curing agent is used in addition to the first polyaddition type curing agent, the usage ratio of the first polyaddition type curing agent to the first polyepoxide component is the first catalyst type. When the curing agent is used in the above ratio, the equivalent ratio of the reactive group of the first polyaddition type curing agent to the epoxy group may be reduced by about 10 to 50% from the above 0.5 to 1.0. .

The first urethane resin used in the present invention is a cross-linked resin obtained by the reaction of a composition containing the first polyisocyanate and the first polyol, and when used as a water-absorbing material mainly comprising the resin, It is a cross-linked resin that has high water absorption to such an extent that performance can be obtained, and preferably has a saturated water absorption of 50 mg / cm ³ or more.

  Specifically, as the first urethane resin having such a high water absorption performance, a (meth) acryl polyol having an average molecular weight of 1000 to 4000, and a first polyol containing a polyoxyalkylene polyol having an average molecular weight of 400 to 5000, Examples thereof include a urethane resin obtained by reacting with the first polyisocyanate.

  By using a (meth) acrylic polyol having an average molecular weight of 1000 to 4000 and a polyoxyalkylene polyol having an average molecular weight of 400 to 5000 as a first polyol for producing the first urethane resin, the first urethane resin is used. It is thought that the inner chain contributes to increasing the speed of dewatering the water absorbed in the water absorption layer.

  The polyoxyalkylene-based polyol is used as a first polyol for causing the water absorption layer to exhibit an antifogging function. As the polyoxyalkylene polyol, a polyol having an oxyethylene chain, an oxypropylene chain, or the like can be used. In particular, the oxyethylene chain is excellent in the function of absorbing water as bound water, and thus is advantageous for forming a water-absorbing layer having reversible absorption and dehydration that has a high dehydration rate during dehydration. Therefore, it is preferable to use a polyol having an oxyethylene chain in consideration of the antifogging property in a low temperature environment such as winter when the ambient temperature is 5 ° C. or lower.

  The average molecular weight of the polyoxyalkylene polyol is 400 to 5000. When the average molecular weight is less than 400, the ability to absorb water as bound water is low, and when the average molecular weight exceeds 5000, Problems such as a decrease in film strength are likely to occur. Considering the water absorption and mechanical strength of the water absorbing layer, the average molecular weight is more preferably 400 to 4500. In the present specification, the material used for the urethane resin and the average molecular weight of the obtained urethane resin refer to the number average molecular weight (Mn). The number average molecular weight (Mn) refers to the number average molecular weight based on polystyrene measured by gel permeation chromatography (GPC).

  In particular, when the polyoxyalkylene-based polyol is polyethylene glycol, the average molecular weight is preferably set to 400 to 2000 in consideration of the ability to absorb water, poor curing and mechanical strength of the water absorption layer. In the case of an oxyethylene / oxypropylene copolymer polyol, the average molecular weight is preferably 1500 to 5000.

  A plurality of types of polyols may be used as the polyoxyalkylene-based polyol. In this case, the polyol to be used includes polyethylene glycol having an average molecular weight of 400 to 2000 that is particularly excellent in the ability to absorb water as bound water. It is preferable. Since polyethylene glycol is particularly excellent in the ability to absorb water as bound water, all polyoxyalkylene polyols may be polyethylene glycol.

  In addition, 80-600 mgKOH / g is preferable and, as for the hydroxyl value of the polyoxyalkylene type polyol used as a 1st polyol, 100-200 mgKOH / g is more preferable. A polyoxyalkylene type polyol can be used individually by 1 type or in combination of 2 or more types.

  The (meth) acrylic polyol has an effect of lowering wear resistance, water resistance, and surface friction coefficient mainly in the water absorbing layer, that is, exhibiting slip property on the surface of the water absorbing layer. In addition to this, this (meth) acrylic polyol has the effect | action which shortens the leveling process of equalizing the film thickness deviation at the time of apply | coating to the base material the composition for water absorption layer formation for forming a water absorption layer.

  (Meth) acrylic polyol has an average molecular weight of 1000 to 4000. If it is less than 1000, the wear resistance of the water-absorbing layer tends to decrease, and if it exceeds 4000, the applicability of the water-absorbing layer-forming composition at the time of forming the water-absorbing layer tends to be poor, and the water-absorbing layer formation tends to be difficult. . In consideration of the density and hardness of the water-absorbing layer to be obtained, the number of hydroxyl groups in the (meth) acrylic polyol is preferably 3 or 4. In addition, 10-300 mgKOH / g is preferable and, as for the hydroxyl value of (meth) acryl polyol, 30-160 mgKOH / g is more preferable.

  In the present invention, the water-absorbing layer has absorbed water by the chain in the first urethane resin obtained by reacting the polyoxyalkylene polyol and the polyol containing the (meth) acrylic polyol with the first polyisocyanate. It has the effect of increasing the water dehydration rate. Since this effect tends to improve as the molecular weight of the (meth) acrylic polyol increases, the average molecular weight of the (meth) acrylic polyol is preferably 2000 or more.

  The (meth) acrylic polyol contributes to improving the durability of the water absorption layer and increasing the water dehydration rate as described above. Considering only the improvement in durability of the water absorption layer, a polyol exhibiting hydrophobicity other than the (meth) acrylic polyol can be used, but it does not contribute to increasing the water dehydration rate. Therefore, it is preferable to include (meth) acrylic polyol as the first polyol for obtaining the first urethane resin, but it may not be an essential component depending on the design of the antifogging article. (Meth) acrylic polyols can be used singly or in combination of two or more.

  A commercial item can also be used for the first polyol. As such a commercially available product, specifically, polyethylene glycol, both of which are trade names manufactured by Lion Corporation, PEG1000 (hydroxyl value: 110 mgKOH / g, molecular weight (Mn): 1000), PEG1500 (hydroxyl value: 200 mgKOH / g, molecular weight (Mn): 1500), PEG 1540 (hydroxyl value: 85 mg KOH / g, molecular weight (Mn): 1540), and the like.

  In addition, as (meth) acrylic polyols, all are trade names of Sumika Bayer Urethane Co., Ltd., Desmophen A450BA / X (hydroxyl value: 33 mgKOH / g), Desmophen A450BA (hydroxyl value: 33 mgKOH / g), Desmophen A365 (hydroxyl group) Value: 92 mgKOH / g).

  As the first polyisocyanate for crosslinking reaction with the first polyol to form the first urethane resin, an organic polyisocyanate such as an organic diisocyanate, preferably a biuret starting from hexamethylene diisocyanate and A trifunctional polyisocyanate having an isocyanurate structure can be used.

  Such a first polyisocyanate has weather resistance, chemical resistance, and heat resistance, and is particularly effective for weather resistance. As the first polyisocyanate, diisophorone diisocyanate, diphenylmethane diisocyanate, bis (methylcyclohexyl) diisocyanate, toluene diisocyanate and the like can be used in addition to the above.

  18-30% is preferable and 20-25% of NCO% showing the mass% of the isocyanate group (NCO group) with respect to the total mass of 1st polyisocyanate is more preferable.

  A commercial item can also be used for the first polyisocyanate. As such a commercial product, specifically, as a hexamethylene diisocyanate type polyisocyanate, Death Module N3200 (trade name, manufactured by Sumika Bayer Urethane Co., Ltd., NCO%: 23%), Death Module N3400 (trade name, Sumika) Bayer Urethane Co., Ltd.).

  As the blending ratio of the first polyisocyanate and the first polyol, the number of isocyanate groups as the whole first polyisocyanate is 1 to 2 times the number of hydroxyl groups as the whole first polyol. It is preferable to adjust the amount, more preferably 1.4 times to 1.8 times. When the amount is less than 1 times, the curability deteriorates and the formed water-absorbing layer is soft, and durability such as weather resistance, solvent resistance, and chemical resistance may be lowered. On the other hand, when the amount exceeds 2 times, the antifogging property is deteriorated because the water absorption and dehydration is inhibited by excessive curing.

  The ratio of the polyoxyalkylene polyol and the (meth) acrylic polyol is adjusted so that the water absorption performance of the first urethane resin obtained is the saturated water absorption amount. For example, in the case of polyethylene glycol and (meth) acrylic polyol, the component ratio is preferably such that polyethyleneglycol: (meth) acrylic polyol = 50: 50 to 70:30 in terms of mass ratio.

In order to increase the curing rate of the first polyol and the first polyisocyanate, an organotin compound as a curing catalyst may be used together with these. Specific examples of the compound include dibutyltin dilaurate, dioctyltin dilaurate, stannous octoate, dibutyltin dioctoate, dibutyltin diacetate, dibutyltin marker butylide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin marker butylide, dioctyltin A thiocarboxylate or the like can be used.
As a compounding quantity, 0.1-5 mass% is preferable with respect to 100 mass% of the total amount of the said polyol and polyisocyanate.

The first cross-linked acrylic resin used in the present invention is a cross-linked resin obtained by the reaction of a composition containing the first cross-linkable (meth) acrylic polymer and the first curing agent for acrylic resin, and the main component thereof is When the water-absorbing material is used, it is a cross-linked resin that has a high water-absorbing property so that anti-fogging performance can be obtained, and preferably has a saturated water-absorbing amount of 50 mg / cm ³ or more.

  The first crosslinkable (meth) acrylic polymer is preferably a linear polymer. Moreover, it is preferable that the molecular weight of a 1st crosslinkable (meth) acrylic polymer is 500-50000 in a number average molecular weight, and 2000-20000 is especially preferable. If the molecular weight is less than 500, the antifogging performance of the water absorbing layer may be lowered. Moreover, when molecular weight exceeds 50000, there exists a possibility that the adhesiveness of a base layer and a water absorption layer may fall.

  The crosslinkable group possessed by the first crosslinkable (meth) acrylic polymer is not particularly limited as long as it is a group capable of reacting with the reactive group possessed by the first acrylic resin curing agent to form a three-dimensional network structure. Specific examples of crosslinkable groups include vinyl groups, epoxy groups, styryl groups, (meth) acryloyloxy groups, amino groups, ureido groups, chloro groups, thiol groups, sulfide groups, hydroxyl groups, carboxy groups, and acid anhydride groups. A carboxy group, an epoxy group, or a hydroxyl group is preferable, and a carboxy group is particularly preferable. The number of crosslinkable groups possessed by the first crosslinkable (meth) acrylic polymer may be any number as long as the antifogging performance and durability required in the present invention are satisfied. 1.0-3.0 mmol is preferable per 1 g of acrylic polymer, and 1.5-2.5 mmol is more preferable.

  The first crosslinkable (meth) acrylic polymer preferably has a hydrophilic group or a hydrophilic polymer chain from the viewpoint of obtaining a crosslinked resin having high water absorption. Or you may provide water absorption to the 1st crosslinked acrylic resin obtained by the 1st hardening | curing agent for acrylic resins having a hydrophilic group and a hydrophilic polymer chain | strand. The first crosslinkable (meth) acrylic polymer is preferably a crosslinkable (meth) acrylic polymer having a cationic group and a crosslinkable group. The cationic group is preferably a group having a quaternary ammonium structure. The ratio of the cationic group in the crosslinkable vinyl polymer is 0.1 to 2.0 mmol per 1 g of the polymer, and 0.4 to 2.0 mmol. 0.5 to 1.5 mmol is particularly preferable.

  The introduction of a crosslinkable group or a cationic group into the first crosslinkable (meth) acrylic polymer may be performed on the polymer after polymerization. However, the monomer having a crosslinkable group or the monomer having a cationic group may be used. You may obtain the 1st crosslinkable (meth) acrylic polymer which has the said crosslinkable group or a cationic group by copolymerizing the raw material monomer containing these using. Usually, the first crosslinkable (meth) acrylic polymer is produced by the latter method.

  In the first cross-linked acrylic resin used in the present invention, the first cross-linkable (meth) acrylic polymer combined with the first cross-linkable (meth) acrylic polymer has a cross-linkage possessed by the first cross-linkable (meth) acrylic polymer. If it is a hardening | curing agent for acrylic resins which has a reactive group reactive to a reactive group, it will not be restrict | limited.

  For example, when the crosslinkable group of the first crosslinkable (meth) acrylic polymer is a carboxy group, an epoxy group or an amino group is preferable, and an epoxy group is particularly preferable. When the crosslinkable group is a hydroxyl group, an epoxy group or an isocyanate group is preferable. When the crosslinkable group is an epoxy group, a carboxy group, an amino group, an acid anhydride group, or a hydroxyl group is preferable. Moreover, the number of reactive groups which 1 molecule | numerator of the 1st hardening | curing agent for acrylic resins has is 1.5 or more on average, and it is preferable that it is 2-8. When the number of reactive groups is within this range, it is possible to obtain a water-absorbent first crosslinked acrylic resin having an excellent balance between antifogging properties and wear resistance.

  Two or more kinds of the first curing agent for acrylic resin can be used in combination. For example, a curing agent that complements the main curing agent can be used in combination. This complementary cross-linking agent is a reactive group that reacts with the cross-linkable group of the first cross-linkable (meth) acrylic polymer (may be the same reactive group as the main curing agent, or a different reactive group. May be a compound having a reactive group that reacts with the reactive group of the main curing agent. A complementary curing agent that reacts with the primary curing agent binds to the first crosslinkable (meth) acrylic polymer via the primary curing agent. By using such a complementary curing agent in combination, the formation of the first crosslinked acrylic resin by the first crosslinkable (meth) acrylic polymer and the main curing agent can be promoted.

  For example, in the combination of a first crosslinkable (meth) acrylic polymer having a carboxy group and a curing agent having an epoxy group, a complementary curing agent having an amino group or a complementary curing agent having an acid anhydride group By using together, formation of the 1st crosslinked acrylic resin is accelerated | stimulated and the crosslinking density in a 1st crosslinked acrylic resin becomes high. Thereby, durability, such as abrasion resistance and water resistance, of the first crosslinked acrylic resin can be improved, which is preferable.

  As the first acrylic resin curing agent when the crosslinkable group of the first crosslinkable (meth) acrylic polymer is a carboxy group, the polyepoxide described in the first cured epoxy resin is preferably used. Examples of the complementary curing agent in this case include the first polyaddition type curing agent and / or the first catalyst type curing agent. These can be the same as described for the first cured epoxy resin, including preferred embodiments.

  The blending ratio of the first crosslinkable (meth) acrylic polymer and the first acrylic resin curing agent used to obtain the first crosslinked acrylic resin is such that the water absorption performance of the obtained first crosslinked acrylic resin is the above saturation. It adjusts so that it may become water absorption. Specifically, the blending ratio of the first crosslinkable (meth) acrylic polymer, which is a raw material component of the first crosslinkable acrylic resin used in the present invention, and the first acrylic resin curing agent is the first crosslinkable amount. It is preferable that the equivalent ratio of the reactive group of the first curing agent for acrylic resin to the crosslinkable group derived from the functional (meth) acrylic polymer is a ratio of 0.8 to 1.2. 1 is more preferable. When the equivalent ratio of the reactive group of the first curing agent for acrylic resin to the crosslinkable group derived from the first crosslinkable (meth) acrylic polymer is in the above range, durability such as wear resistance does not decrease. Thus, a crosslinked acrylic resin having a three-dimensional network structure that is appropriately crosslinked so as to have the above water absorption is obtained.

  The water-absorbing layer in the water-absorbing and anti-fogging film of the anti-fogging glass article of the present invention is composed of a water-absorbing material mainly composed of the first cross-linked resin, for example, at least a cross-linkable component that is a main raw material component of the first cross-linked resin It can form using the composition for water absorption layer formation containing a hardening | curing agent.

  The crosslinkable component and the curing agent, which are the main raw material components of the first crosslinked resin contained in the water absorbing layer forming composition, are as described above, including preferred embodiments, such as the compound used and the ratio when combined. is there. The water-absorbing layer forming composition usually contains a solvent in addition to the crosslinkable component and the curing agent, which are the main raw material components of the first crosslinked resin. Further, if necessary, in addition to these, reactive additives such as coupling agents, fillers, antioxidants, ultraviolet absorbers, infrared absorbers, light stabilizers and other non-reactive additives may be contained. .

  Usually, the reaction with the crosslinkable component and the curing agent for obtaining the water-absorbing material mainly composed of the first cross-linked resin is applied as a water-absorbing layer forming composition (when the water-absorptive antifogging film has an underlayer). Is carried out after coating on the underlayer), but when the composition contains a solvent, these components are reacted in advance in the composition before coating on the coating surface, and then coated on the coating surface, You may make it react after drying. As described above, when the crosslinkable component and the curing agent are reacted to some extent in the solvent as the water-absorbing layer forming composition, the curing reaction is ensured by setting the reaction temperature at the pre-reaction to 30 ° C. or higher. This is preferable because it proceeds.

  As the solvent used in the water-absorbing layer forming composition, when the first cross-linked resin is a first cured epoxy resin, a composition containing a first polyepoxide component, a first curing agent, and other optional components The solvent is not particularly limited as long as it is a solvent having good solubility for the components and is inactive with respect to these blended components. Specifically, alcohols, acetates, ethers, ketones, Water etc. are mentioned.

  If a protic solvent is used as the solvent, depending on the type of the first polyepoxide component, the solvent and the epoxy group may react to make it difficult to form a cured epoxy resin. Therefore, when a protic solvent is used, it is preferable to select a solvent that does not easily react with the first polyepoxide component. Examples of protic solvents that can be used include ethanol and isopropanol. As other solvents, acetone, methyl ethyl ketone, butyl acetate, propylene carbonate, diethylene glycol dimethyl ether, diacetone alcohol, propylene glycol monomethyl ether and the like are preferable.

  As the solvent used in the water-absorbing layer forming composition, when the first cross-linked resin is a first urethane resin, the solubility of the blending component including the polyol, the polyisocyanate, and other optional components is good. The solvent is not particularly limited as long as it is a solvent that is inert to these components, and specifically, it is preferable to use an acetate solvent, a ketone, or diacetone alcohol.

  As the solvent used in the water-absorbing layer forming composition, when the first cross-linked resin is a first cross-linked acrylic resin, the first cross-linkable (meth) acrylic polymer, for the first acrylic resin It is not particularly limited as long as it is a solvent having good solubility for the compounding component including a curing agent and other optional components, and is an inert solvent for these compounding components. Specifically, water, methanol, It is preferable to use a lower alcohol such as ethanol.

  These solvents may use only 1 type and may use 2 or more types together. Moreover, compounding components, such as a crosslinking | crosslinked component which is the main raw material component of 1st crosslinked resin, and a hardening | curing agent, may be prepared as a mixture with the solvent used when manufacturing each component. In such a case, the solvent contained in the mixture may be used as it is as the solvent in the water-absorbing layer-forming composition, and the water-absorbing-layer-forming composition may contain the same or other solvent. May be added.

  Moreover, the amount of the solvent in the water-absorbing layer forming composition is 100 masses in total mass of the total solid content in the various cross-linking components and the hardener, which are the main raw material components of the first cross-linking resin, and other optional blending components. It is preferable that it is 100-500 mass% with respect to%, and 200-350 mass% is more preferable.

  Here, when the first crosslinked resin is the first cured epoxy resin, the blending amounts of the first polyepoxide component and the first curing agent in the water-absorbing layer-forming composition are as follows. Is preferably 15 to 30% by mass, more preferably 18 to 25% by mass, based on the total amount of the composition. The blending amount of the first curing agent in the water-absorbing layer forming composition is, for example, the blending amount of the first polyaddition type curing agent and the first catalytic curing agent with respect to the first polyepoxide component, respectively. As described above. In addition, about the total amount of these compounding quantities in the case of using combining a 1st polyaddition type hardening | curing agent and a 1st catalyst type hardening | curing agent, it is 3-16 mass% with respect to the composition whole quantity. Preferably, 12 to 15% by mass is more preferable.

  In the first cured epoxy resin, the blending ratio when the first polyaddition type curing agent and the first catalyst type curing agent are used in combination depends on the type of the curing agent used. For example, when an amine compound having active hydrogen is used as the first polyaddition type curing agent in combination with an imidazole compound as the first catalyst type curing agent, the total amount of the water absorbing layer forming composition is as follows: It is preferable to mix the amine compound having active hydrogen in a proportion of 3 to 15% by mass and the imidazole compound in a proportion of 0.1 to 1.0% by mass. By setting it as such a mixture ratio, both the advantages which the said 1st polyaddition type hardening | curing agent and a 1st catalyst type hardening | curing agent have can be exhibited effectively.

  Among the additives optionally contained in the water-absorbing layer forming composition, the reactive additive is a component in a component other than the catalyst-type curing agent among the crosslinkable component and the curing agent that are the main raw material components of the first crosslinked resin. Coupling agent having a functional group reactive to a reactive group reactive to the reactive group possessed by the reactive group, specifically, the reactive group reactive to the crosslinking group possessed by the crosslinking component or the crosslinking group possessed by the curing agent Etc. In the water-absorbing layer forming composition, the coupling agent has an adhesive property between the water-absorbing layer and the base layer, or an adhesive property between the water-absorbing layer and the functional layer if necessary. It is a component that is blended for the purpose of improving, and it is one of the components that are preferably blended.

  As the coupling agent to be used, an organometallic coupling agent or a polyfunctional organic compound is preferable. Examples of the organometallic coupling agent include a silane coupling agent (hereinafter referred to as a silane coupling agent), a titanium coupling agent, an aluminum coupling agent, and a zirconium coupling agent. One or more selected from silane coupling agents, titanium coupling agents and zirconium coupling agents are preferred, and silane coupling agents are particularly preferred. These coupling agents preferably have a reactive group that can react with the reactive group that the first polyepoxide component or the first curing agent has and the reactive group that remains on the surface of the underlayer described later. In addition, it can use also for the purpose of adjusting the physical property of a water absorption layer besides the objective of improving the adhesiveness between each layer by having such a reactive group. Here, the coupling agent is preferably a compound having one or more (preferably one or two) bonds between a metal atom and a carbon atom. As the organometallic coupling agent, a silane coupling agent is particularly preferable.

  A silane coupling agent is a compound in which one or more hydrolyzable groups and one or more monovalent organic groups (however, the terminal bonded to the silicon atom is a carbon atom) are bonded to the silicon atom. One of the monovalent organic groups is a functional organic group (an organic group having a reactive group or an organic group exhibiting characteristics such as hydrophobicity). As the organic group other than the functional organic group, an alkyl group having 4 or less carbon atoms is preferable. The number of hydrolyzable groups bonded to the silicon atom is preferably 2 or 3. The silane coupling agent is preferably a compound represented by the following formula (1).

R ³ R ⁴ _c SiX ² _3-c (1)
In the above formula (1), R ³ represents a monovalent functional organic group, R ⁴ represents an alkyl group having 4 or less carbon atoms, and c represents an integer of 0 or 1. R ⁴ is preferably a methyl group or an ethyl group, and particularly preferably a methyl group. X ² is a hydrolyzable group such as a chlorine atom, an alkoxy group, an acyl group, or an amino group, and an alkoxy group having 4 or less carbon atoms is particularly preferable.

  The functional organic group may be a hydrophobic organic group such as a polyfluoroalkyl group or a long-chain alkyl group having 6 to 22 carbon atoms. Preferably, it is an alkenyl group having an addition polymerizable unsaturated group or an alkyl group having a reactive group. The alkyl group having a reactive group may be an alkyl group substituted with an organic group having a reactive group. As for carbon number of such an alkyl group, 1-4 are preferable. As a reactive group, an epoxy group, an amino group, a mercapto group, a ureido group, a hydroxyl group, a carboxyl group, a (meth) acryloyloxy group (hereinafter, “(meth) acryloxy” is used in the notation of a compound as necessary. ), A functional group such as an isocyanate group, and a chlorine atom. Examples of the organic group having such a reactive group include a glycidyl group, an epoxycyclohexyl group, an alkylamino group, a dialkylamino group, an arylamino group, and an N-aminoalkyl-substituted amino group. Among these, a silane coupling agent whose reactive group is an epoxy group, an amino group, a mercapto group, or a ureido group is preferable.

  Examples of such silane coupling agents include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycol. Sidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-phenyl-3- Mino propyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-chloropropyl trimethoxysilane.

  Among these, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Trimethoxysilane, 3-acryloxypropyltrimethoxysilane and the like are preferable.

  In the present invention, among these, in particular, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino) A silane coupling agent having an amino group such as ethyl) -3-aminopropyltrimethoxysilane is preferably used.

  The blending amount of the coupling agent in the water absorbing layer forming composition is not an essential component, so there is no lower limit. However, in order to fully exhibit the effect of the coupling agent blending, the mass ratio of the coupling agent is 5 with respect to the total mass of the first polyepoxide component and the first curing agent in the water absorbing layer forming composition. It is preferable that it is -40 mass%, and 10-30 mass% is more preferable. The upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent. When used for the purpose of improving the adhesion of the water-absorbing layer mainly composed of the first cured epoxy resin, the mass ratio of the coupling agent to the total mass of the first polyepoxide component and the first curing agent is 40 mass. % Or less is preferable, and 30% by mass or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the water-absorbing resin mainly composed of the first cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.

In addition, as a compounding quantity of the coupling agent with respect to the composition for water absorption layer formation, when using a silane coupling agent, it is preferable that it is 2-10 mass%, and is 3-7 mass%. It is more preferable.
In addition, regarding a particularly preferable composition in the water-absorbing layer-forming composition containing a silane coupling agent, an amine compound having 15 to 30% by mass of the first polyepoxide component and active hydrogen relative to the total amount of the composition 3 to 15% by mass, imidazole compound 0.1 to 1.0% by mass, silane coupling agent 2 to 10% by mass, and solvent 50 to 75% by mass.

  Here, when the composition for forming a water absorbing layer contains a coupling agent having an amino group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group is the amine activity in the first curing agent. By combining hydrogen and the amine active hydrogen of the coupling agent, the equivalent ratio with the epoxy group of the first polyepoxide component is calculated so as to be within the preferred range.

  Similarly, when the water-absorbing layer-forming composition contains a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of amine active hydrogen to the epoxy group is the epoxy contained in the first polyepoxide component. By combining the group and the epoxy group of the coupling agent, the equivalent ratio of amine active hydrogen in the first curing agent is calculated so as to be in the preferred range.

Here, when the first crosslinked resin is a first urethane resin, the silane coupling agent has reactivity with the reactive group of the first polyisocyanate and / or the first polyol. A silane coupling agent having a functional group and a hydrolyzable group is preferably used. As such a silane coupling agent, specifically, in the above compound (1), R ³ has a terminal functional group selected from a silane coupling agent having an isocyanate group, an epoxy group, an amino group, or a mercapto group. 1 type or more to be mentioned. In the case of the first urethane resin, a silane coupling agent having an isocyanate group as a functional group is preferable from the viewpoint of binding to the urethane resin.

When the first cross-linked resin is a first cross-linked acrylic resin, the reactive group possessed by the first cross-linkable (meth) acrylic polymer and / or the first acrylic resin curing agent as a silane coupling agent. A silane coupling agent having a functional group and a hydrolyzable group having reactivity with respect to is preferably used. As such a silane coupling agent, specifically, in the compound (1), the terminal functional group of R ³ is an epoxy group, an amino group, a (meth) acryloyloxy group, a mercapto group, or an isocyanate group. 1 or more types chosen from a certain silane coupling agent are mentioned. In the case of the first cross-linked acrylic resin, from the viewpoint of the bondability to the cross-linked acrylic resin, depending on the type of cross-linkable group possessed by the first cross-linkable (meth) acrylic polymer, Is preferably a silane coupling agent having an epoxy group or an amino group as a functional group.

  Even if the first cross-linked resin is a first urethane resin or a first cross-linked acrylic resin, the amount of the silane coupling agent in the water-absorbing layer forming composition is the same as the first cured epoxy. As in the case of the resin, the mass ratio of the silane coupling agent is preferably 5 to 40% by mass, and 10 to 30% by mass with respect to 100% by mass of the total mass of the resin components of the first cross-linked resin. More preferred.

  It is preferable that the water absorbing layer forming composition further contains a filler as an optional component. By including the filler, the mechanical strength and heat resistance of the water-absorbing layer to be formed can be increased, and the curing shrinkage of the resin during the curing reaction can be reduced. As such a filler, a filler made of a metal oxide is preferable. Examples of the metal oxide include silica, alumina, titania, and zirconia. Among these, silica is preferable.

  Moreover, ITO (Indium Tin Oxide) fine particles can also be used as the metal oxide fine particles. Since ITO has infrared absorptivity, heat absorption can be imparted to the water-absorbing crosslinked resin. Therefore, if ITO fine particles are used, in addition to water absorption, an antifogging effect by heat ray absorption can be expected.

  These fillers contained in the water-absorbing layer forming composition are preferably particulate. The average primary particle diameter is preferably 300 nm or less, more preferably 100 nm or less, and particularly preferably 50 nm or less. When the average primary particle diameter is 300 nm or less, the tendency of aggregation of particles in a composition containing the average particle diameter does not increase, and sedimentation of particles can be avoided. Moreover, when forming a water absorption layer with the composition containing this, generation | occurrence | production of the cloudiness (cloudiness value, haze) by scattering can be suppressed, and it is preferable to set it as the said particle diameter from the point of transparency maintenance. The lower limit of the average primary particle diameter is not particularly limited, but particles of about 2 nm that can be produced by the current technology can also be used. Here, the average primary particle diameter of the particles refers to that measured from an observation image with a transmission electron microscope.

Moreover, it is preferable that the compounding quantity of a filler is 0.5-5 mass% with respect to 100 mass% of total mass of the crosslinking | crosslinked component and hardening | curing agent which are the main raw material components of 1st crosslinked resin, 1-3 The mass% is more preferable. Hereinafter, the crosslinkable component, which is the main raw material component of the first crosslinked resin, and the curing agent may be collectively referred to as a “resin component”. The blending amount of the filler with respect to the total mass of 100 mass% of the resin component is 0.5 mass% or more. If so, it is easy to suppress a decrease in the curing shrinkage reduction effect of the water-absorbing material mainly composed of the first cross-linked resin. Moreover, if the compounding quantity of the filler with respect to 100 mass% of total mass of a resin component shall be 5 mass% or less, the space for water absorption can fully be ensured and it is easy to make anti-fogging performance high.

  Silica preferably used as the filler, more preferably silica particles are water or a composition for forming a water absorbing layer as colloidal silica dispersed in an organic solvent such as methanol, ethanol, isobutanol, propylene glycol monomethyl ether, butyl acetate or the like. Can be blended. Examples of colloidal silica include silica hydrosol dispersed in water and organosilica sol in which water is replaced with an organic solvent. When blended in a water-absorbing layer forming composition, an organic solvent preferably used for this composition It is preferable to use an organosilica sol using the same organic solvent as the dispersion medium.

As such an organosilica sol, a commercially available product can be used. Examples of commercially available products include organosilica sol IPA-ST (trade name, Nissan Chemical Industries, Ltd.) in which silica particles having a particle diameter of 10 to 20 nm are dispersed in isopropanol in a proportion of 30% by mass as SiO ₂ content with respect to the total amount of organosilica sol. Manufactured), organosilica sol NBAC-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.) in which the organic solvent of organosilica sol IPA-ST was changed from isopropanol to butyl acetate, and the organic solvent of organosilica sol IPA-ST was changed from isopropanol to methyl ethyl ketone. And organosilica sol MEK-ST (trade name, manufactured by Nissan Chemical Industries, Ltd.). In addition, when using colloidal silica as a silica particle, the quantity of the solvent mix | blended with the composition for water absorption layer formation is adjusted suitably in consideration of the amount of solvent contained in colloidal silica.

The water absorbing layer forming composition preferably contains an antioxidant as an optional component in order to improve the weather resistance of the water absorbing layer to be obtained. If the first cross-linked resin that mainly constitutes the water absorption layer is exposed to heat or light and is oxidized and deteriorated, stress accumulation is likely to occur in the water absorption layer, and thus the antifogging film is easily peeled off. By adding an antioxidant, such a phenomenon can be suppressed.
Antioxidants include phenolic antioxidants that suppress the oxidation of resins by capturing and decomposing peroxy radicals, and phosphorus antioxidants that suppress the oxidation of resins by decomposing peroxides. In the present invention, a phenolic antioxidant is preferably used.

  As the phenolic antioxidant, the following phenolic antioxidants that are usually blended in a crosslinked resin such as a cured epoxy resin, a urethane resin, or a crosslinked acrylic resin can be used without particular limitation. One of these may be used alone, or two of them may be used in combination.

  Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N, N′-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionamide], 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, a ″-(mesitylene-2 4,6-triyl) tri-p-cresol, calcium diethylbis [[[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] phosphonate], 4,6-bis (octylthio) Methyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-di-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [[3- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3,5-di-tert-4-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4 6 (1H, 3H, 5H) -trione, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-xylyl) methyl] -1,3,5 Triazine-2,4,6 (1H, 3H, 5H) -trione, reaction product of N-phenylbenzenamine and 2,4,4-trimethylpentene, 2,6-di-tert-butyl-4- ( 4,6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Examples of commercially available phenolic antioxidants include IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 (trade name, manufactured by Ciba Japan), ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-60, ADK STAB AO-70, ADK STAB AO-80, ADK STAB AO-90 (trade name, manufactured by ADEKA), Sumilizer GA-80, Sumizer MDP-S, Sumizer BBM-S, Sumizer GM, Sumizer GS (F), Sumitomo G Etc.).

  Moreover, about the quantity of antioxidant mix | blended with the composition for water absorption layer formation, it is 0.5 with respect to 100 mass% of total mass of the crosslinking | crosslinked component and hardening | curing agent which are the main raw material components of 1st crosslinked resin. -2 mass% is preferable, and 1-2 mass% is more preferable.

  The water-absorbing layer-forming composition preferably contains an ultraviolet absorber as an optional component in order to improve the weather resistance of the resulting water-absorbing layer, particularly the resistance to ultraviolet rays. Examples of the ultraviolet absorber include conventionally known ultraviolet absorbers, specifically, benzophenone compounds, triazine compounds, benzotriazole compounds, and the like.

  As the benzotriazole ultraviolet absorber, specifically, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol (as a commercial product, TINUVIN 326 (trade name, manufactured by Ciba Japan) and the like, octyl-3- [3-tert-4-hydroxy-5- [5-chloro-2H-benzotriazol-2-yl] propionate, 2- (2H- Benzotriazol-2-yl) -4,6-di-tert-pentylphenol, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- [2-hydroxy-3- (3,4,5, 6-tetrahydrophthalimido-methyl) -5-methylphenyl] benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) Benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, methyl 3- (3- (2H-benzotriazol-2-yl) -5-tert-butyl-4-hydroxyphenyl ) Propionate, 2- (2H-benzothiazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazol-2-yl) -6- ( 1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol and the like. Of these, 2- [5-chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butyl) phenol is preferably used.

  As a triazine ultraviolet absorber, specifically, 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2′-ethyl) hexyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4 -Dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butoxyphenyl) -6- (2,4-bis-butoxyphenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octylcarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine, TINUVIN477 (trade name, Ciba Japan Ltd.) Etsu Chemical Co., Ltd.)), and the like. Of these, 2- (2-hydroxy-4- [1-octylcarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine is preferably used.

  Specific examples of the benzophenone ultraviolet absorber include 2,4-dihydroxybenzophenone, 2,2 ′, 3 (or any of 4, 5, 6) -trihydroxybenzophenone, 2,2 ′, 4,4 ′. -Tetrahydroxybenzophenone, 2,4-dihydroxy-2 ', 4'-dimethoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone and the like. Of these, 2,2 ', 4,4'-tetrahydroxybenzophenone is preferably used.

  The maximum absorption wavelength of light of these exemplified ultraviolet absorbers is in the range of 325 to 425 nm, and many are in the range of about 325 to 390 nm. Thus, the ultraviolet absorber which has an absorptivity with respect to the ultraviolet of a comparatively long wavelength is used preferably from the characteristic.

  In the present invention, these ultraviolet absorbers can be used alone or in combination of two or more. Of these ultraviolet absorbers, the water-absorbing layer-forming composition used in the present invention is preferably a hydroxyl group-containing benzophenone-based ultraviolet absorber as exemplified above since solubility in a solvent and absorption wavelength band are desirable. .

  The blending amount of the ultraviolet absorbent in the water-absorbing layer-forming composition is such that the water-absorbing layer formed using this composition has sufficient ultraviolet resistance without impairing the effects of the present invention, and the main component of the first crosslinked resin. 0.1-2.0 mass% is preferable with respect to 100 mass% of total mass of the crosslinkable component which is a raw material component, and a hardening | curing agent, and 0.5-1.5 mass% is more preferable.

  The composition for forming a water absorbing layer preferably contains an infrared absorber as an optional component in order to give the resulting water absorbing layer a heat insulating effect by infrared shielding. Examples of the infrared absorber include an infrared absorber composed of inorganic compound particles and an infrared absorber composed of an organic dye.

As an infrared absorber made of an inorganic compound, specifically, Re, Hf, Nb, Sn, Ti, Si, Zn, Zr, Fe, Al, Cr, Co, Ce, In, Ni, Ag, Cu, Pt, Examples include particles of metals such as Mn, Ta, W, V, and Mo, oxides, nitrides, sulfides, silicon compounds of the above metals, or inorganic compounds doped with dopants such as Sb, F, Sn, or Sb. It is done. These inorganic compound particles can be used alone or in combination of two or more.
The average primary particle diameter in the inorganic compound particles used as the infrared absorber can be the same as the average primary particle diameter of the filler, including a suitable particle diameter.

  Among the inorganic compound particles used as infrared absorbers, in the present invention, tin-doped indium oxide (ITO) particles, antimony-doped tin oxide (ATO) particles, composite tungsten oxide, lanthanum hexaboride (LaB6) and the like are included. preferable.

Specifically, as the composite tungsten oxide, a general formula: M _x W _y O _z (wherein M element is Cs, Rb, K, Tl, In, Ba, Li, Ca, Sr, Fe, Sn) 1 or more elements selected from: W is tungsten, O is oxygen, and 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0). . The composite tungsten oxide represented by the above general formula functions effectively as an infrared absorber because a sufficient amount of free electrons are generated. Since the composite tungsten oxide particles represented by the above general formula: M _x W _y O _z have a hexagonal, tetragonal, and cubic crystal structure, they have excellent durability. Therefore, the hexagonal, tetragonal, It preferably contains one or more crystal structures selected from cubic crystals. Specific examples of the composite tungsten oxide include Cs _0.33 WO ₃ , Rb _0.33 WO ₃ , K _0.33 WO ₃ , Ba _0.33 WO _{3 and the} like.

  Such a composite tungsten oxide is known to have a maximum value in the wavelength range of 400 to 700 nm and a minimum value in the wavelength range of 700 to 1800 nm in the film in which the particles are uniformly dispersed. It is an infrared absorber.

  The crystal system of the ATO particles and the ITO particles is not limited to a normal cubic crystal, and depending on the type of the binder component (d) described later, for example, a hexagonal ITO having a relatively low infrared absorption ability can be used as necessary. .

  In the present invention, ITO particles are preferably used from the viewpoint of transmittance loss and environmental safety. Here, the mixing ratio of tin oxide and indium oxide in the ITO particles exhibiting infrared absorption ability is In / Sn = 5 to 40 when expressed by the number of indium atoms to the number of tin atoms (In / Sn). Preferably, In / Sn = 7-25.

  Infrared absorbers composed of organic dyes include polymethine dyes, phthalocyanine dyes, naphthalocyanine dyes, metal complex dyes, aminium dyes, imonium dyes, diimonium dyes, anthraquinone dyes, dithiol metal complex dyes, Examples include naphthoquinone dyes, indolephenol dyes, azo dyes, triallylmethane dyes, and the like. These organic dyes can be used alone or in combination of two or more. Moreover, you may use in combination with the said inorganic compound particle.

  The amount of the infrared absorbent in the water-absorbing layer-forming composition is the first cross-linking because the water-absorbing layer formed using this composition has a heat insulating effect by sufficient infrared shielding without impairing the effects of the present invention. 0.5-10 mass% is preferable with respect to 100 mass% of total mass of the crosslinkable component which is the main raw material component of resin, and a hardening | curing agent, and 1.0-5.0 mass% is more preferable.

  In addition, when mix | blending inorganic compound particle | grains as an infrared absorber, an inorganic compound particle | grain fulfill | performs also the function as said filler. Therefore, in that case, it is possible to reduce the blending amount of the filler by the blending amount of the inorganic compound particles.

  The water-absorbing layer-forming composition preferably contains a light stabilizer as an optional component in order to give the obtained water-absorbing layer light stability. Examples of the light stabilizer include hindered amines; nickel complexes such as nickel bis (octylphenyl) sulfide, nickel complex-3,5-di-tert-butyl-4-hydroxybenzyl phosphate monoethylate, nickel dibutyldithiocarbamate, and the like. . In the present invention, these light stabilizers can be used alone or in combination of two or more.

  Among these, as the light stabilizer used in the present invention, hindered amines are preferable, and hindered amine light stabilizers whose amine moiety is capped with an alkyl group or an alkoxy group, specifically, the following general formula (2) Compounds having a substituted piperidine skeleton: A compound in which the 1-position of the 2,2,6,6-tetramethylpiperidine skeleton is substituted with X and the 4-position with R is preferred.

（式（２）中、Ｘはアルキル基またはアルコキシ基を表し、Ｒは一価の有機基を表す。）

(In formula (2), X represents an alkyl group or an alkoxy group, and R represents a monovalent organic group.)

  Specific examples of the alkyl group represented by X in the general formula (2) include linear, branched or cyclic alkyl groups having 1 to 8 carbon atoms. Among these, in this invention, a C1-C3 linear alkyl group is more preferable, and a methyl group, an ethyl group, etc. are especially preferable. Moreover, in the said General formula (2), a C1-C12 linear, branched or cyclic alkoxy group is specifically mentioned as an alkoxy group which X represents. Among these, in the present invention, a linear alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an octyl group, a cyclohexyl group, and the like are particularly preferable.

Specific examples of the hindered amine light stabilizer represented by the above general formula (2) are shown below together with examples of commercially available products.
Bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (commercially available products such as TINUVIN 765 (trade name, manufactured by Ciba Japan), etc.), bis- (1,2,2,6 , 6-pentamethyl-4-piperidyl) -2- (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butyl malonate (as a commercial product, TINUVIN 144 (trade name, Ciba Japan), etc.), decanedioic acid bis (2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl) ester, 1,1-dimethylethyl hydroperoxide and octane reaction product (commercially available) TINUVIN 123 (trade name, manufactured by Ciba Japan Co., Ltd.)), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl (1, , 2,6,6-pentamethyl-4-piperidyl) sebacate (as a commercial product, TINUVIN 292 (trade name, manufactured by Ciba Japan Co., Ltd.)), tetrakis (1,2,2,6,6-pentamethyl) -4-piperidyl) -1,2,3,4-butanetetracarboxylate (commercially available products such as ADK STAB LA-52 (trade name, manufactured by ADEKA), etc.), 1,2,2,6,6-pentamethyl- 4-piperidyl / tridecyl 1,2,3,4-butanetetracarboxylate (commercially available products such as ADK STAB LA-62 (trade name, manufactured by ADEKA), etc.), 1,2,3,4-butanetetracarboxylic acid β, β, β ′, β′-tetramethyl-3,9-diethyl- {2,4,8,10-tetraoxaspiro [5.5] undecane} -α, α′-diol and 1,2, 2 6,6 (commercially STAB LA-63 (trade name, manufactured by ADEKA Corporation)) pentamethyl-4-ester with Piperijinioru can be exemplified.

  The blending amount of the light stabilizer in the water-absorbing layer-forming composition is such that the water-absorbing layer formed using this has sufficient light stability without impairing the effects of the present invention. 0.5-2 mass% is preferable and 1-2 mass% is more preferable with respect to 100 mass% of total mass of the crosslinkable component which is a main raw material component, and a hardening | curing agent.

  A leveling agent, an antifoaming agent, a viscosity adjusting agent, etc. can be further added to the composition for forming a water absorbing layer as necessary from the viewpoint of improving the film formability.

  Examples of the leveling agent include polydimethylsiloxane-based surface conditioners, acrylic copolymer surface conditioners, fluorine-modified polymer-based surface conditioners, and antifoaming agents include silicone-based antifoaming agents, surfactants, Organic antifoaming agents such as ethers and higher alcohols, and viscosity modifiers include acrylic copolymers, polycarboxylic acid amides, modified urea compounds and the like. Each component may be used in combination of two or more of the exemplified compounds. The compounding amount of the various components in the water-absorbing layer forming composition is 0.001 with respect to the total mass of 100% by mass of the crosslinkable component and the curing agent, which are the main raw material components of the first crosslinked resin, for each component. -10 mass%.

  The water-absorbing layer in the antifogging article of the present invention is the above-mentioned first crosslinked resin, for example, a composition containing the first polyepoxide component and the first curing agent, contained in the water-absorbing layer-forming composition. A composition containing the first polyol and the first polyisocyanate, or a composition containing the first crosslinkable (meth) acrylic polymer and the first curing agent for acrylic resin, is obtained by reaction. Consists mainly of the first cured epoxy resin, the first urethane resin, or the first crosslinked acrylic resin having a three-dimensional network structure, and has high water absorption due to the properties of the first crosslinked resin described above. It is a water-absorbing layer having durability such as wear resistance. The reaction conditions will be described in the production method described later.

  Further, a reactive additive such as a silane coupling agent that is optionally added is present in the water-absorbing layer in a form bonded to a part of the three-dimensional network structure of the first cross-linked resin. The non-reactive additive that is optionally added is one that is uniformly dispersed and included in the three-dimensional network structure of the first crosslinked resin and exists in the water absorption layer.

(Underlayer and underlayer material)
The underlayer that the water-absorbing antifogging film according to the present invention optionally has between the base and the water-absorbing layer is composed of a base material mainly composed of a second crosslinked resin having low water absorption. The base material may be composed of only the second crosslinked resin as long as the material has a lower water absorption than the water-absorbing material, and preferably has a saturated water absorption of 30 mg / cm ³ or less. Ingredients may be included. The second cross-linked resin may be a cross-linked resin obtained by reacting a cross-linkable component and a curing agent, or a cross-link obtained by reacting a composition containing a reactive component in addition to the cross-linkable component and the hardener. Resin may be used.

  Examples of the second crosslinked resin include a second cured epoxy resin, a second urethane resin, and a second crosslinked acrylic resin. These may be used alone or in combination of two or more. In the following description, in the second cross-linked resin, the cross-linking component and the curing agent are all referred to as “second ...”.

  In the present invention, it is preferable from the viewpoint of adhesion between the water-absorbing layer and the base layer that the type of the second cross-linked resin is selected to be the same as that of the first cross-linked resin. In the anti-fogging glass article of the present invention, when the water-absorbing and anti-fogging film has an underlayer, the water-absorbing layer in the water-absorbing and anti-fogging film is a layer mainly composed of a water-absorbing first curable epoxy resin. The base layer is preferably a layer mainly composed of a second curable epoxy resin having a lower water absorption than the first curable epoxy resin.

The second cured epoxy resin used in the present invention is a cross-linked resin obtained by the reaction of the composition containing the second polyepoxide component and the second curing agent, and when it is used as a base material mainly composed of it, A cross-linked resin having a lower water absorption than the water-absorbing material, preferably a saturated water absorption of 30 mg / cm ³ or less.

  As described above, in order to increase the water absorption performance of a resin layer generally made of a cured epoxy resin, the glass transition point of the cured epoxy resin is controlled to be low, and the glass transition point of the cured epoxy resin is increased to increase the durability. High control is preferable. In consideration of these, the glass transition point of the second cured epoxy resin mainly constituting the base material is preferably 40 to 150 ° C., preferably 40 to 120 ° C., although it depends on the type of the cured epoxy resin. Is more preferable.

  The first water-absorbing layer mainly constituting the water-absorbing layer has a glass transition point in the above range (-20 to 60 ° C., preferably -5 to 40 ° C.), and further has a low water absorption mainly constituting the underlayer. If the glass transition point of the second cured epoxy resin is within the above range and higher than the glass transition point of the first cured epoxy resin, the antifogging performance and the scratch resistance are compatible at a high level. Easy to do. The difference in glass transition point between the second cured epoxy resin in the underlayer and the first cured epoxy resin in the water absorption layer is preferably 10 ° C. or higher, and more preferably 20 ° C. or higher.

  As the second polyepoxide component used for the second cured epoxy resin, the glycidyl ether type explained in the first polyepoxide component usually used as a raw material component of the cured epoxy resin so that the water absorption is in the preferred range. A polyepoxide appropriately selected from polyepoxides, glycidyl ester polyepoxides, glycidylamine polyepoxides, cyclic aliphatic polyepoxides, and the like can be used.

  The molecular weight of the polyepoxide used as the second polyepoxide component is not particularly limited. However, from the viewpoint of avoiding poor appearance such as insufficient wetting and spreading of the coating liquid at the time of solution coating and unevenness of the coating film, the molecular weight is about 500 to 1,000. Molecular weight polyepoxides are preferred. Further, the number of epoxy groups per molecule of polyepoxide in the second polyepoxide component is not particularly limited as long as it is 2 or more on average, but is preferably 2 to 10, more preferably 2 to 8 2 to 4 are more preferable.

  The second polyepoxide component may be any of an aliphatic polyepoxide, an alicyclic polyepoxide, and an aromatic polyepoxide. For example, a three-dimensional network structure of a cured epoxy resin obtained by selecting an aromatic polyepoxide. It is possible to reduce the water absorption by making the space hard and reducing the space.

  The aromatic polyepoxide that can be used as the second polyepoxide component is preferably a polyepoxide having a structure in which a phenolic hydroxyl group is substituted with a glycidyloxy group. Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol type diglycidyl ethers such as bis (4-glycidyloxyphenyl), phenol novolac type diglycidyl ethers, cresol novolac type diglycidyl ethers, And aromatic polycarboxylic acid polyglycidyl esters such as diglycidyl phthalate. Among these aromatic polyepoxides, bisphenol A diglycidyl ether and bisphenol F diglycidyl ether are preferably used as the second polyepoxide component.

  Even in the alicyclic polyepoxide, although depending on the type and number of the ring structure, the space of the three-dimensional network structure can be reduced by the presence of the ring structure, and the water absorption of the cured epoxy resin can be lowered. An alicyclic polyepoxide is a polyepoxide having an alicyclic hydrocarbon group (such as a 2,3-epoxycyclohexyl group) in which an oxygen atom is bonded between adjacent carbon atoms of the ring. Examples thereof include epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate and bis (3,4-epoxycyclohexylmethyl) adipate.

  Further, even if an aliphatic polyepoxide having no ring structure is used, if the number of cross-linking points is increased, the resulting cured epoxy resin has a dense three-dimensional network structure, and a space for water retention is reduced, resulting in low water absorption. It is considered to be. As the aliphatic polyepoxide used for the second polyepoxide component, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, trimethylolpropane polyglycidyl ether, etc., classified into aliphatic glycidyl ether-based polyepoxides derived from aliphatic polyols are preferable. .

In the second polyepoxide component, in order to increase the number of crosslinking points of the obtained second cured epoxy resin and control the water absorption, for example, the second polyepoxide component is an aliphatic derived from aliphatic polyols. In the case of a glycidyl ether-based polyepoxide, the epoxy equivalent is preferably 100 to 200 g / eq, more preferably 100 to 150 g / eq.
A 2nd polyepoxide component may be comprised from 1 type of these polyepoxides, and may be comprised from 2 or more types.

  In addition, also about the polyepoxide which comprises the said 2nd polyepoxide component, it is possible to use a commercial item similarly to the polyepoxide which comprises the said 1st polyepoxide component. As such a commercial product, in addition to the commercial products described in the first polyepoxide component, jER828 (trade name, manufactured by Mitsubishi Chemical Corporation) as bisphenol A diglycidyl ether, Adeka Resin EP4901 (product) Name, manufactured by Adeka).

  As the second curing agent to be reacted with the second polyepoxide component, it is preferable to use a second polyaddition type curing agent in the same manner as the first curing agent. It is also possible to use a second catalytic curing agent in combination with the second polyaddition curing agent.

  The type of the second polyaddition type curing agent that can be used is the same as that of the first polyaddition type curing agent. That is, the second polyaddition type curing agent is preferably an amino compound having two or more amino groups having active hydrogen, a compound having two or more carboxy groups, or a compound having two or more thiol groups, More preferably, an amino compound having the above active hydrogen is used.

  Here, as the second polyaddition type curing agent, for example, a polyaddition type curing agent having an aromatic ring that is not selected as a preferred polyaddition type curing agent in the first polyaddition type curing agent is selected. By doing so, it is possible to reduce the water absorption of the obtained cured epoxy resin. Depending on the degree of water absorption required for the underlayer, a second cured epoxy obtained by using a compound having an aromatic ring in at least one of the second polyepoxide component and the second polyaddition type curing agent is used. The water absorption of the resin can be set in the desired range.

  Further, even when a polyepoxide having no aromatic ring is used as the second polyepoxide component and a polyaddition type curing agent having no aromatic ring is used as the second polyaddition type curing agent, the crosslinking point is as described above. The water absorption of the obtained second cured epoxy resin can be adjusted to the above desired range by combining so as to increase the amount. Furthermore, the second cured epoxy resin having no aromatic ring thus obtained is superior in terms of weather resistance compared to the second cured epoxy resin having an aromatic ring.

As the second polyaddition type curing agent having no aromatic ring, the same curing agent as the polyaddition type curing agent having no aromatic ring described in the first polyaddition type curing agent can be used. Examples of the polyaddition type curing agent having an aromatic ring include polyamines having an aromatic ring and aromatic polycarboxylic acid anhydrides. Specific examples of the polyamine having an aromatic ring include phenylenediamine, xylylenediamine, diaminodiphenylmethane, and the like, and examples of the aromatic polycarboxylic acid anhydride include phthalic anhydride, trimellitic anhydride, pyropropyl anhydride. And merit acid.
For the second catalyst-type curing agent that can be used as needed in the second cured epoxy resin, the same curing agent as the catalyst-type curing agent described in the first catalyst-type curing agent can be used.

  The mixing ratio of the second polyepoxide component, which is a raw material component of the second cured epoxy resin used in the present invention, and the second curing agent is when the second polyaddition curing agent is used as the second curing agent. It is preferable that the equivalent ratio of the reactive group of the second polyaddition type curing agent to the epoxy group derived from the second polyepoxide component is a ratio of about 0.8 to 1.5. About 5 is more preferable. If the equivalent ratio of the reactive group of the polyaddition type curing agent to the epoxy group is in the above range, the reaction temperature is raised and the polyaddition reaction is accelerated to crosslink at a sufficient number of crosslinking points at room temperature. Thus, a second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having a three-dimensional network structure is obtained.

  In the present invention, when an amino compound having active hydrogen is used as the second polyaddition type curing agent, the equivalent ratio of amine active hydrogen to epoxy group derived from the second polyepoxide component is 0.5 to 1. It is preferably used so as to be a ratio of 5, more preferably used so as to be a ratio of 1.2 to 1.5. Similarly to the above, if the equivalent ratio of amine active hydrogen to epoxy group is in the above range, a dense three-dimensional network structure can be formed by crosslinking at a sufficient number of crosslinking points without increasing the reaction temperature and accelerating the polyaddition reaction. A second cured epoxy resin having a low water absorption as compared with the first cured epoxy resin having the above is obtained.

  Further, if the mass ratio of the second polyaddition type curing agent used as the second curing agent with respect to the second polyepoxide component is too large, the physical properties of the obtained second cured epoxy resin may be insufficient. The ratio of the second polyaddition type curing agent to the second polyepoxide component is preferably 40% by mass or less.

Although the second cured epoxy resin has been described above, the second urethane resin and the second cross-linked acrylic resin also have a lower water absorption than the water-absorbing material, preferably when used as the base material. The second crosslinked resin can be obtained by appropriately selecting and combining the crosslinkable component and the curing agent for each resin so that the saturated water absorption is 30 mg / cm ³ or less.

  The underlayer optionally provided in the water-absorbing and anti-fogging film of the anti-fogging glass article of the present invention is made of a water-absorbing material mainly composed of the second cross-linked resin, preferably the second cured epoxy resin. It can be formed using a composition for forming an underlayer containing a crosslinkable component, which is a main raw material component of the crosslinked resin, and a curing agent, preferably a second polyepoxide component and a second curing agent.

  About the crosslinkable component and the curing agent, which are the main raw material components of the second crosslinked resin contained in the composition for forming the base resin layer, preferably the second polyepoxide component and the second curing agent, the compound used and the combination It is as above-mentioned including preferable aspects, such as a ratio. The composition for forming the base resin layer usually contains a solvent in addition to the crosslinkable component and the curing agent, which are the main raw material components of the second crosslinked resin, preferably the second polyepoxide component and the second curing agent. . If necessary, non-reacting agents such as coupling agents, reactive additives such as tetraalkoxysilane and / or oligomers, fillers, antioxidants, ultraviolet absorbers, infrared absorbers, light stabilizers, etc. Sex additives may be included.

  Usually, the reaction using the base layer forming composition for obtaining the base material mainly comprising the second cross-linked resin, preferably the second cured epoxy resin, is performed by applying the base layer forming composition to the coated surface (substrate). It is performed after application to the above), but when the composition contains a solvent, the reactive component contained in the underlayer-forming composition in the composition before being applied to the application surface is reacted to some extent in advance. Then, it may be applied to the coated surface, dried, and further reacted. As described above, when the reactive component is reacted to some extent in the solvent as the underlayer forming composition, the curing reaction proceeds reliably if the reaction temperature when the reaction is performed in advance is 30 ° C. or higher. preferable.

  As the solvent used in the water absorbing layer forming composition, when the second crosslinked resin is a second cured epoxy resin, the same solvent as the first cured epoxy resin is used, and the second crosslinked resin is the second crosslinked resin. In the case of the urethane resin, the same solvent as the first urethane resin is preferable, and in the case where the second cross-linked resin is the second cross-linked acrylic resin, the same solvent as the first cross-linked acrylic resin is preferable. It can be used including embodiments.

  Further, the amount of the solvent in the composition for forming the underlayer is preferably such that the ratio of the total solid content in the various blending components blended in the second crosslinked resin with respect to 100% by weight of the solvent is 5 to 50% by weight. -25 mass% is more preferable.

  Here, when the second cured epoxy resin is used as the second cross-linked resin, the second polyepoxide component and the second polyaddition-type curing agent in the underlayer-forming composition, and further blended as necessary. The blending amount of the second catalytic curing agent is preferably 4 to 10% by mass with respect to the total amount of the composition for the second polyepoxide component, and the total amount of the composition for the second polyaddition type curing agent. It is preferable that it is 0.1-4.0 mass% with respect to. In addition, when using a 2nd polyaddition type hardening | curing agent and a 2nd catalyst type hardening | curing agent as a 2nd hardening | curing agent, the total amount is 0.1-4.0 mass% with respect to the composition whole quantity. Preferably there is.

  Examples of the coupling agent optionally contained in the underlayer-forming composition include the same compounds as the coupling agent optionally contained in the water-absorbing layer-forming composition. A coupling agent is a component that is blended in the composition for forming a base layer for the purpose of improving the adhesion between the base layer and the substrate and the adhesion between the base layer and the water-absorbing layer. It is.

About the coupling agent arbitrarily mix | blended with the composition for base layer formation, it can be made to be the same as that of the coupling agent used for the said composition for water absorption layer formation including the compound used and a preferable aspect.
Moreover, about the quantity of the coupling agent mix | blended with the composition for base layer formation, for example, when a 2nd hardening epoxy resin is used as a 2nd crosslinked resin, a 2nd polyepoxide component and a 2nd hardening agent are used. It is preferable that the mass ratio of a coupling agent is 5-50 mass% with respect to the total mass of, and 10-40 mass% is more preferable.

The upper limit of the amount of coupling agent is limited by the physical properties and functions of the coupling agent. When used for the purpose of improving the adhesion of the underlayer mainly composed of the second cured epoxy resin, the mass ratio of the coupling agent to the total mass of the second polyepoxide component and the second curing agent is 50 mass. % Or less is preferable, and 40% by mass or less is more preferable.
On the other hand, when adjusting the physical properties such as water absorption of the base material mainly composed of the second cured epoxy resin with the coupling agent or with the second curing agent and the coupling agent, the second polyepoxide component and the second 40 mass% or less is preferable and, as for the mass ratio of the coupling agent with respect to the total mass of 2 hardening | curing agents, 20 mass% or less is more preferable. If the amount of the coupling agent used is not excessive, it is possible to prevent the base material mainly composed of the second cured epoxy resin from being colored due to oxidation or the like when exposed to a high temperature.

In addition, as a compounding quantity of the coupling agent with respect to the composition for base layer formation, for example, when a silane coupling agent is used, it is preferable that it is 0.1-3.0 mass%, and 1-2. More preferably, it is mass%.
Here, regarding a particularly preferable composition in the composition for forming an underlayer containing a silane coupling agent when the second cured epoxy resin is used as the second cross-linked resin, 4 to 10% by mass of the polyepoxide component 2, 0.1 to 4.0% by mass of the amine compound (second curing agent) having active hydrogen, 0.1 to 4.0% by mass of the silane coupling agent, And a composition containing 70 to 95% by mass of the solvent.

  Further, when the composition for forming an underlayer contains a coupling agent having an amino group or a coupling agent having an epoxy group as a coupling agent, the equivalent ratio of the amine active hydrogen to the epoxy group is determined as follows. It is preferable to adjust the blending amount of each component so that this is within the above range.

  A tetraalkoxysilane and / or oligomer thereof (that is, a partially hydrolyzed condensate thereof, hereinafter referred to collectively as a tetraalkoxysilane compound) optionally contained in the composition for forming the underlayer is used for forming the underlayer by mixing it. Decreasing the viscosity of the composition and uniformly carrying out a crosslinking reaction between the crosslinking component, which is the main raw material component of the second crosslinked resin, and the curing agent, preferably the second polyepoxide component and the second curing agent. Component that can be used. Moreover, the reaction point with a base | substrate and a water absorption layer increases, and adhesiveness improves further. Thereby, the weather resistance of the base layer obtained can be improved.

  Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetranormalpropoxysilane, and tetranormalbutoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable. One of these may be used alone, or two of them may be used in combination. Further, the above tetraalkoxysilane may be blended into the underlayer forming composition as an oligomer obtained by partial hydrolysis (co) condensation of about 2 to 3 of the tetraalkoxysilane, and as a mixture of the tetraalkoxysilane and its oligomer. You may mix | blend with the composition for formation.

  Regarding the amount of tetraalkoxysilane and / or oligomer thereof blended in the underlayer-forming composition, for example, when the second cured epoxy resin is used as the second crosslinked resin, the second polyepoxide component and the second 10-40 mass% is preferable with respect to the total mass of the hardening | curing agent of 25-35 mass%.

  In addition to the essential components and the solvent, the underlayer-forming composition contains, if necessary, the same filler, antioxidant, ultraviolet absorber, infrared absorption as those contained in the water-absorbing layer-forming composition. You may mix | blend non-reactive additives, such as an agent and a light stabilizer, with the same amount as the said water absorbing layer forming composition. Further, the same leveling agent, antifoaming agent, viscosity modifier and the like as those contained in the water absorbing layer forming composition can be added in the same amount as in the water absorbing layer forming composition.

[Method for producing antifogging glass article]
The antifogging glass article of the present invention can be produced, for example, by the production method of the present invention having the following steps (1) to (3).
(1) A step of forming a black ceramic layer on a peripheral portion on at least one main surface of the glass substrate (a black ceramic layer forming step),
(2) A step of forming an adhesive layer in the adhesive layer forming region including the laminated region on the black ceramic layer by using an adhesive layer forming composition containing a hydrolyzable metal compound and a solvent (adhesive layer) Forming process),
(3) A step of forming a water-absorbing antifogging film in a predetermined region of the glass substrate after the step (2) (water-absorbing antifogging film forming step).

Hereinafter, each step will be described.
(1) Black ceramic layer formation process In the manufacturing method of this invention, a black ceramic layer is first formed in the peripheral part on the at least one main surface of a glass substrate by this process. The glass substrate to be used and the region for forming the black ceramic layer in the glass substrate are as described above.
In forming the black ceramic layer in a predetermined region on the glass substrate, the black ceramic paste described above is prepared or prepared, and this is applied to the predetermined region. As a method for applying the black ceramic paste to a predetermined region on the glass substrate, a conventionally known method, specifically, a coating method such as a screen printing method or a flexographic printing method can be applied. The coating thickness of the black ceramic paste is set such that the thickness of the fired black ceramic layer is within the above predetermined range.

  Next, after the black ceramic paste applied on the glass substrate is dried as necessary, the black ceramic layer is formed by baking on the glass substrate by firing. Depending on the composition of the black ceramic paste, examples of the drying condition include 600 to 750 ° C. and 0.1 to 0.5 hours. Moreover, about baking conditions, although depending on the composition of the black ceramic paste, 650 to 700 ° C., 0.1 to 0.25 hours, and the like are preferable conditions. As described above, it is economically advantageous to perform the baking simultaneously with a glass substrate heating bending step or the like.

(2) Adhesive layer forming step Next, the glass substrate with the black ceramic layer obtained in the step (1) includes a laminated region where the water-absorbing antifogging film on the black ceramic layer is laminated. Using a composition for forming an adhesive layer containing a hydrolyzable metal compound and a solvent in a formation region, specifically, a region including at least the entire region of the layered region and consisting of the layered region and its vicinity at the maximum An adhesive layer is formed.
The region for forming the adhesive layer and the composition for forming the adhesive layer are as described above. An adhesive layer is obtained by applying the above-mentioned composition for forming an adhesive layer to a predetermined region of a glass substrate with a black ceramic layer and reacting it.

The method for applying the adhesive layer forming composition to a predetermined region of the glass substrate with a black ceramic layer is not particularly limited, but includes a flow coating method, a dip coating method, a spin coating method, a spray coating method, a flexographic printing method, a screen. Known methods such as a printing method, a gravure printing method, a roll coating method, a meniscus coating method, a die coating method, and a wiping method may be used. In addition, you may adjust the area | region which apply | coats the composition for adhesive layer formation by masking the glass substrate with a black ceramic layer etc. as needed at this time.
The coating thickness of the adhesive layer forming composition is set to such a thickness that the thickness of the adhesive layer finally obtained by reaction of the reaction components in the composition is within the above range.

  After apply | coating the composition for contact bonding layer formation on the glass substrate with a black ceramic layer, a solvent is removed by drying as needed, and a reaction component is made to react on the conditions according to the reaction component to be used, and it is set as an contact bonding layer. Specific examples of conditions for removing the solvent by drying include 25 to 200 ° C. and 0.5 to 20 minutes. Moreover, although reaction conditions in the composition for contact bonding layer formation depend on a reaction component, 25-100 degreeC and 0.5-5 minutes are mentioned.

(3) Water-absorbing anti-fogging film forming step Next, the water-absorbing anti-fogging film is formed in a predetermined region on the glass substrate with the black ceramic layer on which the adhesive layer obtained in (2) is formed. A hazy glass article is obtained. When the water-absorbing anti-fogging film is composed of an underlayer and a water-absorbing layer, the water-absorbing anti-fogging film is formed by the following (A) forming the underlayer and (B) forming the water-absorbing layer. . In addition, when a water absorption anti-fog film | membrane is comprised only by a water absorption layer, a water absorption anti-fog film | membrane is formed by performing the (B) process, without performing the (A) process of the following description.

(A) Crosslinkable component and curing agent, which are main raw material components of the second cross-linked resin, solvent, various optional components, preferably reactive to the reactive group of the raw material component of the second cross-linked resin A composition for forming an underlayer containing various optional components including a functional group having a silane coupling agent having a hydrolyzable group and a tetraalkoxysilane compound is formed on a glass substrate with a black ceramic layer on which the adhesive layer is formed. A base layer made of a base material having a water absorption lower than that of the water-absorbing material, preferably having a saturated water absorption of 30 mg / cm ³ or less, which is mainly composed of the second cross-linked resin by coating and reacting in a predetermined region. Forming step,
(B) The reactivity which the crosslinkable component and the hardening | curing agent which are the main raw material components of a 1st crosslinked resin, the solvent, and various arbitrary components, Preferably the raw material component of a 1st crosslinked resin is on the surface of the said base layer. The antifogging performance is mainly composed of the first cross-linked resin by applying and reacting a water-absorbing layer forming composition containing a functional group having reactivity with a group and a silane coupling agent having a hydrolyzable group. A step of forming a water-absorbing layer made of a water-absorbing material having a high water-absorbing property, preferably a saturated water-absorbing amount of 50 mg / cm ³ or more.

The components contained in the underlayer-forming composition and the water-absorbing-layer-forming composition are as described above, and the above-mentioned two types of compositions can be obtained by mixing these components in the usual manner.
In the step (A), in order to form a base layer in a predetermined region on the glass substrate with the black ceramic layer on which the adhesive layer is formed, the base layer forming composition obtained above is applied to the region. The method is not particularly limited, but the flow coating method, dip coating method, spin coating method, spray coating method, flexographic printing method, screen printing method, gravure printing method, roll coating method, meniscus coating method, die coating method, wipe method. Known methods such as In addition, you may adjust the area | region which apply | coats the composition for base layer formation by masking the glass substrate with a black ceramic layer which has an contact bonding layer as needed at this time.
The coating thickness of the composition for forming the underlayer is set such that the thickness of the underlayer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the underlayer-forming composition to a predetermined area on the glass substrate with the black ceramic layer on which the adhesive layer has been formed, remove the solvent by drying if necessary, and cure under conditions suitable for the reaction components used A base layer mainly composed of the second cross-linked resin is processed. Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. In addition, the reaction conditions for obtaining the second cross-linked resin in the underlayer-forming composition are appropriately selected depending on the type of the second cross-linked resin. When the second crosslinked resin is the second cured epoxy resin, specifically, heat treatment at 70 to 150 ° C. for about 1 to 60 minutes can be mentioned. When the second cross-linked resin is the second urethane resin, specifically, heat treatment at 70 to 150 ° C. for about 5 to 60 minutes can be mentioned. When the second crosslinked resin is the second crosslinked acrylic resin, specifically, heat treatment at 70 to 150 ° C. for about 5 to 60 minutes can be mentioned. Further, in the second cured epoxy resin or the second cross-linked acrylic resin, when a UV curable photocurable resin is used, UV irradiation of 100 to 500 mJ / cm ² is performed with a UV curing device or the like for 1 to 5%. For example, processing such as performing for a second.

  Here, in the manufacturing method of this invention, it is preferable to perform reaction of the said composition for base layer formation on fixed humidification conditions. By performing the above reaction under humidified conditions, the reaction time can be shortened in the reaction performed under the same temperature conditions as compared with the case where no humidification is performed. Moreover, if the reaction time is the same, the reaction can be sufficiently performed even if the reaction temperature is set low by humidification. In any case, it is economically advantageous to perform the above reaction under humidified conditions. Furthermore, by performing the above reaction under humidified conditions, the reaction can be performed uniformly throughout the entire layer, and quality variations in the underlayer can be suppressed.

  Specific examples of the humidification condition include 40 to 80% RH, but a condition of 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with temperature conditions, reaction conditions of about 50 to 80% RH, 70 to 100 ° C., and about 5 to 30 minutes may be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and about 10 to 30 minutes.

  As a method of applying the water-absorbing layer forming composition in the step (B) to the surface of the base layer formed in a predetermined region on the glass substrate with the black ceramic layer formed with the adhesive layer by the step (A). Can be the same as the coating method of the composition for forming an underlayer. The coating thickness of the water-absorbing layer forming composition is set such that the thickness of the water-absorbing layer finally obtained by reaction of the reaction components in the composition falls within the above range.

After applying the water-absorbing layer-forming composition on the underlayer, the solvent is removed by drying as necessary, and the water-absorbing layer mainly composed of the first cross-linked resin is subjected to curing treatment under conditions suitable for the reaction components used. And Specific examples of conditions for removing the solvent by drying include 50 to 90 ° C. and 5 to 15 minutes. Moreover, the reaction conditions for obtaining the 1st crosslinked resin in the composition for water absorption layer formation are suitably selected by the kind of 1st crosslinked resin. When the first cross-linked resin is the first cured epoxy resin, specifically, heat treatment at 50 to 120 ° C. for about 10 to 60 minutes can be mentioned. When the first cross-linked resin is the first urethane resin, specifically, heat treatment at 50 to 200 ° C. for about 1 to 60 minutes can be mentioned. When the first cross-linked resin is the first cross-linked acrylic resin, specifically, heat treatment at 80 to 200 ° C. for about 5 to 120 minutes can be mentioned. In addition, in the first cured epoxy resin or the first crosslinked acrylic resin, when UV curable photocurable resin is used, UV irradiation of 50 to 1000 mJ / cm ² is performed for 5 to 10 with a UV curing device or the like. For example, processing such as performing for a second.

Here, in the production method of the present invention, it is preferable for the above reason that the reaction of the water-absorbing layer-forming composition is carried out under constant humidification conditions as in the case of the underlayer-forming composition. Specific examples of the humidification condition include 40 to 80% RH, but a condition of 50 to 80% RH is more preferable. If more preferable reaction conditions are shown together with temperature conditions, reaction conditions of about 50 to 80% RH, 70 to 100 ° C., and about 5 to 30 minutes may be mentioned. More preferable conditions include reaction conditions of 50 to 80% RH, 80 to 100 ° C., and about 10 to 30 minutes.
Thus, the anti-fogging article of the present invention in which the anti-fogging film is formed on the substrate is obtained through the steps (A) and (B).

  The base layer and the water absorbing layer are preferably formed on the interior substrate surface when applied to an architectural window glass, and formed on the vehicle interior substrate surface when applied to a vehicle window glass. preferable.

[Transportation Equipment Items]
The antifogging glass article of the present invention is suitably used for use as an article for transport equipment. Preferred examples of the article for transportation equipment include window glass (front glass, side glass, rear glass), a mirror, and the like in trains, automobiles, ships, aircrafts, and the like.

  The article for transport equipment comprising the antifogging glass article having both the black ceramic layer of the present invention and the water absorption antifogging film has good appearance and visibility, and the water absorption antifogging film surface has excellent antifogging properties. Therefore, adverse effects due to moisture-induced clouding can be eliminated. Further, the water-absorbing anti-fogging film is excellent in durability such as chemical resistance, in particular, durability such as chemical resistance in the water-absorbing anti-fogging film formed on the black ceramic layer. This anti-fogging property can be maintained even in long-term use under various usage conditions including outdoor use.

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

<Preparation of glass substrate with black ceramic layer>
The following A-1 to A-3 were used as a glass substrate for forming a water absorption antifogging film. The glass substrate was polished and washed with cerium oxide, and then the slurry was removed with pure water and drained by air blow to obtain a clean state, which was used for forming the following adhesive layer and water-absorptive antifogging film.
A-1: Soda lime glass substrate (water contact angle 3 °, 200 mm × 200 mm × thickness 2 mm)
A-2: Obtained by applying black ceramic paste N9-104 (trade name, manufactured by Fellow) on one main surface of the soda-lime glass substrate of A-1 and baking at a temperature of 650 ° C. for 15 minutes. Black ceramic layer-attached glass substrate A-3: Black ceramic paste AP51330 (trade name, manufactured by Asahi Glass Co., Ltd.) is applied to the entire main surface of one of the soda-lime glass substrates of A-1, and baked at a temperature of 680 ° C. for 10 minutes. Glass substrate with black ceramic layer obtained

<Preparation of composition for forming adhesive layer>
A composition for forming an adhesive layer for forming an adhesive layer was prepared as follows.
[Production Example B-1]
Tetramethoxysilane (manufactured by Kanto Chemical Co.) 0.3 g was diluted with 9.7 g of methanol (manufactured by Junsei Kagaku Co., Ltd.) to obtain an adhesive layer forming composition B-1. The solid content concentration was 3% by mass.

[Production Example B-2]
Tetraethoxysilane (manufactured by Kanto Chemical Co.) 0.3 g was diluted with 9.7 g of methanol (manufactured by Junsei Kagaku Co., Ltd.) to obtain an adhesive layer forming composition B-2. The solid content concentration was 3% by mass.

[Production Example B-3]
Tetraisocyanate silane (Orgatics SI400; trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.) (0.3 g) was diluted with ethanol (Pure Chemical Co., Ltd.) (9.7 g) to obtain an adhesive layer forming composition B-3. The solid content concentration was 3% by mass.

[Production Example B-4]
Tetrachlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.3 g) was diluted with methanol (manufactured by Junsei Chemical Co., Ltd.) (9.7 g) to obtain an adhesive layer forming composition B-4. The solid content concentration was 3% by mass.

[Production Example B-5]
Tetraisopropoxytitanium (Olgatix TA10; trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.) 0.3 g was diluted with 9.7 g of isopropanol (Pure Chemical Co., Ltd.) to obtain an adhesive layer forming solution B-5. The solid content concentration was 3% by mass.

[Production Example B-6]
Tetra-normal butoxy titanium (Orgatechix TA25; trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.) (0.3 g) was diluted with 9.7 g of methanol (Pure Chemical Co., Ltd.) to obtain an adhesive layer forming composition B-6. The solid content concentration was 3% by mass.

[Production Example B-7]
Tetraisocyanate silane (Orgatics SI400; trade name, manufactured by Matsumoto Fine Chemical Co., Ltd.) (0.1 g) was diluted with ethanol (Pure Chemical Co., Ltd.) (9.9 g) to obtain an adhesive layer forming composition B-7. The solid content concentration was 1% by mass.

[Production Example B-8]
0.05 g of tetrachlorosilane (manufactured by Tokyo Chemical Industry Co., Ltd.) was diluted with 9.95 g of methanol to obtain an adhesive layer forming composition B-8. The solid content concentration was 0.5% by mass.

<Preparation of the composition used for formation of a water absorption anti-fogging film>
Each composition for forming a water absorption anti-fogging film was prepared as follows.

[C-1: Two layers of cured epoxy resin (underlayer + water absorption layer)]
As a composition for forming a water-absorbing antifogging film comprising a base layer and a water-absorbing layer using a cured epoxy resin, a base-layer forming composition C-1a and a water-absorbing layer forming composition C-1b are used. It was prepared by the following method.
(Underlayer forming composition)
In a glass container in which a stirrer and a thermometer are set, 7.93 g of diacetone alcohol (manufactured by Junsei Kagaku), 5.00 g of bisphenol F diglycidyl ether (manufactured by Adeka, trade name: Adeka Resin EP4901), polyoxyalkylenetriamine (Manufactured by Huntsman, trade name: Jeffamine T403) 2.30 g, 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM903) 1.13 g, tetramethoxysilane (manufactured by Tama Chemical Industries) 2 .37 g was added and stirred at 25 ° C. for 30 minutes. Then, it diluted 5 times with diacetone alcohol (made by a pure chemical company), and obtained composition C-1a for base layer formation.

(Water absorbing layer forming composition)
In a glass container in which a stirrer and a thermometer are set, 9.94 g of ethanol (manufactured by Junsei Chemical Co., Ltd.), 0.77 g of methyl ethyl ketone (manufactured by Junsei Chemical Co., Ltd.), aliphatic polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: 3.40 g of Denacol EX-1610), 2.83 g of glycerin polyglycidyl ether (manufactured by Nagase ChemteX Corporation, trade name: Denacol EX-313), organosilica sol (manufactured by Nissan Chemical Industries, trade name: NBAC-ST, SiO ₂ 0.41 g of content 30% by mass), 0.15 g of 2-methylimidazole (manufactured by Shikoku Kasei Co., Ltd.), 1.23 g of polyoxyalkylene triamine (manufactured by Huntsman, trade name: Jeffamine T403) were added with stirring, Stir at 25 ° C. for 1 hour. Subsequently, 1.27 g of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM903) was added with stirring, and the mixture was stirred at 25 ° C. for 3 hours. Further, 10.00 g of methyl ethyl ketone (manufactured by Junsei Chemical Co., Ltd.) and 0.02 g of a leveling agent (trade name: BYK307, manufactured by Big Chemie Co., Ltd.) were added with stirring to obtain a water absorbing layer forming composition C-1b.

[C-2: Crosslinkable acrylic resin single layer (water absorption layer)]
A water absorbing layer forming composition C-2 for forming a water absorbing antifogging film composed of a single water absorbing layer using a crosslinkable acrylic resin was prepared by the following method.
41.53 g of ethyl alcohol (manufactured by Junsei Co., Ltd.), 10.13 g of ion-exchanged water, and 10 g of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.) having a molecular weight of 25000 were added and mixed with stirring until dissolved. Then, 12.72 g of 3-glycidoxypropyrimethoxysilane (made by Shin-Etsu Silicone, trade name: KBM-403), 15.48 g of methyltriethoxysilane (made by Shin-Etsu Silicone, trade name: KBE-13), 1N nitric acid 10.14g was added and it stirred at 23 degreeC for 16 hours, and obtained the composition C-2 for water absorption layer formation.

[C-3: Urethane resin single layer (water absorption layer)]
A water-absorbing layer forming composition C-3 for forming a water-absorbing antifogging film composed of a single water-absorbing layer using a urethane resin was prepared by the following method.
Hexamethylene diisocyanate burette type polyisocyanate (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3200 (NCO%: 23%)) was used as coating agent A. A solution containing polyethylene glycol having an average molecular weight of 1000 at a ratio of 50% by mass and a solution containing acrylic polyol having an average molecular weight of 3000 at a ratio of 50% by mass (both manufactured by Sumika Bayer Urethane Co., Ltd.) were prepared. The mass ratio was polyethylene glycol: acrylic polyol = 60: 40, and this was used as coating solution B. With respect to 100 g of coating agent B, the number of isocyanate groups present in the isocyanate component of coating liquid A is 1.6 times the amount of hydroxyl groups present in the polyol component in coating liquid B. 33 g of coating solution A was added and mixed. Further, isobutyl acetate was added and mixed as a diluent solvent to the mixture of the coating agent A and the coating agent B so that the urethane component content was 35% by mass to obtain a water absorbing layer forming composition C-3.

<Manufacture of test samples for evaluation of antifogging glass articles>
In order to evaluate the antifogging glass article below, a test sample corresponding to each part of the antifogging glass article was manufactured and evaluated.
Test samples of Examples in which a black ceramic layer 3, an adhesive layer 4 and a water-absorptive anti-fogging film 5 are formed in that order on a glass substrate 2 corresponding to the peripheral edge of the antifogging glass article are Examples 1-4 and Examples 6- 16 manufactured. Specifically, an adhesive layer was formed on the glass substrate with black ceramic layer (A-2, A-3) using the composition for forming an adhesive layer obtained in the above production example, and further prepared above. Each test sample was manufactured by forming a water-absorbing anti-fogging film using each composition for forming a water-absorbing anti-fogging film.

Further, for example, in the embodiment in which the adhesive layer 4 and the water-absorptive anti-fogging film 5 are formed in this order on the glass substrate 2 corresponding to the vicinity of the black ceramic layer whose width is indicated by the distance L in FIGS. A test sample was prepared in Example 5. Specifically, an adhesive layer is formed on the glass substrate (A-1) without the black ceramic layer using the composition for forming an adhesive layer obtained in the above production example, and the water absorption antifogging prepared above is further formed. A test sample was produced by forming a water-absorbing anti-fogging film using the film-forming composition.
Furthermore, a test sample corresponding to the central part of the antifogging glass article in which a water-absorbing antifogging film was formed on a glass substrate without a black ceramic layer in Example 21 was produced as an example.

  As test samples of comparative examples, test samples having a black ceramic layer 3 and a water-absorptive anti-fogging film 5 formed on the glass substrate 2 in that order and having no adhesive layer were produced in Examples 17-20. Specifically, a water-absorptive antifogging film is formed on the glass substrate with black ceramic layer (A-2, A-3) using each composition for forming a water-absorptive antifogging film prepared above. Test samples were manufactured.

[Example 1]
Adhesion layer forming composition B-1 is applied to the entire main surface of the glass substrate A-2 with a black ceramic layer having a black ceramic layer by a wipe coating method, and is naturally dried in a room at 25 ° C. to adhere to a thickness of 15 nm. A layer was formed.
On the adhesive layer of the glass substrate A-2 with a black ceramic layer on which the adhesive layer is formed, the underlayer-forming composition C-1a obtained by C-1 is applied by a flow coating method and set to 100 ° C. In the constant temperature layer, heat treatment was performed for 0.5 hour to form a base layer. The thickness of the obtained underlayer was 2 μm.
After taking out glass substrate A-2 with a black ceramics layer which provided the foundation layer and the adhesion layer from the thermostat, and returning to room temperature, composition C-1b for water absorption layer formation obtained above on the whole surface of a foundation layer Was applied by a flow coat method, and was subjected to a heat treatment for 0.5 hours in an electric furnace set at 100 ° C. to form a water absorption layer, whereby a test sample 1 was obtained. The thickness of the obtained water absorption layer was 20 μm.

[Example 2]
In Example 1 above, a test sample 2 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-2 was used instead of the adhesive layer forming composition B-1 in forming the adhesive layer. .

[Example 3]
In Example 1 above, Test Sample 3 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-3 was used instead of the adhesive layer forming composition B-1 in forming the adhesive layer. .

[Example 4]
A test sample 4 was obtained in the same manner as in Example 3, except that the glass substrate A-3 with a black ceramic layer was used instead of the glass substrate A-2 with a black ceramic layer.

[Example 5]
For the manufacturing method shown in Example 3 above, test sample 5 was obtained with A-1 as the type of substrate.

[Example 6]
A test sample 6 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-7 was used instead of the adhesive layer forming composition B-1 in the formation of the adhesive layer in Example 1 above. .

[Example 7]
In Example 1, the test sample 7 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-4 was used instead of the adhesive layer forming composition B-1 in forming the adhesive layer. .

[Example 8]
A test sample 8 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-8 was used instead of the adhesive layer forming composition B-1 in the above Example 1. .

[Example 9]
In Example 1, the test sample 9 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-5 was used instead of the adhesive layer forming composition B-1 in forming the adhesive layer. .

[Example 10]
In Example 1, the test sample 10 was obtained in the same manner as in Example 1 except that the adhesive layer forming composition B-6 was used instead of the adhesive layer forming composition B-1 in forming the adhesive layer. .

[Example 11]
In Example 3 above, the composition used for forming the water-absorptive anti-fogging film was designated as a water-absorbing layer-forming composition C-2, and a glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming an underlayer. A test sample 11 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer. The thickness of the water absorbing layer obtained was 25 μm.

[Example 12]
In Example 7 above, the composition used for forming the water-absorptive antifogging film was used as the water-absorbing layer-forming composition C-2, and a glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming an underlayer. A test sample 12 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer.

[Example 13]
In Example 9 above, the glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming a base layer, with the composition used for forming the water-absorptive antifogging film as the water-absorbing layer-forming composition C-2. A test sample 13 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorbing layer.

[Example 14]
In Example 3 above, the composition used for forming the water-absorptive anti-fogging film was designated as water-absorbing layer-forming composition C-3, and a glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming an underlayer. The test sample 14 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer. The thickness of the water absorbing layer obtained was 15 μm.

[Example 15]
In Example 7 above, the composition used for forming the water-absorptive anti-fogging film was designated as water-absorbing layer-forming composition C-3, and the glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming an underlayer. A test sample 15 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer.

[Example 16]
In Example 9 above, the glass substrate A-2 with a black ceramic layer on which an adhesive layer was formed without forming a base layer, with the composition used for forming the water-absorptive antifogging film as the water-absorbing layer-forming composition C-3 The test sample 16 was obtained by applying the coating layer on the adhesive layer by a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer.

[Example 17]
The underlayer-forming composition C-1a obtained by C-1 was applied to the entire main surface of the glass substrate A-2 with a black ceramic layer having a black ceramic layer by the flow coating method, and the temperature was 100 ° C. In the set constant temperature layer, a heat treatment for 0.5 hours was performed to form a base layer. The thickness of the obtained underlayer was 2 μm. After taking out the glass substrate A-2 with the black ceramic layer provided with the underlayer from the thermostat and returning to room temperature, the entire surface of the underlayer is flow-coated with the water absorbing layer forming composition C-1b obtained above. The test sample 17 was obtained by applying by the method and performing a heat treatment for 0.5 hours in an electric furnace set at 100 ° C. to form a water absorption layer. The thickness of the obtained water absorption layer was 20 μm.

[Example 18]
Test sample 18 was obtained in the same manner as in Example 17 except that glass substrate A-2 with a black ceramic layer was replaced with glass substrate A-3 with a black ceramic layer.

[Example 19]
In Example 17, the composition used for forming the water-absorptive antifogging film is the water-absorbing layer-forming composition C-2, and the black ceramic layer of the glass substrate A-2 with the black ceramic layer is formed without forming the base layer. A test sample 19 was obtained by coating the entire main surface with a flow coating method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer.

[Example 20]
In Example 17, the composition used for forming the water-absorptive antifogging film is the water-absorbing layer-forming composition C-3, and the black ceramic layer of the glass substrate A-2 with the black ceramic layer is formed without forming the base layer. A test sample 20 was obtained by coating the entire main surface with a flow coat method and performing a heat treatment for 0.5 hour in an electric furnace set at 100 ° C. to form a water absorption layer.

[Example 21]
On the entire surface of one main surface of the glass substrate A-1, the base layer forming composition C-1a obtained by C-1 was applied by a flow coating method, and in a constant temperature layer set at 100 ° C., A heat treatment for 0.5 hour was performed to form a base layer. The thickness of the obtained underlayer was 2 μm.
After taking out glass substrate A-1 with a base layer from a thermostat, and returning to room temperature, the water absorption layer forming composition C-1b obtained above was apply | coated to the whole surface of a base layer by the flow coat method, and 100 A heat treatment for 0.5 hour was performed in an electric furnace set at ° C. to form a water absorption layer, and a test sample 21 was obtained. The thickness of the water absorbing layer obtained was 18 μm.

[Evaluation]
The test samples 1 to 21 obtained in each of the above examples were used as specimens, and the adhesion test between the substrate and the water-absorptive antifogging film was performed and evaluated as follows. The results are shown in Table 1 together with the structure of the test sample and the layer thickness of each layer of the adhesive layer and the water-absorptive antifogging film included in the test sample.
(Chemical resistance test)
0.1 ml of acetic acid whose concentration was adjusted to 5% by mass was dropped on the water-absorbing anti-fogging film of the specimen. This specimen was placed in a sealed container and allowed to stand in an environment of 24 ± 1 ° C. for 2 hours, and then removed from the sealed container and washed with water. The appearance of the specimen after washing with water was evaluated based on the following criteria.
◯: No peeling of the water-absorbing antifogging film was confirmed at the acetic acid dropping portion, and no change in appearance was observed.
Δ: Appearance changes such as peeling, cracking, and whitening of the water-absorbing antifogging film were observed in part of the acetic acid dropping portion.
X: Appearance changes such as peeling, cracking, and whitening of the water-absorbing antifogging film were observed throughout the acetic acid dropping portion.

(Durability test during water absorption)
The surface of the water-absorptive anti-fogging membrane of the specimen was placed on a warm water bath at 90 ° C. for a certain period of time, and then the membrane surface was washed with ethanol and evaluated based on the following evaluation criteria.
○: No change in appearance of the water-absorbing antifogging film was observed after 100 hours of exposure.
X: Appearance changes such as peeling, cracking, and whitening of the water-absorbing antifogging film were observed after 100 hours of exposure.

  From the results of Table 1 above, an adhesive layer is provided on the black ceramic layer of the glass substrate with the black ceramic layer using the adhesive layer forming compositions B-1 to B-8, and a water-absorptive antifogging film is formed thereon. It was confirmed that the chemical resistance of the water-absorbing anti-fogging film on the black ceramic layer can be improved to a level equivalent to that of the water-absorbing anti-fogging film of the portion not having the black ceramic layer (Example 21). 1-4, Examples 6-17). Further, according to Example 5, there is no problem in chemical resistance even if an adhesive layer is formed on a portion not having the black ceramic layer to form a water-absorptive anti-fogging film, and in the vicinity of the black ceramic layer in order to improve workability. It was confirmed that an adhesive layer can be formed.

  The anti-fogging glass article of the present invention is an anti-fogging glass article having both a black ceramic layer and a water-absorptive anti-fog film, and has good appearance and visibility and durability such as chemical resistance in the water-absorptive anti-fog film. In particular, the water-absorptive anti-fogging film formed on the black ceramic layer is excellent in durability such as chemical resistance, and is particularly useful as an anti-fogging glass article for transportation equipment.

DESCRIPTION OF SYMBOLS 1 ... Antifogging glass article, 2 ... Glass substrate, 3 ... Black ceramic layer, 4 ... Adhesive layer, 5 ... Water absorption antifogging film, 31 ... Frame-like concealment part, 32 ... Character display part, 33 ... Outer edge area | region, 34 ... dot pattern area

Claims (12)

  A water absorption barrier formed on the main surface such that there is a glass substrate, a black ceramic layer formed on a peripheral portion on at least one main surface of the glass substrate, and a laminated region overlapping on the black ceramic layer. An antifogging glass article comprising a cloudy film and an adhesive layer formed between the water-absorbing antifogging film and the black ceramic layer in at least the laminated region on the main surface, The formation region is an antifogging glass article that does not exceed the region composed of the laminated region and its vicinity.   The adhesive layer is a layer mainly composed of a metal oxide or an organic group-containing metal oxide formed by a sol-gel method using a hydrolyzable metal compound, wherein the metal of the hydrolyzable metal compound is silicon, The antifogging glass article according to claim 1, which is at least one selected from aluminum, titanium and zirconium.   The antifogging according to claim 2, wherein the hydrolyzable metal compound is at least one selected from the group consisting of a trifunctional or tetrafunctional hydrolyzable titanium compound and a trifunctional or tetrafunctional hydrolyzable silicon compound. Glass articles.   The antifogging glass article according to claim 2 or 3, wherein the hydrolyzable metal compound is a tetrafunctional hydrolyzable silicon compound.   The antifogging glass article according to any one of claims 1 to 4, wherein the adhesive layer has a thickness of 1 to 500 nm.   The anti-fogging glass article according to any one of claims 1 to 5, wherein the water-absorbing and anti-fogging film has a water-absorbing layer mainly composed of a water-absorbing crosslinked resin.   The antifogging glass article according to claim 6, wherein the water-absorbing crosslinked resin is selected from a curable epoxy resin, a urethane resin, and a crosslinked acrylic resin.   The water-absorbing anti-fogging film is a layer in which the water-absorbing layer is mainly composed of a water-absorbing curable epoxy resin, and further has a water-absorbing curable property lower than the water-absorbing curable epoxy resin on the glass substrate side from the water-absorbing layer The antifogging glass article according to claim 6 or 7, which has a base layer mainly composed of an epoxy resin.   The antifogging glass article according to any one of claims 6 to 8, wherein the layer closest to the glass substrate of the antifogging film is a raw material component of a cross-linked resin, and the raw material component. A composition containing at least one selected from a functional group having reactivity with a reactive group and a silane coupling agent having a hydrolyzable group, a titanium coupling agent, and a zirconium coupling agent. An antifogging glass article which is a layer formed using   The antifogging glass article according to any one of claims 6 to 9, wherein the thickness of the water absorbing layer is 5 to 50 µm, and the thickness of the base layer when the base layer is provided is 1 to 20 µm.   An article for transport equipment comprising the antifogging glass article according to any one of claims 1 to 10. It is a manufacturing method of the antifogging glass article of any one of Claims 2-10, Comprising: The manufacturing method which has the process of following (1)-(3).
(1) A step of forming a black ceramic layer on a peripheral edge portion on at least one main surface of the glass substrate;
(2) forming an adhesive layer using an adhesive layer forming composition containing a hydrolyzable metal compound and a solvent in a formation region of the adhesive layer including the laminated region on the black ceramic layer;
(3) The process of forming a water absorption anti-fogging film in the predetermined area | region of the said glass substrate after the process of said (2).

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