JP2006078808A - Manufacturing method of article formed of protruding part group on surface, and article manufactured thereby - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of an article formed of a protrusion part group on the surface, having superior appearance having few irregularities as and being suitable for use as a substrate material of a light-scattering reflecting base plate. <P>SOLUTION: In the manufacturing method, a coating layer is formed by coating liquid composed of a protrusion part-forming component, a first solvent which has compatibility with the protrusion part forming component and comprises at least one kind of solvent, and a second solvent which has no compatibility with the protrusion part forming component and comprises at least one kind of solvent. Subsequently, by drying the first solvent and the second solvent, included in the coating layer and by causing phase separation between the protrusion part-forming component and the second solvent, the protrusion part group is formed on the surface of the article. Therein, the drying is performed so that hot air is directly blown against the coating layer, to even the phase separation. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for manufacturing an article in which a convex portion group is formed on the surface, and an article manufactured thereby.

  An article that forms a convex group on the surface is used as a base material for a light-scattering / reflecting substrate. As a manufacturing method of the light scattering reflection substrate, a manufacturing method described in Japanese Patent No. 2698218 (Patent Document 1) is known. In this manufacturing method, a photosensitive resin, which is an organic substance, is applied to one surface of a glass substrate, and the applied photosensitive resin is patterned into a predetermined shape, masked, exposed, and developed to obtain a large number. A step of forming a fine convex portion, a step of heat-treating the glass substrate on which the convex portion is formed to round the corners of the convex portion to form an internal scattering layer, and the glass substrate and the internal scattering layer. And a step of laminating a reflective film made of an inorganic material such as a metal material or a dielectric by a vapor deposition method or a sputtering method.

  As a method for manufacturing a light-scattering / reflecting substrate using phase separation, a manufacturing method described in Japanese Patent Application Laid-Open No. 2000-267086 (Patent Document 2) is known. In this manufacturing method, a first-layer resin coating process on a glass substrate and its drying process, a second-layer coating process and its drying process, and a light-reflecting electrode layer on the second layer by sputtering. Generating.

  However, in the methods of Patent Documents 1 and 2, the problem that the manufacturing process is complicated and the internal scattering layer is made of an organic substance, so that the adhesion with the reflective film made of an inorganic material is poor, and the reflective film is easily peeled off. There is a problem. In addition, when the reflective film is formed by a vacuum film formation method such as vapor deposition or sputtering, the surface adsorbed components and internal unreacted components from the internal scattering layer are released as gas, and the optical characteristics (reflective properties of the reflective film) There is also a problem of altering the refractive index, refractive index, transmitted color tone, and the like.

  In order to solve such problems, the present applicant has previously made several proposals utilizing the sol-gel method and phase separation. For example, in WO 02/064524 (Patent Document 3) and WO 03/052466 (Patent Document 4), a convex film (hereinafter, referred to as a film having a main skeleton made of an inorganic material and a side chain modified with an organic material) We used the same meaning as the convex part group) and a manufacturing (forming) method thereof. Furthermore, in Japanese Patent Laid-Open No. 2003-84106 (Patent Document 5), a convex film made entirely of an inorganic material and a method for forming the same were proposed.

  Japanese Patent Laid-Open No. 2003-266571 (Patent Document 6) proposed a convex film having a main skeleton composed of an inorganic component and an organic component, and a method for forming the same. These production (formation) methods include a step of applying a sol coating solution on one surface of a glass substrate, a drying step, a phase separation by the drying step, and a sputtering method onto a gelled convex film. And a step of generating a light reflecting film layer. These inventions have succeeded in simplifying the manufacturing process, improving the adhesion with the reflective film made of an inorganic material, and preventing the optical properties of the reflective film from being altered.

Japanese Patent No. 2698218 JP 2000-267086 A WO 02/064524 pamphlet WO 03/052466 pamphlet JP 2003-84106 A JP 2003-266571 A

  However, in the manufacturing method using phase separation described in Patent Documents 2 to 6, the coating liquid is applied to the surface of the glass substrate (in the case of Patent Document 2, on the first layer) and then dried (baked). ), A phenomenon occurs in which phase separation between the central portion and the peripheral portion of the coating layer occurs non-uniformly. This occurs because the peripheral portion of the coating layer is easier to dry than the central portion, and phase separation gradually proceeds from the peripheral portion of the coating layer toward the central portion. When such non-uniform phase separation occurs, the size and density of the individual convex portions forming the convex portion group formed on the glass substrate surface tend to be non-uniform. As a result, the scattering characteristics as the light scattering / reflecting substrate tend to be non-uniform. Therefore, further improvement is required for the uniformity of the individual convex portions forming the convex portion group.

In particular, in the manufacture of a liquid crystal display device or the like, a method of simultaneously forming a large number of display devices on the surface of a single glass substrate is common. Therefore, as shown in FIG. 7, a large number of convex portions (15) (hereinafter referred to as cells) of the display device are also formed on one glass substrate (11).
When a large number of cell groups are partially formed on such a substrate surface, a coating method capable of partially forming a coating layer can be used. For example, a printing technique such as a flexographic printing method is preferably used because it does not require a masking process on the substrate surface. However, if it is left at room temperature after coating on the glass substrate surface, a large convex part is formed in the peripheral part of each cell compared to the convex part in the central part of the cell, The phenomenon to be made was seen.

  This is because, in the cell peripheral portion, the drying speed is faster than that in the central portion, so phase separation proceeds in a short time from the coating process to the drying step, whereas the cell central portion has a slight amount. This is probably because phase separation does not proceed with time. The same applies to the case of simply heating and drying in an atmosphere at a constant temperature. In this way, when the solvent is volatilized by room temperature or simple heat drying, the individual convex portions in the peripheral portion of the cell may be larger than the individual convex portions in the central portion. Therefore, frame-shaped unevenness may occur around the cell.

  An object of the present invention is a method for producing an article that can be suitably used as a base material for a light-scattering / reflecting substrate, and that has a convex portion group having excellent uniformity and appearance with little unevenness on the surface, and thereby It is to provide an article to be manufactured. Alternatively, a method for producing an article that can be suitably used for a portion that requires a light scattering function and that has a convex portion group having excellent uniformity and appearance with little unevenness on the surface, and an article produced thereby. Is to provide.

To achieve the above objective,
The manufacturing method according to claim 1 comprises:
Convex part forming component, first solvent compatible with the component and containing at least one solvent, and second solvent not compatible with the component and containing at least one solvent The coating liquid containing is applied to the surface of the article to form a coating layer, the first solvent and the second solvent contained in the coating layer are dried, and the convex portion forming component and the second solvent In the method of manufacturing an article on the surface of which convex portions are formed by causing phase separation between them, the drying is performed by directly blowing hot air against the coating layer to average the phase separation, It is characterized by.

  Moreover, according to the manufacturing method of Claim 2, you may make the said coating liquid contain the flat film-form part formation component which is compatible with both said 1st solvent and said 2nd solvent.

  According to the manufacturing method of Claim 3, any solvent in said 1st solvent may have a boiling point lower than the boiling point of any solvent in said 2nd solvent.

  According to the manufacturing method of claim 4, the temperature of the hot air may be higher than the boiling point of the solvent having the lowest boiling point in the first solvent.

  According to the manufacturing method of claim 5, the temperature of the hot air may be lower than the boiling point of any solvent in the second solvent.

  According to the manufacturing method of the sixth aspect, the coating solution may be a sol coating solution or a resin coating solution as long as phase separation is possible.

  According to the manufacturing method of the seventh aspect, a plurality of the convex portion groups may be formed on the surface of the article.

The article according to claim 8 is:
It is an article manufactured by the manufacturing method of an article for forming the convex part group according to any one of claims 1 to 7 on the surface, and is at least 0.5 mm inside from the outer periphery of the convex part group. Within the range, the ratio of the number of convex portions existing in the predetermined area range of the central portion to the number of convex portions existing in the predetermined area range of any portion other than the central portion is 70 -130% or less.

  According to the manufacturing method according to the present invention, in the drying process of the coating layer formed on the article surface, the coating layer is dried by blowing hot air directly to the central portion and the peripheral portion of the coating layer. The difference in the volatilization time of the solvent group is reduced. Therefore, more average phase separation occurs in the coating layer, and the size of the individual projecting portions forming the projecting portion group formed after drying becomes uniform, resulting in less unevenness.

  From the boundary between the convex part group and the surface of the article, the convex part existing in the area of the same area as the central part and any other part within the range inside at least 0.5 mm of the convex part group. If the number of the shape portions is compared, the ratio of the number of other arbitrary portions to the central portion is within 70 to 130%. Within this range, good appearance can be obtained. Further, the ratio of the aforementioned numbers is preferably within 75 to 125%. Furthermore, it is desirable to be within 90 to 110%.

  Moreover, it is desirable that the range in which the above-described good appearance is obtained is at least 0.3 mm inside the convex portion group. Furthermore, it is more desirable to be at least inside 0.1 mm.

  Therefore, when the article having the convex portion group with improved appearance on the surface is used as the base material of the light scattering reflection substrate, the light scattering property of the light scattering reflection substrate can be improved.

  Hereinafter, the manufacturing method of the article | item which has many convex-shaped parts on the surface which concerns on embodiment of this invention is explained in full detail with reference to drawings. In the following embodiments, a sol coating solution is used as the coating solution. However, the present invention is not limited to this, and a coating solution containing a resin component may be used as long as phase separation is possible.

FIG. 1 shows a flowchart of a method for producing an article having a large number of convex portions on the surface using a sol-like coating liquid as the coating liquid. The method for producing the article of the present invention comprises:
Step S101: coating liquid preparation process,
Step S102: coating liquid coating process,
Step S103: leveling process of the coating layer,
and,
Step S104: drying process of the coating layer with hot air,
Comprising. In addition, if necessary,
Step S105: A high temperature drying step may be added.

When the coating liquid preparation process (step S101) takes a long time compared to other processes, it may be out of the series of flows.
The high temperature drying step (step S105) is affected by the solvent remaining in the film when an upper layer film such as a light-scattering / reflecting film is formed on the convex portion group as in a liquid crystal display device or the like. Necessary if you are concerned. However, this is not always necessary when the upper layer film is not formed on the convex portion group.

(Step S101: Preparation Step of Coating Solution)
First, a sol coating solution in which a film component and a solvent are mixed is prepared.
In general, the sol-gel method is a method in which a metal is made into an organic or inorganic compound solution, the compound is hydrolyzed / condensed in the solution, the sol is solidified as a gel, and an oxide solid is formed by heating the gel. It is. The gelation reaction means that one or more kinds of metal compounds are polymerized by forming a metal-oxygen-metal network by a dehydration condensation polymerization reaction.

  As a component of the sol-like coating liquid for the purpose of phase separation, a convex portion forming component comprising at least one kind of metal compound, and a first solvent comprising at least one kind of solvent having compatibility with the component, There is a need for a second solvent that is not compatible with the component and comprises at least one solvent.

  The aforementioned coating solution may further contain a flat film-shaped part forming component made of at least one metal compound that is compatible with both the first solvent and the second solvent.

  As the material of the metal compound to be used, metal alkoxides of oxides such as silicon, aluminum, titanium, zirconium and tantalum are suitable. These metal alkoxides are easy to obtain, have the advantage of being stable at normal temperature and normal pressure, and having no toxicity. Therefore, the manufacturing process of the convex portion group can be facilitated and the manufacturing cost can be reduced. In addition, since optical absorption does not occur in the visible light region, the transmitted light is not colored, and a convex group that is optimal for use in the transmission mode can be formed.

When an organically modified metal alkoxide is used as the metal compound material of the convex portion forming component, the surface tension becomes relatively small. Therefore, it is suitable when it is desired to increase the difference in surface tension between the convex portion forming component and the second solvent.
As the aforementioned metal compound material, in addition to metal alkoxide, metal carboxylate, metal nitrate, metal chloride, metal oxychloride and the like can also be used.

  If a chelating agent such as acetylacetone is chelated to a metal compound such as metal alkoxide to suppress stabilization treatment or reactivity, the handling becomes easy. It is also convenient for preparing a coating solution. Thereby, it becomes easy to control the phase separation between the metal compounds. Examples of the chelating agent are β-diketones such as acetylacetone and β-ketoesters such as ethyl acetoacetate, but are not limited thereto.

The first solvent acts to homogenize the sol coating solution.
As the second solvent, it is effective to select a solvent having a surface tension larger than that of this component so that phase separation from the convex portion forming component is easy.

  As the first solvent for homogenizing the sol coating solution, alcohols, ketones, esters, ethylene-glycol-monoethyl ether (hereinafter abbreviated as cellosolve), and hydroxyl groups at both ends Glycols and the like can be used. In addition to these single solvents, solvent groups (mixed solvents) can be used.

As alcohols, methanol, ethanol, propanol and the like can be used.
As ketones, acetone, acetylacetone and the like can be used.
As the esters, methyl acetate, ethyl acetate, propyl acetate or the like can be used.
As cellosolves, ethyl cellosolve, butyl cellosolve, etc. can be used.
As glycols, propylene glycol, hexylene glycol and the like can be used.

  The purpose of the mixed solvent described above is to prevent volatilization of the solvent in the coating process. For example, when a printing method such as a flexographic printing method is used as the coating method, the coating solution is exposed to the air for a long time on the roll. For this reason, when only a highly volatile (low boiling point) solvent (referred to as A) is used as the first solvent, the first solvent volatilizes on the roll before coating and phase separation occurs. In order to prevent this, phase separation in the coating process can be prevented by using a low-volatility (high boiling point) solvent (referred to as B) in addition to solvent A as the first solvent. For these solvent A and solvent B, a solvent having a boiling point lower than that of the second solvent is selected.

It is desirable to select a solvent having a large surface tension (for example, 30 mN / m (= dyn / cm) or more) as the second solvent to be phase-separated from the above-mentioned convex portion forming component. As the second solvent, glycerin, a linear glycol generalized with HO— (CH ₂ ) _n —OH and having hydroxyl groups at both ends, or HO— (CH ₂ ) _n (CHOH) _m —OH A generalized polyhydric alcohol group can be used. In addition, formamide, methylformamide, and the like can be used as a solvent having no hydroxyl group. In addition to these single solvents, a mixed solvent (solvent group) can be used.

  In the following description, they are simply referred to as “first solvent group” and “second solvent group”, and “first single solvent or first composite solvent”, “second single solvent or second composite solvent”, respectively. The meaning of

(Step S102: Coating Liquid Application Process)
The sol-shaped coating liquid prepared in the coating liquid preparation step (step S101) is applied to the surface of the article to form a coating layer. For the base material of the article, a substance having a fire resistance temperature equal to or higher than the boiling point of the solvent contained in the sol coating liquid can be used. For example, a glass substrate (soda lime glass, non-alkali glass, quartz glass, etc.), a metal substrate (copper, aluminum, etc.), a semiconductor substrate (silicon wafer, etc.), a resin substrate, a ceramic substrate, etc. can be used.

In the case of application to a part of the substrate as shown in FIG. 7, various printing methods such as a roll coating method (flexographic printing method, etc.) and a screen printing method are generally used. These printing methods have an advantage that a masking process on an article is unnecessary.
In the case of application to the whole base material, spin coating method, spray coating method, curtain coating method, dip coating (dip coating) method, flow coating (flow coating) method and the like are used in addition to various printing methods.

  In this embodiment, a flexographic printing method is used. In this flexographic printing method, a fine concavo-convex pattern for adding a sol-like coating liquid is attached to the printed portion of the coater. Application is performed by transferring (printing) the sol coating liquid on the uneven pattern onto the surface of the substrate. Generally, the transfer pattern for this application is larger than the size of the individual convex portions forming the convex portion group to be manufactured.

(Step S103: Leveling process of coating layer)
Subsequently, the coating layer formed on the substrate surface is leveled. This step is performed to level the uneven transfer pattern applied by a flexographic printing method or the like. This leveling time is preferably set to about 3 minutes because it is necessary to set the leveling time within a time period in which phase separation in the peripheral portion of the coating layer does not proceed. Furthermore, within 1 minute is more desirable. In addition, this process can be included in the movement process to the next drying process.

(Step S104: Drying process of coating layer with hot air)
Subsequently, drying is performed by directly blowing hot air on the coating layer formed on the surface of the substrate to form a convex portion group (metal oxide).
When the sol-form coating liquid is composed only of the convex portion forming component, a large number of convex portions (12) (metal oxide) are formed on the surface of the substrate (11) as shown in FIG. An article (10) having a convex portion group consisting of is obtained. In addition, when the sol-like coating liquid is composed of a convex portion-forming component and a flat film-like portion-forming component, a number of convex shapes are formed on the surface of the substrate (11) as shown in FIG. An article (10) having a convex-shaped group of parts (12) and a flat film-like part (13) (metal oxide) between them is obtained.

  In this step, phase separation occurs simultaneously with drying. If a solvent having a boiling point lower than that of the second solvent group is used for the first solvent group, the volatilization rate is different even if the temperature of the hot air is lower than the lowest boiling point in the first solvent group. Appears and can be phase separated. If the temperature of the hot air is set higher than the lowest boiling point of the first solvent group, the volatilization of the first solvent group having a lower boiling point than that temperature can be promoted, which is effective. In addition, if the temperature is set lower than the lowest boiling point in the second solvent group, the temperature becomes higher than the boiling point of any solvent in the first solvent group, and the volatilization of all the first solvent groups can be further promoted. Because it can, it is more effective.

  This process will be described in the case of a coating layer to which a sol coating solution composed of a convex portion forming component, a flat film portion forming component, a first solvent group, and a second solvent group is applied. When hot air is blown directly, volatilization of the first solvent group that has been effective in homogenization proceeds in the coating layer on the substrate surface. And insolubilization of the convex part forming component group having a small surface tension with respect to the second solvent group having a large surface tension becomes remarkable, and phase separation occurs between the two. Alternatively, phase separation occurs between the flat film forming component dissolved in the second solvent group having a large surface tension and the convex forming component having a small surface tension. As a result, the coating layer is separated into two phases of a droplet-shaped phase made up of the convex portion forming component and a flat phase made up of the flat film-like portion forming component.

  As the drying further proceeds, the volatilization of the second solvent group also proceeds, and as shown in FIG. 2 (b), on the surface of the substrate (11), a large number of convex portions (12) composed of convex portion forming components. Then, a convex-shaped part group consisting of a flat film-like part (13) made of a flat film-like part forming component is obtained between them.

  At this time, in the coating layer where the hot air is directly blown, the atmosphere containing the volatilized solvent group is forcibly exhausted, and drying with new hot air is constantly possible. For this reason, the difference in volatilization time of the solvent group is small between the peripheral portion and the central portion of the coating layer. Therefore, more uniform phase separation occurs, and as a result, the size of the individual convex portions forming the convex portion group to be formed becomes uniform.

  When the hot air blowing speed (wind speed) is in the range of 3 to 15 m / s, it is easy to obtain a good convex portion group. When the wind speed is slower than 3 m / s, replacement between the supplied hot air and the atmosphere containing the volatilized solvent becomes insufficient. Therefore, the volatilization rate of the solvent is slowed down, and phase separation becomes non-uniform. On the other hand, when the wind speed is higher than 15 m / s, the surface of the coating layer is roughened by the hot air and the appearance is deteriorated.

  In the conventional drying method using a hot-air circulation dryer or the like, uniform phase separation does not occur in the peripheral part, and as a result, the size of the convex part in the peripheral part of the convex part group to be formed is not good. It becomes uniform. This is presumably because the replacement of the supplied hot air with the atmosphere containing the volatilized solvent is insufficient.

  In general, in the drying process, the condensation polymerization reaction of the metal compound proceeds, the film becomes dense and a firm film is formed, while the volume shrinkage occurs and stress is generated inside the film. When this stress is increased, a crack is generated in the film, and the adhesion with the substrate is weakened. Stress can be relieved by using a metal compound in which an organic functional group is directly bonded to a metal as a film component. A metal compound in which an organic functional group is directly bonded to this metal is manufactured using an organically modified metal alkoxide as a material.

  As a method of spraying hot air directly onto the coating layer on the substrate surface, a method of spraying the entire substrate (hot air drying method 1) and a method of spraying partially from an elongated slit (hot air drying method 2) can be used. It is. Hereinafter, these two methods will be described.

(Hot air drying method 1)
The conceptual diagram of the drying apparatus (300) for spraying a hot air on the whole base material (11) in which the application layer (14) was formed is shown in FIG.
The drying device (300) can spray hot air (304) onto the entire surface of the base material (11) coated with the sol-like coating liquid placed directly under the device. The drying device (300) includes a hot air generator (303) that generates hot air (304), a blowing port (302) that blows the hot air (304) onto the substrate (11), and hot air ( 304) and a duct (301) for guiding. The hot air generator (303) and the blowing port (302) may be directly connected.

  The width of the opening of the spray port (302) needs to be wider than at least the coating layer (14) on the surface of the substrate (11). Moreover, when there are a plurality of coating layers, it is necessary to at least make the area covering all of them. Furthermore, it is preferable to make it wider than the area of the substrate (11). You may enable it to adjust the distance with the base material (11) for the spraying opening (302) with the mechanism which is not illustrated. It is effective to set the distance from the base material (11) within a range of 10 to 100 mm.

  The base material (11) may be able to be carried into and out of the spray port (302) directly by a transport mechanism such as a belt conveyor or a transport roll. In this embodiment, a base material (11) is conveyed by the conveyance mechanism (305) using a roll (in the case of FIG. 3, right direction).

  The base material (11) on which the coating layer (14) is formed is conveyed to the drying device (300) before the phase separation of the coating layer (14) proceeds. When the base material (11) is stopped just below the spraying port (302), hot air (304) is sent into the spraying port (302) by the hot air generator (303), and the base material (11) and the coating layer on the surface thereof. (14). In this way, the substrate (11) and the coating layer (14) on the surface can be dried.

  The time for blowing the hot air (304) is desirably set to such an extent that nonuniform phase separation does not occur even when heating is stopped. Although it depends on the solvent used and the drying temperature, it is about 5 seconds to 1 minute.

(Hot air drying method 2)
FIG. 4 shows a conceptual diagram of a drying apparatus (400) for partially blowing hot air (304) onto a part of the substrate (11) on which the coating layer (14) is formed.
The drying device (400) includes a hot air generator (303) that generates hot air (304), a blowing port (402) that blows the hot air (304) onto the substrate (11), and hot air ( 304) and a duct (301) for guiding. The hot air generator (303) and the blowing port (402) may be directly connected.

  The base material (11) can be carried into and out of the drying apparatus directly by a transport mechanism such as a belt conveyor or a transport roll. In this embodiment, a base material (11) is conveyed by the conveyance mechanism (305) using a roll.

  FIG. 5 shows the relationship between the base material (11) and the spray port (402). The spray port (402) may be configured to adjust the distance L from the base material (11) by a mechanism (not shown). It is effective to set the distance L to the base material (11) in the range of 1 to 100 mm.

  The tip portion of the spray port (402) forms an elongated slit-like opening. This opening may be provided with a mechanism for adjusting the interval D (short side direction) of the opening. In the example shown in FIG. 5, the distance D between the openings can be adjusted by changing the angle of the two opening adjustment plates (406). It is effective if the distance D between the openings is set in the range of 1 to 20 mm.

  The length (long side direction) of the opening of the spray port (402) needs to be at least longer than the width of the coating layer (14) (direction perpendicular to the transport direction). Moreover, when there exist a some coating layer, it is necessary to make it longer than the distance between the outermost periphery of the coating layer of both ends at least. Furthermore, it is preferable to make it longer than the width of the substrate.

  In addition, the rotation mechanism (not shown) can be used to rotate the blowing port (402) in the direction of conveyance of the base material so that the angle for blowing hot air onto the base material (11) and the coating layer (14) on the surface can be adjusted. Alternatively (see FIG. 6). It is effective that the angle at that time is within a range of ± 30 degrees with respect to the transport direction of the base material (11) with respect to the direction perpendicular to the base material (11).

  Most of the exhaust from the base material (11) flows downstream by inclining the blowing port (402) to the downstream side by the rotating mechanism (not shown) and sending hot air. If an exhaust port (not shown) is installed on the downstream side so as to face the spray port (402), an atmosphere containing a volatilized solvent can be recovered. The recovered atmosphere can be circulated to the hot air generator (303) after removing the solvent contained therein.

  For the aforementioned width D, interval L, spray port angle, and hot air temperature, any combination that does not cause non-uniform phase separation even after drying is selected in consideration of the transport speed of the substrate. Is possible.

The base material (11) on which the coating layer (14) is formed is conveyed to the drying device (400) before the phase separation of the coating layer (14) proceeds. While the base material (11) is transported directly under the blowing port (402), the hot air (304) sent from the hot air generator (303) to the blowing port (402) is directly applied to the base material (11). ) And the coating layer (14) on the surface thereof.
By transporting the base material (11) in the short side direction (in the right direction in the case of FIG. 4) of the opening of the spraying port, the entire surface of the base material (11) and the coating layer (14) on the surface are dried. Is possible.

  If this drying method is used, compared with the hot-air generator of the above-mentioned hot-air drying method 1, a large-area substrate can be efficiently dried with a low-power hot-air generator.

(Step S105: High temperature drying process)
The convex part group formed in the drying process (step S104) by the hot air of the coating layer is a solvent remaining in the film by heating for about 10 to 60 minutes at a temperature higher than the boiling point of the second solvent group. Groups can be removed and completely dried. Since this drying step does not affect the phase separation, it is not necessary to apply hot air directly to the convex portions. Therefore, various drying / baking apparatuses such as a hot air circulation system can be used.

  In addition, when the metal compound having the organic functional group bonded thereto is used as a part of the film component group, if it is necessary to remove the organic functional group, heating at a temperature exceeding the heat resistance temperature of the organic functional group It is effective.

  In the case where the hot air drying method 1 is used in the above-described drying process (step S104) of the coating layer, after the phase separation is completed, the temperature is continuously raised to thereby perform the hot air drying process and the high temperature drying. The steps can be performed in the same apparatus.

  When the hot air drying method 2 is used, continuous production from the coating process to the high temperature drying process is performed by using a hot air circulation type dryer that can be used while transporting the substrate in the high temperature drying process. It can be a process.

  Below, the Example in case a convex part group formation component and a flat film formation component are included in a coating liquid is demonstrated in detail.

[Example 1]
(Step S101: Preparation Step of Coating Solution)
A silica raw material was prepared by the following procedure. 33.0 g of phenyltrimethoxysilane, 20.8 g of γ-methacryloxypropyltrimethoxysilane, and 32.7 g of ethyl cellosolve are mixed. Furthermore, 13.5 g of 1 mol / L (1 N) hydrochloric acid is added to the mixture as a catalyst for promoting hydrolysis, and the mixture is stirred at a temperature of 30 ° C. for 24 hours. As a result, a hydrolysis reaction and a dehydration condensation polymerization reaction occurred, and a silica material was obtained.

  A titania raw material was prepared by the following procedure. 28.4 g of tetraisopropoxytitanium was mixed with 20.0 g of acetylacetone. In this mixed solution, a reaction for chelate coordination of acetylacetone occurred, and it became a titania raw material that is a chelate complex.

  As the convex portion forming component, 17.1 g of the silica raw material described above, 3.9 g of the above titania raw material as the flat film forming component, and ethyl cellosolve (boiling point: 134.8 ° C.) as the first solvent group (composite solvent). ) 15.0 g and xylene glycol (boiling point: 198 ° C.) 32.0 g as a second solvent (single solvent) and glycerin (boiling point: 290 ° C.) 15.0 g are mixed to prepare a sol coating solution. did. As described above, hexylene glycol was added to suppress volatilization in the coating process using the flexographic printing method.

The solid content of the prepared sol-form coating solution is 4.0% by mass when all of the silica raw material and the titania raw material are mineralized (becomes SiO ₂ and TiO ₂ ). The content of glycerin that is the second solvent contained in the solution is 15% by mass.

(Step S102: Coating Liquid Application Process)
The sol-shaped coating solution prepared above is subjected to a soda lime glass having a size of 100 × 100 mm, a thickness of 0.5 mm by a coating device using a flexographic printing method (manufactured by MT System Co., Ltd., FC-33N printer). It apply | coated to the center of the surface of a board | substrate (henceforth a glass substrate hereafter), and the application | coating layer of a magnitude | size and 30x40 mm was formed. The printing speed at this time was 417 mm / s.

(Step S103: Leveling process of coating layer)
The glass substrate on which the coating layer was formed was leveled for about 30 seconds while moving to the drying apparatus (300) shown in the hot air drying method 1.

(Step S104: Drying process of coating layer with hot air)
This will be described with reference to FIG.
After stopping the glass substrate (11) directly under the spraying port (302), the drying device (300) was heated with hot air (304) at a temperature of 200 ° C. at a wind speed of 3 m / s for about 30 seconds. ) And the coating layer (14) on the surface thereof were directly sprayed to dry the entire coating layer. Thus, the dried convex part group was formed in the glass substrate surface. At this time, the gap between the spray port (302) and the glass substrate was 30 mm. As the spray port (302), one having a sufficiently wider opening than the substrate (11) was used.

  The temperature of this hot air (200 ° C.) is higher than the boiling points of ethyl cellosolve (boiling point: 134.8 ° C.) and hexylene glycol (boiling point: 198 ° C.) of the first solvent group, and the boiling point ( 290 ° C.).

(Step S105: High temperature drying process)
A glass in which a convex shelf group is formed near the center of the shelf by installing an attached shelf in the vicinity of the center of the inside of the hermetic hot air circulation dryer (manufactured by Tabai Espec Co., Ltd., Clean Oven PVHC-210). The substrate was placed horizontally and dried by the following procedure.

The glass substrate on which the convex portion group was formed was put into the above-described dryer that had been heated to a temperature of 160 ° C. in advance. Then, the temperature was raised to 300 ° C. in 40 minutes, maintained at 300 ° C. for 10 minutes, and heating was stopped. This glass substrate was taken out after the internal temperature of the drier decreased to about 160 ° C. Thereafter, the glass substrate was naturally cooled. The maximum value (300 ° C.) of the drying temperature is a temperature higher than the boiling points of the first solvent group and the second solvent.
In this way, an article was obtained that formed a sufficiently dried convex part group on the surface.

  In order to investigate the relationship between the flow of hot air from the dryer and the glass substrate, the wind speed on the glass substrate was measured in the horizontal and vertical directions without heating. As a result, the respective maximum wind speeds were 0.43 m / s in the horizontal direction and 0.34 m / s in the vertical direction.

  From this measurement result, although it is described in the specification as “front blowing type horizontal laminar circulation type”, it seems that turbulent flow is generated inside the dryer. Therefore, the hot air having a wind speed of about 11 to 14% of the wind speed (3 m / s) of the hot air in the drying step (step S104) of the coating layer described above is unstablely blown onto the convex portions on the glass substrate. It seems to have been done.

[Example 2]
(Steps S101 to S103: Coating liquid preparation to leveling process)
In the same manner as in Example 1, a coating layer of 30 × 40 mm was formed at the center of the surface of a 100 × 100 mm glass substrate, and moved to the drying apparatus (400) shown in the hot air drying method 2 described above for 30 seconds. Leveled.

(Step S104: Drying process of coating layer with hot air)
This will be described with reference to FIG.
While the glass substrate (11) on which the coating layer (14) is formed is conveyed at a speed of 1.67 mm / s, hot air having a temperature of 150 ° C. is applied at a wind speed of 4.5 m / s by a drying device (400). (304) was directly sprayed on the glass substrate (11) and the coating layer (14) on the surface thereof to dry the entire coating layer. Thus, the dried convex part group was formed in the glass substrate surface.

  The temperature of the hot air (150 ° C.) is higher than the boiling point (134.8 ° C.) of ethyl cellosolve having the lowest boiling point in the first solvent group, and lower than the boiling point (290 ° C.) of glycerin of the second solvent. Temperature.

  The drying apparatus started blowing hot air at a temperature of 150 ° C. before the glass was conveyed. The distance D between the openings of the spray opening was 2 mm, the length of the opening was 300 mm, and the distance L between the spray opening and the glass substrate was 30 mm. The blowing port was inclined 15 degrees so as to blow the air to the downstream side (glass conveying direction). Because the glass substrate was small, no exhaust port was installed.

  Further, as described above, since the conveyance speed of the glass substrate is 1.67 mm / s and the slit width is 2 mm, the coating layer is exposed to hot air at a temperature of 150 ° C. for at least about 1 second. Considering before and after that, the coating layer is exposed to hot air at a temperature close to 150 ° C. for about 10 to 20 seconds.

(Step S105: High temperature drying process)
The glass substrate on which the convex portion group was formed was dried by a high temperature drying step under the same conditions as in Example 1.
In this way, an article was obtained that formed a sufficiently dried convex part group on the surface.

[Comparative Example 1]
(From coating solution preparation to leveling process)
In the same manner as in Example 1, a coating layer of 30 × 40 mm was formed in the center of the surface of a 100 × 100 mm glass substrate, and leveling was performed for about 30 seconds while moving to a hot air circulation dryer.

(Drying process)
The glass substrate on which the coating layer was formed was dried by a high temperature drying process under the same conditions as in Example 1.
In this way, an article was obtained that formed a sufficiently dried convex part group on the surface.

[Comparison between Examples 1 and 2 and Comparative Example 1]
The photograph of the observation result by the optical microscope of the convex part group formed by Example 1 is shown in FIG. The photograph of the observation result by the optical microscope of the convex part group formed by Example 2 is shown in FIG. The photograph of the observation result by the optical microscope of the convex part group formed by the comparative example 1 is shown in FIG. (A) of each figure shows the center part of a convex-shaped part group, (b) shows the peripheral part (about 0.5 mm from an edge) of a convex-shaped part group. The left side of (b) in each figure is the inside of the convex portion group. FIG. 10B is a photograph in the range of about 356 × 463 μm, and the others are photographs in the range of about 183 × 239 μm. However, the display magnifications of (a) and (b) of FIG. 10 are adjusted to match.

  In FIG. 8 (a) and FIG. 8 (b) showing the results of Example 1, there is hardly any difference. In (a) and (b) of FIG. 9 showing the results of Example 2, the convex portion of (b) is somewhat fine. However, visual observation is almost indistinguishable. In either case, the convex portion group is formed with a uniform interval between the convex portions and a uniform size in both the central portion and the peripheral portion.

  On the other hand, (a) and (b) in FIG. 10 showing the results of Comparative Example 1 are clearly different. FIG. 10 (a) is almost indistinguishable from FIG. 8 and FIG. 9 (a). However, FIG. 10B is clearly different from FIGS. 8 and 9B. In FIG. 10B, hemispherical convex portions of about 50 μm and convex portions smaller than the sparsely exist. That is, a non-uniform film is formed in the peripheral portion.

  Table 1 shows the measurement results of the diameter of the convex portion existing in an arbitrary portion (within a range of 100 × 100 μm) of the photographs shown in FIGS. The diameter of the convex portion was measured from a photograph taken by attaching a CCD camera to an optical microscope. Conversion to the actual length was performed using a scale plate that had been taken in at the same magnification in advance. In FIG. 10B, the measurement was performed on the left side close to the inside of the convex group.

  Most of the diameters of the convex portions in the central portion and the peripheral portion (inside 0.5 mm from the edge) of the convex portion group of Example 1 and Example 2 are within the range of 1 to 10 μm. The ratio of the number in the range of 1 to 10 μm with respect to the total number is 98.4% in the central portion of Example 1 and 95.2% in the peripheral portion. And in the central part of Example 2, it is 98.8% and the peripheral part is 99.0%.

  In Example 1, the ratio of the number of convex portions in the peripheral portion (124) to the central portion (126) is 98.4%, which is substantially the same number. In Example 2, the ratio of the number of convex portions in the central portion (167) to the peripheral portion (201) is 120.4%. Although the number of convex portions in the peripheral portion is about 20.4%, there is not much difference in the visual appearance.

  In Comparative Example 1, the diameter of the convex portion in the central portion is mostly within the range of 1 to 10 μm. The ratio of the number in the range of 1 to 10 μm with respect to the total number is 99.0% in the central portion of Example 1 and 80.1% in the peripheral portion. The tendency of the diameter distribution of the convex portion at the central portion of Comparative Example 1 is almost the same level as in Examples 1 and 2.

  However, in Comparative Example 1, the ratio of the number of convex portions in the peripheral portion (37) to the central portion (202) is about 18.3%, indicating that the density of the peripheral portion is small. Further, since the diameter and density of the convex portions are not uniform, it can be seen that different results are obtained when the measurement position of the peripheral portion is changed.

  According to Example 1 and Example 2, in the manufacturing method according to the present invention, it can be confirmed that the size variation and the number variation of the convex portions in the central portion and the peripheral portion of the convex portion group are small. It was. Therefore, the manufacturing method characterized in that hot air is directly blown onto the coating layer according to the present invention to average the phase separation, and the convex portion group having excellent uniformity and appearance with little unevenness. It is suitable for manufacturing an article that forms a surface on the surface.

  According to Comparative Example 1, it was confirmed that in the conventional manufacturing method, the variation in the size and the number of the convex portions in the central portion and the peripheral portion of the convex portion group are large. In particular, it has been confirmed that in the peripheral portion, the convex portions are non-uniform in size and sparsely spaced. Therefore, the conventional manufacturing method that does not blow hot air directly on the coating layer forms a convex part group with excellent uniformity and appearance on the surface in the peripheral part of the convex part group. It is not suitable for manufacturing articles.

  The article formed on the surface with the convex portion group according to the present invention is suitable for, for example, a base material of a light scattering reflection substrate of various display devices represented by a reflective liquid crystal display device and a transflective liquid crystal display device. Can be used. Moreover, it can use suitably for the base material of light-scattering reflective board | substrates, such as a transmission screen for projection type displays. And it can use suitably for the part by which a light-scattering reflection function is calculated | required like the projection screen of various projectors.

It is a flowchart of the manufacturing method of the articles | goods which form the convex part group which concerns on embodiment of this invention on the surface. It is sectional drawing which shows the article | item in which the convex part group which concerns on embodiment of this invention was formed in the surface. (A) represents an example of an article in which the convex part group consists only of convex parts, and (b) represents an example of an article in which the convex part group consists of convex parts and a flat film-like part between them. Yes. It is the schematic of the hot air drying apparatus which concerns on embodiment of this invention. It is the schematic of the other hot air drying apparatus which concerns on embodiment of this invention. It is the schematic showing the relationship between the hot-air blowing outlet and base material of the hot-air drying apparatus of FIG. It is another schematic diagram showing the relationship between the hot-air blowing outlet of the hot-air drying device of FIG. 5 and the substrate. It is the schematic showing that many cells are formed in the base-material surface. It is a partial optical microscope photograph of the convex-shaped part group of the articles | goods which concern on Example 1 of this invention. (A) shows a center part, (b) shows a peripheral part. It is a partial optical microscope photograph of the convex-shaped part group of the articles | goods concerning Example 2 of this invention. (A) shows a center part, (b) shows a peripheral part. It is a partial optical microscope photograph of the convex-shaped part group of the article | item which concerns on the comparative example 1 which is a prior art. (A) shows a center part, (b) shows a peripheral part.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Article 11 which formed convex part group on the surface 11 Base material 12 Convex part 13 Flat film-like part 14 Application layer 15 Cell 300,400 Hot air drying apparatus 301 Duct 302,402 Blowing port 303 Hot air generation according to the present invention Machine 304 Hot air 305 Conveying mechanism 406 using rolls Opening adjustment plate

Claims (8)

Convex part forming component, first solvent compatible with the component and containing at least one solvent, and second solvent not compatible with the component and containing at least one solvent The coating liquid containing is applied to the surface of the article to form a coating layer, the first solvent and the second solvent contained in the coating layer are dried, and the convex portion forming component and the second solvent In the manufacturing method of the article forming the convex portion group formed by causing phase separation between on the surface,
The drying is performed by blowing hot air directly on the coating layer to average the phase separation,
The manufacturing method of the articles | goods which form the convex-shaped part group characterized by these on the surface.   The article for forming a convex portion group according to claim 1, wherein the coating solution further includes a flat film-like portion-forming component that is compatible with both the first solvent and the second solvent. Production method.   3. The convex portion group according to claim 1, wherein any solvent in the first solvent has a boiling point lower than that of any solvent in the second solvent. A method for manufacturing an article.   The manufacturing method of the article | item which forms the convex-shaped group of any one of Claims 1-3 which made temperature of the said hot air higher than the boiling point of the solvent with the lowest boiling point in said 1st solvent. .   The manufacturing method of the articles | goods which form the convex-shaped group of any one of Claims 1-4 which made the temperature of the said hot air the temperature lower than the boiling point of any solvent in said 2nd solvent.   The said coating liquid is a sol-form coating liquid or resin coating liquid which can be phase-separated, The manufacturing method of the articles | goods which form the convex-shaped part group of any one of Claims 1-5 on the surface.   The manufacturing method of the articles | goods which form the convex-shaped part group of any one of Claims 1-6 formed in the surface on the said article | item surface. An article manufactured by a method for manufacturing an article for forming the convex portion group according to any one of claims 1 to 7 on a surface,
The number of convex portions existing within a predetermined area range of the central portion within a range of at least 0.5 mm from the outer periphery of the convex portion group, and the predetermined area range of an arbitrary portion other than the central portion The ratio with the number of convex portions existing in the interior is within 70 to 130%,
An article formed on the surface with a convex portion group characterized by