JP2007203247A - Method for manufacturing coating film having pattern and coating film obtained by the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method which enables the formation of a concave/convex-shaped pattern by a simple means without using any filler precisely at a predetermined position of the coating film surface without bringing any foreign matter and any stain on the coating film surface. <P>SOLUTION: In the process of forming a coating film by applying a coating liquid onto a substrate to form coating layers, and then drying, or in some cases by further applying energy, the formed coating layers are dried by bringing a heating plate with a predetermined pattern having a temperature distribution on a heated surface into contact with the back surface of the substrate, and the coating film having the pattern is manufactured by forming the concave/convex-shaped pattern on the surface. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a coating film having a pattern, a coating film having a pattern obtained by the method, and an article provided with the coating film. More specifically, the present invention can form a concavo-convex pattern at a predetermined position on the coating film surface accurately and by simple means without using a filler without causing foreign matter or dirt on the coating film surface. Method, manufactured by the method, for example, a coating film having a concavo-convex pattern on a surface useful as an adhesive layer, an optical hard coat layer, a gloss adjustment layer, and the like, and the coating film is provided on a substrate It relates to goods.

A coating film having a concavo-convex pattern on the surface is used in various fields. For example, in the field of pressure-sensitive adhesive sheets, when the area of the pressure-sensitive adhesive sheet is large to some extent, air remains easily between the pressure-sensitive adhesive layer and the adherend, and that portion becomes blistered and covers the pressure-sensitive adhesive sheet. There arises a problem that it is difficult to apply it cleanly on the body.
In order to solve such problems, an air flow path has been provided on the pressure-sensitive adhesive layer surface so far, and air is allowed to escape through this flow path when sticking the pressure-sensitive adhesive sheet so that no air remains. Various attempts have been made. For example, an adhesive processed sheet having an adhesive layer in which a large number of independent small convex portions are arranged in the form of dots (for example, see Patent Document 1), a plurality of convex portions, and an adhesive in which a groove portion is formed between adjacent convex portions A pressure-sensitive adhesive sheet having a layer (for example, see Patent Document 2) is disclosed. However, using these techniques to form a concavo-convex pattern on the pressure-sensitive adhesive layer is troublesome and has problems such as poor workability.
On the other hand, in a display such as a CRT or a liquid crystal display, light may be incident on the screen from the outside, and this light may be reflected (referred to as glare or glare) to make it difficult to see the displayed image. With the increase in size, it is becoming increasingly important to solve the above problems.
In order to solve such a problem, various anti-glare measures have been taken for various displays so far. As one of them, for example, a hard coat film used for a polarizing plate in a liquid crystal display or a hard coat film for protecting various displays is subjected to an antiglare treatment for roughening the surface. As the antiglare treatment method for this hard coat film, generally, a method of mixing a filler in a hard coat agent for forming a hard coat layer is employed. However, when ordinary silica particles are used as the filler, it is difficult to uniformly disperse in the coating agent, and the silica particles settle or aggregate, making it difficult to form a stable antiglare hard coat layer. It is.
In the decorative sheet field, a gloss adjusting layer is usually provided in many cases. In general, the gloss adjusting layer is often obtained by moderately suppressing the light reflectance, and is usually produced by applying a coating material for forming a gloss adjusting layer to which an appropriate matting agent is dispersed.
Examples of the matting agent include inorganic particles such as hollow particles such as mica, silica, alumina, calcium carbonate, diatomaceous earth, silica sand, and shirasu balloon, and synthetic resin particles such as polystyrene resin and acrylic resin. Used.
However, when such a matting agent is used, irregularities due to the matting agent particles are formed on the surface, so that there is a problem that the surface roughness is large and it is difficult to obtain a fine surface.
The method of dispersing the filler in such a coating liquid and exposing it to the surface of the coating film has many technical problems in the dispersion state, drying conditions, etc., and depends on the rheological properties of the coating liquid. Another problem is that the design takes time.
By the way, the method of pressing with an embossing roll is known as a method of forming an uneven pattern on the coating film surface without using a filler. For example, as a method for producing a sheet-like material such as an embossed sheet having an antireflection effect and the like on which a regular fine uneven pattern is formed on the surface, an adhesive and a resin are sequentially applied on the surface, A belt-like flexible sheet-like body in which a layer and a resin layer (coating film) are formed in two or more layers is continuously run, the sheet-like body is wound around the rotating concavo-convex roll, and the resin layer is A method for producing a concavo-convex sheet is disclosed, wherein the concavo-convex roll surface is transferred, and the resin layer is cured in a state where the sheet-like body is wound around the concavo-convex roll (for example, And Patent Document 3).
However, in the method of transferring irregularities using such an embossing roll, it is necessary to bring the roll into contact with the surface of the coating film, so there is a problem of poor quality due to the foreign matter adhering to the roll fixing on the coating film surface. It may become.
Utility Model Registration No. 2503717 JP 11-209704 A JP-A-2005-161531

  Under such circumstances, the present invention uses a filler to form a concavo-convex pattern at a predetermined position on the coating film surface accurately and with simple means without causing foreign matter or dirt on the coating film surface. It was made for the purpose of providing a coating film having a concavo-convex pattern on a surface that is useful as a pressure-sensitive adhesive layer, an optical hard coat layer, a gloss adjustment layer, etc. Is.

As a result of intensive studies to achieve the above object, the inventors have formed a coating layer by applying a coating liquid, and then a heating plate provided with a pattern having a predetermined shape having a temperature distribution on the heating surface Is found to be able to achieve its purpose by bringing the coating layer into contact with the back side of the substrate and forming a concavo-convex pattern on the surface thereof. The present invention has been completed.
That is, the present invention
(1) A coating liquid is applied on a substrate to form a coating layer, followed by drying treatment. In some cases, energy is further applied to form a coating film. A heating plate provided with a pattern of a predetermined shape having a temperature distribution is brought into contact with the back surface side of the base material, thereby drying the coating layer and forming an uneven pattern on the surface thereof. A method for producing a coating film having a pattern,
(2) The heating plate has a pattern in which a heating part and a non-heating part are present, and the temperature difference between them is 10 ° C. or more, and the method for producing a coating film having the pattern according to (1) above,
(3) The manufacturing method of the coating film which has a pattern as described in the said (1) or (2) term | inspection whose heating plate is what gave the heat conductive metal plate the several drilling process,
(4) The shape of the hole is substantially circular, the diameter of the hole is 0.3 to 4.0 mm, and the pitch between holes (the distance between the center points of adjacent holes) is A method for producing a coating film having a pattern according to the above item (3), which is 0.5 to 6.0 mm,
(5) The manufacturing method of the coating film which has a pattern in any one of said (1)-(4) term whose viscosity in the temperature of 23 degreeC of a coating liquid is 10-3500 mPa * s,
(6) The manufacturing method of the coating film which has a pattern in any one of said (1)-(5) item whose coating film which has a pattern is an adhesive layer,
(7) The manufacturing method of the coating film which has a pattern in any one of said (1)-(5) item whose coating film which has a pattern is an optical hard-coat layer,
(8) The method for producing a coating film having a pattern according to any one of (1) to (5) above, wherein the coating film having a pattern is a gloss adjusting layer,
(9) The coating film having a pattern according to any one of (1) to (8) above, wherein the coating liquid contains a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, or an active energy ray polymerizable compound. Manufacturing method,
(10) A coating film having a concavo-convex pattern on the surface, which is produced by the method according to any one of (1) to (9) above, and (11) on the base material, An article characterized in that a coating film having a concavo-convex pattern is provided on the surface according to item (10),
Is to provide.

According to the present invention, a concavo-convex pattern can be formed at a predetermined position on a coating film surface accurately and with simple means without using a filler without causing foreign matter or dirt on the coating film surface. .
Moreover, the coating film which has an uneven | corrugated pattern on the surface obtained by this method is useful, for example as an adhesive layer, an optical hard-coat layer, a gloss adjustment layer, etc.

As a coating liquid used in the method for producing a coating film having a pattern of the present invention, a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, or an active energy ray polymerizable compound is contained as a basic component, and further if necessary. Examples of the coating liquid include a crosslinking agent, a tackifier, an antioxidant, an ultraviolet absorber, a coupling agent, a flame retardant, a colorant, a light stabilizer, a leveling agent, and an antifoaming agent.
Examples of the thermoplastic resin include acrylic resins, silicone resins, polyester resins, polyvinyl chloride resins, polyolefin resins, polyamide resins, and polycarbonate resins. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the thermoplastic elastomer (including a rubber-like elastic body) include, for example, a styrene-based thermoplastic elastomer, an olefin-based thermoplastic elastomer, a vinyl-based thermoplastic elastomer, a urethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, and a polyamide-based thermoplastic. Examples thereof include elastomers, fluorine-based thermoplastic elastomers, natural rubbers, and conjugated diene-based synthetic rubbers. These may be used individually by 1 type and may be used in combination of 2 or more type.
Examples of the thermosetting resin include an acrylate polymer having a carbon-carbon double bond or a glycidyl group, an unsaturated polyester, an epoxy resin, a phenol resin, a urea resin, and a melamine resin. These may be used alone or in combination of two or more.
A curing agent is usually used for these thermosetting resins. Examples of the curing agent include organic peroxides, azo compounds, polyisocyanate compounds, polyamines, acid anhydrides, imidazoles, dicyandiamide, Lewis acid, formaldehyde, and the like. It is selected as appropriate.

Examples of the active energy ray-polymerizable compound (one having an energy quantum in an electromagnetic wave or a charged particle beam, that is, a polymerizable compound that is cross-linked and cured by irradiation with ultraviolet rays or an electron beam) include, for example, active energy rays. Mention may be made of polymerizable prepolymers and / or active energy ray polymerizable monomers. The active energy ray polymerizable prepolymer includes a radical polymerization type and a cationic polymerization type. Examples of the radical polymerization type active energy ray polymerizable prepolymer include polyester acrylate, epoxy acrylate, urethane acrylate, and polyol acrylate. The system etc. are mentioned.
On the other hand, as a cationic polymerization type active energy ray polymerizable prepolymer, an epoxy resin is usually used. Examples of the epoxy resins include compounds obtained by epoxidizing polyphenols such as bisphenol resins and novolac resins with epichlorohydrin, etc., and compounds obtained by oxidizing a linear olefin compound or a cyclic olefin compound with a peroxide or the like. Etc.
Examples of the active energy ray polymerizable monomer include bifunctional or higher polyfunctional acrylates.
If desired, a photopolymerization initiator is added to the active energy ray polymerizable compound. Examples of the photopolymerization initiator include radical polymerization type photopolymerizable prepolymers and photopolymerizable monomers among active energy ray polymerizable prepolymers and monomers, such as benzoins, benzophenones, acetophenones, Examples include α-hydroxy ketones, α-amino ketones, α-diketones, α-diketone dialkyl acetals, anthraquinones, and thioxanthones.

Examples of the photopolymerization initiator for the cationic polymerization type photopolymerizable prepolymer include oniums such as aromatic sulfonium ions, aromatic oxosulfonium ions, aromatic iodonium ions, tetrafluoroborate, hexafluorophosphate, hexafluoro The compound which consists of anions, such as antimonate and hexafluoroarsenate, is mentioned. In addition, when using an electron beam as an active energy ray, it is not necessary to use a photoinitiator.
In the present invention, various types of coating liquids can be used depending on the application, such as pressure-sensitive adhesive coating liquid, optical hard coat forming coating liquid, gloss adjusting layer forming coating liquid, etc. Can be used.
When the adhesive coating liquid is used, for example, by using the method of the present invention to be described later, an uneven fine pattern is formed on the surface of the adhesive layer. Distribution route, air retention is less likely to occur, and the sticking property is improved.
When the coating liquid for forming the gloss adjusting layer is used, an uneven fine pattern is formed on the surface of the coating film, and the gloss adjusting effect is exhibited by irregular reflection of light. be able to.
When an optical hard coat forming coating solution is used, an uneven fine pattern is formed on the surface of the coating film, so that it can be used for an antiglare hard coat layer or the like.

The solvent for each coating solution used in the present invention is not particularly limited. Depending on the type of resin component and polymerizable compound contained in the coating solution, for example, aliphatic hydrocarbons such as hexane and heptane, toluene , Aromatic hydrocarbons such as xylene, halogenated hydrocarbons such as methylene chloride and ethylene chloride, alcohols such as methanol, ethanol, propanol and butanol, ketones such as acetone, methyl ethyl ketone, 2-pentanone, isophorone and cyclohexanone, ethyl acetate, It can be appropriately selected from esters such as butyl acetate, cellosolve solvents such as ethyl cellosolve, glycol ether solvents such as propylene glycol monomethyl ether, and the like.
Although there is no restriction | limiting in particular in the density | concentration of the said coating liquid, From the point by which the effect of this invention is exhibited suitably, the viscosity in the temperature of 23 degreeC is about 10-3500 mPa * s, Preferably, it is more than 50-3000 mPa * s. The concentration is preferably 100 to 2500 mPa · s.

There is no restriction | limiting in particular about the base material used in the method of this invention, For example, a paper base material, a plastic film, a plastic sheet, metal foil, a metal sheet etc. are mentioned, It can select suitably according to a use. These base materials may be used singly or in any combination, such as composites of the same kind of materials such as papers or plastic films or plastic sheets, or composites of different materials such as paper and plastic films or plastic sheets. A laminated sheet combining these materials can also be used.
Examples of the paper base include thin paper, craft paper, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, titanium paper, linter paper, paperboard, base paper for gypsum board, For example, a resin-impregnated paper impregnated with a resin for the purpose of reinforcement, or a vinyl wallpaper original fabric provided with a vinyl chloride resin layer on the surface of the paper.
Examples of the plastic film and plastic sheet include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, polyethylene film, polypropylene film, cellophane, diacetyl cellulose film, triacetyl cellulose film, acetyl cellulose butyrate film, and polyvinyl chloride. Film, polyvinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, polymethylpentene film, polysulfone film, polyetheretherketone film, polyethersulfone film, polyetherimide film, Polyimide film, fluororesin film Lum, polyamide film, acrylic resin film, norbornene resin film, a cycloolefin resin film, and the like of these resin sheets.
As metal foil or a metal sheet, what consists of raw materials, such as aluminum, iron, stainless steel, or copper, is used, for example.
When using a plastic film or plastic sheet as a substrate, for the purpose of improving the adhesion with the layer provided on the surface, surface treatment may be applied to one or both sides by an oxidation method or a concavo-convex method as desired. it can. Examples of the oxidation method include corona discharge treatment, plasma treatment, chromic acid treatment (wet), flame treatment, hot air treatment, ozone / ultraviolet irradiation treatment, and examples of the unevenness method include a sand blast method, a solvent, and the like. Treatment methods and the like. These surface treatment methods are appropriately selected depending on the type of the substrate, but in general, the corona discharge treatment method is preferably used from the viewpoints of effects and operability. Moreover, primer treatment can also be performed.
In the present invention, the thickness of the substrate is not particularly limited, and is appropriately selected within a wide range, for example, about 20 μm to 10 mm, depending on the application.

In the method for producing a coating film having a pattern of the present invention, first, a coating liquid containing a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, or an active energy ray polymerizable compound is applied onto the substrate. After forming the coating layer, it is dried.
As a method for applying the coating liquid onto the substrate, a conventionally known method such as a bar coating method, a knife coating method, a roll coating method, a blade coating method, a die coating method, or a gravure coating method can be used. . Under the present circumstances, it applies so that the thickness of a coating layer may become 3-200 micrometers normally after drying, Preferably it is 5-150 micrometers, More preferably, it is 10-100 micrometers.
Next, in the present invention, the coating layer formed in this way is dried as shown below to form an uneven fine pattern on the surface of the dried coating layer or the thermosetting coating layer.
That is, the coating layer is dried or cured by bringing a heating plate provided with a pattern having a predetermined shape having a temperature distribution on the heating surface into contact with the back side of the substrate on which the coating layer is provided. In this way, by bringing the heating plate into contact with the back side of the substrate, a surface tension odor drive flow is induced in the coating layer, and a concentration odor due to solvent evaporation is induced. An uneven fine pattern can be formed on the surface of the coating layer.
In order to induce such a phenomenon effectively, the viscosity of the coating solution to be used is preferably in the range of 10 to 3500 mPa · s at 23 ° C. as described above. The thickness is preferably about 40 to 300 μm.
Moreover, as the said heating plate, it has a pattern in which a heating part and a non-heating part exist, and it is preferable that those temperature differences are 10 degreeC or more, and it is more preferable that it is 12 degreeC or more. The upper limit of the temperature difference is not particularly limited, but is usually about 25 ° C. In addition, the temperature of a heating part is the surface temperature of the said heating plate, and the temperature of a non-heating part is the temperature of the center part of this non-heating part.

As such a heating plate, for example, a heat conductive metal plate that has been subjected to a plurality of perforations can be used. There is no restriction | limiting in particular as said heat conductive metal plate, For example, an aluminum plate, a stainless steel plate, etc. are used. The thickness of the heating plate is preferably 100 to 2000 μm. There is no restriction | limiting in particular in the shape of the hole in a drilling process, Although it can drill in various shapes, such as a circle | round | yen, an ellipse, an ellipse, and a polygonal shape, generally circular drilling is performed. In this case, the diameter of the hole is usually about 0.3 to 4.0 mm, preferably 0.5 to 3.5 mm, and the pitch between the holes (the distance between the center points of adjacent holes) is The thickness is usually 0.5 to 6.0 mm, preferably 0.7 to 5.0 mm. The shortest distance between adjacent holes is usually about 0.2 to 6.0 mm, preferably 0.5 to 5.0 mm. For example, a hole pattern having a pitch between holes (feeding pitch) as shown in FIG. 1 and an interval between rows of holes (die pitch) and arranged in a 60 ° horizontal array is suitable.
In the heating plate drilled in this way, especially when the difference between the temperature of the heating part (surface temperature of the heating plate) and the temperature of the non-heating part (temperature of the central part of the hole) is less than 10 ° C. As the viscosity of the working fluid increases, the outline of the sea-island pattern formed on the coating layer surface becomes unclear. As for the temperature of a heating part, 50-200 degreeC is preferable. If the temperature is too low, the temperature difference between the heated part and the non-heated part is small, and surface tension flow hardly occurs. If the temperature is too high, there is a concern about thermal deformation of the substrate during heating.
The time from the formation of the coating layer until the back surface side of the substrate is brought into contact with the heating plate is usually about 0 to 30 seconds, although it depends on the type of solvent and the film thickness in the coating solution. If this time exceeds 30 seconds, the surface of the coating layer may solidify, and a predetermined pattern shape may not be obtained.
In addition, since the temperature of the coating layer immediately after coating may decrease due to evaporation of the solvent and water vapor in the atmosphere may condense on the coating layer surface, measure the temperature decrease of the coating layer surface with a non-contact thermometer in advance. However, it is preferable to take measures such as adjusting the temperature of the atmosphere. Furthermore, the time for which the back side of the substrate is in contact with the heating plate is preferably 15 to 500 seconds.
In addition, when using a continuous coating apparatus, the hot plate which gave the said drilling process can be processed into a roll shape, and can be used as a heating roll.

In this way, an uneven fine pattern is formed on the surface of the dry coating layer or the thermosetting coating layer. In the present invention, energy is further applied to the coating layer as necessary, and the coating is applied. The layer can be cured. For example, when a coating solution containing an actinic ray curable polymerizable compound is used, after forming a dry coating layer having a concave and convex fine pattern on the surface as described above, an activity such as ultraviolet rays or electron beams is formed on the dried coating layer. Irradiate light to form a cured resin layer. On the surface of the cured resin layer, the fine pattern provided on the surface of the dry coating layer remains as it is.
In addition, when a coating liquid containing a heat energy curable resin is used, after forming a dry coating layer or a thermosetting coating layer having a concavo-convex fine pattern on the surface as described above, thermal energy is applied to these. It can also be applied and fully thermoset. On the surface of the complete thermosetting resin layer, the fine pattern provided on the surface of the dry coating layer or the thermosetting coating layer remains as it is.
The method for producing a coating film having such a pattern of the present invention is a method for producing a concavo-convex pattern accurately and easily at a predetermined position on the coating film surface without causing foreign matter or dirt on the coating film surface. It can be formed without using a filler.
The present invention also provides a coating film having a concavo-convex pattern on the surface and an article provided with the coating film, manufactured by the above-described method of the present invention.
The coating film having a concavo-convex pattern on the surface is useful, for example, as an adhesive layer, an optical hard coat layer, a gloss adjustment layer, and the like.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Example 1
A round plate with a hole diameter of 0.75 mm was fed into a 1 mm thick aluminum plate and processed into a 60 ° plover arrangement with a pitch of 1.0 mm and a mold pitch of 0.90 mm to prepare a heating plate. FIG. 1 shows an enlarged schematic diagram of the heating plate.
This heating plate was placed on a micro heat plate (“MP200DMSH” manufactured by Kitasato Supply Co., Ltd.), and the temperature was controlled so that the surface temperature of the heating plate was maintained at 135 ° C. Further, the temperature of the surface of the heating plate and the center of the hole was measured with an ultrafine thermocouple [Ambes Co., Ltd., “KFT-25-200-050”]. At this time, the temperature difference between the heating portion (the surface of the heating plate) and the non-heating portion (hole center portion) in the heating plate was 19.5 ° C.
On the other hand, 100 parts by mass of an acrylic acid ester copolymer [manufactured by Toyo Ink Manufacturing Co., Ltd., trade name “BPS5750”, solid content 45.5% by mass] is diluted with 40 parts by mass of toluene to obtain a solid content concentration of 32.5% by mass. A pressure-sensitive adhesive coating solution was prepared. The viscosity of this coating solution at a temperature of 23 ° C. was 2000 mPa · s.
Next, on the polyethylene terephthalate (PET) film [trade name “PET25 T-61M Toray” manufactured by Toray Industries, Inc.] having a thickness of 25 μm as a base material, the pressure-sensitive adhesive coating solution is wet-coated with a thickness of 120 μm ( After coating with a Meyer bar so that the thickness after drying is about 40 μm), immediately after forming a coating layer, the back side of the base film is brought into contact with a heating plate maintained at 135 ° C. for 5 minutes. An adhesive layer was formed.
As a result of microscopic observation, an uneven fine pattern corresponding to the hole pattern of the heating plate was formed on the surface of the pressure-sensitive adhesive layer. FIG. 2 shows an enlarged photograph of the fine pattern.

Example 2
A round plate having a hole diameter of 1.0 mm was fed to an aluminum plate having a thickness of 1 mm and processed into a 60 ° plover arrangement with a pitch of 2.0 mm and a mold pitch of 1.8 mm, thereby producing a heating plate.
This heating plate was placed on a micro heat plate (described above), and the temperature was controlled so that the surface temperature of the heating plate was maintained at 105 ° C. The temperature of the surface of the heating plate and the center of the hole was measured with an ultrafine thermocouple (supra). At this time, the temperature difference between the heating portion (the surface of the heating plate) and the non-heating portion (hole center portion) in the heating plate was 12.5 ° C.
Next, on the PET film having a thickness of 25 μm as the base material (described above), the same adhesive coating solution as in Example 1 was applied in the same manner as in Example 1 to form an application layer. The back surface side of the base film was brought into contact with a heating plate maintained at 105 ° C. for 5 minutes to form an adhesive layer.
As a result, an uneven fine pattern corresponding to the hole pattern of the heating plate was formed on the surface of the pressure-sensitive adhesive layer.
Example 3
A round plate having a hole diameter of 3.0 mm was sent to an aluminum plate having a thickness of 1 mm and processed into a 60 ° plover arrangement with a pitch of 4.0 mm and a mold pitch of 3.6 mm to prepare a heating plate.
This heating plate was installed on a micro heat plate (supra), and the temperature was controlled so that the surface temperature of the heating plate was maintained at 70 ° C. The temperature of the surface of the heating plate and the center of the hole was measured with an ultrafine thermocouple (supra). At this time, the temperature difference between the heating portion (the surface of the heating plate) and the non-heating portion (hole center portion) in the heating plate was 13.2 ° C.
Next, on the PET film having a thickness of 25 μm as the base material (described above), the same adhesive coating solution as in Example 1 was applied in the same manner as in Example 1 to form an application layer. The pressure-sensitive adhesive layer was formed by bringing the back side of the base film into contact with the heating plate maintained at 70 ° C. for 5 minutes.
As a result, an uneven fine pattern corresponding to the hole pattern of the heating plate was formed on the surface of the pressure-sensitive adhesive layer.

Example 4
The heating plate and heating conditions were the same as in Example 1, and a coating solution containing an ultraviolet curable polymerizable compound used for the optical hard coat layer was used as the coating solution.
That is, 100 parts by mass of pentaerythritol triacrylate [manufactured by Toa Gosei Co., Ltd., trade name “Aronix M-305”] and 1-hydroxycyclohexyl phenyl ketone which is a photopolymerization initiator [manufactured by Ciba Specialty Chemicals Co., Ltd.] , Trade name “Irgacure 184”] was added to 157.5 parts by mass of propylene glycol monomethyl ether and mixed to prepare a coating solution having a solid concentration of 40% by mass. The viscosity of this coating solution at a temperature of 23 ° C. was 200 mPa · s.
Next, the coating liquid was applied to a 25 μm thick PET film (described above) as a base material to form a coating layer, and then dried under the same conditions as in Example 1. The thickness of the coating layer was 50 μm wet and 20 μm after drying.
Next, the dry coating layer was cured by irradiation with ultraviolet light at an irradiation amount of 230 mJ / cm ² to form a hard coat layer. As a result, an uneven fine pattern was formed on the surface of the hard coat layer.

Comparative Example 1
In Example 1, it implemented similarly to Example 1 except having used the smooth heating plate which does not have a round hole instead of the heating plate which has a round hole.
The surface of the obtained pressure-sensitive adhesive layer was observed with an electron microscope [manufactured by Keyence Corporation, “VHX-100”] and compared with Example 1. As a result, a fine pattern was not formed on the pressure-sensitive adhesive layer surface.
Comparative Example 2
The same heating plate as in Example 3 was used, and the temperature was controlled so that the surface temperature was maintained at 40 ° C. The temperature of the surface of the heating plate and the center of the hole was measured with an ultrafine thermocouple (supra). At this time, the temperature difference between the heating portion (the surface of the heating plate) and the non-heating portion (hole center portion) in the heating plate was 8.1 ° C.
Next, the same adhesive coating liquid as in Example 3 was applied in the same manner as in Example 3 on a PET film having a thickness of 25 μm as the base material (described above), and immediately after forming a coating layer, 40 ° C. The back surface side of the base film was brought into contact with the heating plate held in 5 minutes for 5 minutes to form an adhesive layer.
The obtained pressure-sensitive adhesive layer surface was observed with an electron microscope (supra) and compared with Example 3. As a result, a fine pattern was not formed on the pressure-sensitive adhesive layer surface.
The results of Examples 1 to 4 and Comparative Examples 1 and 2 are shown in Table 1 above.

  The method for producing a coating film having a pattern according to the present invention uses a filler with a concavo-convex pattern accurately and easily at a predetermined position on the coating film surface without causing foreign matter or dirt on the coating film surface. Can be formed without.

It is an expansion schematic diagram of a heating plate. In Example 1, it is an enlarged photograph figure of the fine pattern formed on the adhesive layer.

Claims (11)

  On the base material, a coating solution is applied to form a coating layer, followed by drying treatment. In some cases, when energy is further applied to form a coating film, a temperature distribution is formed on the heating surface after forming the coating layer. A heating plate provided with a pattern having a predetermined shape is brought into contact with the back surface side of the base material, thereby drying the coating layer and forming an uneven pattern on the surface thereof. The manufacturing method of the coating film which has this.   The method for producing a coating film having a pattern according to claim 1, wherein the heating plate has a pattern in which a heating part and a non-heating part are present, and a temperature difference between them is 10 ° C or more.   The method for producing a coating film having a pattern according to claim 1 or 2, wherein the heating plate is obtained by subjecting a thermally conductive metal plate to a plurality of perforations.   The shape of the hole is substantially circular, the diameter of the hole is 0.3 to 4.0 mm, and the pitch between holes (the distance between the center points of adjacent holes) is 0.5. It is-6.0 mm, The manufacturing method of the coating film which has a pattern of Claim 3.   The manufacturing method of the coating film which has a pattern in any one of Claims 1-4 whose viscosity in the temperature of 23 degreeC of a coating liquid is 10-3500 mPa * s.   The coating film which has a pattern is an adhesive layer, The manufacturing method of the coating film which has a pattern in any one of Claims 1-5.   The method for producing a coating film having a pattern according to any one of claims 1 to 5, wherein the coating film having a pattern is an optical hard coat layer.   The method for producing a coating film having a pattern according to any one of claims 1 to 5, wherein the coating film having a pattern is a gloss adjusting layer.   The manufacturing method of the coating film which has a pattern in any one of Claims 1-8 in which a coating liquid contains a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, or an active energy ray polymeric compound.   A coating film having a concavo-convex pattern on the surface, which is produced by the method according to claim 1.   An article, wherein a coating film having a concavo-convex pattern is provided on a surface of the substrate according to claim 10.

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