JP2014150733A - Construction materials, building structure and sheet material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To permanently prevent a spider's web from being formed in a building structure.SOLUTION: As construction materials forming a building structure, construction materials 1 are used, the construction materials 1 comprising a construction materials body 2, and a sheet material 4 stuck to the construction materials body 2 and having a fine rugged structure on its surface.

Description

  The present invention relates to a sheet material for preventing spider web formation, a building material and a building using the sheet material.

  If a spider nests on the outer wall or roof of a building, it is unsanitary, and there is a problem that dirt or dust adheres to the nest and damages the landscape of the building. On the other hand, it is conceivable to remove the spiders with insecticides, but the nests that have been made still remain and damage the landscape. Thus, Patent Document 1 discloses a composition for removing a spider web containing an alkaline substance.

  However, although the spider web removal composition described in the cited document 1 can remove the spider web, it cannot prevent the spider web itself from being formed. In other words, every time a spider's nest is made, it must be removed, which takes time. Therefore, for example, cited document 2 discloses a nesting-preventing aerosol for preventing spiders from forming a nest.

JP 2009-142190 A JP 2008-162951 A

  However, in the anti-nesting aerosol agent described in Cited Document 2, even if such anti-nesting aerosol agent is spread on the outer wall of a building, for example, the effect is reduced over time due to rain or dirt. End up.

  The present invention has been made in view of the above problems, and an object of the present invention is to prevent a spider web from being permanently formed in a building.

The nesting prevention sheet material for moths according to the present invention is characterized in that a fine concavo-convex structure having an average interval between convex portions or concave portions of 10 μm or less is formed on the surface.
Moreover, the building material of this invention is provided with a building material main body and said sheet | seat material affixed on the building material main body.
According to the present invention, it is possible to prevent the formation of spider webs on the surface by providing the sheet material on the surface of which a fine concavo-convex structure having an average interval of convex portions or concave portions of 10 μm or less is provided.

In the building material described above, it is desirable that the average interval between the convex portions or concave portions of the fine concavo-convex structure of the sheet material is 400 nm or less.
According to the present invention having such a configuration, the sheet material can be provided with antireflection performance, and the landscape and design of the building are not impaired.

The building of the present invention is characterized in that the above-mentioned sheet is stuck on the surface of the building material.
In addition, the carport of the present invention is characterized in that the above sheet material is affixed to the surface.

  According to the present invention, it is possible to prevent a spider web from being permanently formed in a building.

It is sectional drawing of the building material of this embodiment. It is typical sectional drawing which shows the process of manufacturing the anodic oxidation alumina which has a fine uneven structure on the surface of a roll-shaped metal mold | die. It is a block diagram which shows typically the structure of an example of the manufacturing apparatus which manufactures the optical sheet piece which has a fine concavo-convex structure on the surface.

Hereinafter, an embodiment of a building material of the present invention and a building using the building material will be described with reference to the drawings.
FIG. 1 is a cross-sectional view of the building material of this embodiment. As shown in the figure, the building material 1 of the present embodiment has, for example, a building material main body 2 (plate material in FIG. 1) such as plate-like wood, and a fine concavo-convex structure on the surface. It is comprised by the sheet | seat material 4 stuck on the surface. The building of the present invention is constructed using the building material 1 (for example, a column material, a beam material, a wall material, etc.) having a sheet material having a fine uneven structure on the surface in this way.

  The building material main body 2 includes, for example, wood including veneer, plywood, correction material, etc., metal such as stainless steel and aluminum, ceramics and glass used for tiles, and resin materials such as polycarbonate. In addition, as such a building material main body, what can be prepared in a factory beforehand is preferable.

  In addition, buildings and parts where such building material 1 can be used include carports, terraces, balconies, gutters, eaves, shutters, window glass, roofing materials, housing materials, solariums, greenhouses, warehouses, outdoors The part which may contact the exteriors, such as illumination and furniture, is mentioned. The building is not limited to a building but includes a structure such as a carport.

The sheet material is a light transmissive sheet-like member, and a fine concavo-convex structure in which an average interval between convex portions or concave portions is 10 μm or less is formed on one surface thereof. As described above, since the fine uneven structure having an average interval between the convex portions or the concave portions of 10 μm or less is formed on the surface of the sheet material, the reed cannot stay on the surface of the sheet and cannot form a reed nest. In addition, even when trying to expand the spider web created in the vicinity of the sheet material, the spider web cannot be expanded because the spider and spider web cannot remain on the sheet surface.
The average interval (period) between the convex portions or the concave portions of the fine structure of the sheet material is preferably not more than the visible light wavelength, that is, not more than 400 nm, because the sheet material can further have antireflection performance.

Further, an adhesive layer 6 made of an adhesive material is provided in advance on the surface opposite to the surface on which the fine uneven structure of the sheet material 4 is formed, and the sheet material 4 is adhered to the surface of the building material body 2 by this adhesive layer 6. Has been. As a method of bonding, after the hot melt adhesive is applied to the surface of the building material main body 2 to form the adhesive layer 6, the surface opposite to the surface on which the fine uneven structure of the sheet material 4 is formed is the building material main body 2. A method of adhering to the surface using a pressure roll can be used. Further, the adhesive layer 6 may be provided in advance on the surface of the building material main body 2 or the surface opposite to the surface on which the fine uneven structure of the sheet material is formed.
The sheet material 4 can be thermocompression bonded to the building material body 2. As a method of thermocompression bonding, after the building material body 2 is melt-extruded and the surface temperature of the building material body 2 is cooled to 130 to 160 ° C., the surface opposite to the surface on which the fine uneven structure of the sheet material 4 is formed, A method of thermocompression bonding using a pressure bonding roll to the surface of the building material main body 2 can be used. Further, the building material main body 2 may be thermocompression bonded to the sheet material 4 after being reheated using a heater or the like. In addition, if the surface temperature of the building material main body 2 is 130-160 degreeC, sufficient thermocompression-bonding strength can be obtained, without lose | disappearing a fine uneven structure.

  In addition, although this embodiment demonstrates the case where a building is built beforehand using the building material 1 in which the sheet material 4 was affixed to the building material main body 2, the building of this invention is an existing building. The case where the sheet material 4 is stuck on the surface of the building material to be configured is also included.

Hereinafter, the manufacturing method of the sheet | seat material used for the above building materials is demonstrated.
The sheet material used for the building material of the present embodiment is formed, for example, by transferring fine irregularities on the surface of a roll mold having a fine irregular structure on the surface to the sheet material. First, a roll mold for manufacturing an optical sheet according to the present embodiment (hereinafter referred to as “roll mold”) will be described.

The roll-shaped mold of the present embodiment obtains a member having a fine concavo-convex structure of anodized alumina on the surface by anodizing the surface of the aluminum substrate by the following steps (a) to (f).
(A) a first oxide film forming step of forming an oxide film on the surface of the aluminum base material by anodizing the mirror-finished aluminum base material in the electrolyte under a constant voltage;
(B) an oxide film removing step for removing the oxide film and forming pore generation points for anodization on the surface of the aluminum substrate;
(C) Second oxide film formation for forming an oxide film having pores corresponding to the pore generation point by anodizing the aluminum substrate on which the pore generation point has been formed in the electrolytic solution again at a constant voltage Process,
(D) a pore diameter expansion process step of expanding the diameter of the pores;
(E) After the step (d), an oxide film growth step in which anodization is again performed in the electrolytic solution under a constant voltage;
(F) Repeating step of obtaining a fine concavo-convex shape pattern in which anodized alumina having a plurality of pores is formed on the surface of an aluminum substrate by repeatedly performing a pore diameter expansion treatment step (d) and an oxide film growth step (e) .

  According to the method having the steps (a) to (f), the surface of the mirror-finished aluminum base material has a tapered shape whose diameter gradually decreases in the depth direction from the opening, and is periodically arranged. A large number of pores are formed, and as a result, a mold is obtained in which anodized alumina having a plurality of pores (fine concavo-convex structure) is formed on the surface.

Although the regularity of the arrangement of the pores is slightly reduced, the step (a) may be omitted from the step (c) depending on the use of the material to which the mold surface is transferred.
In the present embodiment, a cylindrical aluminum substrate is used as the aluminum substrate, but a flat aluminum substrate may be used.

Hereinafter, steps (a) to (f) will be described in detail.
Step (a):
Prior to the step (a), a mirror surface treatment is performed by cutting the surface of the aluminum base material with a cutting tool to obtain a mirror surface. Prior to the step (a), a pretreatment for removing the oxide film on the surface of the aluminum substrate may be performed. Examples of the method for removing the oxide film include a method of dipping in a chromic acid / phosphoric acid mixed solution.

The surface of the mirror-finished aluminum substrate 10 shown in FIG. 2 (a) is anodized in an electrolytic solution under a constant voltage, so that the surface of the aluminum substrate 10 is reduced as shown in FIG. 2 (b). An oxide film 14 having holes 12 is formed.
Examples of the electrolytic solution include an acidic electrolytic solution and an alkaline electrolytic solution, and an acidic electrolytic solution is preferable. Examples of the acidic electrolyte include oxalic acid, sulfuric acid, and a mixture thereof.

  When oxalic acid is used as the electrolytic solution, the concentration of oxalic acid is preferably 0.7 M or less. If the concentration of oxalic acid exceeds 0.7M, the current value during anodic oxidation becomes too high, and the surface of the oxide film may become rough.

  Moreover, by setting the voltage at the time of anodization to 30 to 60 V, it is possible to obtain a mold in which anodized alumina having highly regular pores with a pitch of about 100 nm is formed on the surface. Regardless of whether the voltage during anodization is higher or lower than this range, the regularity tends to decrease, and the pitch may be larger than the wavelength of visible light.

  The temperature of the electrolytic solution is preferably 60 ° C. or lower, and more preferably 45 ° C. or lower. When the temperature of the electrolytic solution exceeds 60 ° C., a phenomenon called “burning” tends to occur, and the pores may be broken or the surface may melt and the regularity of the pores may be disturbed.

When sulfuric acid is used as the electrolytic solution, the concentration of sulfuric acid is preferably 0.7 M or less. If the concentration of sulfuric acid exceeds 0.7M, the current value at the time of anodization may become too high to maintain a constant voltage.
Further, by setting the voltage during anodization to 25 to 30 V, it is possible to obtain a mold having anodized alumina formed on the surface with highly regular pores having a pitch of about 63 nm. Regardless of whether the voltage during anodization is higher or lower than this range, the regularity tends to decrease, and the pitch may be larger than the wavelength of visible light.

In the step (a), the oxide film 14 formed by anodization for a long time becomes thick and the regularity of the arrangement of the pores can be improved. At this time, the thickness of the oxide film 14 is reduced to 0. By setting the thickness to 0.01 to 30 μm or less, macro unevenness due to crystal grain boundaries is further suppressed, and a mold more suitable for manufacturing an article for optical use can be obtained.
As for the thickness of the oxide film 14, 0.5-10 micrometers is more preferable, and 1-3 micrometers is still more preferable. The thickness of the oxide film 14 can be observed with a field emission scanning electron microscope or the like.

Step (b):
By removing the oxide film 14 formed in the step (a), as shown in FIG. 2 (c), the aluminum substrate (referred to as a barrier layer) under the removed oxide film 14 is provided. Periodic depressions formed corresponding to the pores 12, that is, the pore generation points 16 are exposed.

  By removing the formed oxide film 14 once and forming the anodic oxidation pore generation points 16, the regularity of the finally formed pores can be improved (for example, Masuda, “Applied Physics”). ", 2000, 69, No. 5, p. 558.).

  Examples of the method for removing the oxide film 14 include a method in which aluminum is not dissolved but a solution that selectively dissolves alumina is used. Examples of such a solution include a chromic acid / phosphoric acid mixed solution.

Step (c):
The aluminum substrate 10 on which the pore generation points 16 are formed is anodized again in the electrolytic solution under a constant voltage, and an oxide film is formed again.
In step (c), anodization is performed under the same conditions (electrolyte concentration, electrolyte temperature, chemical conversion voltage, etc.) as in step (a).

  As a result, as shown in FIG. 2 (d), an oxide film 14 'in which cylindrical pores 12' are formed can be formed. In the step (c), deeper pores can be obtained as the anodic oxidation time is increased. However, in the case of manufacturing a mold for manufacturing an optical article such as an antireflection article, 0 is used here. It is only necessary to form an oxide film having a thickness of about 0.01 to 0.5 μm, and it is not necessary to form an oxide film having a thickness as large as that formed in the step (a).

Step (d):
After the step (c), a pore diameter enlargement process for enlarging the diameter of the pores 12 ′ formed in the step (c) is performed to increase the diameter of the pores 12 ′ as shown in FIG. The pore is 12 ″.

  As a specific method of the pore diameter expansion treatment, a method of immersing in a solution dissolving alumina and expanding the diameter of the pores formed in the step (c) by etching can be mentioned. Examples of such a solution include a phosphoric acid aqueous solution of about 5% by mass. The longer the time of step (d), the larger the pore diameter.

Step (e):
Anodization is performed again to form small-diameter pores 18 extending downward from the bottom of the pores 12 ″ expanded in the step (d) as shown in FIG. 2 (f).
Anodization may be performed under the same conditions as in step (c). Deeper pores can be obtained as the anodic oxidation time is lengthened.

Step (f):
By repeating step (d) and step (e), as shown in FIG. 2G, the shape of the pores is tapered so that the diameter gradually decreases in the depth direction from the opening. As a result, a mold R in which anodized alumina having a plurality of periodic pores is formed on the surface can be obtained. It is preferable that the last end is step (d).

  By appropriately setting the conditions of the step (d) and the step (e), for example, the time for anodization and the time for the pore diameter expansion treatment, various shapes of pores can be formed. Therefore, these conditions may be set as appropriate according to the use of the article to be manufactured from the mold. In addition, when this mold is for manufacturing an antireflection article such as an antireflection film, the pitch and depth of the pores can be arbitrarily changed by appropriately setting the conditions as described above. It is also possible to design a refractive index change.

  The mold thus obtained has a fine concavo-convex structure on the surface as a result of the formation of many periodic pores on the surface. And when the pitch of the pores in this fine concavo-convex structure is not more than the wavelength of visible light, that is, not more than 400 nm, a so-called moth-eye structure is obtained.

  Here, the “pitch” refers to the distance from the center of the recess (pore) of the fine concavo-convex structure to the center of the recess (pore) adjacent thereto. When the pitch is smaller than 400 nm, visible light is not scattered, and the sheet material can have an antireflection function.

  When the mold is for producing an antireflection article such as an antireflection film, the pitch of the pores is not more than the wavelength of visible light, and the depth of the pores is preferably 50 nm or more, and 100 nm. More preferably.

The depth refers to the distance from the opening of the concave portion (pore) of the fine concavo-convex structure to the deepest portion.
If the depth of the pores is 50 nm or more, the reflectance of the surface of the article for optical use formed by the transfer of the mold surface, that is, the transfer surface is lowered.

  The aspect ratio (depth / pitch) of the mold pores is preferably 1.0 to 4.0, preferably 1.3 to 3.5, more preferably 1.8 to 3.5. Most preferred is 0-3.0. When the aspect ratio is 1.0 or more, a transfer surface with low reflectance can be formed, and the incident angle dependency and wavelength dependency thereof are sufficiently reduced. If the aspect ratio is greater than 4.0, the mechanical strength of the transfer surface tends to decrease.

  In this way, a roll-shaped mold having a fine concavo-convex structure and streaky concavo-convex shape formed on the outer peripheral surface is obtained. Using this roll-shaped mold, a long sheet material having a fine concavo-convex structure and streaky concavo-convex shape transferred on the surface is produced. Hereinafter, a method for manufacturing the sheet material will be described.

(manufacturing device)
When forming a sheet material having a fine concavo-convex structure on the surface, a manufacturing apparatus 20 shown in FIG. 3 is used.
As described above, the manufacturing apparatus 20 converts the roll-shaped mold 22 having a fine concavo-convex structure formed on the outer peripheral surface thereof to be rotationally driven, and the long base 24 serving as a base material of the sheet material into the roll-shaped mold 22. A continuous supply mechanism, a nip roll 26 that presses the long base material 24 against the outer peripheral surface of the roll-shaped mold 22, and an active energy ray-curable resin composition 28 with the roll-shaped mold 22 and the long shape. A nozzle 30 that is supplied between the substrate 24 and an active energy ray source 32 that irradiates the active energy ray toward the active energy ray curable composition 28 at a position downstream of the nip roll 26.

  The nip roll 26 is driven by a pneumatic cylinder 34 at a position upstream of the roll mold 22 in the rotation direction, and is configured to press the long base material 24 against the outer peripheral surface of the roll mold 22. The active energy ray-curable composition 28 accommodated in the tank 36 is fed from the nozzle 30 to the long base material in the region where the long base material 24 is pressed against the outer peripheral surface of the roll mold 22. 24 and the roll-shaped mold 22 are supplied.

  The active energy ray irradiating device 28 installed under the roll-shaped mold 22 is activated through the base material 24 to the active energy ray-curable resin composition 28 disposed between the base material 24 and the roll-shaped mold 22. By irradiating energy rays and curing the active energy ray curable resin composition 28, a cured resin layer 38 having a shape complementary to the fine concavo-convex structure of the roll-shaped mold 22 is formed on the substrate 24.

The sheet material 40 on which the cured resin layer 38 is formed on the surface of the substrate 24 is peeled off from the roll-shaped mold 22 by the peeling roll 40.
And an adhesive agent is made to adhere to the surface on the opposite side to the side in which the fine concavo-convex structure of the manufactured sheet material 40 was formed, and an adhesive layer is formed. And the building material shown in FIG. 1 can be manufactured by adhere | attaching the sheet | seat material 40 on the building material main body manufactured previously by the contact bonding layer. The sheet material produced in this way has an anti-reflection function, is transparent, and can be colored, so that a spider's web can be formed without impairing the landscape and design of the building. Can be prevented.

  In the description of the present embodiment, the active energy ray-curable resin composition 28 is disposed between the roll-shaped mold 22 and the base material 24. However, for simplicity of explanation, such a state is also used. This is referred to as a state in which the roll-shaped mold 22 and the base material 24 are in contact with each other. Further, the active energy ray-curable resin composition 28 is not disposed between the roll-shaped mold 22 and the base material 24, and heat is applied while pressing the base material 24 against the roll-shaped mold 22. A shape complementary to the fine concavo-convex structure may be directly formed on the surface of 24.

  The substrate 24 is preferably a film or sheet formed by injection molding or press molding. The material of the substrate 24 is a light transmissive material, for example, polycarbonate resin, polystyrene resin, polyester resin, polyurethane resin, acrylic resin, polyether sulfone, polysulfone, polyether ketone, cellulose. Resin, triacetyl cellulose, polyolefin, polyolefin, alicyclic polyolefin, glass and the like.

(Active energy ray-curable resin composition)
The active energy ray-curable resin composition 28 is a composition containing a polymerizable compound, a polymerization initiator, and an internal release agent.

  The viscosity at 25 ° C. of the composition is preferably 10,000 mPa · s or less, more preferably 5000 mPa · s or less, and even more preferably 2000 mPa · s or less. When the viscosity at 25 ° C. of the composition is 10,000 mPa · s or less, the composition can follow the fine concavo-convex structure, and the fine concavo-convex structure can be accurately transferred. The viscosity of the composition is measured at 25 ° C. using a rotary E-type viscometer.

(Polymerizable compound)
Examples of the polymerizable compound include monomers, oligomers, and reactive polymers having a radical polymerizable bond and / or a cationic polymerizable bond in the molecule.
Examples of the monomer having a radical polymerizable bond include a monofunctional monomer and a polyfunctional monomer.

  Monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t- Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, alkyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, Phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl ( )) (Meth) acrylate derivatives such as acrylate, hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate; (meth) acrylic acid, (meth) acrylonitrile; styrene, α -Styrene derivatives such as methylstyrene; (meth) acrylamide derivatives such as (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide and the like. These may be used alone or in combination of two or more.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, isocyanuric acid ethylene oxide modified di (meth) acrylate, triethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, polybutylene glycol di (Meth) acrylate, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (3- ( Ta) acryloxy-2-hydroxypropoxy) phenyl) propane, 1,2-bis (3- (meth) acryloxy-2-hydroxypropoxy) ethane, 1,4-bis (3- (meth) acryloxy-2-hydroxypropoxy) ) Butane, dimethylol tricyclodecane di (meth) acrylate, ethylene oxide adduct di (meth) acrylate of bisphenol A, propylene oxide adduct di (meth) acrylate of bisphenol A, neopentyl glycol di (meth) hydroxypivalate Bifunctional monomers such as acrylate, divinylbenzene, and methylenebisacrylamide; pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide Functional tri (meth) acrylate, trimethylolpropane propylene oxide modified triacrylate, trimethylolpropane ethylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate and other trifunctional monomers; succinic acid / trimethylolethane / acrylic acid 4 or more functional monomers such as dipentaerystol hexa (meth) acrylate, dipentaerystol penta (meth) acrylate, ditrimethylolpropane tetraacrylate, tetramethylolmethanetetra (meth) acrylate; bifunctional or more Urethane acrylates, bifunctional or higher functional polyester acrylates, and the like. These may be used alone or in combination of two or more.

  Examples of the monomer having a cationic polymerizable bond include monomers having an epoxy group, an oxetanyl group, an oxazolyl group, a vinyloxy group, and the like, and a monomer having an epoxy group is particularly preferable.

  Examples of the oligomer or reactive polymer include unsaturated polyesters such as a condensate of unsaturated dicarboxylic acid and polyhydric alcohol; polyester (meth) acrylate, polyether (meth) acrylate, polyol (meth) acrylate, epoxy (meth) Examples thereof include acrylates, urethane (meth) acrylates, cationic polymerization type epoxy compounds, homopolymers of the above-described monomers having a radical polymerizable bond in the side chain, and copolymerized polymers.

(Polymerization initiator)
When utilizing a photocuring reaction, examples of the photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl, benzophenone, p-methoxybenzophenone, 2,2-diethoxy. Acetophenone, α, α-dimethoxy-α-phenylacetophenone, methylphenylglyoxylate, ethylphenylglyoxylate, 4,4′-bis (dimethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropane- Carbonyl compounds such as 1-one; sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, benzoyl Examples include diethoxyphosphine oxide. These may be used alone or in combination of two or more.

  When using an electron beam curing reaction, examples of the polymerization initiator include benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone, t- Thioxanthone such as butylanthraquinone, 2-ethylanthraquinone, 2,4-diethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl Dimethyl ketal, 1-hydroxycyclohexyl-phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholy Phenyl) -butanone and other acetophenones; benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and other benzoin ethers; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl)- Acylphosphine oxides such as 2,4,4-trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; methylbenzoylformate, 1,7-bisacridinylheptane, 9-phenyl Examples include acridine. These may be used alone or in combination of two or more.

  When utilizing a thermosetting reaction, examples of the thermal polymerization initiator include methyl ethyl ketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperoxide, t-butyl peroxy octoate, organic peroxides such as t-butylperoxybenzoate and lauroyl peroxide; azo compounds such as azobisisobutyronitrile; N, N-dimethylaniline, N, N-dimethyl-p- Examples thereof include a redox polymerization initiator combined with an amine such as toluidine.

  As for the quantity of a polymerization initiator, 0.1-10 mass parts is preferable with respect to 100 mass parts of polymeric compounds. When the amount of the polymerization initiator is less than 0.1 parts by mass, the polymerization is difficult to proceed. When the amount of the polymerization initiator exceeds 10 parts by mass, the cured film may be colored or the mechanical strength may be lowered.

(Internal release agent)
When the active energy ray-curable resin composition contains an internal release agent, continuous transferability can be improved.
If the internal mold release agent is to improve the releasability between the cured product of the active energy ray-curable resin composition and the mold surface, and is compatible with the active energy ray-curable resin composition, In particular, the composition is not limited.

  Examples of the internal release agent include (poly) oxyalkylene alkyl phosphate compounds, fluorine-containing compounds, silicone compounds, compounds having a long chain alkyl group, polyalkylene wax, amide wax, and Teflon powder (Teflon is a registered trademark). Etc. These may be used alone or in combination of two or more. Among these, those containing a (poly) oxyalkylene alkyl phosphate compound as a main component are preferable.

  By including the same (poly) oxyalkylene alkyl phosphate compound as the mold release agent as the internal release agent, the release property between the cured resin layer, which is the cured product, and the mold becomes particularly good. Further, since the load at the time of releasing is extremely low, the fine concavo-convex structure is hardly damaged, and as a result, the fine concavo-convex structure of the mold can be transferred efficiently and accurately.

As the (poly) oxyalkylene alkyl phosphate compound, a compound represented by the following formula (1) is preferable from the viewpoint of releasability.
(HO) 3-n (O =) P [-O- (R2O) m-R1] n (1)
R1 is an alkyl group, R2 is an alkylene group, m is an integer of 1 to 20, and n is an integer of 1 to 3.

As R1, a C1-C20 alkyl group is preferable and a C3-C18 alkyl group is more preferable.
R2 is preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 2 to 3 carbon atoms.
m is preferably an integer of 1 to 10.

  The (poly) oxyalkylene alkyl phosphate compound may be a monoester (n = 1), a diester (n = 2), or a triester (n = 3). In the case of a diester or triester, a plurality of (poly) oxyalkylene alkyl groups in one molecule may be different from each other.

Examples of commercially available (poly) oxyalkylene alkyl phosphate compounds include the following.
Johoku Chemical Co., Ltd .: JP-506H (n≈1-2, m≈1, R1 = butyl, R2 = ethylene),
Accelerator manufactured: Mold with INT-1856 (structure not disclosed),
Nikko Chemicals: TDP-10 (n≈3, m≈10, R1 = C12-15, R2 = ethylene), TDP-8 (n≈3, m≈8, R1 = C12-15, R2 = ethylene) TDP-6 (n≈3, m≈6, R1 = C12-15, R2 = ethylene), TDP-2 (n≈3, m≈2, R1 = C12-15, R2 = ethylene), DDP-10 (N≈2, m≈10, R1 = C12-15, R2 = ethylene), DDP-8 (n≈2, m≈8, R1 = C12-15, R2 = ethylene), DDP-6 (n≈2 , M≈6, R1 = C12-15, R2 = ethylene), DDP-4 (n≈2, m≈4, R1 = C12-15, R2 = ethylene), DDP-2 (n≈2, m≈2) , R1 = C12-15, R2 = ethylene), TLP-4 (n≈3, m≈4, R1 = lauryl, 2 = ethylene), TCP-5 (n ≒ 3, m ≒ 5, R1 = cetyl, R2 = ethylene), DLP-10 (n ≒ 3, m ≒ 10, R1 = lauryl, R2 = ethylene).
A (poly) oxyalkylene alkyl phosphate compound may be used individually by 1 type, and may use 2 or more types together.

  The amount of the (poly) oxyalkylene alkyl phosphate compound is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass, with respect to 100% by mass of the polymerizable compound. -0.1 mass% is further more preferable. When the amount of the (poly) oxyalkylene alkyl phosphate compound is 1% by mass or less, a decrease in the performance of the cured resin layer can be suppressed. Moreover, the fall of adhesiveness with a base material is suppressed, As a result, the resin residue (molding defect) to a mold and peeling of the cured resin layer from articles | goods are suppressed. If the amount of the (poly) oxyalkylene alkyl phosphate compound is 0.01% by mass or more, the releasability from the mold is sufficient, and the resin residue (unsatisfactory release) on the mold is suppressed.

  The active energy ray-curable resin composition may contain a component that improves mold release properties other than the (poly) oxyalkylene alkyl phosphate compound for the purpose of further improving mold release properties. Examples of the component include a fluorine-containing compound, a silicone compound, a phosphate ester compound, a compound having a long-chain alkyl group, a solid wax (polyalkylene wax, amide wax, Teflon powder (Teflon is a registered trademark), etc.), etc. And the like, and the like.

(Other ingredients)
The active energy ray-curable resin composition is made of a non-reactive polymer, an active energy ray sol-gel reactive composition, an antistatic agent, an additive such as a fluorine compound for improving antifouling, and fine particles as necessary. A small amount of a solvent may be contained.

Examples of non-reactive polymers include acrylic resins, styrene resins, polyurethanes, cellulose resins, polyvinyl butyral, polyesters, thermoplastic elastomers, and the like.
Examples of the active energy ray sol-gel reactive composition include alkoxysilane compounds and alkyl silicate compounds.

  Examples of the alkoxysilane compound include tetramethoxysilane, tetra-i-propoxysilane, tetra-n-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane, methyltriethoxysilane, Examples include methyltripropoxysilane, methyltributoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, trimethylpropoxysilane, and trimethylbutoxysilane.

  Examples of the alkyl silicate compound include methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate, n-butyl silicate, n-pentyl silicate, acetyl silicate and the like.

  As the active energy ray irradiation device 32, a high-pressure mercury lamp, a metal halide lamp, a fusion lamp or the like is preferable. In this case, the amount of light irradiation energy is preferably 100 to 10,000 mJ / cm 2.

  The inventors of the present application formed a building material (Examples 1 to 3) in which a sheet material having a fine concavo-convex structure was pasted on the surface and a building material (Comparative Example 1) in which no sheet material was pasted, formed by the method described above Was applied to the back of the carport roof and the pole, and an experiment was conducted to examine whether a spider's web would be stretched.

In this example, the following mold A and mold B were used.
(Manufacture of mold A)
As the aluminum base material of the mold A, an aluminum disk having a purity of 99.99% by mass, a thickness of 2 mm, and a diameter of 65 mm was subjected to feather polishing and electropolishing.
In said process (a), 0.3 M oxalic acid aqueous solution was adjusted to 16 degreeC, the aluminum base material was immersed in this, and the anodic oxidation was performed for 30 minutes by DC 40V. Thereby, the oxide film which has a pore in the aluminum base material was formed.

In the step (b), the aluminum base material on which the oxide film was formed was immersed for 6 hours in a 70 ° C. aqueous solution in which 6% by mass of phosphoric acid and 1.8% by mass of chromic acid were mixed.
In the step (c), the aluminum base material from which the oxide film was dissolved and removed was immersed in a 0.3 M oxalic acid aqueous solution adjusted to 16 ° C. and anodized at 40 V for 30 seconds.

In the step (d), a pore diameter enlargement process was performed to immerse in a 5% by mass phosphoric acid aqueous solution adjusted to 32 ° C. for 8 minutes to enlarge the pores of the oxide film.
And anodization (step (e)) and pore diameter enlargement treatment (step (d)) are alternately repeated five times, and anodized alumina having substantially conical pores with an average interval of 100 nm and an average depth of 180 nm. A mold having a surface formed thereon was obtained.

  The mold obtained was immersed in a release agent (0.1% by weight aqueous solution of “TDP-8” manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and air-dried overnight to release the mold. A treated mold A was obtained.

(Manufacture of mold B)
As an aluminum base material of the mold B, an aluminum disk having a purity of 99.99% by mass, a thickness of 2 mm, and a diameter of 65 mm was subjected to feather polishing and electropolishing.
In step (a), a 0.3 M oxalic acid aqueous solution is adjusted to 15 ° C., an aluminum base material is immersed in this, and the power supply of the DC stabilizing device is repeatedly turned ON / OFF to intermittently supply current to the aluminum base material. And anodized. The operation of applying a constant voltage of 80 V every 30 seconds for 5 seconds was repeated 60 times.

In the step (b), the aluminum base material on which the oxide film was formed was immersed for 6 hours in a 70 ° C. aqueous solution in which 6% by mass of phosphoric acid and 1.8% by mass of chromic acid were mixed.
In the step (c), the aluminum base material from which the oxide film was dissolved and removed was immersed in a 0.05 M oxalic acid aqueous solution adjusted to 16 ° C., and anodized at 80 V for 7 seconds.

In the step (d), a pore diameter expansion treatment was performed to immerse in a 5% by mass phosphoric acid aqueous solution adjusted to 32 ° C. for 20 minutes to expand the pores of the oxide film.
Then, anodization (step (e)) and pore diameter enlargement treatment (step (d)) are alternately repeated five times, and anodization having substantially conical pores with an average interval of 180 nm and an average depth of 180 nm. A mold having alumina formed on the surface was obtained.

  The mold obtained was immersed in a release agent (0.1% by weight aqueous solution of “TDP-8” manufactured by Nikko Chemicals Co., Ltd.) for 10 minutes, and then pulled up and air-dried overnight to release the mold. A processed mold B was obtained.

Moreover, the following resin compositions A and B were used as the active energy ray-curable resin composition.
(Preparation of active energy ray-curable resin composition A)
As a polymerizable component, 20 parts by mass of dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd., “DPHA”), 20 parts by mass of pentaerythritol triacrylate (Daiichi Kogyo Seiyaku Co., Ltd., “New Frontier PET-3”), As a polymerization initiator, 35 parts by mass of polyethylene glycol diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “A-200”) and 25 parts by mass of N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd., “DMAA”) , 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Japan, “IRGACURE184”), and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Japan, IRGACURE819 ”) 0.5 parts by mass, Agent (Tomoe Corporation, "mold Uiz INT-1856") was mixed with 0.1 parts by weight, to prepare an active energy ray curable resin composition A (resin composition A).

(Preparation of active energy ray-curable resin composition B)
As a polymerizable component, 22 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., “DPHA”) and 78 parts by mass of ethoxylated pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., “ATM-35E”) Parts, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (manufactured by Ciba Japan, “IRGACURE184”), and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (Ciba -Japan Co., Ltd., "IRGACURE819") 0.5 parts by mass and release agent (Sakai Kogyo Co., Ltd., "Mold with INT-1856") 0.1 parts by mass are mixed, and active energy ray curability is mixed. Resin composition B (resin composition B) was prepared.
In this example, the following sheet materials A and B were manufactured using the molds A and B and the resin compositions A and B.

(Sheet material A)
A sheet material A having a fine concavo-convex structure on the surface was produced using the production apparatus shown in FIG.
As the active energy ray-curable resin composition 28, the above resin composition A was used, and as the roll-shaped mold 22, the above mold A was used. As the base material 24, an acrylic film was used.

And after supplying the resin composition A to the surface of the base material 24 which consists of an acrylic film, and transferring the fine uneven structure of the surface of the roll-shaped metal mold | die 22 to the resin composition A, a high pressure mercury lamp is used from the acrylic film side. The resin composition A was cured by irradiating with ultraviolet rays at an energy of 1000 mJ / cm ² . Then, the cured product of the resin composition A was released from the mold A together with the acrylic film.

  As a result, on the base material 24, the surface having a fine concavo-convex structure having an average interval between adjacent protrusions of 100 nm and an average height of protrusions of 180 nm (aspect ratio: 1.8) on the surface is 3 μm. A film-like laminated structure (sheet material A) in which the surface layers were laminated was obtained.

(Sheet material B)
Similarly to the sheet material A, a sheet material B having a fine concavo-convex structure on the surface was manufactured using the manufacturing apparatus shown in FIG.
As the active energy ray-curable resin composition 28, the above resin composition B was used, and as the roll-shaped mold 22, the above mold B was used. Moreover, as the base material 24, an acrylic film (Sanduren SD014NRT manufactured by Kaneka Corporation) was used.

And after supplying the resin composition B to the surface of the base material 24 which consists of an acrylic film, and transferring the fine uneven structure of the surface of the roll-shaped metal mold | die 22 to the resin composition B, a high pressure mercury lamp is used from the acrylic film side. The resin composition A was cured by irradiating with ultraviolet rays at an energy of 1000 mJ / cm ² . Then, the cured product of the resin composition A was released from the mold B together with the acrylic film.

As a result, on the surface of the substrate 24, the surface having a fine concavo-convex structure having an average interval between adjacent protrusions of 180 nm and an average height of protrusions of 180 nm (aspect ratio: 1.0) is 3 μm. A film-like laminated structure (sheet material B) in which the surface layers were laminated was obtained.
The sheet materials A and B were examined for adhesion, scratch resistance, transparency, and antireflection performance. The results are shown in Table 1.

“Adhesiveness” in the table means the adhesiveness at the interface between the cured layer and the base film, and in accordance with JIS K5600-5-6, a cross-cut peel test using a 100 grid with an interval of 2 mm is performed. And evaluated according to the following criteria.
A: All 100 lattices are in close contact.
◯: In 100 lattices, the closely attached lattices are 91-99.
(Triangle | delta): The grid | lattice which is closely_contact | adhered among 100 grids is 51-90.
×: 0 to 50 lattices in close contact with each other in 100 lattices.

In addition, in the “abrasion resistance” in the table, a steel wool (cut into 2 cm ² ) placed on the surface of an article using an abrasion tester (“HEiDON TRIBOGEAR TYPE-30S” manufactured by Shinto Kagaku Co., Ltd.) A load of 400 g (100 gf / cm ² ) and 1 kg (250 gf / cm ² ) was applied to Nippon Steel Wool Co., Ltd. Bonster # 0000, and the reciprocating distance was 30 mm and the head speed was averaged 10 times at an average of 100 mm / sec. The appearance of the surface of the article was evaluated. In the appearance evaluation, an article was attached to one side of a 2.0 mm thick black acrylic plate (manufactured by Mitsubishi Rayon Co., Ltd., acrylite), held over a fluorescent lamp indoors, and visually evaluated according to the following criteria.
A: Scratches cannot be confirmed.
A: Less than 10 scratches that can be confirmed.
(Triangle | delta): The crack which can be confirmed is 10 or more and less than 30.
X: 30 or more scratches that can be confirmed.

Moreover, about the "transparency" in a table | surface, the haze of the molded object (film) was measured using the haze meter (made by Suga Test Instruments Co., Ltd.) based on JISK7361-1.
Moreover, about the "antireflection performance" in a table | surface, the sample affixed on the black acrylic board was used for the wavelength of 380 nm-780 nm on condition of an incident angle of 5 degrees using Hitachi spectrophotometer U-4100. The relative reflectance was measured, and the reflectance at 550 nm, which is the visibility reflectance, was evaluated.

The manufactured sheet materials A and B were applied to the carports of Examples 1-3 below.
(Example 1) As a base material 24, a building material using a sheet material A prepared using “Acryprene” (product number: HBS010P, thickness: 75 μm) manufactured by Mitsubishi Rayon Co., Ltd. is applied to the roof back surface and pole of a carport. did.

(Example 2) As a base material 24, a building material using a sheet material B prepared using "Acryprene" (product number: HBS010P, thickness: 75 µm) manufactured by Mitsubishi Rayon Co., Ltd. is applied to the roof back surface and pole of a carport did.

(Example 3) As the base material 24, the building material using the sheet material A created using Sanduren SD014NRT manufactured by Kaneka Corporation was applied to the roof back surface of the carport and the pole.

(Comparative example 1) The building material which has not stuck the sheet material on the surface was applied to the carport.
As a result, in the carport of Example 1-3, a spider's web was not stretched even after half a year. In contrast, in the carport of Comparative Example 1, a spider web was stretched and removed after 3 months, but a spider web was stretched again after another month.

  From the above results, it was confirmed that it was possible to prevent the spider web from being stretched according to the building material in which the sheet material on which the fine uneven structure of the present embodiment was formed was attached to the surface.

1 Building Material 2 Building Material Body 4 Sheet Material 6 Adhesive Layer

Claims (5)

  A ridge nesting prevention sheet material, characterized in that a fine concavo-convex structure having an average interval of protrusions or recesses of 10 μm or less is formed on the surface. The building material body,
A building material comprising: the sheet material according to claim 1 attached to the building material main body.   The building material according to claim 2, wherein an average interval between convex portions or concave portions of the fine uneven structure of the sheet material is 400 nm or less.   A building comprising the sheet material according to claim 1 attached to a surface of a building material.   A carport, wherein the sheet material according to claim 1 is attached to a surface.

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