JP2017002573A - Folded plate, flat plate and resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a folded plate where the occurrence of cracks is prevented in a folded portion formed by folding a flat plate, a flat plate used to obtain such a folded plate, and a resin composition used to form a coat layer.SOLUTION: A folded plate 1 is used as a roofing material or an external wall material of a building structure. The folded plate 1 has a base material 2 formed by using materials including the thermoplastic resin, and a coat layer 3 provided at the side of an upper surface 21 of the base material 2 and formed by using resin composition. The resin composition contains silicon denaturation (meta) acryl resin and urethane (meta) acrylate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a folded plate, a flat plate, and a resin composition.

As a roofing material for warehouses and garages, a metal flat plate, and a bellows shape in which a peak obtained by folding the flat plate and a valley obtained by folding the flat plate are alternately repeated Folded plates and the like are known.
Further, in recent years, as a flat plate used as a roofing material, for example, a base material made of a resin material, which is excellent in transparency and has a function of providing lighting, external visual recognition, and the like, and a base material The thing provided with the coating layer provided in one surface is proposed (for example, refer patent document 1).
However, when trying to form a folded plate using a flat plate provided with such a base material and a coating layer, when the flat plate is folded into a mountain fold so that the coating layer side is convex, a mountain portion is formed, There is a problem that a crack occurs in the coat layer at the mountain portion, and it is difficult to form a folded plate using the flat plate.

JP 2009-198169 A

  An object of the present invention is to form a folded plate in which cracks are prevented from being generated in a bent portion formed by folding a flat plate, a flat plate used to obtain such a folded plate, and a coating layer. It is providing the resin composition used for this.

Such an object is achieved by the present inventions (1) to (8) below.
(1) A folded plate used as a roofing material or exterior wall material of a building,
A base material formed using a material containing a thermoplastic resin, and a coating layer provided on at least one surface side of the base material and formed using a resin composition;
The said resin composition contains a silicon modified (meth) acrylic resin and urethane (meth) acrylate, The folded board characterized by the above-mentioned.
(2) The folded plate according to (1), wherein the coat layer has a thickness of 3 μm or more and 30 μm or less.
(3) The folded plate according to (1) or (2), wherein the content ratio of the urethane (meth) acrylate in the resin composition is 3 parts by mass or more and 50 parts by mass or less.
(4) The folded plate according to any one of (1) to (3), wherein the thermoplastic resin is a polycarbonate resin.
(5) The folded plate according to any one of (1) to (4), wherein the resin composition further includes a hydrophilizing additive.
(6) The folded plate according to any one of (1) to (5), wherein the resin composition further includes a curing agent.
(7) A flat plate for obtaining a folded plate used as a roofing material or an outer wall material of a building by bending,
A base material containing a thermoplastic resin, and a coating layer provided on at least one surface side of the base material and formed using a resin composition;
The resin composition includes a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.
(8) A resin composition used for obtaining a coat layer provided on a folded plate used as a roofing material or an outer wall material of a building or a flat plate to be bent,
A resin composition comprising a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.

  According to the folded board of this invention, it can prevent that a crack generate | occur | produces in the peak part formed by bending a flat plate.

It is a perspective view which shows a part of folded plate of this invention. It is a figure which shows a part of shaping | molding apparatus used for the manufacturing method of the folded plate shown in FIG. It is a figure for demonstrating the manufacturing method of the folded plate shown in FIG. It is a figure for demonstrating the manufacturing method of the folded plate shown in FIG. It is a figure for demonstrating the manufacturing method of the folded plate shown in FIG. It is a figure for demonstrating the manufacturing method of the folded plate shown in FIG.

Hereinafter, a folded plate, a flat plate and a resin composition of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
The folded plate of the present invention is a folded plate used as a roofing material or exterior wall material of a building, and is provided on a base material formed using a material containing a thermoplastic resin, on the upper surface side of the base material, A coating layer formed using a resin composition, and the resin composition includes a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.
Further, the flat plate of the present invention is a flat plate for obtaining a folded plate used as a roofing material or an outer wall material of a building by bending, a base material containing a thermoplastic resin, and an upper surface side of the base material And a coating layer formed using a resin composition, wherein the resin composition includes a silicon-modified (meth) acrylic resin and a urethane (meth) acrylate.
The resin composition of the present invention is a resin composition used for obtaining a coat layer provided on a folded plate used as a roofing material or outer wall material of a building or a flat plate to be bent. ) Acrylic resin and urethane (meth) acrylate.
According to these, it can prevent reliably that a crack generate | occur | produces in the peak part formed by bending a flat plate.
In the present specification, “(meth) acrylate” is a general term for methacrylate and acrylate.

Below, the folded plate of this invention is demonstrated.
《Folded plate》
FIG. 1 is a perspective view showing a part of a folded plate of the present invention. In FIG. 1, the thickness direction of the folded plate is emphasized. In FIG. 1, for convenience of explanation, the x axis, the y axis, and the z axis are illustrated as three axes orthogonal to each other. The tip side of the illustrated arrow is “+ side”, and the base end side is “−”. Side ". In the following, a direction parallel to the x-axis is referred to as “x-axis direction”, a direction parallel to the y-axis is referred to as “y-axis direction”, and a direction parallel to the z-axis is referred to as “z-axis direction”. The + z side (upper side in FIG. 1) is referred to as “upper”, and the −z side (lower side in FIG. 1) is referred to as “lower”.
A folded plate 1 shown in FIG. 1 is used as a roofing material or an outer wall material of a building such as a warehouse or a garage, and is obtained by folding a rectangular flat plate into a mountain fold in a plan view in a vertical direction (+ z direction). A bellows-like shape in which protruding peak portions 11 and valley portions 12 protruding in the vertical direction (−z direction) obtained by folding into valley folds are alternately provided along the horizontal direction (x direction in FIG. 1). It is a member.
The mountain portion 11 includes an upper surface (first top surface) 111 having a long rectangular shape, and two inclined surfaces inclined downward from a pair of edges along the longitudinal direction (y-axis direction) of the upper surface 111. 15 (first inclined surface 15a and second inclined surface 15b). On the other hand, the valley portion 12 includes two bottom surfaces (second top surface) 121 having a long rectangular shape and two inclined portions extending upward from a pair of edges along the longitudinal direction (y-axis direction) of the bottom surface 121. It is comprised by the inclined surface 15 (2nd inclined surface 15b and 3rd inclined surface 15c). These ridges 11 and valleys 12 are alternately provided along the horizontal direction, and the adjacent ridges 11 and valleys 12 are configured such that the adjacent inclined surfaces 15 are the same second inclined surface 15b. Is done. In the present embodiment, the top surface 111 and the bottom surface 121 have substantially the same shape in plan view.
Further, a mountain folded portion (folded portion) 16 is formed by being folded into a mountain fold at the joint portion (boundary portion) between the edge portion of the upper surface 111 and the edge portion of the inclined surface 15, and the edge portion of the bottom surface 121 and the inclined surface 15 are formed. A valley fold portion (fold portion) 17 is formed that is bent into a valley fold at a joint portion (boundary portion) with the edge portion of the.

In the present embodiment, the angle (inner angle of the mountain bent portion 16) θ between the upper surface 111 and the inclined surface 15 is equal to the angle (inner angle of the valley bent portion 17) θ between the bottom surface 121 and the inclined surface 15. Yes. In the present embodiment, the inner angle θ of the mountain bent portion 16 and the inner angle θ of the valley bent portion 17 are equal, but these inner angles θ may be different from each other.
The angle θ is not particularly limited, but is usually preferably set to 80 ° to 150 °, more preferably set to 115 ° to 130 °, and specifically, a so-called angle θ set to 126 °. Examples include 88 folded plates and so-called 15 folded plates in which the angle θ is set to 119 °.

In the present embodiment, the plan view shape of the folded plate 1 is a quadrilateral shape, but the plan view shape of the folded plate 1 is not limited to this, and for example, a shape other than a quadrangle such as a circle, an ellipse, a pentagon, a hexagon, etc. It may be a polygon or the like.
Such a folded plate 1 includes a base material 2 obtained from a material containing a thermoplastic resin, and a coat layer (protective layer, functional layer) provided on one surface side of the base material 2 and obtained from a resin composition. 3). The function as the protective layer is wear resistance and weather resistance, and the functional layer is antifouling.
The folded plate 1 is installed so that the base material 2 faces the indoor side and the coat layer 3 faces the outdoor side so that the one surface becomes the upper surface 21.
The substrate 2 imparts mechanical strength such as rigidity to the folded plate 1.
On the other hand, the coat layer 3 is composed of a cured product obtained by curing a resin composition containing a silicon-modified (meth) acrylic resin and urethane (meth) acrylate, and functions as a protective layer for the substrate 2. The coat layer 3 that functions as a protective layer is, for example, a function that suppresses or prevents the base material 2 from being deteriorated by rainwater, sunlight, or the like (for example, corrosion or corrosion resistance), so-called weather resistance, and scattered matter from the outside. It has a function to suppress or prevent the substrate 2 from being scratched by the above, such as so-called wear resistance. The coat layer 3 also functions as a functional layer having antifouling properties.
Such a base material 2 and the coat layer 3 (folded plate 1) are substantially transparent, and have a function of visual recognition or daylighting outdoors. Here, “substantially transparent” means colorless transparent and colored transparent, and means that the total light transmittance in the thickness direction of the folded plate 1 is 70% or more. In addition, the base material 2 and the coat layer 3 may not have a daylighting function and may have a light shielding property.

Hereinafter, the base material 2 and the coat layer 3 included in the folded plate 1 will be described in detail.
[Base material]
As described above, the base material 2 is located on the indoor side and imparts mechanical strength to the folded plate 1.
The substrate 2 is a member that is formed using a material containing a thermoplastic resin and has a substantially transparent quadrangular shape in plan view and a bellows shape in side view.
Examples of the thermoplastic resin include polystyrene resins, polyethylene resins, polypropylene resins, polyester resins such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate resins, vinyl chloride resins, polyacetal resins, and the like. Of these, one or a combination of two or more can be used. Among these, polycarbonate resins are particularly preferable. Since the cured product of polycarbonate resin is rich in mechanical strength such as transparency (translucency) and rigidity, the transparency and impact resistance of the folded plate 1 are improved by using the polycarbonate resin for the substrate 2. Can be made.
The polycarbonate resin is not particularly limited, but an aromatic polycarbonate is preferable. This aromatic polycarbonate is synthesized, for example, by interfacial polycondensation reaction between bisphenol and phosgene, transesterification reaction between bisphenol and diphenyl carbonate, and the like.
Examples of the bisphenol include bisphenol A and bisphenol (modified bisphenol) that is the origin of the repeating unit of the polycarbonate represented by the following formula (1).

(In the formula, X is selected from an alkyl group having 1 to 18 carbon atoms, an aromatic group, and a cyclic aliphatic group, Ra and Rb are alkyl groups having 1 to 12 carbon atoms, m, n is 0-4 respectively, and p is an integer of 1 or more.)

  Specific examples of the bisphenol represented by the formula (1) include 4,4 ′-(pentane-2,2-diyl) diphenol, 4,4 ′-(pentane-3,3-diyl) diphenol, 4,4 ′-(butane-2,2-diyl) diphenol, 1,1 ′-(cyclohexanediyl) diphenol, 2-cyclohexyl-1,4-bis (4-hydroxyphenyl) benzene, 2,3- Biscyclohexyl-1,4-bis (4-hydroxyphenyl) benzene, 1,1′-bis (4-hydroxy-3-methylphenyl) cyclohexane, 2,2′-bis (4-hydroxy-3-methylphenyl) Examples include propane.

Further, in the present specification, a polymer alloy containing the polycarbonate resin exemplified above is also treated as a polycarbonate resin. Examples of such a polycarbonate resin as a polymer alloy include a polymer alloy made of a polycarbonate resin and an acrylonitrile-butadiene-styrene copolymer (ABS resin).
Among the polycarbonate resins as described above, a bisphenol type polycarbonate resin having a bisphenol skeleton is preferable. Thereby, the transparency and impact resistance of the substrate 2 can be further increased.

In addition to the thermoplastic resin described above, the constituent material of the base material 2 may be, for example, an antioxidant, a colorant, a filler, a plastic, for example, in order to improve weather resistance, visibility, and adhesion with the coat layer 3. Agents, ultraviolet absorbers, heat ray absorbers, and the like.
As the base material 2, a single layer structure obtained from a material containing a thermoplastic resin or a multilayer structure obtained by laminating two or more single layer films obtained from a material containing a thermoplastic resin may be used. it can. In addition, when it is a multilayer structure, it may be comprised with the same material and may be comprised with a different material. For example, as the base material 2 having a multilayer structure, a first weather-resistant layer (scratch-resistant layer) excellent in weather resistance, a functional layer, and a second weather-resistant layer (scratch-resistant layer) excellent in weather resistance are in this order. And those laminated with When the base material 2 has a multilayer structure in which the first weather resistant layer, the functional layer, and the second weather resistant layer as described above are laminated in this order, the first weather resistant layer and the second weather resistant layer are respectively For example, what was obtained using the material containing a polycarbonate-type resin, a ultraviolet absorber, and a plasticizer is mentioned. Examples of the functional layer include those obtained using a material containing a polycarbonate-based resin, a heat ray absorbent, and a plasticizer.
Further, for the purpose of improving the adhesion to the coating layer 3 on the upper surface 21 of the base material 2, surface roughening treatment such as sandblasting or solvent treatment, corona discharge treatment, chromic acid treatment, flame treatment, etc. Surface oxidation treatment such as hot air treatment, ozone / ultraviolet irradiation treatment, and electron beam irradiation treatment may be performed.
The thickness of the substrate 2 is preferably 0.1 mm or more and 10 mm or less, more preferably 1 mm or more and 5 mm or less, and further preferably 1.5 mm or more and 2 mm or less. When the thickness of the substrate 2 is less than the lower limit, depending on the material constituting the substrate 2, the mechanical strength of the folded plate 1 is lowered, and the thickness of the substrate 2 is less than the upper limit. If it exceeds, it may be difficult to bend the flat plate to form the folded plate 1.

[Coat layer]
As described above, the coat layer 3 is composed of a cured product obtained by curing a resin composition containing a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.
As described above, the coat layer 3 is located on the outdoor side and protects the base material 2, that is, protects the base material 2 from deterioration such as corrosion (corruption) and corrosion resistance caused by rainwater, sunlight, etc. It functions as a protective layer that maintains the properties (eg, transparency) of the substrate 2. It also has an antifouling function that makes it easier to remove dirt.
This coat layer 3 is obtained by applying the resin composition to the upper surface 21 of the substrate 2 and curing (solidifying) it. The “cured (solidified)” means not only a state of being completely cured (solidified) but also an arbitrary semi-cured state between cured and uncured.
In the present invention, the resin composition contains a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.
Since the coat layer 3 obtained from such a resin composition has a relatively high hardness, the outer surface of the folded plate 1 (the outer surface of the coat layer 3) 31 is scratched by an impact from the outside. Can be reduced, that is, it has excellent scratch resistance against impacts from outside.
Moreover, the coat layer 3 obtained from the resin composition also has moderate flexibility (flexibility) while having a relatively high hardness as described above. The “flexibility” refers to ease of bending, and refers to characteristics excellent in flexibility and elongation.

Here, when forming a folded plate using a flat plate, as described above, the peak portion 11 is formed by bending the flat plate into a mountain fold. In the formation of the mountain portion 11, in the mountain bending portion 16 provided in the mountain portion 11, the coat layer 3 positioned on the outer side has the mountain bending portion 16 as a boundary than the base material 2 positioned on the inner side. A large tensile stress is applied. For this reason, the conventional folded plate does not have a configuration in which the coat layer can sufficiently withstand the tensile stress, and as a result, cracks have occurred in the coat layer at the peaks (mountain bent portions).
On the other hand, in the folded plate 1, the coat layer 3 is obtained by a resin composition containing the aforementioned material, that is, a resin composition containing not only a silicon-modified (meth) acrylic resin but also urethane (meth) acrylate. Therefore, the coat layer 3 has appropriate flexibility (flexibility). As described above, when the coat layer 3 has an appropriate flexibility, even if the tensile stress is applied to the coat layer 3 in the folded plate 1, the coat layer 3 can be appropriately bent. Therefore, even if the flat plate is bent, that is, as the folded plate 1 including the mountain bent portion 16 in the mountain portion 11, the occurrence of cracks in the mountain bent portion 16 is prevented. In particular, even if the mountain bent portion 16 has an angle θ of 126 ° or 119 °, the occurrence of cracks in the mountain bent portion 16 is reliably prevented.

Hereinafter, the material which comprises the resin composition containing a silicone modified (meth) acrylic resin and urethane (meth) acrylate is demonstrated sequentially.
(Silicon-modified (meth) acrylic resin)
The silicon-modified (meth) acrylic resin has a main chain in which a structural unit derived from a (meth) acrylic monomer having a (meth) acryloyl group is repeated, and a structural unit linked to this main chain and having a siloxane bond is repeated. And a polymer (prepolymer) provided with a repetitive body.
This silicon-modified (meth) acrylic resin provides the coating layer 3 with transparency by providing the main chain, and provides the coating layer 3 with scratch resistance and antifouling properties by providing the repeating body. . The reason why the scratch resistance of the coat layer 3 is improved is that the surface hardness of the coat layer 3 is increased by providing the repetitive body.
As described above, the silicon-modified (meth) acrylic resin has a main chain, thereby contributing to the improvement of the transparency of the coat layer 3 and the flexibility (softness) of the coat layer 3.
Specific examples of the main chain include those composed of repeating structural units derived from a monomer having at least one (meth) acryloyl group of the following formulas (4) and (5).

(In Formula (4), n represents an integer of 1 or more, R 1 independently represents a hydrocarbon group, an organic group, or a hydrogen atom, and R 0 independently represents a hydrocarbon group or a hydrogen atom. .)

(In formula (5), m represents an integer of 1 or more, R2 independently represents a hydrocarbon group, an organic group, or a hydrogen atom, and R0 independently represents a hydrocarbon group or a hydrogen atom. .)

Moreover, it is preferable that the terminal or side chain of the main chain has a hydroxyl group (—OH). That is, in the case of the formula (4) or the formula (5), it is preferable that R1 or R2 is a hydrogen atom. Thereby, when a polycarbonate is used as the base material 2, the adhesiveness with the polycarbonate can be improved. For this reason, the adhesiveness with respect to the base material 2 of the coating layer 3 increases, and it can prevent that the coating layer 3 peels from the base material 2 unintentionally. Moreover, when using the hardening | curing agent provided with an isocyanate group as a hardening | curing agent mentioned later, the said hydroxyl group reacts with the isocyanate group with which a hardening | curing agent is provided, and forms the crosslinked structure by a urethane bond. For this reason, hardening of a resin composition can be accelerated | stimulated and it can contribute to formation of the coating layer 3. FIG.
A repeating body having a structure in which a unit having a siloxane bond is repeated is bonded to at least one terminal or side chain of the main chain having such a structure.
Since the siloxane bond has a high bonding force, the coating layer 3 having better heat resistance and weather resistance can be obtained by providing a repeating body having a siloxane structure. Moreover, since the hard coating layer 3 can be obtained because the bonding strength of the siloxane bond is high, the scratch resistance against impact from the outside of the folded plate 1 can be further increased.
Moreover, when this repeating body (siloxane bond) is exposed from the outer surface 31, the surface state of the coating layer 3 will be in the state excellent in hydrophilicity. For this reason, rainwater that has poured onto the folded plate 1 easily spreads on the outer surface 31, so that the rainwater enters between the coat layer 3 and dirt or dust adhering to the outer surface 31. As a result, dirt, dust and the like can be lifted from the coat layer 3 and washed out of the folded plate 1 together with rainwater. That is, the self-cleaning performance is exhibited by the coat layer 3. Thus, by providing a repeating body, since the obtained coat layer 3 can exhibit self-cleaning performance, the antifouling property of the coat layer 3 is further improved.
In addition, it is thought that after the folded plate 1 is constructed, the outer surface 31 becomes hydrophilic due to this repeated body after being exposed to sunlight for a long time. This is because when the folded plate 1 is irradiated with ultraviolet rays (sunlight) for a long time, the bond between the main chain and the repetitive body, the main chain itself, and the like are cut, and the siloxane bond provided in the repetitive body is applied to the outer surface 31 It is thought to be due to exposure.
Specific examples of the repeated product include those composed of repeating structural units having at least one siloxane bond represented by the following formulas (2) and (3).

(In formula (2), X ₁ represents a hydrocarbon group or a hydroxyl group.)

(In formula (3), X ₂ represents a hydrocarbon group or a hydroxyl group, and X ₃ represents a divalent group in which hydrogen is removed from the hydrocarbon group or hydroxyl group.)

Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and an isopropyl group, a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, a phenyl group, a naphthyl group, and 2 -An aryl group such as a methylphenyl group, an aralkyl group such as a benzyl group, a diphenylmethyl group, and a naphthylmethyl group, a phenyl group, and a biphenyl group.
Specific examples of such a repeating product include those having polyorganosiloxane and those having silsesquioxane. The silsesquioxane may have any structure such as a random structure, a cage structure, or a ladder structure (ladder structure).
In addition, a hydroxyl group (—OH) is exposed at the terminal or side chain of the repeat. Thereby, the adhesiveness with respect to the base material 2 of the coating layer 3 can be increased more, and it can prevent more suitably that the coating layer 3 peels from the base material 2 unwillingly. Moreover, when using the hardening | curing agent provided with an isocyanate group as a hardening | curing agent mentioned later, the said hydroxyl group reacts with the isocyanate group with which a hardening | curing agent is provided, and forms the crosslinked structure by a urethane bond. For this reason, hardening of a resin composition can be accelerated | stimulated and it can contribute to formation of the coating layer 3. FIG.
Moreover, it is preferable that the unsaturated double bond is introduce | transduced into the terminal or side chain of a repeating body. Thereby, it couple | bonds with the (meth) acryloyl group with which urethane (meth) acrylate is equipped, and the network of a silicone modified (meth) acrylic resin and urethane (meth) acrylate can be formed. Therefore, the obtained coating layer 3 can be obtained by more uniformly dispersing the silicon-modified (meth) acrylic resin and the urethane (meth) acrylate. As a result, the coating layer 3 has the above-described characteristics as a whole. More uniformly.
Further, the content of the silicon-modified (meth) acrylic resin in the solid content contained in the resin composition is not particularly limited, but is preferably 15 parts by mass or more and 70 parts by mass or less, and 20 parts by mass or more and 60 parts by mass. The following is more preferable. When the content is less than the lower limit, the hardness of the coat layer 3 obtained from the resin composition may be reduced depending on materials other than the silicon-modified (meth) acrylic resin constituting the resin composition. . Moreover, when content rate exceeds the said upper limit, content of materials other than silicon modified (meth) acrylic resin in a resin composition will reduce relatively, and the bending of the coating layer 3 obtained by the resin composition will be carried out. May be reduced.

(Urethane (meth) acrylate)
Urethane (meth) acrylate is a compound having a main chain having a urethane bond (-OCONH-) and a (meth) acryloyl group linked to the main chain. Urethane (meth) acrylate is a monomer or oligomer.
Since this urethane (meth) acrylate has a urethane bond, it is a compound excellent in flexibility. For this reason, further flexibility (softness | flexibility) can be provided to the coating layer 3 by including urethane (meth) acrylate. Therefore, the flexibility of the coat layer 3 can be increased as described above by including not only silicon-modified (meth) acrylate but also urethane (meth) acrylate in the resin composition. Therefore, even if the folded plate 1 provided with the peak portion 11 is formed using the flat plate obtained from this resin composition, cracks are generated in the mountain bent portion 16 included in the peak portion 11 of the folded plate 1. Can be reliably prevented.

In the urethane (meth) acrylate, the number of urethane bonds in one molecule is preferably 2 or more. Thereby, the flexibility of the coat layer 3 can be further increased.
In the urethane (meth) acrylate, the number of (meth) acryloyl groups in one molecule is preferably 2 or more, and more preferably 2. That is, the urethane (meth) acrylate is more preferably a bifunctional urethane (meth) acrylate. When the number of acryloyl groups is 2 or more, when the silicon (meth) acrylic resin has an unsaturated double bond or the like, it can be bonded to the silicon (meth) acrylic resin to form a network. Curing of the coat layer 3 can be promoted. Further, when the number of (meth) acryloyl groups is 2 or more, the hardness of the coat layer 3 can be increased to some extent by increasing the crosslinking density of the coat layer 3. For this reason, the characteristics such as scratch resistance and solvent resistance of the coat layer 3 can be improved.
In particular, since the bifunctional urethane (meth) acrylate is linear, by including the bifunctional urethane (meth) acrylate, the flexibility of the coat layer 3 obtained using the resin composition is further increased. Therefore, it is possible to more reliably prevent cracks from occurring in the mountain bent portion 16.
Moreover, when it is bifunctional urethane (meth) acrylate, it is preferable that the two (meth) acryloyl groups are each couple | bonded with the terminal of a urethane bond. Thereby, since urethane (meth) acrylate makes longer chain shape, the improvement of the flexibility of coat layer 3 can further be aimed at.
Such a urethane (meth) acrylate can be obtained as a reaction product of an isocyanate compound obtained by reacting a polyol and a polyisocyanate and a (meth) acrylate monomer having a hydroxyl group.
Examples of the polyol include polyether polyol, polyester polyol, and polycarbonate diol.
Examples of the polyether polyol include those containing polyethylene oxide, polypropylene oxide, ethylene oxide-propylene oxide random copolymer in the structure.
The polyester polyol can be obtained, for example, by subjecting a diol and a dicarboxylic acid or dicarboxylic acid chloride to a polycondensation reaction, or esterifying the diol or a dicarboxylic acid to cause an ester exchange reaction. Dicarboxylic acids include adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid, terephthalic acid, isophthalic acid, phthalic acid, etc., and diols include ethylene glycol, 1,4-butanediol, 1 , 6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, tetrapropylene glycol and the like are used.
The polycarbonate diol uses, for example, a method of manufacturing using a diol and a carbonate ester compound as raw materials, a method of manufacturing using an alkylene carbonate and a diol as raw materials, a method of manufacturing using a dialkyl carbonate or diaryl carbonate and a diol, and the like. I can do it. Examples of the diol include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 2 -Ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, polyoxyethylene glycol, etc. are used, and one or more May be used in combination.
As the polyisocyanate, linear or cyclic aliphatic polyisocyanate or aromatic polyisocyanate is used. Examples of the linear or cyclic aliphatic polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate. Examples of the aromatic polyisocyanate include toluene diisocyanate and tolylene diisocyanate.
Examples of the acrylate monomer having a hydroxyl group include pentaerythritol triacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, and polyethylene glycol monoacrylate.

The weight average molecular weight of such urethane (meth) acrylate is preferably 100 or more and 5000 or less, and more preferably 300 or more and 3000 or less. As a result, the balance between the flexibility and hardness of the resulting coating layer 3 is good, and the folded plate 1 is more reliably prevented from cracking in the mountain fold 16 and is unwilling. It is difficult to break.
The weight average molecular weight of urethane (meth) acrylate can be measured by GPC (gel permeation chromatography), for example.
Moreover, the content rate of the urethane (meth) acrylate in the solid content contained in the resin composition is not particularly limited, but is preferably 3 parts by mass or more and 50 parts by mass or less, and 5 parts by mass or more and 45 parts by mass or less. More preferably. When the content is less than the lower limit, depending on the material other than the urethane (meth) acrylate constituting the resin composition, the flexibility of the obtained coating layer 3 becomes poor. Moreover, when content rate exceeds the said upper limit, content of materials other than urethane (meth) acrylate in a resin composition will reduce relatively, and there exists a possibility that the abrasion resistance of the obtained coating layer 3 may fall. There is.
In addition, when mixing such urethane (meth) acrylate as described above into the resin composition, a reactive diluent may be used. The reactive diluent preferably has a function of lowering the viscosity and uniformly dispersing it in the resin composition without impairing the performance of the urethane (meth) acrylate. Specifically, Acrylic acid esters are preferably used.
The reactive diluent is preferably 10 parts by mass or more and 40 parts by mass or less, and more preferably 15 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the urethane (meth) acrylate. Thereby, urethane (meth) acrylate can be uniformly mixed in the resin composition.
The resin composition containing the silicon (meth) acrylic resin and the urethane (meth) acrylate as described above further includes at least one of a curing agent, a hydrophilizing additive, an ultraviolet absorber, a photopolymerization initiator, and the like. It is preferable to include.

Hereinafter, the curing agent, the hydrophilizing additive, the ultraviolet absorber, the photopolymerization initiator, and the like will be described.
(Curing agent)
The curing agent is used as a crosslinking agent that bonds (crosslinks) the silicon-modified (meth) acrylates.
Although it does not specifically limit as this hardening | curing agent, For example, the polyisocyanate etc. which have 2 or more of isocyanate groups are mentioned, Especially it is more preferable that it is bifunctional isocyanate which has 2 isocyanate groups.
By using polyisocyanate as a curing agent, the hydroxyl group provided in the silicon-modified (meth) acrylate reacts with the isocyanate group provided in the polyisocyanate to form a crosslinked structure by urethane bonds. For this reason, hardening of a resin composition can be accelerated | stimulated and it can contribute to formation of the coating layer 3. FIG.
In particular, since the bifunctional isocyanate is linear, the use of the bifunctional isocyanate as a curing agent imparts flexibility (flexibility) to the resulting coat layer 3.
Moreover, the content rate of the hardening | curing agent in solid content contained in a resin composition is although it does not specifically limit, It is preferable that it is 5 to 50 mass parts, and it is 10 to 45 mass parts. More preferred. There exists a possibility that the hardness of the obtained coating layer 3 may fall that the content rate of a hardening | curing agent is less than the said lower limit. Further, if the content of the curing agent exceeds the upper limit, the content of materials other than the curing agent in the resin composition is relatively reduced, depending on the type of material contained in the resin composition, etc. There is a possibility that the flexibility of the coat layer 3 obtained by the resin composition is lowered.

(Hydrophilic additive)
Since the hydrophilizing additive is excellent in hydrophilicity, the outer surface 31 of the resulting coating layer 3 can be hydrophilized in a shorter period of time by including this, and thus the folded plate 1 is applied. Thus, the self-cleaning performance of the coat layer 3 after a short period of time can be improved.
Such a hydrophilizing additive may be any as long as it has a function of hydrophilizing the outer surface 31, but a compound having a siloxane bond is particularly preferable. Since the compound having a siloxane bond is particularly excellent in self-cleaning performance, the antifouling property of the coat layer 3 can be further improved by including the compound.
Further, the hydrophilic additive is preferably a compound containing a fluorine-containing part having fluorine. Fluorine has a small surface free energy and tends to gather on the outer surface 31 side of the resulting coat layer 3. For this reason, by using the compound containing a fluorine-containing part, the surface state of the coat layer 3 immediately after construction of the folded plate 1 becomes a state in which fluorine included in the compound containing the fluorine-containing part is exposed from the outer surface 31.
For these reasons, it is particularly preferable to use a fluorine-containing polysiloxane containing a siloxane bond and a fluorine-containing part as the hydrophilizing additive. By using the resin composition containing fluorine-containing polysiloxane, the folded plate 1 can exhibit better antifouling properties after a short period of time after construction. This is because the fluorine-containing part exposed from the outer surface 31 immediately after the construction hydrolyzes and undergoes a condensation reaction due to the influence of water (rainwater) for a while after the folded plate 1 is constructed. The state is considered to be because the siloxane bond is exposed on the outer surface 31 and the state is excellent in hydrophilicity. In addition, it is thought that the hydrolysis / condensation reaction of the fluorine-containing part is carried out in a relatively short period of time after construction. For this reason, it will be in the state excellent in self-cleaning property by showing hydrophilicity after construction and a short period of time. For this reason, by using fluorine-containing polysiloxane as a hydrophilizing additive, the coat layer 3 can exhibit better antifouling properties after a short period after construction.
Further, the content of the hydrophilizing additive in the solid content contained in the resin composition is not particularly limited, but is preferably 0.01 parts by mass or more and 10 parts by mass or less, and 0.1 parts by mass or more and 5 parts by mass or less. More preferably, it is less than or equal to parts. If the content of the hydrophilizing additive is less than the lower limit, depending on the type of the hydrophilizing additive, etc., there is a possibility that the self-cleaning performance of the coat layer 3 after a short period after construction may not be sufficiently exhibited. is there. In addition, even if the content of the hydrophilizing additive exceeds the above upper limit, no further improvement in self-cleaning performance is seen, and depending on the type of material contained in the resin composition, transparency may be impaired There is sex.

(UV absorber)
Specific examples of the ultraviolet absorber include triazine-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers, and one or two of them can be used in combination. Among these, a triazine-based ultraviolet absorber is preferably used, and among the triazine-based ultraviolet absorbers, a hydroxyphenyl triazine-based ultraviolet absorber is more preferable. Thereby, deterioration by the ultraviolet-ray of the coating layer 3 can be prevented or suppressed more reliably, and the weather resistance of the folded plate 1 can be increased more.
Moreover, the content rate of the ultraviolet absorber in the solid content contained in the resin composition is not particularly limited, but is preferably 0.1 parts by mass or more and 20 parts by mass or less, and preferably 1 part by mass or more and 10 parts by mass or less. More preferably. There exists a possibility that the weather resistance of the coating layer 3 may fall that the content rate of a ultraviolet absorber is less than the said lower limit depending on the kind etc. of a ultraviolet absorber. Further, even when the content of the ultraviolet absorber exceeds the upper limit, no further improvement in weather resistance is observed, and the base material 2 of the coat layer 3 depends on the type of material contained in the resin composition. There is a possibility that the adhesiveness to the film and the transparency of the coat layer 3 may be impaired.

(Photopolymerization initiator)
Specific examples of the photopolymerization initiator include benzoin or benzoin alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, and benzoin isopropyl ether, aromatic ketones such as benzophenone and benzoylbenzoic acid, and alpha such as benzyl. Benzyl ketals such as dicarbonyls, benzyl dimethyl ketal, benzyl diethyl ketal, acetophenone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2 -Hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one, 2-methyl-1- [4 -(Methyl E) acetophenones such as phenyl] -2-morpholinopropanone-1, anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 2,4-dimethylthioxanthone, 2-isopropylthioxanthone, Thioxanthones such as 2,4-diisopropylthioxanthone, Phosphine oxides such as bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 1-phenyl-1,2-propanedione-2- (o-) Alpha-acyl oximes such as ethoxycarbonyl) oxime, amines such as ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, and the like can be used. Among these, 1- (4-dodecyl) is particularly preferable. Phenyl 2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propan-1-one, 1- (4-isopropylphenyl)- Acetophenones such as 2-hydroxy-2-methyl-propan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 are preferred.
Further, the content of the polymerization initiator in the solid content contained in the resin composition is not particularly limited, but is preferably 0.5 parts by mass or more and 15 parts by mass or less, and preferably 1 part by mass or more and 10 parts by mass or less. More preferably. When the content of the polymerization initiator is less than the lower limit, depending on the type of the polymerization initiator and the like, but it is difficult to sufficiently cure the resin composition applied on the upper surface 21 of the substrate 2 Further, even when the content of the polymerization initiator exceeds the upper limit, no further improvement is observed.

(Other materials)
The resin composition may contain other materials other than the materials described above.
Other materials include, for example, resin materials other than the above-described silicon-modified (meth) acrylic resin, colorants, sensitizers, stabilizers, surfactants, antioxidants, anti-reduction agents, antistatic agents, surface conditioning. Agents and solvents.
Examples of the solvent include aliphatic hydrocarbons such as hexane, heptane and cyclohexane, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propanol and butanol, ketones such as methyl ethyl ketone, 2-pentanone and isophorone, Examples thereof include esters such as ethyl acetate, butyl acetate and methoxypropyl acetate, cellosolve solvents such as ethyl cellosolve, and glycol solvents such as methoxypropanol, ethoxypropanol and methoxybutanol. These can be used alone or in combination.

The resin composition used for forming the coating layer 3 as described above may be in a liquid or solid form at room temperature.
Moreover, the resin composition as described above includes a silicon-modified (meth) acrylic resin, a bifunctional urethane (meth) acrylate, a bifunctional isocyanate as a curing agent, and a fluorine-containing polysiloxane as a hydrophilizing additive. It is particularly preferable that By including bifunctional urethane (meth) acrylate and bifunctional isocyanate, the flexibility of the obtained coating layer 3 can be made more favorable. Therefore, in the folded plate 1 obtained by bending the flat plate, the occurrence of cracks in the peak portion 11 (mountain bent portion 16) is more reliably prevented.
Further, in the coat layer 3 obtained from the resin composition containing such a material, the fluorine included in the fluorine-containing polysiloxane is exposed to the outer surface 31 immediately after formation.
Thereafter, after the folded plate 1 is applied and after a short period of time, the siloxane bond provided in the fluorine-containing polysiloxane is exposed to the outer surface 31, and as a result, the outer surface 31 exhibits hydrophilicity.
And after constructing the folded plate 1, since the siloxane bond with which the silicon modified (meth) acrylic resin is provided is exposed, the hydrophilicity of the outer surface 31 is maintained.
For this reason, the coating layer 3 obtained from the resin composition containing the above material has a surface state in which it is easy to efficiently wipe off dirt immediately after construction, and excellent self-cleaning properties over a long period after construction. It becomes a surface state capable of exhibiting. For this reason, the coating layer 3 exhibits particularly excellent antifouling properties over a long period of time by using a resin composition containing the above materials.

In the folded plate 1 that exhibits such excellent antifouling properties, the water contact angle of the outer surface 31 immediately after its formation is preferably 80 ° or more.
Further, the folded plate 1 has an initial value (the outer surface 31 measured immediately after the formation of the coat layer 3) when the water contact angle of the outer surface 31 after the coating layer 3 is irradiated with sunlight for 7 days (short term). It is preferably a value that is 10 ° or more lower than the water contact angle. Further, in the folded plate 1, the water contact angle of the outer surface 31 after irradiating the coat layer 3 with sunlight for 180 days (long term) is preferably 60 ° or less, and preferably 10 to 50 °. More preferred.
If the water contact angle of the outer surface 31 is as described above, the outer surface 31 immediately after construction exhibits water repellency, and the outer surface 31 exhibits hydrophilicity for a long period after construction. Can exhibit a particularly excellent antifouling property over a long period of time.
Here, the water contact angle is an index of the wettability of the surface. The smaller the value, the easier the surface gets wet with water, and the higher the value, the higher the water repellent property.
The water contact angle in this specification can be determined using the θ / 2 method. The θ / 2 method is a method for obtaining the contact angle from the angle of the straight line connecting the left and right end points and the vertex of the droplet with respect to the solid surface. Further, in the θ / 2 method, using a DROPMASTER-300 manufactured by Kyowa Interface Science, a certain amount of distilled water is dropped from the syringe onto the outer surface 31 of the coat layer 3 and the outside of the straight line connecting the left and right end points and the vertex of the droplet. The contact angle can be determined from the angle with respect to the surface 31.
Moreover, the said construction should just be the coating layer 3 facing the sun, and the angle of installation etc. are not specifically limited.
The thickness of the coat layer 3 formed of such a resin composition is preferably 3 μm or more and 30 μm or less, more preferably 4 μm or more and 20 μm or less, and even more preferably 5 μm or more and 18 μm or less. . If the thickness of the coat layer 3 is less than the lower limit, depending on the amount of the ultraviolet absorber contained in the resin composition, the weather resistance of the folded plate 1 may be lowered. On the other hand, when the thickness of the coat layer 3 exceeds the upper limit, when the folded plate 1 is formed by bending a flat plate, the processing conditions (for example, the bending angle or There is a possibility that the temperature at the time of bending will be limited.

Next, the manufacturing method of the folded plate 1 is demonstrated.
FIG. 2 is a view showing a part of a molding apparatus used in the method of manufacturing the folded plate shown in FIG. 3-6 is a figure for demonstrating the manufacturing method of the folded plate shown in FIG. 1, and is a cross-sectional view which shows schematically the method of manufacturing a folded plate by bending a flat plate. FIG. 2 shows a part of the forming apparatus 9 for forming the folded plate 1.
<Folded plate manufacturing method>
The folded plate 1 having the above-described configuration can be obtained by, for example, the following manufacturing method.
Specifically, the manufacturing method of the folded plate 1 includes a coating layer forming step in which a resin composition is applied on the upper surface 21 of the substrate 2 to form a coating layer, and the coating layer is cured to form the flat plate 4. A flat plate forming step and a folded plate forming step of forming the folded plate 1 by bending the flat plate 4.

Hereinafter, each step will be described.
In manufacturing the folded plate 1, the resin composition is prepared in advance by mixing the materials constituting the resin composition described above. Further, the substrate 2 may be subjected to the surface treatment as described above, if necessary.
(Coating layer forming process)
First, after applying a resin composition on the upper surface 21 of the base material 2 and forming an application layer on the base material 2, the application layer is cured. Thereby, the coat layer 3 which is the hardened | cured material of a resin composition can be formed on the base material 2. FIG.
The method for applying the resin composition to the upper surface 21 is not particularly limited, but known methods such as a roll coating method, a flow coating method, a spray coating method, a curtain coating method, a dip coating method, a die coating method, a bar coating method, and the like. The bar coating method is particularly preferable. Thereby, the resin composition can be applied to the upper surface 21 with a more uniform thickness. In addition, the bar coating method is more effective in forming the coating layer more quickly because the resin composition can be easily applied over the entire upper surface 21 as compared with other methods.

(Flat plate forming process)
Thereafter, the coated resin composition (coating layer) is cured to form a coat layer 3 that is a cured product of the resin composition.
The coating layer is preferably cured by a method of irradiating with ultraviolet rays. For example, when a solvent is contained in the resin composition, the temperature of the base material 2 and the temperature of the atmosphere surrounding the base material 2 and the coating layer are increased to sufficiently dry the solvent contained in the coating layer. It is preferable to cure the coating layer later.
The method for drying the coating layer is not particularly limited, and examples thereof include a method of heating using an oven or the like. Although it does not specifically limit as heating conditions, It is preferable that heating temperature is 40 to 150 degreeC, and it is preferable that heating time is 10 second or more and 20 minutes or less. Thereby, it can prevent more reliably that breakage, such as a crack, arises in the coat layer 3 finally obtained. Moreover, the coating layer can be efficiently dried.
Examples of the method of irradiating with ultraviolet rays include a method using a general electroded or electrodeless high pressure mercury lamp or metal halide lamp. Although the irradiation time which irradiates with an ultraviolet-ray is not specifically limited, It is preferable that they are 10 second or more and 20 minutes or less. Within the irradiation time, the adhesiveness of the coating layer can be deactivated efficiently and more reliably, and the coating layer can be cured more quickly and more reliably.
Depending on the material contained in the resin composition, the coating layer may be cured by irradiating the coating layer with energy rays such as light rays other than ultraviolet rays and electron beams.
When irradiating an application layer with an electron beam, for example, a low voltage electron beam irradiation apparatus of about 100 KeV can also be used. In addition, when hardening an application layer with an electron beam, the resin composition does not need to contain the photoinitiator mentioned above.
Further, if necessary, the coating layer that has been irradiated with ultraviolet rays (electron beam) may be heated and cured. The method of curing the coating layer by heating is not particularly limited, and examples thereof include a method of heating using an oven or the like. In addition, you may harden | cure, for example by exposing a coating layer to the environment of normal temperature (for example, about 25 degreeC), without heating a coating layer.
The curing conditions for curing the coating layer by heating or exposure to a room temperature environment are not particularly limited, but the processing temperature is preferably 25 ° C. or higher and 100 ° C. or lower, and the processing time is 1 hour or longer and 240 ° C. Preferably it is less than or equal to hours. Thereby, it can prevent more reliably that breakage, such as a crack, arises in the coat layer 3 finally obtained. In addition, the coating layer can be efficiently cured.
The flat plate 4 can be obtained through such steps.

(Folded plate forming process)
Next, the folded plate 1 is formed by bending the flat plate 4.
The molding apparatus 9 shown in FIG. 2 includes a concave member 91 having a concave portion 911 and a pressing member 93 for pressing the flat plate 4 into the concave portion 911.
The concave member 91 has a bottomed rectangular tube shape, and includes a rectangular bottom portion 913 and an outer wall portion 914 having a rectangular frame shape standing from an outer edge portion of the bottom portion 913. A concave portion 911 is formed by the bottom portion 913 and the outer wall portion 914, and the concave portion 911 has a length along the y-axis direction longer than a length along the x-axis direction. Further, the flat plate 4 is placed on the concave portion 911 with its longitudinal direction along the y-axis direction, but the y-axis of the concave portion 911 is longer than the length of the flat plate 4 to be placed in the short direction (x-axis direction). The length along the direction is longer.
The width (length in the x-axis direction) of the inner wall surface of the outer wall portion 914 is substantially constant along the z-axis direction. The opening 912 of the recess 911 is formed by the inner edge 915 a of the upper surface 915 of the outer wall 914. Further, the upper surface 915 of the outer wall portion 914 is substantially flat, so that when the flat plate 4 is placed on the upper surface 915, the flat plate 4 is supported by the upper surface 915.
The pressing member 93 has a quadrangular prism shape extending in the y-axis direction. Further, the pressing member 93 has a shape in which the outer dimension of the distal end portion 931 is smaller than the inner dimension of the concave portion 911, whereby the distal end portion 931 of the pressing member 93 can be inserted into the concave portion 911. Therefore, the mountain fold 16 and the valley fold 17 can be formed by the pressing member 93 by pressing the pressing member 93 into the recess 911 while the flat plate 4 is placed on the upper surface 915 of the concave member 91.

Using such a forming apparatus 9, the folded plate 1 is formed as follows.
<1> First, as shown in FIG. 3A, the flat plate 4 is arranged on the concave member 91 so as to close the opening of the concave portion 911. At this time, the flat plate 4 is disposed so that the coat layer 3 faces the concave portion 911 and the base material 2 faces the pressing member 93.
<2> Next, the pressing member 93 is pressed toward the bottom 913 of the recess 911. Thereby, as shown in FIG.3 (b), the part currently mounted on the recessed part 911 of the flat plate 4 is pushed in in the recessed part 911. FIG. Thereby, the flat plate 4 is bent into a mountain fold.
Note that the pressing force of the pressing member 93 and the depth at which the flat plate 4 is pushed are appropriately set according to the angle (inner angle) θ of the mountain bent portion 16 and the valley bent portion 17 of the folded plate 1 to be formed.
Next, after pressing for a predetermined time, the pressing of the pressing member 93 is released. Thereby, as shown to Fig.4 (a), the one mountain bending part 16 is formed.
Here, the processing temperature at the time of bending the flat plate 4 is not particularly limited, but the flat plate 4 can be bent at, for example, about 25 ° C. or more and 50 ° C. or less. As described above, the flat plate 4 of the present embodiment can be bent easily even at the above temperature. Further, the flat plate 4 of the present embodiment is advantageous in terms of cost because it can be bent while suppressing generation of cracks without increasing the temperature more than necessary. From such a viewpoint, it is particularly preferable that bending can be performed at room temperature (about 25 ° C.). However, heating at 50 ° C. or less may be performed from the viewpoint of cost, thickness, and the like, and the bending process becomes easier to perform by heating.
<3> Next, as shown in FIG. 5, a second mountain bent portion is formed as shown in FIG. 5 at a predetermined interval from the mountain bent portion 16 formed as shown in FIG. 16 is formed. Thereby, the one peak part 11 can be obtained.
<4> Next, as shown in FIG. 6A, the flat plate 4 is turned upside down so that the base plate 2 faces the concave portion 911 and the coating layer 3 faces the pressing member 93. 91. At this time, the flat plate 4 is arranged on the concave member 91 at a predetermined interval from the peak portion 11 formed in <3>.
Next, as shown in FIG. 6B, the single bent portion 17 is formed by pressing the pressing member 93 toward the bottom 913 of the recess 911 in the same manner as in the above <2>. Next, a second valley bent portion 17 is formed in the same manner as in the above <3>. Thereby, one trough part 12 can be obtained.
By repeating such an operation, the bellows-like folded plate 1 having a plurality of valleys 12 and peaks 11 can be obtained.
In the present embodiment, the folded plate 1 is formed using the concave member 91 and the pressing member 93 as described above, but the flat plate 4 is formed at the above-described processing temperature even if the method is different from this method. By doing so, the folded plate 1 can be formed more easily, and cracking of the folded plate 1 can be prevented more reliably.

As mentioned above, although the folded plate, flat plate, and resin composition of this invention were demonstrated about embodiment of illustration, this invention is not limited to this, Each part which comprises a folded plate, a flat plate, and a resin composition, and each The material can be replaced with any configuration that can perform a similar function. Arbitrary components and materials may be added.
Moreover, the folded plate of this invention is not limited to the use as a roofing material or outer wall material of a building as mentioned above.
Further, the folded plate has a configuration in which the coating layer is disposed on the upper surface of the base material in the above embodiment, but the configuration of the folded plate is not limited thereto, and for example, both the upper surface and the back surface of the base material are coated. A layer may be disposed.

Hereinafter, specific examples of the present invention will be described. Note that the present invention is not limited to this.
1. Production of folded plates (Example 1)
1-1. Formation of a coating layer First, in forming a coating layer, a resin composition is adjusted.
Specifically, silicon-modified (meth) acrylic resin (trade name “MFG Coat SD-101”, manufactured by DIC Corporation): 38 parts by weight, a mixture of bifunctional urethane acrylate and acrylic ester (trade name “UA” -122P ", manufactured by Shin-Nakamura Chemical Co., Ltd .: 27.2 parts by weight of a bifunctional urethane acrylate, 6.8 parts by weight of an acrylic ester): 34 parts by weight and a bifunctional isocyanate (trade name" Bernock DN- "as a curing agent) 955S "(manufactured by DIC Corporation): 17 parts by weight, fluorine-containing polysiloxane as a hydrophilizing additive (trade name" Zeffle GH-701 ", manufactured by Daikin Industries, Ltd.): 1 part by weight, and hydroxyphenyltriazine-based ultraviolet rays Absorbent (trade name “Tinuvin 400”, manufactured by BASF): 5 parts by weight and 1-hydroxy as a photopolymerization initiator Phenyl ketone: were mixed with 5 parts by weight, the mixture is non-volatile content to obtain a resin composition by diluting with butyl acetate to be 50%.
The obtained resin composition was applied to a base material (Sumitomo Bakelite Co., Ltd. polycarbonate plate (Polyca Ace ECK100UU): thickness 2 mm) so that the thickness (coat layer thickness) after drying with a wire bar was 15 μm. Thus, an application layer was obtained.

1-2. Formation of flat plate Next, the coating layer was dried in an oven at 100 ° C. for 5 minutes.
Subsequently, the coating layer which had been dried was irradiated with ultraviolet rays using a high-pressure mercury lamp at an irradiation intensity of 100 mW / cm ² and an integrated light amount of 700 mJ / cm ² .
Next, after the masking film was bonded with a laminate roll, it was cured by heating in an oven at 60 ° C. for 72 hours.
Thereby, the flat plate with which the coating layer was formed on the base material was obtained by obtaining the coating layer with a dry film thickness of 15 micrometers.

1-3. Formation of Folded Plate Next, a folded plate was formed by bending a flat plate using the molding apparatus shown in FIG.
Specifically, first, a flat plate was arranged on the concave member so as to close the opening of the concave portion. At this time,
The flat plate was disposed so that the coat layer was on the concave side and the substrate was on the pressing member side. In addition, the temperature of the heat source provided inside the concave member was adjusted so that the temperature near the opening of the concave member was about 40 ° C.
Next, the pressing member was pressed toward the bottom of the recess to form one mountain fold. Next, a second mountain fold was formed in the same manner as described above with a predetermined interval from the formed valley. One mountain part was obtained by forming two mountain folding parts.
Next, after the flat plate is turned upside down with respect to the concave portion, and the flat plate is arranged on the concave member so as to be spaced from the formed peak portion, the pressing member is pressed toward the bottom of the concave portion. Thus, one valley fold was formed. Next, a second valley fold was formed in the same manner as described above at a predetermined interval from the formed valley fold. By forming two valley folds, one valley was obtained.
And by repeating such operation, the folded board provided with the several trough part and peak part was obtained. In the formation of the folded plate, the finally obtained folded plate has an angle (inner angle) θ of the bent portion of 126 ° and the height of the folded plate (distance from the outer surface of the peak portion to the back surface of the valley portion. ) Bending was performed while adjusting the insertion depth of the pressing member, the pressing force, and the like so as to obtain a so-called 88 folded plate (see FIG. 1) with T of 88 cm.

(Examples 2 to 8)
The thickness and type of the base material, the type and content of the material constituting the resin composition, and the thickness of the coat layer were changed as shown in Table 1, and a folded plate was produced in the same manner as in Example 1. .
(Comparative Example 1)
Except for using urethane (meth) acrylate, using tetrafunctional acrylate and trifunctional isocyanate, and changing the content of each material constituting the resin composition as shown in Table 1, the same as in Example 1 above. I got a folded plate.
(Comparative Example 2)
A folded plate was obtained in the same manner as in Example 1 except that trifunctional isocyanate was used without using urethane (meth) acrylate, and the content of each material constituting the resin composition was changed as shown in Table 1. It was.

In Table 1, each structure of the folded plate of each Example and each comparative example was shown.
In Table 1, a silicon-modified (meth) acrylic resin (trade name “MFG Coat SD-101”, manufactured by DIC Corporation) is referred to as “silicon-modified (meth) acrylic resin”, a bifunctional urethane acrylate and an acrylate ester. Mixture (trade name “UA-122P”, manufactured by Shin-Nakamura Chemical Co., Ltd.) “bifunctional urethane acrylate / acrylic ester”, bifunctional isocyanate (trade name “Burnock DN-955S”, DIC Corporation) as a curing agent "Bifunctional isocyanate", fluorine-containing polysiloxane (trade name "Zeffle GH-701", manufactured by Daikin Industries, Ltd.) "Fluorine-containing polysiloxane", hydroxyphenyltriazine-based ultraviolet absorber (trade name "Tinvin 400") , Manufactured by BASF) as "UV absorber", photopolymerization initiator, -Hydroxycyclohexyl phenyl ketone as “photopolymerization initiator”, pentaerythritol tetraacrylate as “tetrafunctional acrylate”, trifunctional isocyanate (trade name “Bernock DN-992S”, manufactured by DIC Corporation) as “trifunctional isocyanate” Indicated.
Moreover, the thickness of the coating layer of each Example and each comparative example was measured with the non-contact film thickness measuring apparatus MCS500 (made by Carl Zeiss).

2. Evaluation Each Example and Comparative Example obtained as described above was evaluated as follows.
2-1. Evaluation of occurrence of cracks Regarding the folded plates of the examples and comparative examples, whether or not cracks occurred in the fold-folded portion was visually determined as follows.
○: No cracks were observed.
X: Generation | occurrence | production of the crack was seen.
2-2. Evaluation of antifouling property (self-cleaning property) The folded plates of the examples and comparative examples were exposed outdoors for 180 days with the coating layer side facing the sun, and then carbon black (Orion Engineer) as simulated contamination on the outer surface of the coating layer. An aqueous solution in which 5 wt% of decarbons FW-200) was dispersed was sprayed and dried in an oven at 60 ° C. for 1 hour. After drying, it was washed with ion-exchanged water for 5 minutes, visually checked for appearance, and judged according to the following criteria.
○: Dirt is not noticeable (good self-cleaning property).
X: Dirt is conspicuous (no self-cleaning property).
2-3. Evaluation of Abrasion Resistance Samples were prepared by cutting the folded plates of each Example and Comparative Example from arbitrary locations to a size of 60 mm × 60 mm. Using these samples, a sandfall wear test was performed in accordance with ASTM D 673. Thereafter, the haze value of each sample was measured, and the haze increment of the sample before and after the sandfall wear test was calculated. Further, a polycarbonate substrate having a length of 60 mm, a width of 60 mm, and a thickness of 2 mm was prepared as a reference, and a sandfall wear test similar to the above was performed on this reference, and then a haze value was calculated.
In addition, the sandfall wear test is performed by using a sandfall wear tester manufactured by Ueshima Seisakusho Co., Ltd., tilting the sample 45 ° to the sample holder of the tester and fixing the sample to be rotatable. Carbon random # 80) was allowed to fall freely and the sample was scratched.
The measurement conditions of the sand fall test were a collision speed of 13 km / hr, a height at which the impact object dropped on the sample surface (outer surface of the coat layer) was 60 cm, and a sand fall amount was 800 g.
○: The same haze value as the reference or lower than the reference (
Excellent wear resistance)
X: Haze value is higher than the reference (not wear-resistant)
2-4. Evaluation of weather resistance With the coated layer side of each example and comparative example facing the light source side, the weather test was conducted by irradiating light with a sunshine weather meter (Suga Test Instruments Co., Ltd .: S80HB) for 2000 hours. did. The yellowness before and after the weathering test was measured according to ASTM D1925, and the yellowness difference before and after the weathering test was determined. The weather resistance was judged according to the following criteria, and “◯” was good.
○: Yellowness difference before and after test is less than 2 ×: Yellowness difference before and after test is 2 or more 2-5. Hydrophilic evaluation (contact angle measurement)
The water contact angle immediately after forming the folded plates of each Example and Comparative Example, the water contact angle after 7 days of outdoor exposure with the coat layer side of each folded plate facing the sun, and 180 days of outdoor exposure The water contact angle was measured, and each water contact angle was determined according to the following criteria to evaluate the hydrophilicity of the coat layer.
The water contact angle was determined using the θ / 2 method. Specifically, using a contact angle meter DROPMASTER-300 manufactured by Kyowa Interface Science, a certain amount of distilled water is dropped onto the coating layer, and the contact angle is determined from the angle with respect to the outer surface of the straight line connecting the left and right end points of the droplet. Asked. 60 ° or less was regarded as acceptable.
A: The water contact angle is 80 ° or more (the outer surface of the coat layer is hydrophobic).
B: Water contact angle is more than 60 ° and less than 80 °.
C: The water contact angle is 60 ° or less (the outer surface of the coat layer is hydrophilic).

Table 1 shows the evaluation results of each example and each comparative example.
As shown in Table 1, in the folded plate of each example, the occurrence of cracks at the peak portion was not observed. Moreover, the folded plate of each Example was excellent also in antifouling property and a weather resistance. Moreover, the folded plate of each Example is excellent in abrasion resistance, From this, it is thought that the folded plate of each Example is excellent in the abrasion resistance with respect to the impact from the outside.
On the other hand, in the comparative example, a satisfactory result was not obtained.

DESCRIPTION OF SYMBOLS 1 Folded plate 11 Mountain part 12 Valley part 111 Upper surface 121 Bottom surface 15 Inclined surface 15a 1st inclined surface (inclined surface)
15b Second inclined surface (inclined surface)
15c 3rd inclined surface (inclined surface)
16 Folding part 17 Valley folding part 2 Base material 21 Upper surface 3 Coat layer 31 Outer surface 4 Flat plate 9 Molding device 91 Concave member 93 Press member 911 Concave part 912 Opening part 913 Bottom part 914 Outer wall part 915 Upper surface 915a Inner edge part 931 Tip part θ Angle

Claims (8)

Folded plates used as building roofing materials or exterior wall materials,
A base material formed using a material containing a thermoplastic resin, and a coating layer provided on at least one surface side of the base material and formed using a resin composition;
The said resin composition contains a silicon modified (meth) acrylic resin and urethane (meth) acrylate, The folded board characterized by the above-mentioned.   The folded plate according to claim 1, wherein the coat layer has a thickness of 3 μm to 30 μm.   The folded plate according to claim 1 or 2, wherein a content of the urethane (meth) acrylate in the resin composition is 3 parts by mass or more and 50 parts by mass or less.   The folded plate according to any one of claims 1 to 3, wherein the thermoplastic resin is a polycarbonate resin.   The folded plate according to any one of claims 1 to 4, wherein the resin composition further includes a hydrophilizing additive.   The folded sheet according to any one of claims 1 to 5, wherein the resin composition further contains a curing agent. A flat plate for obtaining a folded plate used as a roofing material or an outer wall material of a building by bending,
A base material containing a thermoplastic resin, and a coating layer provided on at least one surface side of the base material and formed using a resin composition;
The resin composition includes a silicon-modified (meth) acrylic resin and urethane (meth) acrylate. A resin composition used for obtaining a coat layer provided on a folded plate or a folded flat plate used as a roofing material or outer wall material of a building,
A resin composition comprising a silicon-modified (meth) acrylic resin and urethane (meth) acrylate.