Laminate, method for manufacturing laminate, information management method, and information management system

Abstract

To provide a laminate excellent in durability and visibility in an outdoor use, and also to provide a manufacturing method of a laminate, an information management method and an information management system.SOLUTION: A laminate 1 includes a base layer 10, a printed part 12 formed on a surface of the base layer 10 and a surface protective layer 14 protecting the printed part 12. The printed part 12 is obtained through curing an active energy ray-curable ink. The active energy ray-curable ink includes (A) a hydroxyl group-containing monomer and / or a silane compound. The base layer 10 includes a curative component cross-linking to the component (A) included in the printed part 12.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a laminate, a method for manufacturing a laminate, an information management method, and an information management system.

Background Art

[0002] For the purpose of information display, decoration, etc. of existing structures such as bridges, resin laminated sheets, etc. are used. As an example, the case of information display of existing structures such as bridges will be described. The history information of the existing structure is not only a medical record representing the state of the structure, but also an important clue for evaluating the effectiveness of past repainting, the particularity of the structure, etc. Therefore, a series of materials related to repainting and as-built drawings are sorted and stored, and after the repainting construction, a painting record table describing the type of paint used for repainting, the painting date, the manufacturer name, etc. is recorded on the structure. For materials such as such painting record tables, the above-mentioned resin laminated sheets, etc. are used.

[0003] In relation to such technologies, for example, Patent Document 1 discloses a structure including a substrate, a code located on the surface side of the substrate, and a coating layer that covers the surface side of the code and has translucency.

[0004] Further, Patent Document 2 discloses a civil engineering and architectural concrete member formed using a cement hardened body such as concrete, mortar, or cement paste, which is composed of a first unit structure body composed of a first cement hardened body having a first lightness and a second unit structure body composed of a second cement hardened body having a second lightness different from the first lightness, and a first structure body in which a barcode pattern corresponding to member information regarding the civil engineering and architectural concrete member is uniformly formed from one end face in the direction of the other end face, and a second structure body composed of a third cement hardened body, and in the first structure body, one end face on which the barcode pattern appears is embedded in the second structure body in a state where it appears on the surface of the second structure body. A civil engineering and architectural concrete member is disclosed.

Prior Art Documents

Patent Document

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, in the technologies of the above-mentioned patent documents, there is room for improvement in outdoor durability. In addition, in the case of a laminated sheet for the purpose of information display, decoration, etc., it is required to maintain not only durability but also visibility of its content.

[0007] The present invention has been made in view of such circumstances, and an object thereof is to provide a laminate, a method for manufacturing a laminate, an information management method, and an information management system that are excellent in outdoor durability and visibility.

Means for Solving the Problems

[0008] As a result of intensive studies to achieve the above object, the present inventor has found that a laminate includes a base layer, a printed portion formed on the surface of the base layer, and a surface protection layer that protects the printed portion, the printed portion is formed by curing an active energy ray-curable ink, the active energy ray-curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, and the base layer contains a curing agent component crosslinked with the (A) component contained in the printed portion, and has thus completed the present invention.

[0009] That is, the present invention is as follows.

[0010] (1) A laminate comprising a base layer, a printed portion formed on the surface of the base layer, and a surface protective layer for protecting the printed portion, wherein the printed portion is formed by curing an active energy ray-curable ink, and the active energy ray-curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, and the base layer contains a curing agent component crosslinked with the component (A) contained in the printed portion. (2) The laminate according to (1), wherein the base layer contains at least one selected from the group consisting of a fluororesin, a (meth)acrylic silicone resin, a urethane resin, a (meth)acrylic resin, and a silicone resin as a main agent, and contains at least one selected from the group consisting of an isocyanate-based curing agent, a carbodiimide-based curing agent, and a silane-based curing agent as a curing agent. (3) A method for manufacturing a laminate including a base layer and a printed portion formed on the surface of the base layer, the method comprising a curing step of applying an active energy ray-curable ink to the surface of the base layer in a semi-cured state and irradiating the active energy ray to form the printed portion on the surface of the base layer and crosslink the printed portion and the base layer, wherein the active energy ray-curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, and the semi-cured base layer contains a curing agent component including a functional group capable of reacting with the component (A) contained in the printed portion. (4) The method for manufacturing a laminate according to (3), wherein in the curing step, after applying the active energy ray-curable ink to the base layer having a gel fraction of 50 to 80%, the active energy ray is irradiated. (5) An information management method for managing management information related to a structure, wherein the laminate according to (1) or (2) is an information management laminate in which the printed portion has at least a code for identifying management information related to the structure, and the method includes a step of acquiring the management information related to the structure by reading the code with a reader. (6) An information management system for managing management information related to a structure, in the laminate described in (1) or (2), the printing unit includes at least a code for identifying management information related to the structure, an information management laminate, a user terminal having a reader capable of reading the code of the information management laminate and obtaining code information corresponding to the management information, a server having a database in which the management information related to the structure and the code information are stored in association with each other, and a screen display unit for displaying the management information; the user terminal obtains the code information by reading the code with the reader, transmits the code information to the server, the server collates the code information received from the user terminal with the database, obtains the management information related to the structure corresponding to the code information, transmits the management information to the screen display unit, and the screen display unit displays the received management information, which is an information management system for managing management information related to a structure.

Advantages of the Invention

[0011] According to the present invention, it is possible to provide a laminate, a method for manufacturing the laminate, an information management method, and an information management system that are excellent in durability and visibility outdoors.

Brief Description of the Drawings

[0012]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Mode for Carrying Out the Invention

[0013] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an exemplification for explaining the present invention, and is not intended to limit the present invention to the following contents. The present invention can be appropriately modified and implemented within the scope of its gist.

[0014] In the drawings, the same elements will be denoted by the same reference numerals, and redundant explanations will be omitted. Also, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings unless otherwise specified. Furthermore, the dimensional ratios in the drawings are not limited to the illustrated ratios.

[0015] In this specification, unless otherwise specified, "(meth)acryl" includes methacryl and acryl. For example, "(meth)acryl" means methacryl, acryl, or both. The same applies to other terms using "(meth)".

[0016] <Laminate, laminate for information management>

[0017] FIG. 1 is a schematic cross-sectional view of a laminate according to the first embodiment.

[0018] The laminate 1 according to the present embodiment includes a base layer 10, a printing portion 12 formed on the surface of the base layer 10, and a surface protection layer 14 that protects the printing portion 12. The printing portion 12 is formed by curing an active energy ray curable ink, and the active energy ray curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound. The base layer 10 contains a curing agent component crosslinked with the component (A) contained in the printing portion 12, and is the laminate 1 (base layer 10 / printing portion 12 / surface protection layer 14).

[0019] The laminate 1 is caused to display colors, characters, numerals, patterns, codes, etc. by the printing unit 12. The printing unit 12 is printed using an active energy ray-curable ink containing at least the (A) component. When the ink is cured by irradiation with active energy rays and crosslinked with the components contained in the base layer 10 that receives the ink, it is considered that the adhesion to the base layer 10 can be improved and the durability can also be improved by forming a crosslinked portion between the base layer 10 and the printing unit 12 or by the anchor effect between the base layer 10 and the printing unit 12. In addition, since highly accurate printing is possible, it is considered that high visibility can also be imparted (however, the actions and effects of the present embodiment are not limited to these).

[0020] The laminate 1 according to the present embodiment can be suitably used as a laminate for a structure to be attached to a structure and used, a decorative laminate used outdoors, or the like. As an example of the laminate for a structure, for example, a laminate for managing structure information such as a structure record sheet is exemplified, and for example, a sign for recording information regarding a structure can be mentioned. Specific examples include a painting record sheet, a corrosion prevention record sheet, and a bridge history board sheet.

[0021] The painting record sheet displays the painting date, the painting implementer, the topcoat, the intermediate coat, and the paint materials and paint manufacturing company names used for the undercoat, etc. for reference in subsequent inspections and repainting. Inspectors and implementation managers can confirm the elapsed years of painting and the painting specifications by checking the information on the painting record sheet.

[0022] Here, the case of repainting a bridge will be described as an example. Even within the same bridge, if there are spans with different structural forms and bridging environments, the repair methods for repainting will also be different. Therefore, it may be necessary to divide the bridge into certain section units and formulate a painting plan for each section unit. For example, it is divided into section units such as arch-truss sections, simple girder sections, Gerber girder sections, continuous plate girder sections, etc., and a repainting plan is formulated for each unit, and repainting is carried out under different repainting conditions. When repainting is carried out in such a construction procedure, it is necessary for the local painting contractor to obtain information on what kind of painting has been carried out for the said section unit. At that time, the painting record sheet attached to the structure is visually recognized to obtain the painting information therefrom.

[0023] The painting record sheet is, for example, displayed on the web of the girder end of the bridge with paint or a vinyl chloride-based sheet, and is displayed in white or black so as not to fade. However, since the painting record sheet is exposed to wind, rain, and ultraviolet rays outdoors for a long time, there is a problem that it deteriorates and it becomes difficult to read the characters. In this regard, since the laminate 1 according to the present embodiment is excellent in visibility and can suppress deterioration due to ultraviolet rays and the like, it contributes to the solution of such a problem. Therefore, the laminate 1 according to the present embodiment can be suitably used as an information management laminate for managing management information regarding a structure.

[0024] The laminate 1 according to the present embodiment is also suitable as a structure decoration member (laminate) for decorating a structure in addition to a structure information management member (laminate) such as a structure record sheet. As described above, since the laminate 1 is excellent in visibility and can suppress deterioration due to ultraviolet rays and the like, even if the printing portion 12 is a decorative pattern, design, etc., it can be clearly visually recognized over a long period of time. Therefore, the decoration for the purpose of imparting the aesthetic and design properties of the structure can be clearly maintained over a long period of time.

[0025] Hereinafter, each member of the laminate 1 according to the present embodiment will be described.

[0026] (Base layer 10)

[0027] In this embodiment, an active energy ray-curable ink is used for forming the printing unit 12. However, the base layer 10 can also function as a receiving layer that receives (catches) the ink to prevent ink bleeding in order to realize high-precision characters and images, and can maintain the printing unit 12 clearly.

[0028] The base layer 10 preferably has excellent adhesion to a base material (not shown in FIG. 1), an old coating film, an anticorrosive tape, etc., and also has excellent adhesion to the printing unit 12. From such a viewpoint, the base layer 10 preferably contains at least one resin selected from the group consisting of a fluororesin, a (meth)acrylic silicone resin, a urethane resin, a (meth)acrylic resin, and a silicone resin. The content of these resins in the base layer 10 is not particularly limited, but is preferably 40% by mass or more and 100% by mass or less. This lower limit is more preferably 45% by mass or more, still more preferably 50% by mass or more, and even more preferably 55% by mass or more. This upper limit is more preferably 90% by mass or less, still more preferably 80% by mass or less, and even more preferably 75% by mass or less. When used in combination with a curing agent, the total amount is preferably within the above range. Further, when the above resin is used as a main agent and used in combination with a curing agent, the mass ratio of the main agent to the curing agent is preferably 99:1 to 50:50, and preferably 95:5 to 70:30.

[0029] Examples of the fluororesin include fully fluorinated resins such as polytetrafluoroethylene (tetrafluorinated resin, abbreviation: PTFE); partially fluorinated resins such as polychlorotrifluoroethylene (trifluorinated resin, abbreviation: PCTFE, CTFE), polyvinylidene fluoride (abbreviation: PVDF), polyvinyl fluoride (abbreviation: PVF); fluorinated resin copolymers such as perfluoroalkoxy fluororesin (abbreviation: PFA), ethylene tetrafluoride·propylene hexafluoride copolymer (abbreviation: FEP), ethylene·ethylene tetrafluoride copolymer (abbreviation: ETFE), ethylene·chlorotrifluoroethylene copolymer (abbreviation: ECTFE), etc.

[0030] Examples of the (meth)acrylic silicone resin include silicone resins having a (meth)acrylic group. Specific examples of the (meth)acrylic silicone resin include copolymers of a (meth)acrylate polymer and a dialkylpolysiloxane such as dimethylpolysiloxane, copolymers of a silanol group-containing monomer or a silyl group-containing monomer and a (meth)acrylic group-containing monomer, polymers using a hydroxyl group-containing monomer during synthesis, alkyd resins, and modified resins obtained by combining an acrylic resin modified with another resin and a silicone resin.

[0031] Examples of the urethane resin include resins containing a polyol and a polyisocyanate. For example, a two-component urethane resin obtained by combining a resin having two or more hydroxyl groups (polyol) as the main component and a polyisocyanate as the curing agent may be used. Specific examples can be obtained by reacting a polyol component, a polyisocyanate component, and optionally a chain extender.

[0032] The polyol component is a compound having at least two hydroxyl groups in the compound. Examples include polyhydric alcohols, polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols, polyacrylic polyols, castor oil, etc. Among these, polyether polyols, polyester polyols, and polycarbonate polyols are preferred. The polyol component may be used alone or in combination of two or more.

[0033] The polyisocyanate component is a compound having at least two isocyanate groups in the compound. Examples thereof include aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and araliphatic polyisocyanates. Among these, aliphatic polyisocyanates and araliphatic polyisocyanates are preferred. By using an aliphatic polyisocyanate or an araliphatic polyisocyanate, discoloration of the silylated urethane resin can be suppressed. The polyisocyanate component may be used alone or in combination of two or more.

[0034] Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as 1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methyl caproate, and lysine diisocyanate.

[0035] Examples of the alicyclic polyisocyanate include alicyclic diisocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, 1,4-bis(isocyanate methyl)cyclohexane, isophorone diisocyanate, and norbornane diisocyanate.

[0036] Examples of the aromatic polyisocyanate include aromatic diisocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 4,4'-diphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

[0037] Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates such as 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 1,4-bis(1-isocyanate-1-methylethyl)benzene, 1,3-bis(α,α-dimethylisocyanatemethyl)benzene, and the like.

[0038] Preferred examples of the polyisocyanate component include 1,6-hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3-bis(isocyanatemethyl)cyclohexane, 1,4-bis(isocyanatemethyl)cyclohexane, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, norbornane diisocyanate, 1,3-bis(α,α-dimethylisocyanatemethyl)benzene, and the like.

[0039] The polyisocyanate component includes the multimers (e.g., dimers and trimers) of the above-described polyisocyanates, reaction products or polymers, such as dimers and trimers of diphenylmethane diisocyanate, reaction products of trimethylolpropane and tolylene diisocyanate, reaction products of trimethylolpropane and hexamethylene diisocyanate, polymethylene polyphenyl isocyanate, polyether polyisocyanate, polyester polyisocyanate, and the like.

[0040] In addition, the polyisocyanate component includes modified products. Examples of modified products of polyisocyanates include polyisocyanates having structures such as uretdione, isocyanurate, urethane, urea, allophanate, biuret, carbodiimide, iminooxadiazinedione, oxadiazinetrione, oxazolidone, and the like.

[0041] Examples of the (meth)acrylic resin include resins having (meth)acrylic acid monomer and / or (meth)acrylic acid derivative monomer, etc. Examples of the (meth)acrylic acid derivative monomer include (meth)acrylic acid ester, cyanoacrylate, and the like.

[0042] Examples of the (meth)acrylic acid ester include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, and the like.

[0043] The (meth)acrylic resin may be a copolymer further having other monomers such as styrene. Specific examples of other monomers include styrene, acrylonitrile, butadiene, maleic anhydride, and the like.

[0044] Examples of the silicone resin include resins containing organopolysiloxane, modified silicone resins, and the like.

[0045] The base layer 10 preferably has excellent adhesion to a base material (not shown in FIG. 1), an old coating film, a corrosion preventive tape, etc., and also has excellent adhesion to the printing section 12. From such a viewpoint, the base layer 10 preferably contains at least one hardener selected from the group consisting of an isocyanate-based hardener, a carbodiimide-based hardener, and a silane-based hardener. Such a hardener has a functional group capable of reacting with the component (A) of the active energy ray curable ink, and thus is preferable because it can effectively promote the above-described crosslinking reaction. Examples of the reactive functional group include an isocyanate group, a carbodiimide group, and a silane group. By using such a hardener used in the printing section 12, the above-described crosslinking formation and the like can be effectively promoted. In this case, it is preferable that at least a part of the crosslinking formation component is contained in the base layer 10 as a cured product. For example, in the case of an isocyanate-based hardener, an aspect in which isocyanate is consumed (partially or entirely) by a crosslinking reaction or the like and is contained inside the base layer 10 as a cured product is exemplified. Similarly, with respect to the other components exemplified above, an aspect in which they are contained inside the base layer 10 as a cured product may also be possible.

[0046] Examples of the isocyanate-based hardener include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), methylcyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate, dimer acid diisocyanate, lysine diisocyanate, etc., and modified products of these polyisocyanates. Specific examples of the modified products include biuret modified products, isocyanurate modified products, adduct modified products (for example, trimethylolpropane adducts), allophanate modified products, uretdione modified products, etc.

[0047] Examples of the carbodiimide-based curing agent include carbodiimide compounds such as N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide, N-[3-(dimethylamino)propyl]-N'-ethylcarbodiimide methiodide, N-tert-butyl-N'-ethylcarbodiimide, N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide meso-p-toluenesulfonate, N,N'-di-tert-butylcarbodiimide, N,N'-di-p-tolylcarbodiimide; carbodiimide compounds obtained by a known condensation reaction of polyisocyanate in the presence of a carbodiimidization catalyst; carbodiimide compounds using polyisocyanate and polyalkylene oxide as raw materials, and the like.

[0048] Examples of silane-based curing agents include aminoalkyltrialkoxysilanes such as aminomethyltrimethoxysilane, aminomethyltriethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, β-aminoethyltripropoxysilane, β-aminoethyltriisopropoxysilane, β-aminoethyltributoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane; (aminoalkyl) alkyldialkoxysilanes such as β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, β-aminoethylmethyldipropoxysilane, β-aminoethylmethyldiisopropoxysilane, β-aminoethylmethyldibutoxysilane, β-aminoethylethyldimethoxysilane, β-aminoethylethyldiethoxysilane, β-aminoethylethyldipropoxysilane, β-aminoethylethyldiisopropoxysilane, β-aminoethylethyldibutoxysilane, β-aminoethylpropyldimethoxysilane, β-aminoethylpropyldiethoxysilane, β-aminoethylpropyldipropoxysilane, β-aminoethylpropyldiisopropoxysilane, β-aminoethylpropyldibutoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldipropoxysilane, γ-aminopropylmethyldiisopropoxysilane, γ-aminopropylmethyldibutoxysilane, γ-aminopropylethyldimethoxysilane, γ-aminopropylethyldiethoxysilane, γ-aminopropylethyldipropoxysilane, γ-aminopropylethyldiisopropoxysilane, γ-aminopropylethylmethyldibutoxysilane, γ-aminopropylpropyldimethoxysilane, γ-aminopropylpropyldiethoxysilane, γ-aminopropylpropyldipropoxysilane, γ-aminopropylpropyldiisopropoxysilane, γ-aminopropylpropyldibutoxysilane, and corresponding aminoalkyldialkyl (mono) alkoxysilanes, etc.

[0049] As the combination of the main agent and the curing agent of the base layer 10, it is preferable that the main agent contains at least one selected from the group consisting of a fluororesin, a (meth)acrylic silicone resin, a urethane resin, a (meth)acrylic resin, and a silicone resin, and the curing agent contains at least one selected from the group consisting of an isocyanate-based curing agent, a carbodiimide-based curing agent, and a silane-based curing agent. By making the main agent and the curing agent such a combination, the durability and the adhesion of the base layer 10 and the printing portion 12 are further improved. The reason for this is not clear, but it is presumed as follows. First, the above-mentioned resins tend to have a high binding energy and are considered to improve the durability (moreover, weather resistance) outdoors. And as will be described later, by irradiating active energy rays, the printing portion 12 is formed on the surface of the base layer 10 and the printing portion 12 and the base layer 10 are crosslinked, so that it is also possible to further improve the adhesion between the printing portion 12 and the base layer 10 (however, the actions and effects of the present embodiment are not limited to these).

[0050] The base layer 10 preferably contains a pigment. Preferable examples of the pigment include inorganic pigments such as titanium oxide, black iron oxide, red iron oxide, yellow iron oxide, carbon black, and cobalt blue, and organic pigments such as phthalocyanine-based pigments and azo-based pigments. Further, the pigment volume concentration (PVC: Pigment Volume Concentration) of the base layer 10 is preferably 10 to 50%. The PVC can be obtained based on the following formula (1). PVC (%) = Vp / (Vp + Vb) × 100 ····· (1) (In the formula, Vp represents the volume of the pigment, and Vb represents the volume of other components.)

[0051] The visible light transmittance of the base layer 10 is preferably 0 to 10%. The base layer 10 preferably has little color difference from the adhering portion of the structure to which the laminate 1 is adhered (for example, the structural base such as a bridge), and a large color difference from the printing portion 12. Having little color difference from the adhering portion of the structure enables integration with the structure, and having a large color difference from the (B) printing layer improves the visibility of the (B) printing layer. The color difference from the structural base is preferably in the range of 0 to 1.0, and the color difference from the (B) printing layer is preferably 10 or more. Note that the color difference can be measured by a spectrophotometer.

[0052] (Printing portion 12)

[0053] For the formation of the printing portion 12, an active energy ray-curable ink is used. As a result, it is possible to form a convex printing portion 12 or a fine printing portion 12 with high precision and simply, and it is also possible to exhibit excellent curability even without a solvent. In the laminate 1, the case where the printing portion 12 has a layer structure is exemplified, but in this embodiment, it is not necessarily required to have a layer structure. As will be described later, when it is desired to display characters and / or patterns such as letters, numbers, codes, marks, patterns, etc., it goes without saying that the printing portion 12 may be arranged on a part of the surface of the base layer 10 so as to be the desired characters and / or patterns (see FIG. 2).

[0054] When using an active energy ray-curable ink, after printing on the base layer 10, by irradiating active energy rays such as ultraviolet rays or electron beams, the ink composition can be cured to form colors, letters, numbers, codes, marks, patterns, etc. Examples of the active energy rays include ultraviolet rays and electron beams. Among these, ultraviolet rays are preferred from the viewpoints of cost and handleability.

[0055] The method for forming the printing portion 12 (printing method) is not particularly limited, but is preferably inkjet printing from the viewpoint of easily printing arbitrary characters, codes, designs, etc.

[0056] Also, in the present embodiment, from the viewpoint of the visibility of the printing unit 12, the pigment concentration of the printing unit 12 is preferably 2 to 15%. Examples of usable pigments include inorganic pigments such as carbon black, yellow iron oxide, cadmium yellow, composite oxides (nickel-titanium type, chromium-titanium type, bismuth-vanadium type, cobalt-aluminum type, cobalt-aluminum-chromium type, ultramarine blue), titanium oxide, etc., and organic pigments such as quinacridone type, diketopyrrolopyrrole type, benzimidazolone type, isoindolinone type, anthrapyrimidine type, phthalocyanine type, perylene type, dioxazine type, azo type, etc. Among these, it is preferable to use inorganic pigments from the viewpoint of weather resistance. And, examples of components other than the pigment include resins, ultraviolet absorbers, radical scavengers, surface modifiers, viscosity modifiers, etc. Since the printing unit 12 is formed using an active energy ray-curable ink, the ink contains photopolymerizable compounds such as monomers and oligomers, and components that become resins after curing such as photopolymerization initiators. Further, the active energy ray-curable ink can also contain components that volatilize during the formation of the printing unit, such as organic solvents.

[0057] The L of the base layer 10 * a * b * The L value of the colorimetric system and the L of the printing unit 12 * a * b * The difference from the L value of the colorimetric system is not particularly limited, but is preferably 10.0 or more, and more preferably 20.0 or more. By setting the difference in the L values of the base layer 10 and the printing unit 12 within such a range, the visibility of the printing unit 12 can be made even better. L * a * b * The L value of the colorimetric system can be measured by a spectrophotometer.

[0058] From the perspective of improving the adhesion between the base layer 10 and the printing section 12, it is preferable to form the printing section 12 before the complete curing of the base layer 10. For example, when the base layer 10 is in a semi-cured state, the printing section 12 penetrates partially into the surface, and an anchor effect is produced by forming a mixed layer at the interface. Also, a crosslinked formation section is formed by the combination of the components contained in the base layer 10 and a part of the printing section 12 through a crosslinking reaction or the like, and it is expected that the adhesion will be improved (however, the effects of the present embodiment are not limited to these).

[0059] (Surface protection layer 14)

[0060] The surface protection layer 14 preferably has excellent visible light transmittance and excellent ultraviolet ray shielding property in order not to interfere with the visibility of the printing section 12 and to protect the printing section 12 from external factors such as sunlight, wind, and rain. And the surface protection layer 14 is preferably a layer having excellent adhesion to the printing section 12 and the base layer 10.

[0061] From the above-described perspective, the visible light transmittance of the surface protection layer 14 is preferably 80 to 100%. And the lower limit of this visible light transmittance is more preferably 90% or more. The visible light transmittance can be measured in accordance with JIS A5759.

[0062] From the above-described perspective, the ultraviolet light transmittance of the surface protection layer 14 is preferably less than 50% with respect to ultraviolet light of 300 to 380 nm. And the upper limit of this ultraviolet light transmittance is more preferably 45% or less, and still more preferably 40% or less. The ultraviolet light transmittance can be measured in accordance with JIS A5759.

[0063] By using the surface protection layer 14 with a visible light transmittance and an ultraviolet light transmittance in the range of 300 to 380 nm within the above range, and arranging it to have a region where the surface protection layer 14 is in contact with both the base layer 10 and the printing portion 12, it is expected that the visibility will be further improved, the deterioration caused by ultraviolet rays and the like can be more effectively suppressed, and the durability will be further excellent. As a result, it is expected to impart durability and visibility more suitable for outdoor structure record tables, decorative uses, and the like.

[0064] Also, from the viewpoint of protecting the printing portion 12 even in an outdoor environment, the elongation rate of the surface protection layer 14 at -5°C is preferably 50 to 200%. The lower limit of the elongation rate at -5°C is more preferably 70% or more, still more preferably 80% or more, even more preferably 90% or more. Also, the upper limit of the elongation rate at -5°C is more preferably 170% or less, still more preferably 150% or less, even more preferably 130% or less. This elongation rate can be measured in accordance with the method described in the examples below.

[0065] And, from the viewpoint of protecting the printing portion 12 even in an outdoor environment, the elongation rate of the surface protection layer 14 at 30°C is preferably 50 to 200%. The lower limit of the elongation rate at 30°C is more preferably 70% or more, still more preferably 80% or more, even more preferably 90% or more, and even more preferably 100% or more. Also, the upper limit of the elongation rate at 30°C is more preferably 170% or less, still more preferably 150% or less, even more preferably 140% or less, and even more preferably 130% or less. This elongation rate can be measured in accordance with the method described in the examples below.

[0066] In this embodiment, it is preferable that the surface protection layer 14 has a combination in which the elongation rate at -5°C and the elongation rate at 30°C described above are respectively within the above ranges, and the ratio of the elongation rate at 30°C to the elongation rate at -5°C is within the above range. For example, it is preferable that the elongation rate at -5°C is 50 to 200%, and the elongation rate at 30°C is 50 to 200%.

[0067] From the viewpoint of protecting the printing part 12 even in an outdoor environment, the ratio of the elongation rate at 30°C to the elongation rate at -5°C (30°C / -5°C) of the surface protection layer 14 is preferably 0.8 to 1.2. The lower limit of this elongation rate ratio is more preferably 0.85 or more, and even more preferably 0.89 or more. Also, the upper limit of this elongation rate ratio is more preferably 1 or less, and even more preferably 0.95 or less.

[0068] Since the elongation rate and the ratio of the elongation rate of the surface protection layer 14 are the above conditions, even when there is a large temperature difference due to morning and evening or seasons (such as summer and winter), problems such as cracking of the surface protection layer 14 or peeling from the printing part 12 can be effectively suppressed. Therefore, the durability can be further improved, such as maintaining high visibility over a longer period of time.

[0069] From the perspective of being able to control the elongation rate, the ratio of elongation rates, etc. described above with high precision, the surface protective layer 14 preferably contains at least one resin selected from the group consisting of fluororesins, (meth)acrylic silicone resins, (meth)acrylic resins, and urethane resins. These resins can be those described as resins usable for the base layer 10. The content of these pigments in the surface protective layer 14 is not particularly limited, but is preferably 70% by mass or more and 100% by mass or less. This lower limit is more preferably 80% by mass or more, still more preferably 90% by mass or more, and even more preferably 95% by mass or more. This upper limit is more preferably 99.9% by mass or less. When used in combination with a curing agent, the total amount is preferably within the above range. Also, when using the above resin as the main agent and in combination with a curing agent, the mass ratio of the main agent to the curing agent is preferably 99:1 to 50:50, and more preferably 95:5 to 70:30. Incidentally, it is more preferable to use the same type of resin for the resin of the surface protective layer 14 as that of the base layer 10. By including the same type of resin in the surface protective layer 14 and the base layer 10, the adhesiveness between the surface protective layer 14 and the base layer 10 is improved, which is advantageously conducive to the protection of the printing portion 12.

[0070] From the perspective of being able to control the elongation rate, the ratio of elongation rates, etc. described above with high precision, the surface protective layer 14 more preferably contains at least one crosslinking agent selected from the group consisting of isocyanate-based curing agents, carbodiimide-based curing agents, and silane-based curing agents. These can be appropriately used those described for the base layer 10.

[0071] The thickness of the base layer 10 is not particularly limited, but is preferably 10 to 120 μm, more preferably 10 to 80 μm, and still more preferably 20 to 60 μm.

[0072] The thickness of the printing portion 12 is not particularly limited, but is preferably 3 to 60 μm, more preferably 5 to 40 μm, and still more preferably 10 to 25 μm.

[0073] The thickness of the surface protection layer 14 is not particularly limited, but is preferably 5 to 50 μm, more preferably 10 to 40 μm, and still more preferably 20 to 30 μm.

[0074] For the laminate 1 according to the present embodiment, the thicknesses of the base layer 10, the printing portion 12, and the surface protection layer 14 are preferably the above combinations. As a preferred example, a combination in which the thickness of the base layer 10 is 10 to 120 μm, the thickness of the printing portion 12 is 3 to 60 μm, and the thickness of the surface protection layer 14 is 5 to 50 μm can be cited. By setting the combination of these thicknesses, the balance between durability and visibility can be further improved.

[0075] FIG. 2 is a schematic cross-sectional view of a laminate according to the second embodiment.

[0076] The laminate 2 according to the second embodiment is different from the laminate 1 of the first embodiment in that the surface protection layer 14 has a region in contact with both the base layer 10 and the printing portion 12. In the second embodiment, the printing portion 12 is arranged on a part of the surface of the base layer 10 so as to be a desired character and / or pattern, rather than a layer structure.

[0077] The printing portion 12 can be formed as a portion that displays at least one selected from the group consisting of characters, numbers, marks, patterns, and codes, and can be formed by printing. In the case of the laminate 2, the printing portions 12a, 12b, 12c, 12d, 12e, 12f, 12g arranged on the base layer 10 constitute characters, numbers, marks, patterns, codes, and the like.

[0078] For example, when the laminate 2 is used as a member of a painting record sheet, the printing portion 12 can display information such as the painting date, the painter, the topcoat, the intermediate coat, and the primer, and the paint material and the paint manufacturer name used. For example, in the case of marks, patterns, and codes, those corresponding to this information are displayed.

[0079] For example, when the laminate 2 is used as a decorative member, as the printing section 12, for example, marks, patterns, etc. can be displayed.

[0080] For example, when the printing section 12 displays a code, specific examples thereof include one-dimensional codes (one-dimensional barcodes, JAN codes, etc.), two-dimensional codes (stacked two-dimensional codes such as PDF417 and Code49, matrix two-dimensional codes such as QR Code (registered trademark), etc.). In particular, two-dimensional codes are preferable in that they have a higher storage density than one-dimensional codes and can store a large amount of information even in a small area. The laminate 2 having such a printing section 12 can be suitably used as an information management laminate.

[0081] In the present embodiment, the printing section 12 is formed using an active energy ray curable ink. However, when the printing section 12 displays characters, numbers, marks, patterns, codes, etc., as in the second embodiment, even if these are fine, it has the advantage that they can be formed with high precision and simply.

[0082] FIG. 3 is a schematic cross-sectional view of a laminate according to the third embodiment.

[0083] The laminate 3 according to the third embodiment further includes a base material 20 on the surface of the base layer 10 of the laminate 1 of the first embodiment. The base material 20 is formed on the surface of the laminate 3 opposite to the surface of the base layer 10 on which the printing section 12 is formed. That is, the laminate 3 is a laminate including the base material 20, the base layer 10, the printing section 12, and the surface protection layer 14 for protecting the printing section 12 in this order (base material 20 / base layer 10 / printing section 12 / surface protection layer 14). The base layer 10, the printing section 12, and the surface protection layer 14 can adopt the contents described in the first embodiment.

[0084] (Base material)

[0085] Examples of the base material 20 include applicable base materials such as steel structures and concrete structures. Specific examples of steel structures include, for example, steel-frame buildings, bridges, iron towers, pedestrian bridges, road sides, river management facilities such as steel floodgates, and gas tanks. Specific examples of concrete structures include, for example, reinforced concrete structures or steel-reinforced concrete structures, structures such as bridges and viaducts. In addition, it can also be applied to outdoor structures such as outdoor signs, signs, memorial tree plates, tombstones, house walls, and gateposts.

[0086] As the method for adhering the base layer 10 and the base material 20, known methods can be adopted, and examples include painting, adhesion, sticking, welding, etc.

[0087] FIG. 4 is a schematic cross-sectional view of the laminate according to the fourth embodiment.

[0088] The laminate 4 according to the fourth embodiment further includes a sheet 30 on the surface of the base layer 10 of the laminate 1 of the first embodiment. The sheet 30 is formed on the surface of the laminate 4 opposite to the surface of the base layer 10 on which the printing portion 12 is formed. That is, the laminate 4 is a laminate including the sheet 30, the base layer 10, the printing portion 12, and the surface protection layer 14 for protecting the printing portion 12 in this order (sheet 30 / base layer 10 / printing portion 12 / surface protection layer 14).

[0089] (Sheet)

[0090] Examples of the sheet 30 include, for example, plastic films and the like. Specific examples of the plastic film include, for example, acrylic resin films, vinyl chloride resin films, ABS resin (acrylonitrile-butadiene-styrene copolymer) films, styrene resin films, polycarbonate resin films, polyethylene terephthalate films, polyethylene naphthalate films and other ester-based resins, polyethylene films, polypropylene films, ethylene-propylene copolymer and other polyolefin-based resin films, amide-based resin films, polyurethane-based resin films, and the like. By providing the sheet 30, for example, it can function as a barrier film for improving overcoat adhesion.

[0091] The thickness of the sheet 30 is not particularly limited, but is preferably 10 to 120 μm, more preferably 20 to 100 μm, and even more preferably 30 to 80 μm. is preferable.

[0092] FIG. 5 is a schematic cross-sectional view of the laminate according to the fifth embodiment.

[0093] The laminate 5 according to the fifth embodiment further includes a functional layer 40 on the surface of the surface protection layer 14 of the laminate 4 of the fourth embodiment. That is, the laminate 5 is a laminate including the sheet 30, the base layer 10, the printing portion 12, the surface protection layer 14 that protects the printing portion 12, and the functional layer 40 in this order (sheet 30 / base layer 10 / printing portion 12 / surface protection layer 14 / functional layer 40).

[0094] (Functional layer)

[0095] The type of the functional layer 40 is not particularly limited as long as the effects (visibility, etc.) of the present embodiment can be obtained, and known ones can be used. Specific examples of the functional layer 40 include, for example, a low contamination layer, a photocatalyst layer, a water repellent layer, a hydrophilic layer, an antistatic layer, an antibacterial layer, an antiviral layer, and the like.

[0096] The thickness of the functional layer 40 is not particularly limited, but from the viewpoint of ensuring visibility, the total thickness is preferably 1 to 120 μm, more preferably 10 to 100 μm, and even more preferably 15 to 50 μm.

[0097] Examples of the method for laminating the functional layer 40 include methods such as painting, adhesion, welding, printing, and lamination.

[0098] FIG. 6 is a schematic cross-sectional view of the laminate according to the sixth embodiment.

[0099] The laminate 6 according to the sixth embodiment further includes an adhesive layer 50, a non-uniformity adjusting layer 60, and a base material 20 on the surface of the sheet 30 of the laminate 4 of the fourth embodiment. That is, the laminate 6 is a laminate including a base material 20, a non-uniformity adjusting layer 60, an adhesive layer 50, a base layer 10, a printing portion 12, and a surface protection layer 14 that protects the printing portion 12 in this order (base material 20 / non-uniformity adjusting layer 60 / adhesive layer 50 / base layer 10 / printing portion 12 / surface protection layer 14 / functional layer 40).

[0100] (Adhesive layer)

[0101] The adhesive layer 50 is a layer that imparts adhesiveness. For example, in the case of the laminate 5 having the adhesive layer 50, it is convenient for users such as workers because it only needs to be attached to the application base material at the work site or construction site, and it contributes to labor saving and process simplification at the work site or construction site.

[0102] The material of the adhesive layer 50 is not particularly limited, but preferably contains at least one component selected from the group consisting of acrylic adhesives, rubber adhesives, urethane adhesives, and silicone adhesives. Further, the adhesive layer 50 may contain a rust prevention component such as zinc as other components. By containing such a rust prevention component, corrosion factors can be effectively blocked, and the sacrificial corrosion prevention function is improved.

[0103] The adhesive layer 50 only needs to be able to bond the sheet 30 and the unevenness adjustment layer 60 (or the base material 20 in the case where there is no unevenness adjustment layer 60 not shown in the figure). Therefore, the adhesive layer 50 may be laminated over the entire surface of the sheet 30, or may be laminated only on a part of the surface of the sheet 30. Similarly, the adhesive layer 50 may be laminated over the entire surface of the unevenness adjustment layer 60, or may be laminated only on a part of the surface of the sheet 30.

[0104] The unevenness adjustment layer 60 is a layer for smoothing the surface of the base material 20 which is the applied base material. By providing the unevenness adjustment layer 60, an unevenness adjustment effect of adjusting and / or rectifying the surface of the base material 20 can be obtained. Therefore, even when the installation surface of the base material 20 is not smooth, by providing the unevenness adjustment layer 60, the adhesiveness with the base material 20 can be made excellent.

[0105] The material of the unevenness adjustment layer 60 only needs to be something that can be used as an unevenness adjustment material or an unevenness adjustment agent, and its type is not particularly limited. A suitable one can be selected in consideration of the materials of the adhesive layer 50, the base material 20, etc. The unevenness adjustment layer 60 preferably contains at least one component selected from the group consisting of epoxy resin-based, cement-based, etc.

[0106] Examples of the lamination method of the adhesive layer 50 and the unevenness adjustment layer 60 include painting and the like.

[0107] The base material 20 is an applied base material, and the base material 20 described in the third embodiment etc. can be targeted.

[0108] <Method for manufacturing the laminate>

[0109] The manufacturing method of the laminate 1 of the present embodiment includes a base layer 10 and a printing portion 12 formed on the surface of the base layer 10. On the surface of the base layer 10 in a semi-cured state, an active energy ray curable ink is applied, and by irradiating active energy rays, the printing portion 12 is formed on the surface of the base layer 10, and a curing step of crosslinking the printing portion 12 and the base layer 10 is included. The active energy ray curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, and the semi-cured base layer 10 contains a curing agent component containing a functional group capable of reacting with the (A) component contained in the printing portion. It can be obtained by the manufacturing method of the laminate 1.

[0110] In the curing step, the active energy ray curable ink is applied to the semi-cured base layer 10 before complete curing. When irradiating with active energy rays, the (A) component of the active energy ray curable ink and the functional group of the curing agent component contained in the base layer 10 are crosslinked, so that the adhesiveness due to chemical bonding and anchor effect by the ink can be exhibited. That is, according to the present embodiment, while curing the applied active energy ray curable ink to form the printing portion 12, the adhesiveness of the base layer 10 and the printing portion 12 can be expressed to such an extent that sufficient durability outdoors and visibility of the printing portion 12 can be ensured (however, the effects of the present embodiment are not limited to these).

[0111] As described for the printing portion 12, the printing method is not particularly limited, but inkjet printing is preferably used. As the active energy rays, ultraviolet rays, electron beams, etc. can be used, but ultraviolet rays are preferred.

[0112] The printing conditions for the active energy ray-curable ink are not particularly limited, and known conditions can be adopted. For example, inkjet printing, offset printing (lithography), flexographic printing (relief printing), gravure printing (intaglio printing), screen printing (stencil printing), etc. In the present embodiment, since it is possible to produce small quantities of multiple varieties and the degree of freedom of the design obtained is high, it is more preferable to use inkjet printing. Further, the surface to be printed may be heated before printing, and post-treatments such as drying by active energy ray curing or heating may be performed after printing.

[0113] And, the manufacturing method of the laminate 1 according to the present embodiment preferably further includes a laminating step of laminating a surface protective layer 14 on the surface of the printed portion 12 after the above-described curing step. Thereby, the laminate 1 having the base layer 10, the printed portion 12, and the surface protective layer 14 can be obtained. At that time, it is preferable to laminate the surface protective layer 14 so as to have a region in contact with both the base layer 10 and the printed portion 12. Thereby, the printed portion 12 can be more effectively protected, and more excellent durability can be imparted to the laminate 1.

[0114] The lamination method and lamination conditions of the lamination step are not particularly limited, and known methods and conditions can be adopted. For example, air spray, airless spray, curtain flow, roll coater, roller curtain, die coater, flow coater, inkjet printing, etc. can be mentioned.

[0115] In the curing step, it is preferable to irradiate active energy rays after applying the active energy ray-curable ink to the base layer 10 having a gel fraction of 50 to 80%. The lower limit of this gel fraction is more preferably 60% or more. Also, the upper limit of this gel fraction is more preferably 70% or less. By the gel fraction of the base layer 10 before the active energy ray irradiation being within such a range, it is expected that the anchor effect on the printed portion 12 and the like will be further improved.

[0116] From such a perspective, in the manufacturing method according to this embodiment, it is preferable that, before the curing step, a step of semi-curing the base layer 10 is further included so that the gel fraction of the base layer 10 is 50 to 80%. By providing such a step, more precise control of the cured state becomes possible, and the adhesiveness between the printing portion 12 and the base layer 10 can be controlled with higher precision.

[0117] Also, in the curing step, it is preferable to cure the base layer 10 by irradiating active energy rays so that the gel fraction becomes 90 to 100%. The lower limit of this gel fraction is more preferably 92% or more. Also, the upper limit of this gel fraction is more preferably 99% or less. By controlling the gel fraction of the base layer 10 before and after the irradiation of the active energy rays, the adhesiveness between the printing portion 12 and the base layer 10 can be controlled with higher precision.

[0118] Note that the gel fraction refers to the ratio of the mass B (g) of the dried filtrate after filtering a sample A (g) placed in 50 mL of an acetone solution and left standing at 23°C for 24 hours, and can be obtained based on the following formula (2). Gel fraction (%) = (B - pigment weight) / (A - pigment weight) × 100 ··· (2) (In the formula, A represents the mass (g) of the sample before standing, and B represents the mass (g) of the dried filtrate filtered after standing.)

[0119] In the case of the laminate 2 according to the second embodiment as well, the laminate 2 can be produced by the same steps as in the first embodiment. For example, when the printing portion 12 does not have a layer structure but displays colors, characters, numbers, patterns, codes, etc., it may be printed using an active energy ray curable ink so as to be such colors, characters, numbers, patterns, codes, etc.

[0120] In the cases of the third to sixth embodiments, the laminates 2 to 6 can be manufactured by sequentially performing the lamination methods described for each layer.

[0121] For example, in the case of the laminate 3 according to the third embodiment, a manufacturing method is exemplified which further includes a step of installing the base layer 10 of the obtained laminate 1 on the base material 20 after performing the curing step. In this case, it may also be a construction method.

[0122] In the case of the laminate 4 according to the fourth embodiment, a manufacturing method is exemplified which further includes a step of laminating the sheet 30 on the surface of the base layer 10 on the side opposite to the surface on which the printing portion 12 is formed after performing the curing step.

[0123] In the case of the laminate 5 according to the fifth embodiment, a manufacturing method is exemplified which further includes a step of laminating the sheet 30 on the surface of the base layer 10 on the side opposite to the surface on which the printing portion 12 is formed, and a step of laminating the functional layer 40 on the surface of the surface protection layer 14 on the side opposite to the surface in contact with the printing portion 12 after performing the curing step. In this case, the order of the step of laminating the sheet 30 and the step of laminating the functional layer 40 is not particularly limited, and either may be performed first.

[0124] In the case of the laminate 6 according to the sixth embodiment, a manufacturing method is exemplified which includes a step of laminating the sheet 30 on the surface of the base layer 10 on the side opposite to the surface on which the printing portion 12 is formed, a step of laminating the adhesive layer 50 on the surface of the sheet 30 on the side opposite to the surface on which the base layer 10 is formed, and a step of laminating the unevenness adjusting layer 60 on the surface of the adhesive layer 50 on the side opposite to the surface on which the sheet 30 is formed after performing the curing step, and further includes a step of installing the unevenness adjusting layer 60 of the obtained laminate 6 on the base material 20. In this case, it may also be a construction method.

[0125] <Information management method, information management system>

[0126] The above-described laminates 1 to 6 can be suitably used as information management laminates. For example, the printing unit 12 includes at least one selected from the group consisting of characters indicating management information regarding a structure, numbers indicating management information regarding a structure, patterns (e.g., marks, designs, etc.) indicating management information regarding a structure, and codes for identifying management information regarding a structure, and can be suitably used as an information management laminate (laminates 1 to 6) for managing management information regarding a structure. Such an information management laminate can be suitably used in a construction method (structure construction method) for assembling a structure such as a bridge or a construction method (structure repair method / structure repair method) for repairing and / or mending a structure. For example, such an information management laminate (laminates 1 to 6) can be suitably used as a construction method of a structure including a step of attaching the laminate to the surface of the structure.

[0127] For example, when newly assembling a structure, the above-described information management laminate on which information (such as painting information) regarding the structure is described or recorded is installed on the surface of the structure. When repairing and / or mending an existing structure, the above-described information management laminate on which information (such as painting information) after repair and / or after mending is described or recorded is installed on the surface of the structure. In this way, the information management laminate according to the present embodiment can be used in the construction method of a structure.

[0128] Further, according to the present embodiment, an information management method using the above-described information management laminate can be provided. That is, the information management method according to the present embodiment is an information management method for managing management information regarding a structure, and the above-described laminates 1 to 6 are information management laminates in which the printing unit 12 includes at least a code for identifying management information regarding a structure, and is an information management method for managing management information regarding a structure including a step of acquiring management information regarding a structure by reading the code with a reader.

[0129] The laminates 1 to 6 according to this embodiment are suitable for outdoor structure record sheets and the like, have excellent durability, and also have excellent visibility of the printing portion 12. By using such laminates 1 to 6 as information management laminates for reading codes, even when installed outdoors for a long time, the code (printing portion 12) can be read with high accuracy using a reader. As a result, workers performing repair or maintenance work on the structure can read information (such as paint information) related to the structure from the code with high accuracy at the work site or construction site where the structure is installed. As the code, the above-described one-dimensional code, two-dimensional code, etc. can be used, but a two-dimensional code is preferred.

[0130] And as a usage mode of the code, it is also possible to perform reading and recording. For example, it can also be a management method for managing management information related to a structure, further including a step of recording the management information related to the structure in the code. It would also be possible to write or overwrite information after repair / post-repair in a one-dimensional code or two-dimensional code.

[0131] The information management method according to this embodiment can be implemented, for example, as an information management system described later.

[0132] FIG. 7 is a schematic diagram showing an example of the information management system according to this embodiment.

[0133] The information management system 7 according to this embodiment is an information management system that manages management information regarding a structure. The printing unit 12 (see FIGS. 1 to 6) includes an information management laminate 71 having at least a code 71C (for example, see laminates 1 to 6, etc.), a user terminal 72 having a reader capable of reading the code of the information management laminate 71 and obtaining code information corresponding to the management information, a server 74 having a database 73 in which management information regarding the structure and the code information are stored in association with each other, and a screen display unit 75 for displaying the management information; the user terminal 72 obtains the code information by reading the code 71C with the reader, transmits the code information to the server 74, the server 74 collates the code information received from the user terminal 72 with the database 73, obtains the management information regarding the structure B corresponding to the code information, and transmits the management information to the screen display unit 75, and the screen display unit 75 displays the received management information. It is an information management system 7 that manages management information regarding the structure B.

[0134] An information management laminate 71 having a code 71C is installed on the structure B. The code 71C records code information corresponding to the management information regarding the structure B. By querying the database 73 with the code information read by the reader (not shown) of the user terminal 72, the management information of the structure B can be obtained. This will be described in detail below.

[0135] First, a user having the user terminal 72 (for example, a worker who repairs and / or mends the structure B, etc.) uses the reader (not shown) of the user terminal 72 to read the code 71C (two-dimensional code, etc.) and obtain the code information. The read code information is queried against the database 73 of the server 74 via the Internet 76. In the database 73, management information regarding the structure is stored in association with the code information. Then, the management information of the structure B corresponding to the read code information is obtained from the database 73 (see arrow S1).

[0136] Subsequently, the management information of the structure B obtained from the database 73 is transmitted via the Internet to the screen display unit 75, and the management information is displayed on the screen display unit 75 (see arrow S2). For example, at the site where the structure B is installed, the user can obtain the required management information (for example, the current paint information of the structure, etc.) from the screen display unit 75 and use it for repair work or maintenance work.

[0137] In FIG. 7, as an example, the mode in which the screen display unit 75 is provided in the user terminal 72 is illustrated. However, from the viewpoint that the user can easily obtain management information at the work site or construction site, it is preferable that the user terminal 72 has the screen display unit 75.

[0138] Examples of the user terminal 72 include a personal computer, a mobile phone such as a smartphone, and an electronic tablet. However, from the viewpoint of portability, a smartphone or an electronic tablet is preferable. For example, the code 71C can be read using the camera of a smartphone or an electronic tablet. And the management information can be confirmed using the screen of the smartphone or the electronic tablet as the screen display unit 75.

[0139] In the information management method and the information management system 7 according to the present embodiment, since the information management laminate 71 that can maintain excellent durability and visibility even when exposed outdoors for a long time is used, the management information of the structure can be read from the code 71C with high accuracy and easily via the code information.

Example

[0140] The present invention will be described in more detail with the following examples and comparative examples, but the present invention is not limited to the following examples. Note that %, and parts are based on mass standards unless otherwise specified.

[0141] The following materials were used. (Surface protection layer) · Fluororesin-based main agent: "Lumiflon (registered trademark) LF800" (manufactured by AGC, solid content 60%, OH value 20 mg KOH / g) · Acrylic silicone resin-based main agent: "ACRYDIC A-871" (manufactured by DIC, solid content 50%, OH value 25 mg KOH / g) · Acrylic resin: "ACRYDIC A-1300" (manufactured by DIC, solid content 60%, OH value 0 mg KOH / g) · Urethane resin-based main agent: "HA6500" (manufactured by Resonaak, solid content 52%, OH value 40 mg KOH / g) · Epoxy resin-based main agent: "jER (registered trademark) 1001" (manufactured by Mitsubishi Chemical, solid content 100%, OH value (epoxy equivalent) 475 mg KOH) · Isocyanate-based curing agent: Curing agent "Coronate 2760" (manufactured by Tosoh, solid content 99%, NCO% 20%) · Amine-based curing agent: Amine-based curing agent "Laccamide 17-202DN" (manufactured by DIC, solid content 60%, NCO% (amine value) 170) · UV absorber: "JF-79" (manufactured by Johoku Chemical, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole) · Radical scavenger: "Tinuvin 292" (manufactured by BASF, hindered amine light stabilizer) (Printing section) · Hydroxyl group-containing monomer: "Placcel FA2D" (manufactured by Daicel, unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone) · Silane compound: "KBM-5103" (manufactured by Shin-Etsu Silicone, 3-acryloxypropyltrimethoxysilane) · Monofunctional monomer: "Light Acrylate PO-A" (manufactured by Kyoeisha Chemical, phenoxyethyl acrylate) · Multifunctional monomer: "Light Acrylate 1.6HX - A" (manufactured by Kyoeisha Chemical Co., Ltd., 1,6 - hexanediol diacrylate) · Photoinitiator: "Omnirad TPO" (manufactured by IGM Resins, diphenyl(2,4,6 - trimethylbenzoyl)phosphine oxide) · Coloring pigment: "Asahi #50" (manufactured by Asahi Carbon Co., Ltd., carbon black) · Surface conditioner: "BYK - UV3500" (manufactured by BYK, silicone - based surface conditioner) (Base layer) · Fluororesin - based main agent: "Lumiflon (registered trademark) LF800" · Aqueous fluororesin - based main agent: "Lumiflon (registered trademark) FE4400" (manufactured by AGC, solid content 51%) · Acrylic silicone resin - based main agent: "ACRYDIC A - 870" (manufactured by DIC, solid content 50%, OH value 25mgKOH / g) 」 · Acrylic resin - based main agent: "ACRYDIC A - 1300" · Urethane resin - based main agent: "HA6500" · Epoxy resin - based main agent: "jER (registered trademark) 1001X70" (manufactured by Mitsubishi Chemical Corporation, solid content 100%, OH value (epoxy equivalent) 475mgKOH) · Isocyanate - based curing agent: Curing agent "Coronate 2760" · Aqueous carbodiimide - based curing agent: Curing agent "Carbodilite V - 10" (manufactured by Nisshinbo Chemical Inc.) · Amine - based curing agent: Curing agent "Laccamide 17 - 202" · Black coloring pigment: "Raven 420Powder" (manufactured by BILRA, solid content 100%) · White coloring pigment: 「TITONE R-62N」 (manufactured by Sakai Chemical Industry Co., Ltd., solid content 100%)

[0142] <Example 1>

[0143] (Production of laminate 1)

[0144] On the base layer 10 with a gel fraction of 70%, an ultraviolet-curable ink was applied by inkjet printing, and active energy rays were irradiated using an ultraviolet LED lamp with an emission peak wavelength of 385 nm to cure the ink, forming the printed portion 12 over the entire surface of the base layer 10, and crosslinking the base layer 10 and the printed portion 12. The gel fraction of the base layer 10 after ultraviolet irradiation was 95%. Subsequently, a paint for forming a surface protection layer mixed with a curing agent was applied by air spraying over the printed portion 12 and dried at 23°C and 50% RH for 7 days to form the surface protection layer 14, obtaining a laminate 1 (see Fig. 1) having the surface protection layer 14, the printed portion 12, and the base layer 10. Note that the surface protection layer 14, the printed portion 12, and the base layer 10 of Example 1 have the compositions described in Table 1, with the content in mass% described for each layer. That is, Example 1 has a surface protection layer 14 containing 89.5 mass% of a fluororesin, 9.9 mass% of an isocyanate-based curing agent, 0.3 mass% of an ultraviolet absorber, and 0.3 mass% of a radical scavenger, totaling 100 mass%; a printed portion 12 containing 10 mass% of a hydroxyl group-containing monomer, 41.5 mass% of a monofunctional monomer, 35 mass% of a polyfunctional monomer, 10 mass% of a photopolymerization initiator, 3 mass% of a coloring pigment, and 0.5 mass% of a surface conditioner, totaling 100 mass%; and a base layer 10 containing 63 mass% of a fluororesin, 7 mass% of an isocyanate-based curing agent, 0.5 mass% of a black coloring pigment, and 29.5 mass% of a white coloring pigment, totaling 100 mass%. For the obtained laminate 1, the thickness of the surface protection layer 14 was about 30 μm, the thickness of the printed portion 12 was 20 μm, and the thickness of the base layer 10 was about 30 μm. Also, the color difference between the steel material used as the base material and the obtained laminate 1 was 0.30.

[0145] <Examples 2 to 6、8~ 12>

[0146] The surface protective layer 14, the printing section 12, and the base layer 10 were each changed to the compositions described in the respective tables, and the laminate 1 was obtained in the same manner as in Example 1 except that the film thicknesses of the respective layers were changed to the film thicknesses described in the respective tables.

[0147] <Comparative Examples 1 to 4>

[0148] A laminate was obtained in the same manner as in Example 1 except that the surface protective layer, the printing layer, and the base layer were each changed to the compositions described in Table 3 and the film thicknesses of the respective layers were changed to the film thicknesses described in the respective tables.

[0149] <Evaluation Method>

[0150] For each of the obtained laminates, evaluations of each physical property were performed in accordance with the methods shown below.

[0151] (Elongation rate of the surface protective layer, ratio of elongation rates)

[0152] The surface protective layer was applied to a polypropylene (PP) plate by air spray coating (30 μm) and cured in an environment of 23°C and 50% RH for 7 days. A test piece was obtained by cutting out the produced film into a size of 10 mm × 50 mm. The 10-mm end portion of the test piece was fixed with the gripping tool of a universal testing machine, and a tensile test was performed using the universal testing machine while maintaining the test piece at -5°C in a thermostatic bath. The 10-mm end portion of the test piece was fixed with the gripping tool of the universal testing machine. The tensile speed was set at 5 mm / min, and the elongation at the time when the test piece broke was measured. The elongation rate was calculated by the following formula (3). Elongation rate (%) = { (Length of the test piece at break in the tensile test - Length of the test piece before the test) / (Length of the test piece before the test)} × 100 = Elongation at break (mm) / 30 (mm) × 100 (3) Similarly, the elongation rate at 30°C was determined. From these values, the ratio of the elongation rate at -5°C to the elongation rate at 30°C (-5°C / 30°C) was determined.

[0153] (Elongation rate of the base layer, ratio of elongation rates)

[0154] The elongation rate of the base layer at -5°C was determined in the same manner as for the surface protective layer. Similarly, the elongation rate at 30°C was determined. From these values, the ratio of the elongation rate at -5°C to the elongation rate at 30°C (-5°C / 30°C) was determined.

[0155] (Gel fraction of the base layer)

[0156] The gel fraction at the time of forming the printing portion (before ultraviolet irradiation) and the gel fraction after the curing step (after ultraviolet irradiation) were determined by the following method. The gel fraction refers to the ratio of the mass B (g) of the dried filtrate after standing the sample A (g) in 50 mL of an acetone solution at 23°C for 24 hours and can be determined based on the following formula (2). Gel fraction (%) = (B - pigment weight) / (A - pigment weight) × 100 ··· (2) (In the formula, A represents the mass (g) of the sample before standing, and B represents the mass (g) of the dried filtrate filtered after standing.)

[0157] <Evaluation of the aesthetic appearance>

[0158] The aesthetic appearance of the laminate 1 was evaluated by confirming the appearance of the laminate 1 by the evaluation method of JIS K 5659. And it was evaluated based on the following criteria. 〇: No cracks, peeling, or swelling were observed, and no occurrence of any of color, gloss, flatness, flow, indentation, unevenness, and holes was observed. △: No cracks, peeling, or swelling were observed, and the area with any abnormality of color, gloss, flatness, flow, indentation, unevenness, and holes was less than 5%. ×: Cracks, peeling, or swelling were observed, or the area with any abnormality of color, gloss, flatness, flow, indentation, unevenness, and holes was 5% or more.

[0159] <Evaluation of interlayer adhesion>

[0160] The initial adhesion was evaluated in accordance with JIS K5600-5-6:1999 (25 squares at 2 mm intervals) for the product cured for 7 days in an environment of 23°C and 50% RH after the laminate was produced. The interlayer adhesion after the wet and heat cycle test was evaluated in accordance with JIS K5600-5-6:1999 (25 squares at 2 mm intervals) after conducting the temperature cycle test in accordance with JIS K5659:2018 on specimens cured for 7 days in an environment of 23°C and 50% RH after laminate fabrication. These interlayer adhesions were evaluated based on the following criteria. 〇: No peeling was observed in any of the grids. △: Less than 15% peeling was observed for all grids. ×: 15% or more peeling was observed for all grids.

[0161] <Evaluation of water resistance>

[0162] After fabrication, the laminate cured for 7 days in an environment of 23°C and 50% RH was immersed in ion-exchanged water and left standing in a 23°C environment for 7 days. After the immersion, it was taken out of the water and the water resistance was evaluated by immediately observing the appearance. ○: No cracks, peeling, or swelling were observed on the surface of the laminate. △: Any of cracks, peeling, or swelling was observed on the surface of the laminate, and the area was less than 5%. ×: Any of cracks, peeling, or swelling was observed on the surface of the laminate, and the area was 5% or more.

[0163] <Evaluation of alkali resistance>

[0164] The alkali resistance durability of the laminate cured for 7 days in an environment of 23°C and 50% RH after fabrication was evaluated in accordance with JIS K5659:2018. ○: No cracks, peeling, or swelling were observed on the surface of the laminate. △: Any of cracks, peeling, or swelling was observed on the surface of the laminate, and the area was less than 5%. ×: Any of cracks, peeling, or swelling was observed on the surface of the laminate, and the area was 5% or more.

[0165] <Evaluation of visual appearance after the accelerated weathering test>

[0166] The xenon lamp method of JIS K 5600-7-7 was carried out for 2000 hours to evaluate the visual appearance after the accelerated weathering test. And the evaluation was based on the following criteria. 〇: The gloss retention rate was 60% or more, and the level of whitening was 1 or 0. △: The gloss retention rate was 40% or more, and the level of whitening was 2, 1 or 0. ×: The gloss retention rate was 30% or more, and the level of whitening was 3, 2, 1 or 0.

[0167] The manufacturing conditions and evaluation results of each example and each comparative example are shown in each table.

[0168]

Table 1

[0169]

Table 2

[0170]

Table 3

[0171] From the above, according to this example, it was at least confirmed that the laminate is excellent in durability and visibility and suitable for outdoor structure record sheets and the like.

Explanation of Signs

[0172] 1, 2, 3, 4, 5, 6... laminates 7... information management system 10... base layer 12, 12a, 12b, 12c, 12d, 12e, 12f, 12g... printing part '14... surface protection layer 20... base material 30... sheet 40... functional layer 50... adhesive layer 60... unevenness adjustment layer 71... laminate for information management 71C…code 72…user terminal 73…database 74…server 75…screen display unit 76…Internet B…structure S1, S2…arrow

Claims

1. A laminate comprising a base layer, a printed portion formed on the surface of the base layer, and a surface protection layer for protecting the printed portion, wherein the printed portion is formed by curing an active energy ray curable ink, the active energy ray curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, the base layer contains a curing agent component crosslinked with the component (A) contained in the printed portion, the base layer contains at least one selected from the group consisting of a fluororesin and a silicone resin as a main component, a laminate.

2. The base layer, contains at least one selected from the group consisting of an isocyanate curing agent, a carbodiimide curing agent, and a silane curing agent as a curing agent, The laminate according to claim 1.

3. A method for manufacturing a laminate including a base layer and a printed portion formed on the surface of the base layer, wherein a curing step is included, in which an active energy ray curable ink is applied to the surface of the base layer in a semi-cured state and irradiated with active energy rays to form the printed portion on the surface of the base layer and crosslink the printed portion and the base layer, the active energy ray curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, the semi-cured base layer contains a curing agent component including a functional group capable of reacting with the component (A) contained in the printed portion, the curing step irradiates the active energy rays after applying the active energy ray curable ink to the base layer having a gel fraction of 50 to 80%, A method for manufacturing a laminate.

4. An information management method for managing management information related to a structure, wherein the laminate includes a base layer, a printed portion formed on the surface of the base layer, and a surface protection layer for protecting the printed portion, the printed portion is formed by curing an active energy ray curable ink, the active energy ray curable ink contains (A) a hydroxyl group-containing monomer and / or a silane compound, the base layer contains a curing agent component crosslinked with the component (A) contained in the printed portion, and the printed portion is an information management laminate having at least a code for identifying management information related to the structure, including a step of acquiring the management information related to the structure by reading the code with a reader, An information management method for managing management information related to a structure.

5. The base layer is contains, as a main ingredient, at least one selected from the group consisting of a fluororesin, a (meth)acrylic silicone resin, a urethane resin, a (meth)acrylic resin, and a silicone resin, contains, as a curing agent, at least one selected from the group consisting of an isocyanate-based curing agent, a carbodiimide-based curing agent, and a silane-based curing agent, An information management method for managing management information regarding the structure according to claim 4.

6. An information management system for managing management information regarding a structure, including a base layer, a printing portion formed on the surface of the base layer, and a surface protection layer for protecting the printing portion, the printing portion being formed by curing an active energy ray-curable ink, the active energy ray-curable ink containing (A) a hydroxyl group-containing monomer and / or a silane compound, and the base layer containing a curing agent component crosslinked with the component (A) contained in the printing portion, in a laminate, the printing portion having at least a code for identifying management information regarding the structure, an information management laminate; a user terminal having a reader capable of reading the code of the information management laminate and obtaining code information corresponding to the management information; a server having a database in which the management information regarding the structure and the code information are stored in association with each other; a screen display portion for displaying the management information; comprising; the user terminal obtains the code information by reading the code with the reader and transmits the code information to the server, the server collates the code information received from the user terminal with the database, obtains the management information regarding the structure corresponding to the code information, and transmits the management information to the screen display portion, the screen display portion displays the received management information, An information management system for managing management information regarding a structure.

7. The base layer is contains, as a main ingredient, at least one selected from the group consisting of a fluororesin, a (meth)acrylic silicone resin, a urethane resin, a (meth)acrylic resin, and a silicone resin, contains, as a curing agent, at least one selected from the group consisting of an isocyanate-based curing agent, a carbodiimide-based curing agent, and a silane-based curing agent, An information management system for managing management information regarding the structure according to claim 6.

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