JP2011208099A - Coating composition and sheet using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coating composition that gives a sheet excellent weatherability, transparency, and substantivity thereof, and a sheet having a protective layer formed of the composition.SOLUTION: The coating composition contains: ionizing-radiation curable resin; and a silicate compound having a reactive functional group A. The sheet has the surface protection layer formed by crosslinking and curing the coating composition.

Description

  The present invention relates to a coating agent and a sheet using the same.

  Contaminants such as dust, dust and oil in the air are likely to adhere to the interior and exterior such as entrance doors and exterior materials of general residences, flooring and exterior walls of public facilities, or buildings and structures installed outdoors. When exposed to wind and rain with the contaminants attached, the contaminants remain in a linear shape along the rain lines, and there is a problem in that the appearance is remarkably deteriorated. Therefore, self-cleaning performance (antifouling properties) is required for these interior and exterior materials and sheets used on the surface of buildings. In order to improve the self-cleaning performance (antifouling property), a method of improving the hydrophilicity of the protective layer by using an additive such as silica in addition to the blending of silicone and fluorine is usually employed. However, in order to ensure sufficient self-cleaning performance (antifouling properties), it is necessary to use a large amount of additive, and therefore, there is a problem that the additive is dropped from the protective layer or the hydrophilicity is lowered due to scratches. there were. Patent Document 1 describes that an organosilicate compound is employed as an additive. However, in this case as well, problems such as the need for a large amount of additive as described above, dropping of the additive, and a decrease in hydrophilicity due to scratches have not been solved.

By the way, since the interior and exterior materials and buildings as described above are exposed to direct sunlight and wind and rain every day, the sheets used for the surface protection of these interior and exterior materials and buildings are required to have extremely severe weather resistance. ing. Various sheets have been studied in order to improve weather resistance (see Patent Documents 2 to 4).
In Patent Documents 2 to 4, all of the protective layer contains an additive such as a light stabilizer or an ultraviolet absorber to improve the weather resistance. However, when the content of the additive in the protective layer is improved, due to compatibility with the binder resin forming the protective layer, these additives bleed out, causing stickiness. It was. On the other hand, if the content of the additive is such that it does not bleed out, sufficient performance of these additives cannot be obtained, and there is also a problem that satisfactory products cannot be obtained in terms of weather resistance.

  Furthermore, the weather resistance and self-cleaning performance of the sheets used for the interior and exterior materials and structures as described above are noted, and for example, application to applications that require transparency such as window glass protection sheets and greenhouses. It has come to be requested. It is generally known that when a light stabilizer or an ultraviolet absorber is added to the protective layer, it causes a decrease in transparency or a discoloration such as yellowing. It is in a situation where severe challenges are imposed.

Japanese Patent No. 2869443 JP 2007-245442 A JP 2009-66966 A JP 2009-66967 A

  The present invention provides a sheet having a protective layer formed by the coating composition that provides the sheet with excellent self-cleaning performance and its durability, weather resistance, and transparency. It is intended to do.

As a result of intensive studies to achieve the above object, the present inventor has found that a coating agent composition containing an ionizing radiation curable resin and a specific silicate compound can solve the above problems. The present invention has been completed based on such findings.
That is, the gist of the present invention is as follows.

1. A coating agent composition comprising an ionizing radiation curable resin and a silicate compound having a reactive functional group A.
2. 2. The coating agent composition according to 1 above, wherein the reactive functional group A is a functional group having an ethylenic double bond.
3. 3. The coating agent composition according to 2 above, wherein the reactive functional group A is a (meth) acryloyl group.
4). 4. Coating agent composition in any one of said 1-3 whose content of silicate compound is 1-15 mass parts with respect to 100 mass parts of ionizing radiation-curable resin.
5. 5. The coating agent composition as described in any one of 1 to 4 above, wherein the ionizing radiation curable resin is caprolactone-based urethane acrylate.
6). 6. The coating agent composition according to 5 above, wherein the caprolactone-based urethane acrylate has a number average molecular weight (number average molecular weight in terms of polystyrene measured by GPC method) of 1,000 to 10,000.
7). A sheet having a surface protective layer obtained by crosslinking and curing the coating agent composition according to any one of 1 to 6 above.
8). 8. The sheet according to 7 above, which has at least a substrate and a surface protective layer, and the surface protective layer is provided on the outermost surface.
9. 9. The sheet according to 8 above, wherein the base material contains at least one antistatic agent selected from a polyether / polyolefin block copolymer and a polyether ester amide.

  ADVANTAGE OF THE INVENTION According to this invention, the sheet | seat which has the self-cleaning performance excellent in the sheet | seat and its durability, weather resistance, and transparency, and the sheet | seat which has the outstanding self-cleaning performance, weather resistance, its sustainability, and transparency Can be obtained.

It is a schematic diagram which shows the cross section of the sheet | seat of this invention. It is a schematic diagram which shows another aspect of the cross section of the sheet | seat of this invention. It is a schematic diagram which shows another aspect of the cross section of the sheet | seat of this invention.

[Coating agent]
The coating agent of the present invention is a coating agent composition comprising an ionizing radiation curable resin and a silicate compound having a reactive functional group A. Hereinafter, each component will be described.

<Ionizing radiation curable resin>
The ionizing radiation curable resin used in the present invention can be appropriately selected from a polymerizable monomer, a polymerizable oligomer or a prepolymer conventionally used as an ionizing radiation curable resin. From the viewpoint of obtaining characteristics, those that are difficult to bleed out, have a coatability of about 95 to 100% as a solid content standard, and are less likely to cause curing shrinkage when cured. Representative examples of such ionizing radiation curable resins are described below. “(Meth) acrylate” means “acrylate or methacrylate”.

  As the polymerizable monomer, a (meth) acrylate monomer having a radically polymerizable unsaturated group in the molecule is suitable, and in particular, a polyfunctionality having two or more ethylenically unsaturated bonds in the molecule ( (Meth) acrylate is preferred, and one kind may be used alone, or two or more kinds may be used in combination. As a functional group number, 2-8 are preferable, 2-6 are more preferable, and 3-4 are more preferable.

  In the present invention, together with the polyfunctional (meth) acrylate, for the purpose of adjusting the viscosity, monofunctional (meth) acrylates such as methyl (meth) acrylate are within a range that does not impair the purpose of the present invention. It can be used together as appropriate. A monofunctional (meth) acrylate may be used individually by 1 type, and may be used in combination of 2 or more type.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, such as epoxy (meth) acrylate, urethane (meth) acrylate, polyether urethane (meth) acrylate, and caprolactone urethane Preferred examples include (meth) acrylates, polyester (meth) acrylate series, and polyether (meth) acrylate series oligomers, with urethane (meth) acrylate series being more preferred. Among these oligomers, polyfunctional polymerizable oligomers are preferable, and the number of functional groups is preferably 2 to 16, more preferably 2 to 8, and still more preferably 2 to 6.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group. These polymerizable oligomers may be used individually by 1 type, and may be used in combination of 2 or more type.

  When an ultraviolet curable resin is used as the ionizing radiation curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the ultraviolet curable resin. The initiator for photopolymerization can be appropriately selected from those conventionally used and is not particularly limited.

(Caprolactone urethane acrylate)
Among the above-mentioned polymerizable oligomers, caprolactone urethane acrylate, in particular, in combination with a silicate compound having a reactive functional group A described later, provides excellent self-cleaning performance, weather resistance, durability, and transparency. Therefore, it is preferable. The caprolactone-based urethane acrylate can be usually obtained by a reaction of a caprolactone-based polyol, an organic isocyanate, and a hydroxy acrylate.

Here, as a caprolactone-type polyol, what is marketed can be used, Preferably it has two hydroxyl groups, Preferably the number average molecular weight is 500-3000, More preferably, the thing of 750-2000 is mentioned. It is done. Moreover, polyols other than caprolactone, for example, polyols such as ethylene glycol, diethylene glycol, 1.4-butanediol, 1.6-hexanediol, etc., can be used by mixing one or more kinds in an arbitrary ratio.
As the organic polyisocyanate, those having two isocyanate groups are preferable, and from the viewpoint of suppressing yellowing, isophorone diisocyanate, hexamethylene diisocyanate, 4.4'-dicyclohexylmethane diisocyanate, trimethylhexamethylene diisocyanate, and the like are preferable. . Preferred examples of the hydroxy acrylate include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, caprolactone-modified 2-hydroxyethyl acrylate, and the like.

  The caprolactone-based urethane acrylate can be synthesized by a reaction of these polycaprolactone-based polyols, organic polyisocyanate, and hydroxy acrylate. As a synthesis method, a method in which a polycaprolactone-based polyol and an organic polyisocyanate are reacted to form a polyurethane prepolymer containing -NCO groups at both ends and then reacted with hydroxyacrylate is preferable. Reaction conditions and the like may be in accordance with conventional methods.

  The caprolactone-based urethane acrylate preferably used in the present invention has a number average molecular weight (polystyrene converted number average molecular weight measured by GPC method) of preferably from 1,000 to 10,000, and more preferably from 2,000 to 10,000. That is, the caprolactone urethane acrylate is preferably an oligomer. If the number average molecular weight is within the above range (oligomer), the processability is excellent, and the coating agent composition has an appropriate thixotropy, so that the surface protective layer can be easily formed.

<< A silicate compound having a reactive functional group A >>
In this invention, a silicate compound is used in order to provide self-cleaning property to the to-be-coated article of the coating agent composition of this invention. The silicate compound used in the present invention is not particularly limited as long as it is a silicate compound having a reactive functional group A reactive with caprolactone urethane acrylate. Preferred examples of the reactive functional group B include a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group, and is preferably at least one selected from these. Of these, a (meth) acryloyl group is preferable.
The silicate compound having the reactive functional group A is preferably a compound represented by the following general formula (1).

Wherein (1), R ¹ to R ³ is a hydrogen atom or an organic group having 1 to 10 carbon atoms, more of R ¹ and R ² may be the same or different. R ⁴ is a functional group containing a reactive functional group B.
Preferred examples of the organic group having 1 to 10 carbon atoms include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an aralkyl group. These groups may be substituted or unsubstituted, and the alkyl group and alkenyl group may be linear or branched. Of these, an alkyl group having 1 to 4 carbon atoms is more preferable.
Further, n ₁ is preferably 1 to 30, 1 to 10 is more preferable.

  More specifically, a compound represented by the following general formula (2) is preferable.

In formula (2), R ^{5 to} R ⁷ are the same as R ^{1 to} R ³ , respectively. R ¹¹ is the same as R ¹ , and particularly preferably a hydrogen atom or a methyl group. R ⁸ and R ¹⁰ represent a single bond or a divalent organic group. R ⁹ is a single bond, a carbonyl group (—CO—), an ether bond (—O—), an ester bond (—COO—), a thioether bond (—S—) amide bond (—CONH—), or an imino bond. (—NH—), carbonate bond (—OCOO—), and a group in which a plurality of these are linked are shown. Preferred examples of the divalent organic group include an alkanediyl group, an alkenediyl group, an arylene group, and an arylenealkanediyl group. These groups may be substituted or unsubstituted, and the alkanediyl group and alkenediyl group may be linear or branched. Among these, a C1-C4 alkanediyl group is more preferable. R ⁹ is more preferably an ester bond (—COO—).
Further, n ₂ is preferably 1 to 30, 1 to 10 is more preferable.

  The content of the silicate compound having the reactive functional group A is preferably 1 to 15 parts by mass, more preferably 3 to 15 parts by mass, and further 5 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. preferable. If content of a silicate compound is in the said range, the favorable crosslinked state of a caprolactone type urethane acrylate will be obtained. Moreover, since the surface protective layer using the coating agent composition of this invention has moderate hydrophilicity, the wettability of water increases and it can have the outstanding self-cleaning property. That is, interior and exterior materials and buildings are exposed to wind and rain, but since the surface protective layer has hydrophilicity, rainwater tends to form a thin film on the surface protective layer, so that adhesion of contaminants itself is suppressed. Or, attached contaminants are easily removed.

<Alkyl silicate compound>
The coating agent of the present invention preferably contains an alkyl silicate compound. The alkyl silicate compound in the present invention is a compound represented by the following general formula (3).

In the formula (3), R ^{11 to} R ¹⁴ represent a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and a plurality of R ¹¹ and R ¹² may be the same or different. Good. Further, there is no possibility that all R ¹¹ to R ¹⁴ do not simultaneously hydrogen atoms. The R ¹¹ to R ^14, from the viewpoint of improving the self-cleaning and its sustainability, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.
Moreover, n ₃ from the viewpoint of improving the durability and self-cleaning, preferably 1 to 30, 5 to 15 is more preferable.

  The content of the alkyl silicate compound is preferably 1 to 15 parts by mass, more preferably 3 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin, from the viewpoint of improving the self-cleaning property and its sustainability. -15 mass parts is further more preferable.

《Hindered amine light stabilizer》
The coating agent of the present invention preferably contains a hindered amine light stabilizer. In the present invention, the light stabilizer is not limited as long as it is a hindered amine, but is preferably a hindered amine light stabilizer having a reactive functional group B.
The reactive functional group B is not particularly limited as long as it has reactivity with the ionizing radiation curable resin. For example, the functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, or an allyl group. Are preferable, and at least one selected from these is preferable. Of these, a (meth) acryloyl group is preferable.
Examples of such a light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis ( 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate, 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) ) -1,3,5-triazine) and the like are preferred.

  The content of the hindered amine light stabilizer having the reactive functional group B is preferably 1 to 10 parts by weight, more preferably 3 to 10 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the ionizing radiation curable resin. Part is more preferred. If the content of the hindered amine light stabilizer is within the above range, the light stabilizer does not bleed out and sufficient light stability is obtained, so that excellent weather resistance is obtained.

《Triazine UV absorber》
As the triazine-based ultraviolet absorber preferably used in the present invention, a hydroxyphenyl triazine-based ultraviolet absorber is preferable. Examples of such an ultraviolet absorber include 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine. 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2 , 4-Bis [2-hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyl) Oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [4-[(2-hydroxy-3- (2 ′) -Ethyl) Xyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and the like are preferable, and these are used alone or in combination of two or more. be able to.

  The content of the triazine-based ultraviolet absorber is preferably 1 to 10 parts by mass, more preferably 3 to 10 parts by mass, and still more preferably 5 to 10 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin. If the content of the triazine-based ultraviolet absorber is within the above range, the absorber does not bleed out and sufficient ultraviolet absorbing ability can be obtained, so that excellent weather resistance can be obtained. In general, when adding 1 part by mass or more of the UV absorber to 100 parts by mass of the binder resin, the absorber may bleed out. I couldn't. However, when a triazine-based ultraviolet absorber is used in the present invention, a large amount of ultraviolet absorber of 1 part by mass or more is added depending on the combination of the ultraviolet absorber, ionizing radiation curable resin, and a predetermined light stabilizer. However, it was possible to obtain excellent weather resistance without bleeding out of the absorbent.

《Various additives》
The coating agent of the present invention can contain various additives as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.

[Sheet]
The sheet of the present invention is not particularly limited as long as it has an aspect having a surface protective layer formed by crosslinking and curing the coating agent composition of the present invention. In the sheet of the present invention, the surface protective layer can be used alone, but it is preferable to form a surface protective layer formed by crosslinking and curing the coating agent composition on the substrate. Preferred applications of the sheet of the present invention include applications that require transparency, applications for decorative sheets, and the like.

《Uses that require transparency》
First, the case where the sheet | seat of this invention is used for the use which requires transparency, such as a protection sheet of a window glass, a greenhouse, is demonstrated.

<Base material>
In the sheet of the present invention used for applications requiring transparency (hereinafter sometimes referred to as sheet I), the base material used is preferably a plastic film or a plastic sheet, a polyolefin resin, a vinyl resin, Preferred are polyester resins, acrylic resins, polyamide resins, cellulose resins, polystyrene resins, polycarbonate resins, polyarylate resins, polyimide resins, and the like.

  Moreover, it is preferable that a base material contains an antistatic agent from a viewpoint of providing self-cleaning property to the sheet | seat of this invention. Preferred examples of the antistatic agent include polymer antistatic agents containing a polyether structure such as polyether / polyolefin copolymer, polyether ester, polyether ester amide, polyether amide, and polyether amide imide. Can be used alone or in combination. Of these, polyether / polyolefin copolymers and polyether ester amides are more preferable.

  Here, as the polyether / polyolefin copolymer, in addition to a block copolymer in which a polyether portion made of polyethylene glycol or polypropylene glycol and a polyolefin portion made of polyethylene or polypropylene are alternately bonded, a random copolymer or a graft copolymer is used. Although a polymer is mentioned, it is preferable that it is a block copolymer from a viewpoint of providing self-cleaning property. Commercially available products of these antistatic agents can be used. For example, commercially available products such as “Pelestat 300”, “Pelestat 230”, and “Pelestat 303” are available as antistatic agents for polyether / polyolefin copolymers. Examples of the antistatic agent for ether ester amide include commercially available products such as “Pelestat 6321”.

  Content of the antistatic agent in a base material is about 5-30 mass parts with respect to 100 mass parts of resin used for a base material, Preferably it is 10-20 mass parts. If content of an antistatic agent is the said range, the self-cleaning property which was efficiently excellent with respect to the sheet | seat of this invention can be provided.

In order to improve the adhesion with the layer provided thereon, these base materials may be subjected to an oxidation method such as corona discharge treatment, chromium oxidation treatment, hot air treatment, ozone / ultraviolet treatment method on one or both sides as desired. Further, physical or chemical surface treatments such as a concavo-convex method such as a sand blast method and a solvent treatment method can be performed.
The base material may be subjected to a treatment such as forming a primer layer for reinforcing interlayer adhesion between the base material and the surface protective layer, adhesion to various adherends, or a back surface primer layer. Good. The material used for forming the primer layer is not particularly limited, and examples thereof include acrylic resins, vinyl chloride-vinyl acetate copolymers, polyesters, polyurethanes, chlorinated polypropylenes, and chlorinated polyethylenes. The material used for the back primer layer 7 is appropriately selected depending on the adherend.
Moreover, if it is in the range which does not inhibit transparency, the pattern for adjusting a color and the pattern from a design viewpoint may be formed previously.

  Although there is no restriction | limiting in particular about the thickness of a base material, When durability is ensured and versatility is considered, it is about 20-200 micrometers normally, Preferably it is the range of 30-150 micrometers.

<Surface protective layer>
The surface protective layer is a layer formed by crosslinking and curing the coating agent composition of the present invention. More specifically, it is a layer formed by applying a coating composition on the above-mentioned substrate and crosslinking and curing it by irradiating ionizing radiation or the like.
The coating composition is applied by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, preferably gravure coating so that the thickness after curing is usually about 1 to 20 μm. Do. Moreover, it is preferably 2 to 20 μm from the viewpoint of obtaining excellent weather resistance and its durability, as well as transparency and self-cleaning performance.

  The uncured resin layer formed by coating the coating agent composition of the present invention becomes a surface protective layer by irradiating with ionizing radiation such as an electron beam and ultraviolet rays and crosslinking and curing. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable.

The irradiation dose is preferably such that the crosslinking density of the caprolactone urethane acrylate is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  The surface protective layer may have a recess. There is no restriction | limiting in particular about the method of giving a recessed part to a surface protective layer, For example, it gives by embossing. The embossing may be performed by a normal method using a known single-wafer or rotary embossing machine.

  The sheet I obtained in this manner has excellent weather resistance, its durability, transparency, and further excellent self-cleaning performance when the silicate compound is contained in the coating agent. And it is used suitably for the use which requires transparency, such as a protection sheet of a window glass, a greenhouse.

《Cosmetic sheet》
The sheet of the present invention is also suitably used as a decorative sheet. For example, the sheet I used for the above-described applications requiring transparency, or the sheet I with a pattern on the sheet I can be used as a decorative sheet. Will be described.

  1 and 2 are schematic views showing a cross section of a preferred embodiment of a sheet of the present invention (hereinafter sometimes referred to as sheet II) used as a decorative sheet. In the embodiment shown in FIG. 1, the pattern printing layer 3 and the surface protective layer 6 are laminated in this order on the substrate 2, and in the embodiment shown in FIG. 2, the pattern printing layer 3 and the transparent resin layer are formed on the substrate 2. 4, a primer layer 5 and a surface protective layer 6 obtained by crosslinking and curing the coating agent composition of the present invention are laminated in this order. In FIG. 2, a back primer layer 7 is provided on the back surface of the substrate 2, and an adhesive layer 8 is provided between the pattern printing layer 3 and the transparent resin layer 4. Furthermore, the transparent resin layer 4 is provided with a colored resin layer 9 having a recess on the surface of the primer layer and wiping the recess. Hereinafter, each layer will be described in detail.

<Substrate 2>
The base material 2 used in the present invention is not particularly limited as long as it is usually used for a decorative sheet. Various papers, woven fabrics and nonwoven fabrics of various fibers, plastic films, plastic sheets, metal foils, metal Sheets, metal plates, wood-based plates such as wood, ceramic materials, and the like can be appropriately selected depending on the application. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film. Of these, in consideration of processability, plastic films and plastic sheets are preferable, among which polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene copolymer, polyolefin-based heat. A polyolefin resin substrate such as a plastic elastomer is preferable, and polypropylene and a polyolefin thermoplastic elastomer are preferable in consideration of processability.

As the polypropylene-based resin, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, an α-olefin copolymer of 2 to 20 carbon atoms other than propylene, and the like are also preferable. In addition, a propylene-α-olefin copolymer containing 15 mol% or more of an individual monomer of ethylene, butene-1,4-methylpentene-1, hexene-1, or octene-1 is also preferred.
As the polyolefin-based thermoplastic elastomer, a mixture of isotactic polypropylene in the hard segment and atactic polypropylene in the soft segment in a mass ratio of 80:20 is preferable.

The polyolefin resin substrate can be obtained by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.
Although there is no restriction | limiting in particular about the thickness of the base material 2, From a viewpoint of workability, a softness | flexibility, intensity | strength, etc., it is preferable that it is the range of 50-150 micrometers, and it is further more preferable that it is the range of 50-120 micrometers.

  Moreover, the base material 2 can also perform a physical or chemical surface treatment, and can provide a primer layer similarly to the base material of the said sheet | seat I. Furthermore, it can also color using a pigment and dye. The coloring mode of the base sheet includes transparent coloring and opaque landing (hiding coloring), and these can be arbitrarily selected depending on the application.

<Pattern printing layer 3>
The pattern printed layer 3 shown in FIGS. 1 and 2 is intended to impart decorativeness to the decorative sheet of the present invention, and preferably comprises a picture layer 3a and a colored layer 3b. In addition, as will be described in detail later, when the color of the base material 2 is used as it is and it is not necessary to conceal it, only the pattern layer 3a may be applied, while the pattern is not required. Only the colored layer 3b may be applied.
The pattern print layer is usually formed using ink, and can be formed by a known printing method such as gravure printing, silk screen printing, offset printing, gravure offset printing, and ink jet printing.

  The pattern layer 3a gives the base material 2 decorativeness, and is formed by printing various patterns using ink and a printing machine. Patterns include stone patterns that mimic the surface of rocks, such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multicolor printing with normal yellow, red, blue, and black process colors, as well as by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.

As the pattern ink used for the pattern layer 3a, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed.
The binder resin may be appropriately selected from known binders such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation curable resin according to required physical properties and printability. For example, cellulose resins such as nitrocellulose, cellulose acetate, cellulose acetate propionate; poly (meth) methyl acrylate, poly (meth) butyl acrylate, methyl (meth) acrylate-butyl (meth) acrylate- ( In addition to an acrylic resin such as a (meth) acrylic acid 2-hydroxyethyl copolymer, a simple substance such as urethane resin, vinyl chloride-vinyl acetate copolymer, polyester resin, alkyd resin, or a mixture containing these can be used.
These resins can be used singly or in combination of two or more.

  Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and acetic acid-2 -Ester organic solvents such as ethoxyethyl; Alcohol organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloro Chlorinated organic solvents, such as styrene; and inorganic solvents such as water. These solvents (or dispersion media) can be used singly or in combination of two or more.

  Further, a cross-linking agent may be added to the pattern ink. Examples of the crosslinking agent include isocyanate group-containing compounds, epoxy group-containing compounds, carbodiimide group-containing compounds, oxazoline group-containing compounds, silanol group-containing compounds, and the like, but isocyanate group-containing compounds are preferred.

The colored layer 3b is a uniform and uniform layer that normally covers the entire surface of the substrate 2, and is a layer that is provided as desired for the purpose of improving the design of the decorative sheet of the present invention. It is also referred to as a concealing layer or a whole surface solid layer, and gives the intended color to the surface of the substrate 2. Usually, it is formed with an opaque color, but it may be formed with a colored transparent color to make use of the pattern of the base. Moreover, when utilizing that the base material 2 is white, or when the base material 2 itself is appropriately colored, it is not necessary to form the colored layer 3b.
As the ink used for the colored layer 3b, the same ink as that used in the pattern layer 3a can be used.

<Transparent resin layer 4>
The transparent resin layer 4 shown in FIG. 2 protects the pattern printing layer 3 in the sheet of the present invention and imparts weather resistance to the sheet of the present invention. The transparent resin layer 4 of the present invention is not limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent.

  As the transparent resin layer 4, for example, a layer formed of a thermoplastic resin can be suitably used. Specifically, soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Polymers, ionomers, acrylic esters, methacrylic esters and the like can be mentioned. In the present invention, polyolefin resin such as polypropylene is particularly preferable as the transparent resin layer 4.

  The transparent resin layer 4 may be colored as necessary. In this case, it can be colored by adding a colorant (pigment or dye) to the thermoplastic resin as described above. As the colorant, known or commercially available pigments or dyes can be appropriately used. These can select 1 type, or 2 or more types, and what is necessary is just to set the addition amount of a coloring agent suitably according to a desired hue.

  Further, the transparent resin layer 4 preferably contains an ultraviolet absorber (UVA) or a light stabilizer as a weather resistance improver. The ultraviolet absorber (UVA) absorbs harmful ultraviolet rays and improves the long-term weather resistance and stability of the decorative sheet of the present invention. In addition, the light stabilizer (HALS) itself absorbs little ultraviolet light, but stabilizes it by efficiently capturing harmful free radicals generated by ultraviolet energy.

  The ultraviolet absorber may be either inorganic or organic, and as the inorganic ultraviolet absorber, titanium oxide, cerium oxide, zinc oxide or the like having an average particle size of about 5 to 120 nm can be preferably used. Moreover, as an organic type ultraviolet absorber, a benzotriazole type, a triazine type, a benzophenone type, a salicylate type, an acrylonitrile type etc. can be mentioned preferably, for example. Of these, triazines are preferred because they have a high ability to absorb ultraviolet rays and do not easily deteriorate even with high energy such as ultraviolet rays. Preferable examples of the triazine-based ultraviolet absorber include those used for the above-described coating agent.

Preferred examples of the light stabilizer include hindered amines (HALS) as contained in the coating agent described above.
Further, as the ultraviolet absorber or light stabilizer, a reactive ultraviolet absorber or light stabilizer having a polymerizable group such as a (meth) acryloyl group in the molecule can be used.

The content of the ultraviolet absorber in the transparent resin layer 4 is usually in the range of 0.1 to 1 part by mass, preferably 0.3 to 0.8 parts per 100 parts by mass of the resin forming the transparent resin layer 4. It is the range of mass parts. When it is 0.1 part by mass or more, sufficient weather resistance can be imparted to the decorative sheet of the present invention, and when it is 1 part by mass or less, bleeding does not occur.
The content of the light stabilizer in the transparent resin layer 4 is usually in the range of 0.05 to 0.8 parts by mass, preferably 0.1 to 0 with respect to 100 parts by mass of the resin forming the transparent resin layer 4. .5 parts by mass. When it is 0.05 part by mass or more, sufficient weather resistance can be imparted to the decorative sheet of the present invention, and when it is 0.8 part by mass or less, bleeding does not occur.

  Further, the transparent resin layer 4 contains various additives such as a filler, a matting agent (matting agent), a flame retardant, a lubricant, an antistatic agent, an antioxidant, and a soft component (for example, rubber) as necessary. It may be included.

The method for forming the transparent resin layer 4 is not particularly limited, and various methods can be used. For example, a method of laminating a preformed sheet or film on an adjacent layer, a method of applying a resin composition capable of forming the transparent resin layer 4 on an adjacent layer by melt extrusion, and together with the adjacent layer Any method such as laminating can be employed.
In the present invention, it is preferable to form the transparent resin layer 4 by melt extrusion, and it is desirable that the transparent resin layer 4 is coated with a polyolefin resin by melt extrusion. Specifically, the transparent resin layer 4 is suitably formed by forming the adhesive layer 8 on the pattern printing layer 3 in advance, and melt-extruding and applying a polypropylene-based thermoplastic elastomer on the adhesive layer 8. be able to. What is necessary is just to implement the method of melt extrusion according to the well-known method using a T die etc., for example.
In addition, although the thickness of the transparent resin layer 4 can be suitably set according to the use of the final product, the usage method, and the like, it is generally preferably 20 to 250 μm, particularly preferably about 50 to 200 μm.

(Transparent resin layer recess)
The transparent resin layer 4 may have a recess as shown in FIG. There is no restriction | limiting in particular about the method of giving a recessed part in a transparent resin layer, For example, it gives by embossing. Embossing is a method of performing embossing simultaneously in the process of laminating the transparent resin layer 4 on the pattern printing layer 3 (so-called doubling embossing method) in addition to the usual method using a known sheet-fed or rotary embossing machine. May be used.

  In addition, in order to improve the adhesiveness with an adjacent layer, the corona discharge process can also be performed to the surface (front surface) and / or back surface of the transparent resin layer 4 as needed. The method and conditions for the corona discharge treatment may follow a known method.

<Colored resin layer 9>
It is preferable that the colored resin layer 9 is formed by wiping the concave portion provided in the transparent resin layer 4 in terms of improving designability and weather resistance. The wiping process refers to a process of filling a colored ink composition while scratching the surface with a doctor blade in a recess provided by embossing.

  The colored ink composition preferably dissolves a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a polycarbonate resin such as polycarbonate urethane acrylate or polycarbonate urethane acrylate and acrylic polyol as a binder resin. (Or dispersed). As the colorant and solvent contained in the color ink composition, the same colorants and solvents as described above for the pattern printing layer can be used. Preferred examples of the binder resin include colored ink compositions described in JP-A-2008-105372 (paragraphs 0042 to 0050).

  In this case, the mass ratio of the acrylic component to the urethane component in the polycarbonate-based urethane acrylate is not particularly limited, but the mass ratio of urethane component: acrylic component is 80:20 to 20:20 in terms of weather resistance and solvent resistance. The range is preferably 80, and more preferably 70:30 to 30:70. In addition, when the content of the acrylic and urethane components is within the above range, the coating film is not excessively hard and sufficient processing suitability is obtained, and white streaks (whitening) occur on the resin surface during the bending process. Such a problem does not occur.

  The mass ratio of the polycarbonate urethane acrylate and the acrylic polyol is preferably in the range of 100: 0 to 10:90 of the polycarbonate urethane acrylate alone, preferably in the range of 80:20 to 20:80, and 70:30 to 30: A range of 70 is more preferred. Within this range, it becomes hard due to two-component crosslinking with isocyanate, so that solvent resistance is improved and sufficient flexibility is obtained. Further, excellent weather resistance is also obtained. In addition, if it is only acrylic polyol, not only the weather resistance is lowered, but also this causes a reaction with isocyanate, so the adhesion with the ionizing radiation curable resin changes in the posting, and stable performance may not be exhibited. .

  The colored resin layer 9 is formed by introducing the ink composition into the concave portion of the transparent resin layer 4 as described above. The design effect is improved by the synergistic effect of the colored resin layer 9 formed in the recess and the pattern printing layer 3. In particular, by forming a colored resin layer in the concave portion of the wood grain conduit groove irregularities, it is possible to express a design closer to the actual wood grain, thereby increasing the commercial value. Moreover, weather resistance can be provided to the colored resin layer 9 by including an ultraviolet absorber (UVA) or a light stabilizer (HALS) in the ink composition used for the wiping process as described above.

<Adhesive layer 8>
The adhesive layer 8 has a function of leveling the unevenness of the pattern printing layer 3 and improving the adhesion between the base material 2 and the transparent resin layer 4, and is made of a transparent resin layer.
As the ink used for forming the adhesive layer 8, a binder, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, an ultraviolet absorber, a light stabilizer, a curing agent, and the like are appropriately mixed as necessary. used. The binder is not particularly limited, but an acrylic / polyurethane copolymer is preferable because it has flexibility, toughness and elasticity. In consideration of the environment, it is preferable not to use a resin system containing chlorine.

Moreover, it is preferable that the application quantity of the adhesive bond layer 8 is the range of 2-25 g / m < ² >. If 2 g / m ² or more, sufficient adhesion is obtained in the substrate 2 and the transparent resin layer 4, economically preferable to be 25 g / m ² or less. From the above points, the coating amount of the ink depends on the type of the substrate 4 but is usually more preferably in the range of 3 to ²⁰ g / m ² .
Moreover, as thickness of the adhesive bond layer 8, it is the range of 2-25 micrometers normally, and the range of 3-20 micrometers is preferable.

<Primer layer 5>
In the sheet II of the present invention, the primer layer 5 is preferably laminated on the transparent resin layer 4.
The primer layer 5 is preferably one appropriately selected from binder resins used in the ink composition for forming the colored resin layer 9 described above. That is, it is preferable to use a polycarbonate urethane acrylate or a resin composed of a polycarbonate urethane acrylate and an acrylic polyol. By using these resins, extremely high weather resistance can be imparted to the sheet II of the present invention.

  In order to further improve the weather resistance, the primer layer 5 preferably contains a weather resistance improver similar to that used in the transparent resin layer 4, and includes an ultraviolet absorber (UVA) and a light stabilizer (HALS). ) Is preferably contained. The content of the ultraviolet absorber is preferably 0.1 to 25 parts by mass, more preferably 1 to 25 parts by mass, and further preferably 3 to 20 parts by mass with respect to 100 parts by mass of the resin forming the primer layer 5. Yes, particularly preferably 5 to 20 parts by mass. The content of the light stabilizer is preferably 0.05 to 7 parts by mass, more preferably 0.5 to 5 parts by mass, and still more preferably 1 to 100 parts by mass of the resin forming the primer layer 5. 5 parts by mass, particularly preferably 2 to 5 parts by mass.

  The thickness of the primer layer 5 is not particularly limited as long as the effect of the present invention is achieved, but from the viewpoint of obtaining sufficient weather resistance, a range of 0.5 to 10 μm is preferable, and a range of 1 to 5 μm is more preferable. Is preferred.

  The primer layer can be formed by a known printing method, coating method, or the like using the resin composition as it is or in a state dissolved or dispersed in a solvent. In addition, the primer layer 5 may have an uneven shape as shown in FIG. 2 or may be a uniform and uneven shape. From the viewpoint of improving the designability, it is preferable that the surface has irregularities.

<Surface protective layer 6>
The sheet II of the present invention has a surface protective layer 6 on the outermost surface. The surface protective layer 6 is the same as the surface protective layer of the sheet I of the present invention described above. Moreover, it is preferable that the surface protective layer 6 has a recessed part from a viewpoint of the designability improvement. The method for forming a recess in the surface protective layer 6 is the same as that for the surface protective layer of the sheet I.

  Further, the surface protective layer 6 may have an uneven shape as shown in FIG. 2 or may be a uniform and uneven surface. From the viewpoint of improving the designability, it is preferable that the surface has irregularities. Moreover, as shown in FIG. 3, you may provide a recessed part in the surface protective layer which is uniform and does not have an unevenness | corrugation. As a method for forming the recess in this case, a method similar to that for providing the recess in the transparent resin layer 4 such as embossing can be used.

[Decorative board]
The decorative board of the present invention is formed by laminating the sheet on the adherend so that the surface protective layer of the sheet of the present invention is the outermost surface layer. Although the above-mentioned sheet I and sheet II can be adopted as the decorative plate, it is preferable to laminate the sheet II from the viewpoint of design.

  The adherend to which the sheet of the present invention is applied is not particularly limited, and those similar to known decorative sheets can be used. For example, wood materials, metals, ceramics, plastics, glass and the like can be mentioned. In particular, the sheet of the present invention can be suitably used for metal materials such as steel plates and wood materials. Specific examples of steel plates include hot-dip galvanized steel plates, and specific examples of wooden materials include veneers made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. Wood veneer, wood plywood, particle board, medium density fiberboard (MDF), and the like.

The method for laminating the sheet of the present invention on various adherends is not particularly limited, and for example, a method of adhering the sheet to the adherend with an adhesive can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber, and the like.
In addition, when adhering the sheet | seat of this invention to various adherends with an adhesive agent, since the adhesiveness can be improved, providing a back surface primer layer 7 is preferable.

  The decorative board manufactured in this way is, for example, interior decoration materials for buildings such as walls, ceilings and floors, surface decorative boards for furniture such as window frames, doors and handrails, furniture or cabinets such as light electrical appliances and OA equipment. It can preferably be used as an exterior material such as a surface decorative board and an entrance door. In particular, since the decorative board of the present invention is excellent in weather resistance and has high processability, it is preferably attached to a steel sheet and used as an exterior material such as an entrance.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation methods)
(1) Evaluation of self-cleaning property The sheet obtained in the examples and comparative examples was installed outdoors at an inclination of 45 °, and an outdoor exposure test was performed for 3 months. Thereafter, the adhesion and deposition state of the surface dirt were evaluated according to the following criteria.
○: There was almost no adhesion or deposition of dirt. △: There was some adhesion or deposition of dirt, but there was no problem in practical use.

(2) Evaluation of sustainability of self-cleaning properties The sheets obtained in Examples and Comparative Examples were washed with water after applying salad oil colored with a red dye. Thereafter, the adhesion and deposition state of the surface dirt were evaluated according to the following criteria.
◎: There was no change. ○: There was almost no adhesion or deposition of dirt. △: There was some adhesion or deposition of dirt, but there was no problem in practical use.

(3) Warm water whitening resistance The sheets obtained in Examples and Comparative Examples were immersed in warm water at 50 ° C. and held for 2 days, and then the whitening state of the sheet surface was evaluated according to the following criteria.
○: No change in appearance △: There was a slight change in appearance, but there was no practical problem ×: The change in appearance was remarkable

(4) Surface resistance measurement The surface resistance value rate of the sheet | seat obtained by the Example and the comparative example was measured using the digital insulation meter (made by Toa Denpa Kogyo).
(5) Charge decay rate half-life The charge decay rate half-life of the sheets obtained in the examples and comparative examples was measured using an Honest meter (manufactured by Sind static electricity).

(6) Evaluation of weather resistance (weather resistance test)
Sheets obtained in Examples and Comparative Examples were set on a metal weather manufactured by Daipura Wintes Co., Ltd. and light conditions (illuminance: 60 mW / cm ² , black panel temperature 63 ° C., intralayer humidity 50% RH) for 20 hours. , A weather resistance test that is allowed to stand for 4 hours under condensation conditions (illuminance: 0 mW / cm ² , black panel temperature 30 ° C., layer humidity 98% RH) and 800 hours under water spray conditions (10 seconds before and after the condensation conditions). went. After the test, after maintaining for 2 days under the condition of 25 ° C. and 50% RH, the appearance of cracks and whitening on the sheet surface was evaluated according to the following criteria.
◎: There was no change in appearance. ○: There was almost no change in appearance. △: There was a slight change in appearance, but there was no problem in practical use.

(7) Evaluation of weather resistance adhesion About the sheet | seat which performed the said weather resistance test, the operation which affixed the cellophane (trademark) made from Nichiban on the surface and peeled rapidly was performed once. At this time, whether or not each layer provided on the substrate was peeled was confirmed by visual observation and evaluated according to the following criteria.
○: There was no peeling of the layer. Δ: There was some peeling of the layer, but there was no problem in practical use. ×: The peeling of the layer was remarkable.

(8) Stickiness (Evaluation of bleed out)
After the sheet | seat obtained by the Example and the comparative example was stored for 24 hours on 80 degreeC conditions, the surface of the decorative sheet was touched with the finger | toe, and the following reference | standard evaluated.
○: There was no stickiness △: There was some stickiness due to bleeding such as UV absorbers, but there was no problem in practical use ×: Stickiness due to bleeding was remarkable

(9) Evaluation of solvent resistance A gauze is attached to a weight of 300 g / cm ² with a rubber band and soaked with ethyl acetate. The surface of the sheet | seat obtained by each Example and the comparative example was reciprocated 50 times to the horizontal direction, the surface of the sheet | seat was visually observed, and the following reference | standard evaluated.
○: No change in the sheet surface was observed. Δ: A slight change in the sheet surface was observed, but there was no problem in practical use. ×: The change in the sheet surface was remarkable.

(10) Evaluation of yellowing In each Example and Comparative Example, the hue of the sheet surface immediately after electron beam irradiation was evaluated according to the following criteria.
○: Yellowing was not observed at all △: Yellowing was slightly observed, but there was no problem in practical use ×: Yellowing was remarkable

(11) Evaluation of scratch resistance About the sheet | seat obtained by each Example and the comparative example, using steel wool, the load of 300 g / cm < ² > was applied and rubbed 5 times and the external appearance was evaluated visually. The evaluation criteria are as follows.
○: Almost no change in appearance △: Slight scratch or gloss change in appearance ×: Scratch in appearance, gloss change

(12) Evaluation of transparency About the sheet | seat obtained by each Example and the comparative example, the surface state was evaluated on the following reference | standard.
○: There was no haze feeling (cloudy feeling). Δ: There was a slight haze feeling, but there was no problem in practical use.

Example 1
A resin sheet made of a transparent polypropylene resin (thickness: 80 μm) was prepared as the substrate 2. After the front and back surfaces were subjected to corona discharge treatment, a primer layer-forming composition having the following composition was applied to the surface (2.5 g / m ² ) to form a primer layer (thickness: 2 μm). Next, an ionizing radiation curable resin composition containing a silicate compound having a reactive functional group having the following composition is prepared, a coating film is formed by a gravure coating method, and an electron beam is applied under conditions of 175 keV and 5 Mrad (50 kGy). By irradiating and curing the coating film, a surface protective layer (5 g / m ² ) was formed to obtain a sheet. The thickness of the surface protective layer was 5 μm.
Said evaluation was performed about the obtained sheet | seat. The evaluation results are shown in Table 1.

Composition of primer layer forming composition A composition obtained by mixing the following resin composition and curing agent in a ratio of 100: 5 (mass ratio).
Resin composition:
Polycarbonate urethane acrylate and acrylic polyol (mass ratio of urethane component to acrylic component in polycarbonate urethane acrylate: 70/30, mass ratio of urethane acrylate to acrylic polyol: 50/50): 100 parts by mass Hydroxyphenyltriazine UV absorption Agent (“Tinuvin 400 (trade name)”, manufactured by Ciba Japan Co., Ltd.): 15 parts by mass Hydroxyphenyltriazine-based ultraviolet absorber (“Tinuvin 479 (trade name)”, manufactured by Ciba Japan Co., Ltd.): 4 parts by mass Hindered amine light stabilizer ("Tinuvin 123 (trade name)", manufactured by Ciba Japan Co., Ltd.): 3 parts by mass curing agent:
Hexane methylene diisocyanate

Composition of ionizing radiation-curable resin composition Polyether urethane acrylate oligomer (trifunctional, molecular weight: 2000): 100 parts by mass Silicate compound having a vinyl group at the terminal represented by the following chemical formula (4): 10 parts by mass Triazine UV Absorber (“Tinuvin 479 (trade name)”, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5- Triazine, manufactured by Ciba Japan Co., Ltd .: a light stabilizer having 2 parts by mass of a reactive functional group (trade name “Sanol LS-3410”, 1,2,2,6,6-pentamethyl-4-piperidinyl methacrylate , Manufactured by Ciba Japan Co., Ltd.): 6 parts by mass

Example 2
In Example 1, the ionizing radiation curable resin was replaced with caprolactone-based urethane acrylate (trifunctional, molecular weight: about 1200), and the addition amounts of the ultraviolet absorber and the light stabilizer were 2 parts by mass and 6 parts by mass, respectively. Were produced in the same manner as in Example 1.
Said evaluation was performed about the obtained sheet | seat. The evaluation results are shown in Table 1.

Example 3
In Example 2, a transparent polypropylene resin (thickness: 80 μm) containing a polymer type antistatic agent (“Pelestat 300 (trade name)” manufactured by Sanyo Chemical Industries, Ltd., polyether / polyolefin block copolymer) as a base material in Example 2. , Antistatic agent content: 12.5% by mass) A sheet was produced in the same manner as in Example 2.
Said evaluation was performed about the obtained sheet | seat. The evaluation results are shown in Table 1.

Example 4
As the substrate 2, a resin sheet made of a colored polypropylene resin (thickness: 80 μm) was prepared. After performing corona discharge treatment on the front surface and the back surface, a wood grain pattern was formed on the surface by gravure printing to obtain a pattern printing layer 3. On the other hand, a back primer layer 7 (thickness 2 μm) using urethane resin as a binder was formed on the back surface by gravure printing.
Next, a transparent resin layer 4 (thickness 80 μm) obtained by melting a polypropylene-based thermoplastic elastomer with a T-die is formed, and a coating liquid made of a two-component curable urethane resin is applied to form an adhesive layer 8 (dried) In addition, the transparent resin layer 4 was laminated by a dry laminating method.
Next, the surface of the transparent resin layer 4 was heated with an infrared non-contact type heater to soften the surface of the transparent resin layer 4. Immediately thereafter, the surface of the transparent resin layer 4 opposite to the base 2 was embossed by hot pressure to form an uneven pattern of a wood grain conduit groove pattern.
Next, the surface of the transparent resin layer 4 was subjected to a corona discharge treatment and then subjected to a wiping process. The ink composition used for the wiping process was prepared by adding 5% by mass of a colorant (including carbon black, isoindolinone and quinacridone) to the primer layer forming composition used in Example 1, and silica particles (untreated silica “ What was added so that it might be set to 15 mass% (commercial item) average particle diameter of 3 micrometers) was used as the ink composition.
The ink composition was applied to the transparent resin layer 4 and subjected to wiping to form a colored resin layer 9 in the concave portion of the transparent resin layer 4. The application amount was 1.5 g / m ² . Next, the ink composition used to form the colored resin layer 9 was applied to form a primer layer 5 (2.5 g / m ² ).
Next, in the ionizing radiation curable resin composition used in Example 2, 10 parts by mass of silica having an average particle size of 5 μm (oil absorption amount: 200 to 300 ml) with respect to 100 parts by mass of caprolactone-based urethane acrylate in the composition. / 100 g, apparent specific gravity: 0.08 to 0.16 g / cm ³ ), 5 parts by mass of silica having an average particle diameter of 4 μm (oil absorption 0 to 50 ml / 100 g, apparent specific gravity: 0.45 to 0.85 g / cm ³ ) A coating film was formed by gravure coating using a composition to which an amount of 5 parts by mass of wax (aliphatic wax, melting point: 110 to 200 ° C.) was added. Then, the surface protective layer (5 g / m < ² >) was formed by irradiating an electron beam on conditions of 175 keV and 5 Mrad (50 kGy), and carrying out the crosslinking hardening of the said coating film, and obtained the sheet | seat. The thickness of the surface protective layer was 5 μm.

Comparative Example 1
Example 2 is the same as Example 2 except that the silicate compound in the ionizing radiation curable resin composition is changed to ethyl silicate ("ethyl silicate 28 (trade name)", manufactured by Colcoat Co., Ltd., monomer). Thus, a sheet was produced.

Comparative Example 2
In Example 2, except that the silicate compound in the ionizing radiation curable resin composition was changed to ethyl silicate ("Ethyl silicate 48 (trade name)", Colcoat Co., Ltd., 10-mer), the same as in Example 2. Thus, a sheet was produced.

Comparative Example 3
In Example 2, a sheet was produced in the same manner as in Example 2 except that the silicate compound in the ionizing radiation curable resin composition was removed.

  ADVANTAGE OF THE INVENTION According to this invention, the sheet | seat which has the coating composition which provides the self-cleaning performance excellent in the sheet | seat and its sustainability, weather resistance, and transparency, and the protective layer formed with this composition can be provided. The sheet of the present invention is used for applications that require transparency, such as window glass protective sheets and plastic houses, entrance doors and exterior materials for general residences, interior and exterior such as floor materials and exterior walls of public facilities, buildings, It is effective as a use for structures installed outdoors.

1. Cosmetic sheet Base material 3. Pattern printing layer 3a. Picture layer 3b. 3. Colored layer 4. Transparent resin layer Primer layer 6. Surface protective layer 7. Back primer layer 8. 8. Adhesive layer Colored resin layer

Claims (9)

  A coating agent composition comprising an ionizing radiation curable resin and a silicate compound having a reactive functional group A.   The coating composition according to claim 1, wherein the reactive functional group A is a functional group having an ethylenic double bond.   The coating composition according to claim 2, wherein the reactive functional group A is a (meth) acryloyl group.   The coating agent composition according to any one of claims 1 to 3, wherein the content of the silicate compound is 1 to 15 parts by mass with respect to 100 parts by mass of the ionizing radiation curable resin.   The coating agent composition according to claim 1, wherein the ionizing radiation curable resin is a caprolactone-based urethane acrylate.   6. The coating agent composition according to claim 5, wherein the caprolactone-based urethane acrylate has a number average molecular weight (polystyrene equivalent number average molecular weight measured by GPC method) of 1,000 to 10,000.   A sheet having a surface protective layer obtained by crosslinking and curing the coating agent composition according to claim 1.   The sheet according to claim 7, wherein the sheet has at least a base material and a surface protective layer, and the surface protective layer is provided on the outermost surface.   The sheet according to claim 8, wherein the base material contains at least one antistatic agent selected from a polyether / polyolefin block copolymer and a polyether ester amide.

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