JP2017180018A - Building board - Google Patents
Building board Download PDFInfo
- Publication number
- JP2017180018A JP2017180018A JP2016072646A JP2016072646A JP2017180018A JP 2017180018 A JP2017180018 A JP 2017180018A JP 2016072646 A JP2016072646 A JP 2016072646A JP 2016072646 A JP2016072646 A JP 2016072646A JP 2017180018 A JP2017180018 A JP 2017180018A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- active energy
- energy ray
- ink
- building board
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 196
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000012463 white pigment Substances 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 239000011241 protective layer Substances 0.000 claims abstract description 22
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 21
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005083 Zinc sulfide Substances 0.000 claims abstract description 15
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 15
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 9
- 239000010445 mica Substances 0.000 claims abstract description 9
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- 239000000454 talc Substances 0.000 claims abstract description 9
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
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- 239000008199 coating composition Substances 0.000 claims description 31
- 239000000758 substrate Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- 238000012216 screening Methods 0.000 claims description 2
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- 125000000524 functional group Chemical group 0.000 description 6
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- IQGIEMYBDGDBMR-UHFFFAOYSA-N (3-methyl-5-prop-2-enoyloxypentyl) prop-2-enoate Chemical compound C=CC(=O)OCCC(C)CCOC(=O)C=C IQGIEMYBDGDBMR-UHFFFAOYSA-N 0.000 description 1
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
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- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical class C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 description 1
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- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
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- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Finishing Walls (AREA)
- Laminated Bodies (AREA)
- Chemical And Physical Treatments For Wood And The Like (AREA)
Abstract
Description
本発明は、建築板に関し、基材と着色インク層との間に介在しかつインクの発色性及び硬化性に優れる介在層を備える建築板に関するものである。 The present invention relates to a building board, and more particularly to a building board provided with an intervening layer that is interposed between a base material and a colored ink layer and is excellent in color development and curability of ink.
近年、様々な意匠が施された建築板が使用されているが、意匠性の高い建築板を作製するためには、インクジェットプリンターを用いる印刷方法等が利用されている。 In recent years, building boards to which various designs have been applied have been used, and in order to produce a building board having high design properties, a printing method using an ink jet printer or the like is used.
特開２０１２−１１１０６９号公報（特許文献１）は、木質基材の表面にインクジェット印刷により印刷層を形成してなる加飾木材を記載するが、印刷層の可視光領域における透過率を調整することで、天然木材の照りを高度に維持できることを記載している。 Japanese Unexamined Patent Publication No. 2012-111069 (Patent Document 1) describes a decorative wood formed by forming a printing layer on the surface of a wooden substrate by ink jet printing, but adjusts the transmittance in the visible light region of the printing layer. Therefore, it is described that the shine of natural wood can be maintained at a high level.
特開２０１４−２２６９１３号公報（特許文献２）は、印刷層の表面にインクジェット印刷により形成される印刷層を備える塗装建材を記載するが、透明な受理層よりも下層に有色の下塗層を設け、この下塗層を利用することで、深み感や立体感に優れた外観を現出する塗装建材を提供できることを記載している。 Japanese Patent Application Laid-Open No. 2014-226913 (Patent Document 2) describes a painted building material having a printed layer formed by inkjet printing on the surface of a printed layer, but a colored undercoat layer below the transparent receiving layer. It is described that it is possible to provide a painted building material that exhibits an appearance that is excellent in depth and three-dimensionality by using this undercoat layer.
特開２０１４−１９３５７５号公報（特許文献３）は、木質基材の表面に着色透明の下地膜を形成し、下地膜上に印刷模様をインクジェット印刷することで、木質基材の色合いを隠蔽することを避けることができ、結果として、色合いの深み感があり、立体的な印象の外観となる化粧板を提供できることを記載している。 Japanese Unexamined Patent Publication No. 2014-193575 (Patent Document 3) forms a colored transparent base film on the surface of a wooden base material, and conceals the color of the wooden base material by inkjet printing a printed pattern on the base film. It can be avoided, and as a result, it is described that it is possible to provide a decorative board that has a deep sense of color and has a three-dimensional appearance.
特許文献１〜３に記載されるように、印刷層の意匠性を向上させるため、様々な手法が提案されているものの、インクの発色性については十分に検討されていないのが現状である。 As described in Patent Documents 1 to 3, although various methods have been proposed in order to improve the design properties of the printed layer, the color development property of the ink has not been sufficiently studied.
そこで、本発明の目的は、上記従来技術の問題を解決し、基材と着色インク層との間に介在しかつインクの発色性及び硬化性に優れる介在層を備える建築板を提供することにある。 Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, and to provide a building board provided with an intervening layer that is interposed between a base material and a colored ink layer and is excellent in ink color development and curability. is there.
本発明者は、インクの発色性について検討したところ、基材と着色インク層との間に介在する介在層に着色顔料を配合することで、下層に位置する建築板の基材や塗膜等を隠蔽することができ、インクの発色性を向上できることが分かったが、着色顔料の中でも、白色顔料を用いることで、インクの発色性を大幅に向上できることを見出した。 The inventor examined the color developability of the ink, and by blending the color pigment in the intervening layer interposed between the base material and the colored ink layer, the base material, the coating film, etc. of the building board located in the lower layer It was found that the color development of the ink can be improved and the color developability of the ink can be improved. However, it has been found that the color developability of the ink can be greatly improved by using a white pigment among the colored pigments.
しかしながら、本発明者は、塗料組成物の中でも活性エネルギー線硬化型塗料組成物に酸化チタンのような白色顔料を配合した場合、塗料組成物の硬化性が悪く、発色性との両立が困難になることが分かった。また、塗料組成物の硬化性が悪いと、硬化後の塗膜の付着性（特に初期付着性）が悪く、耐久性を低下させる原因となる。このような状況下、本発明者は、酸化チタンが紫外線等を吸収してしまい硬化性を低下させているものと考え、他の様々な白色顔料について検討したところ、硫化亜鉛等の特定の白色顔料をインク受容層用の活性エネルギー線硬化型塗料組成物に配合した場合、塗料組成物の硬化性を低下させることなくインクの発色性を向上できることを見出し、本発明を完成させるに至った。 However, the present inventor, when blending a white pigment such as titanium oxide with the active energy ray-curable coating composition among the coating compositions, the curability of the coating composition is poor and it is difficult to achieve both color development. I found out that Further, when the coating composition has poor curability, the coating film after curing has poor adhesion (particularly initial adhesion), which causes a decrease in durability. Under such circumstances, the present inventor considered that titanium oxide absorbs ultraviolet rays and the like to reduce curability, and examined various other white pigments. As a result, a specific white color such as zinc sulfide was obtained. It has been found that when a pigment is blended in an active energy ray-curable coating composition for an ink receiving layer, the color development of the ink can be improved without lowering the curability of the coating composition, and the present invention has been completed.
即ち、本発明の建築板は、基材と、着色インク層と、基材及び着色インク層の間に介在する介在層と、少なくとも着色インク層を覆うように形成された表面保護層とを備える建築板であって、前記介在層が、硫化亜鉛、硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ、アルミナよりなる群から選択される少なくとも１種を含む白色顔料を含みかつ活性エネルギー線硬化型塗料組成物により形成される白色顔料層を有し、前記着色インク層が、活性エネルギー線硬化型インク組成物により形成されることを特徴とする。 That is, the building board of the present invention includes a base material, a colored ink layer, an intervening layer interposed between the base material and the colored ink layer, and a surface protective layer formed so as to cover at least the colored ink layer. An active energy ray-curable coating material, wherein the intermediate layer includes a white pigment containing at least one selected from the group consisting of zinc sulfide, barium sulfate, calcium carbonate, talc, mica, silica, and alumina. It has a white pigment layer formed of a composition, and the colored ink layer is formed of an active energy ray-curable ink composition.
本発明の建築板の好適例においては、前記白色顔料層は、少なくとも、前記着色インク層に隣接するインク受容層である。 In a preferred embodiment of the building board of the present invention, the white pigment layer is at least an ink receiving layer adjacent to the colored ink layer.
本発明の建築板の好適例においては、前記表面保護層が、活性エネルギー線硬化型塗料組成物により形成される。 In the suitable example of the building board of this invention, the said surface protection layer is formed with an active energy ray hardening-type coating composition.
本発明の建築板の他の好適例においては、前記白色顔料が、硫化亜鉛を含む。 In another preferred embodiment of the building board of the present invention, the white pigment contains zinc sulfide.
本発明の建築板の他の好適例においては、前記介在層は、前記着色インク層に隣接するインク受容層と、前記基材及び前記インク受容層の間に位置する下塗り層とを備えており、該下塗り層が、活性エネルギー線硬化型塗料組成物により形成される。 In another preferred embodiment of the building board of the present invention, the intervening layer includes an ink receiving layer adjacent to the colored ink layer, and an undercoat layer positioned between the substrate and the ink receiving layer. The undercoat layer is formed of an active energy ray-curable coating composition.
本発明によれば、基材と着色インク層との間に介在しかつインクの発色性及び硬化性に優れる介在層を備える建築板を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, a building board provided with the intervening layer which is interposed between a base material and a colored ink layer, and is excellent in the color development property and sclerosis | hardenability of an ink can be provided.
以下に、本発明の建築板を詳細に説明する。本発明の建築板は、基材と、着色インク層と、基材及び着色インク層の間に介在する介在層と、少なくとも着色インク層を覆うように形成された表面保護層とを備える建築板であって、前記介在層が、硫化亜鉛、硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ、アルミナよりなる群から選択される少なくとも１種を含む白色顔料を含みかつ活性エネルギー線硬化型塗料組成物により形成される白色顔料層を有し、前記着色インク層が、活性エネルギー線硬化型インク組成物により形成されることを特徴とする。 Below, the building board of this invention is demonstrated in detail. A building board of the present invention comprises a base plate, a colored ink layer, an intervening layer interposed between the base material and the colored ink layer, and a surface protective layer formed so as to cover at least the colored ink layer. The intermediate layer includes a white pigment containing at least one selected from the group consisting of zinc sulfide, barium sulfate, calcium carbonate, talc, mica, silica, and alumina, and an active energy ray-curable coating composition. The colored ink layer is formed of an active energy ray-curable ink composition.
本発明の建築板を構成する基材は、建材である限り特に限定されるものではない。建材の具体例としては、例えば、単板、合板、パーティクルボード、中密度繊維板（ＭＤＦ）等の木材を原料とする木質建材板；窯業系サイディングボード、フレキシブルボードや、珪酸カルシウム板、石膏スラグバーライト板、木片セメント板、石綿セメント板、パルプセメント板、プレキャストコンクリート板、軽量気泡コンクリート（ＡＬＣ）板、石膏ボード等の窯業建材板；及びアルミニウム、鉄、ステンレス等の金属建材板等が挙げられる。これら基材の中でも、木質建材板の木目のように模様の付いた基材である場合、介在層によって基材の模様を隠蔽することができる為、本発明によって達成されるインクの発色性の向上効果がより有効なものとなる。基材の表面性状は、特に制限はなく、表面が平滑なものであっても、凹凸形状を有するものであってもよい。また、基材は、シーラーやプライマー等によって下地処理が施されていてもよい。本発明の建築板において、基材の厚みは、特に制限されるものではないが、例えば３〜３０ｍｍである。 The base material which comprises the building board of this invention is not specifically limited as long as it is a building material. Specific examples of building materials include, for example, wooden building material boards made of wood such as single board, plywood, particle board, medium density fiber board (MDF); ceramic siding boards, flexible boards, calcium silicate boards, gypsum slag Barite board, wood chip cement board, asbestos cement board, pulp cement board, precast concrete board, lightweight cellular concrete (ALC) board, ceramic building material board such as gypsum board; and metal building material board such as aluminum, iron, stainless steel, etc. It is done. Among these base materials, in the case of a base material having a pattern like a wood grain of a wood building material board, the pattern of the base material can be concealed by the intervening layer, so that the color development property of the ink achieved by the present invention is improved. The improvement effect becomes more effective. The surface property of the substrate is not particularly limited, and may be a surface having a smooth surface or an uneven shape. In addition, the base material may be subjected to a base treatment with a sealer, a primer, or the like. In the building board of the present invention, the thickness of the base material is not particularly limited, but is, for example, 3 to 30 mm.
本発明の建築板を構成する介在層は、例えば、着色インク層に隣接するインク受容層を有することが好ましい。インク受容層は、主に着色インク層を定着させる目的で、基材上に配置されるが、基材上に下塗り層が形成されている場合、該下塗り層上に配置される。本発明の建築板においては、インク受容層が、硫化亜鉛、硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ、アルミナよりなる群から選択される少なくとも１種を含む白色顔料を含んでもよく、この場合、インク受容層の硬化性を低下させることなくインクの発色性を向上させることができる。なお、インク受容層以外の介在層が白色顔料を含む限りにおいて、当該白色顔料層より下の層の模様を隠蔽し、インクの発色性を向上できるため、インク受容層が必ずしも白色顔料を含まなくてもよい。ただし、インク受容層は着色インク層に隣接する（つまり介在層のうち最も上に位置する）層であるから、インク受容層が白色顔料を含むことは、模様の隠蔽が可能な層が多くなり、インクの発色性を一層向上できる点で有利である。 The intervening layer constituting the building board of the present invention preferably has, for example, an ink receiving layer adjacent to the colored ink layer. The ink receiving layer is disposed on the base material mainly for the purpose of fixing the colored ink layer. When an undercoat layer is formed on the base material, the ink receiving layer is disposed on the undercoat layer. In the building board of the present invention, the ink receiving layer may contain a white pigment containing at least one selected from the group consisting of zinc sulfide, barium sulfate, calcium carbonate, talc, mica, silica, and alumina. In addition, the color developability of the ink can be improved without reducing the curability of the ink receiving layer. As long as the intervening layer other than the ink receiving layer contains a white pigment, the ink receiving layer does not necessarily contain a white pigment because the pattern of the layer below the white pigment layer can be concealed and the color development of the ink can be improved. May be. However, since the ink receiving layer is a layer adjacent to the colored ink layer (that is, the uppermost layer among the intervening layers), the inclusion of the white pigment in the ink receiving layer increases the number of layers that can conceal the pattern. This is advantageous in that the color developability of the ink can be further improved.
白色顔料の中でも、硫化亜鉛を含むことが好ましく、具体的には硫化亜鉛からなる、又は硫化亜鉛と硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ、アルミナの１種以上（中でも硫酸バリウム）とを含むことが好ましい。 Among white pigments, it is preferable to contain zinc sulfide, specifically zinc sulfide, or one or more of zinc sulfide and barium sulfate, calcium carbonate, talc, mica, silica, alumina (particularly barium sulfate). It is preferable to include.
上記インク受容層中において、上述の白色顔料の含有量は、１０〜５０質量％であることが好ましい。中でも、白色顔料（特に硫化亜鉛からなる、又は硫化亜鉛と硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ、アルミナの１種以上（中でも硫酸バリウム）とを含む白色顔料）の含有量は、インク発色性をより向上させる観点で１５質量％以上であることが好ましく、より好ましくは２０質量％以上、さらに好ましくは２５質量％以上である。このようにインク発色性を向上させるために比較的多量の白色顔料を含めても、本発明で用いる白色顔料はインク受容層の硬化性を損ないにくい点で有利である。また、白色顔料の含有量は、インク受容層の硬化性の観点から４５質量％未満が好ましく、より好ましくは４０質量％以下、さらに好ましくは３５質量％以下である。 In the ink-receiving layer, the content of the white pigment is preferably 10 to 50% by mass. Among them, the content of white pigment (particularly zinc sulfide, or white pigment containing zinc sulfide and one or more of barium sulfate, calcium carbonate, talc, mica, silica, and alumina (particularly barium sulfate)) is the color of the ink. From the viewpoint of further improving the properties, the content is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more. Thus, even if a relatively large amount of white pigment is included in order to improve the ink color developability, the white pigment used in the present invention is advantageous in that the curability of the ink receiving layer is hardly impaired. Further, the content of the white pigment is preferably less than 45% by mass from the viewpoint of curability of the ink receiving layer, more preferably 40% by mass or less, and further preferably 35% by mass or less.
また、上記インク受容層は、少なくとも上記白色顔料を含む活性エネルギー線硬化型塗料組成物により形成され得るものであるが、後述するように、インク受容層上に形成される着色インク層も活性エネルギー線硬化型塗料組成物により形成されるため、層間付着性を向上させることができる。なお、活性エネルギー線硬化型塗料組成物の詳細な説明については、後述する。 The ink receiving layer can be formed of an active energy ray-curable coating composition containing at least the white pigment. As described later, the colored ink layer formed on the ink receiving layer is also active energy. Since it is formed with a wire curable coating composition, interlayer adhesion can be improved. The detailed description of the active energy ray-curable coating composition will be described later.
本発明の建築板において、インク受容層の厚みは、特に制限されるものではないが、例えば１０〜１００μｍである。本発明で用いる白色顔料は活性エネルギー線硬化性を損ないにくいので、白色顔料を含有するインク受容層は、比較的高い厚みを有しても、活性エネルギー線硬化性に優れる点で有利である。白色顔料を含有するインク受容層の厚みは、２０〜７０μｍであることが好ましく、２０〜４０μｍであることがより好ましい。 In the building board of the present invention, the thickness of the ink receiving layer is not particularly limited, but is, for example, 10 to 100 μm. Since the white pigment used in the present invention hardly impairs the active energy ray curability, the ink receiving layer containing the white pigment is advantageous in that it has excellent active energy ray curability even if it has a relatively high thickness. The thickness of the ink receiving layer containing a white pigment is preferably 20 to 70 μm, and more preferably 20 to 40 μm.
本発明の建築板を構成する着色インク層は、建築板に意匠を施す目的で、インク組成物を用いてインク受容層上で印刷を行うことによって形成されてよい。また、このような目的から、着色インク層は、通常、着色顔料を含む。着色顔料としては、公知の材料が使用でき、例えば、カーボンブラック、酸化鉄、複合酸化物（ニッケル・チタン系、クロム・チタン系、ビスマス・バナジウム系）、酸化チタン等の無機顔料や、キナクリドン系、ジケトプロロピール系、ベンズイミダゾロン系、イソインドリノン系、アンスラピリミジン系、フタロシアニン系、スレン系、ジオキサジン系、アゾ系等の有機顔料が挙げられる。上記着色インク層中において、着色顔料の含有量は、１〜２０質量％であることが好ましく、１〜１０質量％であることがより好ましい。 The colored ink layer constituting the building board of the present invention may be formed by printing on the ink receiving layer using an ink composition for the purpose of giving a design to the building board. For such purposes, the colored ink layer usually contains a colored pigment. As the coloring pigment, known materials can be used. For example, carbon black, iron oxide, composite oxides (nickel / titanium system, chromium / titanium system, bismuth / vanadium system), inorganic oxides such as titanium oxide, and quinacridone series And organic pigments such as diketoprolope, benzimidazolone, isoindolinone, anthrapyrimidine, phthalocyanine, selenium, dioxazine, and azo. In the colored ink layer, the content of the color pigment is preferably 1 to 20% by mass, and more preferably 1 to 10% by mass.
また、本発明の建築板においては、着色インク層が活性エネルギー線硬化型インク組成物により形成され得る。この場合、インク受容層と着色インク層の層間付着性を向上させることができる。なお、活性エネルギー線硬化型インク組成物の詳細な説明については、後述する。 In the building board of the present invention, the colored ink layer can be formed of an active energy ray-curable ink composition. In this case, interlayer adhesion between the ink receiving layer and the colored ink layer can be improved. The detailed description of the active energy ray-curable ink composition will be described later.
本発明の建築板において、着色インク層の厚みは、特に制限されるものではないが、例えば５〜４０μｍである。 In the building board of the present invention, the thickness of the colored ink layer is not particularly limited, but is, for example, 5 to 40 μm.
本発明の建築板を構成する表面保護層は、主に着色インク層の表面を保護する目的で、少なくとも着色インク層を覆うように配置されている。例えば、インク受容層等の介在層の表面全体が着色インク層で被覆されている場合、表面保護層は、着色インク層等の介在層の表面にのみ形成され、インク受容層等の介在層の一部が露出している場合、表面保護層は、着色インク層の表面と、露出したインク受容層等の介在層の表面に形成される。 The surface protective layer constituting the building board of the present invention is disposed so as to cover at least the colored ink layer for the purpose of mainly protecting the surface of the colored ink layer. For example, when the entire surface of an intervening layer such as an ink receptive layer is covered with a colored ink layer, the surface protective layer is formed only on the surface of the intervening layer such as a colored ink layer. When a part is exposed, the surface protective layer is formed on the surface of the colored ink layer and the surface of the intervening layer such as the exposed ink receiving layer.
また、上記表面保護層は、着色インク層やインク受容層等の介在層の表面に形成されるため、これら層との付着性を高めることが好ましいが、建築板の最表面を構成しており、耐擦り傷性等の耐久性が求められる場合もある。この場合、上記表面保護層は、性質の異なる複数の層で構成されることが好ましい。例えば、着色インク層やインク受容層等の介在層に接するが建築板の最も外側に位置していない表面保護層（このような表面保護層を中塗り層と称してもよい）を作る際には、付着性や耐摩耗性を向上させる観点から、表面保護層用（中塗り層用）の塗料組成物を調製することができ、また、建築板の最も外側に位置するが着色インク層やインク受容層等の介在層には接していない表面保護層（このような表面保護層を上塗り層と称してもよい）を作る際には、耐久性を向上させる観点から、表面保護層用（上塗り層用）の塗料組成物を調製することができる。 In addition, since the surface protective layer is formed on the surface of an intervening layer such as a colored ink layer or an ink receiving layer, it is preferable to improve adhesion with these layers, but it constitutes the outermost surface of the building board. In some cases, durability such as scratch resistance is required. In this case, the surface protective layer is preferably composed of a plurality of layers having different properties. For example, when making a surface protective layer that contacts an intervening layer such as a colored ink layer or an ink receiving layer but is not located on the outermost side of the building board (such a surface protective layer may be referred to as an intermediate coating layer). Is capable of preparing a coating composition for a surface protective layer (for an intermediate coating layer) from the viewpoint of improving adhesion and wear resistance, and is located on the outermost side of a building board. When making a surface protective layer that is not in contact with an intervening layer such as an ink receiving layer (such a surface protective layer may be referred to as an overcoat layer), from the viewpoint of improving durability, the surface protective layer ( A coating composition for the top coat layer) can be prepared.
本発明の建築板において、表面保護層の厚み（複数枚の層で構成される場合はその合計の厚み）は、特に制限されるものではないが、例えば１０〜１００μｍである。 In the building board of the present invention, the thickness of the surface protective layer (the total thickness in the case of a plurality of layers) is not particularly limited, but is, for example, 10 to 100 μm.
また、本発明の建築板においては、層間付着性を向上させる観点から、上記表面保護層が、活性エネルギー線硬化型塗料組成物により形成されることが好ましい。なお、活性エネルギー線硬化型塗料組成物の詳細な説明については、後述する。 Moreover, in the building board of this invention, it is preferable that the said surface protective layer is formed with an active energy ray hardening-type coating composition from a viewpoint of improving interlayer adhesiveness. The detailed description of the active energy ray-curable coating composition will be described later.
本発明の建築板は、基材とインク受容層との付着性を向上させる観点から、基材とインク受容層の間に下塗り層を備えてもよい。ここで、下塗り層は、層間付着性を向上させる観点から、活性エネルギー線硬化型塗料組成物により形成されることが好ましい。また、下塗り層が白色顔料を含有してもよく、これにより基材の模様を隠蔽することができる。使用できる白色顔料やその含有量等は、前述のとおりである。なお、活性エネルギー線硬化型塗料組成物の詳細な説明については、後述する。 The building board of the present invention may include an undercoat layer between the substrate and the ink receiving layer from the viewpoint of improving the adhesion between the substrate and the ink receiving layer. Here, the undercoat layer is preferably formed of an active energy ray-curable coating composition from the viewpoint of improving interlayer adhesion. Further, the undercoat layer may contain a white pigment, whereby the pattern of the substrate can be concealed. The white pigments that can be used and their contents are as described above. The detailed description of the active energy ray-curable coating composition will be described later.
本発明の建築板において、下塗り層の厚みは、特に制限されるものではないが、例えば１０〜５０μｍである。 In the building board of the present invention, the thickness of the undercoat layer is not particularly limited, but is, for example, 10 to 50 μm.
本発明の建築板においては、インク受容層等の介在層が活性エネルギー線硬化型塗料組成物により形成され、着色インク層が活性エネルギー線硬化型インク組成物により形成されるものであり、また、表面保護層及び下塗り層も、活性エネルギー線硬化型塗料組成物により形成されることが好適であるが、これら組成物は、塗料組成物がエアスプレー塗装、エアレススプレー塗装、静電塗装、ロールコーター塗装、フローコーター塗装等の塗布方法によって塗装されるのに対し、インク組成物がインクジェットプリンターによる印刷（即ち、インクジェット方式）等の印刷手段によって印刷されるといった点に違いはあるものの、紫外線等の活性エネルギー線の照射により硬化を起こす組成物である点で共通しており、いずれの組成物も、通常、活性エネルギー線重合性モノマーを含む。活性エネルギー線重合性モノマーとは、紫外線等の活性エネルギー線の照射により重合反応を開始可能なモノマーであり、例えば、活性エネルギー線照射時に反応性を示す官能基として、アクリロイルオキシ基やメタクリロイルオキシ基を有するものが好適である。活性エネルギー線重合性モノマーの重合後に得られるポリマーは、バインダー樹脂として機能する。なお、活性エネルギー線重合性モノマーは、官能基の数に応じて、官能基数が１である単官能モノマー、官能基数が２である２官能モノマー及び官能基数が３以上の多官能モノマーに分類できる。 In the building board of the present invention, an intervening layer such as an ink receiving layer is formed of an active energy ray curable coating composition, and a colored ink layer is formed of an active energy ray curable ink composition. The surface protective layer and the undercoat layer are also preferably formed of an active energy ray-curable coating composition. However, these compositions may be applied by air spray coating, airless spray coating, electrostatic coating, roll coater. Although there is a difference in that the ink composition is printed by a printing means such as printing by an ink jet printer (that is, an ink jet method), while it is painted by a coating method such as painting or flow coater coating, ultraviolet It is common in that it is a composition that cures when irradiated with active energy rays. Contain the active energy ray-polymerizable monomer. The active energy ray polymerizable monomer is a monomer capable of initiating a polymerization reaction upon irradiation with an active energy ray such as ultraviolet rays. For example, an acryloyloxy group or a methacryloyloxy group can be used as a functional group exhibiting reactivity upon irradiation with an active energy ray. Those having the following are preferred. The polymer obtained after the polymerization of the active energy ray polymerizable monomer functions as a binder resin. The active energy ray polymerizable monomer can be classified into a monofunctional monomer having 1 functional group, a bifunctional monomer having 2 functional groups, and a polyfunctional monomer having 3 or more functional groups, depending on the number of functional groups. .
上記活性エネルギー線重合性モノマーのうち、単官能モノマーは、その分子量が１０００以下であるものが好ましく、具体例としては、ステアリルアクリレート、アクリロイルモルホリン、トリデシルアクリレート、ラウリルアクリレート、Ｎ，Ｎ−ジメチルアクリルアミド、デシルアクリレート、２−フェノキシエチルアクリレート、イソデシルアクリレート、イソボルニルアクリレート、ジシクロペンタニルアクリレート、ジシクロペンテニルアクリレート、イソオクチルアクリレート、オクチルアクリレート、ジシクロペンテニルオキシエチルアクリレート、シクロヘキシルアクリレート、Ｎ−ビニルカプロラクタム、イソアミルアクリレート、２−エチルヘキシル−ジグリコールアクリレート、ＥＯ（エチレンオキシド）変性２−エチルヘキシルアクリレート、ネオペンチルグリコールアクリル酸安息香酸エステル、Ｎ−ビニル−２−ピロリドン、Ｎ−ビニルイミダゾール、テトラヒドロフルフリルアクリレート、メトキシジプロピレングリコールアクリレート、（２−メチル−２−エチル−１，３−ジオキソラン−４−イル）メチルアクリレート、環状トリメチロールプロパンフォルマルアクリレート、エトキシ−ジエチレングリコールアクリレート、４−ヒドロキシブチルアクリレート等が挙げられる。なお、これら単官能モノマーは、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Among the active energy ray polymerizable monomers, the monofunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include stearyl acrylate, acryloylmorpholine, tridecyl acrylate, lauryl acrylate, N, N-dimethylacrylamide. , Decyl acrylate, 2-phenoxyethyl acrylate, isodecyl acrylate, isobornyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, isooctyl acrylate, octyl acrylate, dicyclopentenyloxyethyl acrylate, cyclohexyl acrylate, N-vinyl Caprolactam, isoamyl acrylate, 2-ethylhexyl-diglycol acrylate, EO (ethylene oxide) modified Ruhexyl acrylate, neopentyl glycol acrylic acid benzoate, N-vinyl-2-pyrrolidone, N-vinylimidazole, tetrahydrofurfuryl acrylate, methoxydipropylene glycol acrylate, (2-methyl-2-ethyl-1,3-dioxolane) -4-yl) methyl acrylate, cyclic trimethylolpropane formal acrylate, ethoxy-diethylene glycol acrylate, 4-hydroxybutyl acrylate and the like. In addition, these monofunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
上記活性エネルギー線重合性モノマーのうち、２官能モノマーは、その分子量が１０００以下であるものが好ましく、具体例としては、１，１０−デカンジオールジアクリレート、２−メチル−１，８−オクタンジオールジアクリレート、２−ブチル−２−エチル−１，３−プロパンジオールジアクリレート、１，９−ノナンジオールジアクリレート、１，８−オクタンジオールジアクリレート、１，７−ヘプタンジオールジアクリレート、ポリテトラメチレングリコールジアクリレート、３−メチル−１，５−ペンタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート、トリプロピレングリコールジアクリレート、１，４−ブタンジオールジアクリレート、及びジプロピレングリコールジアクリレート等が挙げられる。なお、これら２官能モノマーは、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Among the active energy ray polymerizable monomers, the bifunctional monomer preferably has a molecular weight of 1000 or less. Specific examples include 1,10-decanediol diacrylate and 2-methyl-1,8-octanediol. Diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate, 1,9-nonanediol diacrylate, 1,8-octanediol diacrylate, 1,7-heptanediol diacrylate, polytetramethylene Glycol diacrylate, 3-methyl-1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, hydroxypivalate neopentyl glycol diacrylate, tripropylene glycol diacrylate 1,4-butanediol diacrylate, and dipropylene glycol diacrylate, and the like. In addition, these bifunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
上記活性エネルギー線重合性モノマーのうち、３官能以上の多官能モノマーは、その分子量が２０００以下であるものが好ましく、具体例としては、トリメチロールプロパントリアクリレート、エトキシ化トリメチロールプロパントリアクリレート、プロポキシ化トリメチロールプロパントリアクリレート、ペンタエリスリトールトリアクリレート、エトキシ化グリセリントリアクリレート、ペンタエリスリトールテトラアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ＥＯ変性ジグリセリンテトラアクリレート、ジトリメチロールプロパンテトラアクリレート、ジペンタエリスリトールペンタアクリレート、及びジペンタエリスリトールヘキサアクリレート等が挙げられる。なお、これら多官能モノマーは、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。 Among the active energy ray polymerizable monomers, the trifunctional or higher polyfunctional monomer preferably has a molecular weight of 2000 or less. Specific examples thereof include trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxy. Trimethylolpropane triacrylate, pentaerythritol triacrylate, ethoxylated glycerin triacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, EO-modified diglycerin tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol pentaacrylate, and Examples include dipentaerythritol hexaacrylate. In addition, these polyfunctional monomers may be used individually by 1 type, and may be used in combination of 2 or more type.
上記活性エネルギー線硬化型インク組成物中において、活性エネルギー線重合性モノマーの含有量は、使用目的により任意に決定できるが、０．１〜９０質量％であることが好ましく、１０〜９０質量％であることが更に好ましい。一方、活性エネルギー線硬化型塗料組成物における活性エネルギー線重合性モノマーは、任意成分である。 In the active energy ray-curable ink composition, the content of the active energy ray polymerizable monomer can be arbitrarily determined depending on the purpose of use, but is preferably 0.1 to 90% by mass, and preferably 10 to 90% by mass. More preferably. On the other hand, the active energy ray polymerizable monomer in the active energy ray curable coating composition is an optional component.
また、上記活性エネルギー線硬化型塗料組成物及び活性エネルギー線硬化型インク組成物には、アクリレートオリゴマーを使用してもよい。アクリレートオリゴマーとは、アクリロイルオキシ基（ＣＨ２＝ＣＨＣＯＯ−）を一つ以上有するオリゴマーであり、官能基数は２〜６であることが好ましい。また、アクリレートオリゴマーは、分子量が２０００〜２００００であることが好ましい。なお、該分子量は、ポリスチレン換算の重量平均分子量である。そして、アクリレートオリゴマーの具体例としては、アミノアクリレートオリゴマー［アミノ基に由来する基を複数持つアクリレートオリゴマー］、ウレタンアクリレートオリゴマー［ウレタン結合（−ＮＨＣＯＯ−）を複数持つアクリレートオリゴマー］、エポキシアクリレートオリゴマー［エポキシ基に由来する基を複数持つアクリレートオリゴマー］、シリコーンアクリレートオリゴマー［シロキサン結合（−ＳｉＯ−）を複数持つアクリレートオリゴマー］、ポリエステルアクリレートオリゴマー［エステル結合（−ＣＯＯ−）を複数持つアクリレートオリゴマー］及びポリブタジエンアクリレートオリゴマー［ブタジエン単位を複数持つアクリレートオリゴマー］等が挙げられる。なお、上記活性エネルギー線硬化型塗料組成物において、アクリレートオリゴマーの含有量は、使用目的により任意に決定できるが、例えば０．１〜５０質量％であることが好ましい。一方、活性エネルギー線硬化型インク組成物におけるアクリレートオリゴマーは、任意成分である。 In addition, an acrylate oligomer may be used in the active energy ray curable coating composition and the active energy ray curable ink composition. An acrylate oligomer is an oligomer having one or more acryloyloxy groups (CH 2 ═CHCOO—), and preferably has 2 to 6 functional groups. The acrylate oligomer preferably has a molecular weight of 2000 to 20000. In addition, this molecular weight is a weight average molecular weight of polystyrene conversion. Specific examples of the acrylate oligomer include amino acrylate oligomer [acrylate oligomer having a plurality of groups derived from amino groups], urethane acrylate oligomer [acrylate oligomer having a plurality of urethane bonds (-NHCOO-)], epoxy acrylate oligomer [epoxy Acrylate oligomer having a plurality of groups derived from a group], silicone acrylate oligomer [acrylate oligomer having a plurality of siloxane bonds (—SiO—)], polyester acrylate oligomer [acrylate oligomer having a plurality of ester bonds (—COO—)] and polybutadiene acrylate Examples include oligomers [acrylate oligomers having a plurality of butadiene units]. In addition, in the said active energy ray hardening-type coating composition, although content of an acrylate oligomer can be determined arbitrarily by the intended purpose, it is preferable that it is 0.1-50 mass%, for example. On the other hand, the acrylate oligomer in the active energy ray-curable ink composition is an optional component.
また、上記活性エネルギー線硬化型塗料組成物が、インク受容層用の塗料組成物である場合、活性エネルギー線重合性モノマーやアクリレートオリゴマーに加えて、上述した白色顔料を含んでもよく、一方、上記活性エネルギー線硬化型インク組成物は、着色インク層を形成するため、通常、着色顔料を含む。なお、上記活性エネルギー線硬化型塗料組成物及び活性エネルギー線硬化型インク組成物には、上述した成分以外にも、塗料業界やインク業界で通常使用される添加剤、例えば、光重合開始剤、光安定剤、重合禁止剤、有機溶剤、酸化防止剤、シランカップリング剤、可塑剤、消泡剤、表面調整剤、湿潤分散剤、レオロジーコントロール剤、紫外線吸収剤等を本発明の目的を害しない範囲内で適宜選択して配合してもよい。 In addition, when the active energy ray-curable coating composition is a coating composition for an ink receiving layer, in addition to the active energy ray-polymerizable monomer and acrylate oligomer, the active energy ray-curable coating composition may contain the above-described white pigment. The active energy ray-curable ink composition usually contains a colored pigment in order to form a colored ink layer. In addition to the above-described components, the active energy ray-curable coating composition and the active energy ray-curable ink composition include additives commonly used in the paint industry and the ink industry, such as a photopolymerization initiator, Light stabilizers, polymerization inhibitors, organic solvents, antioxidants, silane coupling agents, plasticizers, antifoaming agents, surface conditioners, wetting and dispersing agents, rheology control agents, ultraviolet absorbers, etc. It may be appropriately selected and blended within the range not to be used.
上記活性エネルギー線硬化型塗料組成物及び活性エネルギー線硬化型インク組成物は、必要に応じて適宜選択される各種成分を混合することによって調製できる。また、塗装又は印刷後に形成される各層に対して、メタルハライドランプ、高圧水銀ランプ又は紫外線ＬＥＤ等を用いて紫外線光等の活性エネルギー線を照射して、硬化させることが好ましい。各層を硬化させるために照射する活性エネルギー線の波長は、光重合開始剤の吸収波長と重複していることが好ましく、活性エネルギー線の主波長が３６０〜４２５ｎｍであることが好ましい。なお、本発明のインク受容層等の介在層は活性エネルギー線硬化性に優れるので、積算光量が比較的少量であってもよく、特に限定されないが、１００〜５００ｍＪ／ｃｍ２であることが好ましい。 The active energy ray curable coating composition and the active energy ray curable ink composition can be prepared by mixing various components appropriately selected as necessary. Moreover, it is preferable to cure each layer formed after painting or printing by irradiating active energy rays such as ultraviolet light using a metal halide lamp, a high-pressure mercury lamp, or an ultraviolet LED. The wavelength of the active energy ray irradiated for curing each layer preferably overlaps with the absorption wavelength of the photopolymerization initiator, and the main wavelength of the active energy ray is preferably 360 to 425 nm. Since the intervening layer such as the ink receiving layer of the present invention is excellent in active energy ray curability, the integrated light amount may be relatively small, and is not particularly limited, but is preferably 100 to 500 mJ / cm 2. .
次に、図を参照しながら、本発明の建築板の実施態様について説明する。図１は、本発明の建築板の一実施態様の概略断面図である。図１の建築板１は、基材２と、該基材２上に配置された下塗り層３と、該下塗り層３上に配置されたインク受容層４と、該インク受容層４上に配置された着色インク層５と、着色インク層５の表面と露出したインク受容層４の表面に配置された表面保護層６とを備える。図１の建築板１においては、基材２とインク受容層４の間に下塗り層３を備えるが、本発明の建築板はこれに限定されるものではなく、インク受容層が基材上に直接配置されていてもよい。また、図１の建築板１においては、インク受容層４表面の一部に着色インク層５が形成されているため、表面保護層６は、着色インク層５の表面と、露出したインク受容層４の表面に形成されている。 Next, the embodiment of the building board of this invention is demonstrated, referring a figure. FIG. 1 is a schematic cross-sectional view of one embodiment of a building board of the present invention. The building board 1 in FIG. 1 includes a base material 2, an undercoat layer 3 disposed on the base material 2, an ink receiving layer 4 disposed on the undercoat layer 3, and an ink receiving layer 4. A colored ink layer 5 and a surface protective layer 6 disposed on the surface of the colored ink layer 5 and the exposed surface of the ink receiving layer 4. In the building board 1 of FIG. 1, the undercoat layer 3 is provided between the base material 2 and the ink receiving layer 4, but the building board of the present invention is not limited to this, and the ink receiving layer is formed on the base material. It may be arranged directly. In the building board 1 of FIG. 1, since the colored ink layer 5 is formed on a part of the surface of the ink receiving layer 4, the surface protective layer 6 includes the surface of the colored ink layer 5 and the exposed ink receiving layer. 4 is formed on the surface.
また、本発明は、基材と、着色インク層と、前記基材及び前記着色インク層の間に介在する介在層とを備え、前記着色インク層及び前記介在層が活性エネルギー線硬化型組成物より形成される建築板における前記介在層に用いられる白色顔料のスクリーニング方法も包含する。この方法は、候補白色顔料の、介在層よりも基材側の層の模様を隠蔽する機能及び活性エネルギー線の吸収能に基づき、候補白色顔料を選抜する工程を有する。選抜した候補白色顔料を介在層に含めた建築板が所望のインク発色性及び硬化性を有することに基づき、候補白色顔料をさらに選抜することがより好ましい。
候補白色顔料は、硫化亜鉛、硫酸バリウム、炭酸カルシウム、タルク、マイカ、シリカ又はアルミナを含有する白色顔料であってもよいし、それ以外の白色顔料であってもよい。
The present invention further comprises a base material, a colored ink layer, and an intervening layer interposed between the base material and the colored ink layer, wherein the colored ink layer and the intervening layer are active energy ray-curable compositions. It also includes a screening method for white pigment used in the intervening layer in the building board formed. This method has a step of selecting the candidate white pigment based on the function of concealing the pattern of the layer on the substrate side of the candidate white pigment from the intervening layer and the ability to absorb active energy rays. It is more preferable to further select the candidate white pigment based on the fact that the building board including the selected candidate white pigment in the intervening layer has the desired ink coloring property and curability.
The candidate white pigment may be a white pigment containing zinc sulfide, barium sulfate, calcium carbonate, talc, mica, silica or alumina, or other white pigment.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
以下に実施例を示すが、本発明はこれによってなんら限定されるものではない。なお、実施例中の「部」は、質量部を意味する。 Examples are shown below, but the present invention is not limited thereto. In the examples, “parts” means parts by mass.
＜製造例１＞下塗り塗料Ａの調製
ウレタンアクリレートオリゴマー（商品名：ＣＮ９８９３、サートマー社製）１５部、アクリロイルモルホリン１５部、２−ヒドロキシエチルアクリレート１０部、アルコキシ化ヘキサンジオールジアクリレート２３．５部、アルコキシ化フェノールアクリレート１０部、タルク２０部、顔料分散剤（商品名：フローレンＧ７００、共栄社製）１部、レオロジーコントロール剤（商品名：ＢＹＫ４１０、ビックケミー社製）０．４部、開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（商品名：ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦ社製）４部、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド（商品名：ＬＵＣＩＲＩＮ ＴＰＯ、ＢＡＳＦ社製）１部、及び消泡剤（商品名：フローレンＡＣ−３２６Ｆ、共栄社製）０．１部をディスパーで１時間攪拌混合し、活性エネルギー線硬化型塗料である下塗り塗料Ａを調製した。調製した塗料をろ過し、不純物を取り除いた。
<Production Example 1> Preparation of undercoat paint A 15 parts of urethane acrylate oligomer (trade name: CN9873, manufactured by Sartomer), 15 parts of acryloylmorpholine, 10 parts of 2-hydroxyethyl acrylate, 23.5 parts of alkoxylated hexanediol diacrylate, 10 parts of alkoxylated phenol acrylate, 20 parts of talc, 1 part of pigment dispersant (trade name: Floren G700, manufactured by Kyoeisha), 0.4 part of rheology control agent (trade name: BYK410, manufactured by Big Chemie), 1- as an initiator 4 parts hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF), 1 part of 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) Foam Product Name: Flowlen AC-326F, manufactured by Kyoeisha) was mixed with stirring for 1 hour 0.1 parts of a disper to prepare a primer coating A is an active energy ray-curable coating material. The prepared paint was filtered to remove impurities.
＜製造例２＞下塗り塗料Ｂの調製
ウレタンアクリレートオリゴマー（商品名：ＣＮ９８９３、サートマー社製）１５部、アクリロイルモルホリン１５部、２−ヒドロキシエチルアクリレート１０部、アルコキシ化ヘキサンジオールジアクリレート２３．５部、硫化亜鉛２０部、炭酸カルシウム１０部、顔料分散剤（商品名：フローレンＧ７００、共栄社製）１部、レオロジーコントロール剤（商品名：ＢＹＫ４１０、ビックケミー社製）０．４部、開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（商品名：ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦ社製）４部、２，４，６−トリメチルベンゾイル−ジフェニル−フォスフィンオキサイド（商品名：ＬＵＣＩＲＩＮ ＴＰＯ、ＢＡＳＦ社製）１部、及び消泡剤（商品名：フローレンＡＣ−３２６Ｆ、共栄社製）０．１部をディスパーで１時間攪拌混合し、活性エネルギー線硬化型塗料である下塗り塗料Ｂ−１を調製した。調製した塗料をろ過し、不純物を取り除いた。
<Production Example 2> Preparation of undercoat paint B 15 parts of urethane acrylate oligomer (trade name: CN9873, manufactured by Sartomer), 15 parts of acryloylmorpholine, 10 parts of 2-hydroxyethyl acrylate, 23.5 parts of alkoxylated hexanediol diacrylate, 20 parts of zinc sulfide, 10 parts of calcium carbonate, 1 part of pigment dispersant (trade name: Floren G700, manufactured by Kyoeisha), 0.4 part of rheology control agent (trade name: BYK410, manufactured by Big Chemie), 1-hydroxy as an initiator -Cyclohexyl-phenyl-ketone (trade name: IRGACURE184, manufactured by BASF) 4 parts, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: LUCIRIN TPO, manufactured by BASF) 1 part, and defoaming Agent (Product name: Furore AC-326F, manufactured by Kyoeisha) and stirred for 1 hour mixing 0.1 parts of a disperser, to prepare a primer coating B-1 is a radiation-curable coating material. The prepared paint was filtered to remove impurities.
表１に示した配合を用いて、下塗り塗料Ｂ−１と同様の方法で下塗り塗料Ｂ−２〜Ｂ−２０を調製した。 Using the formulation shown in Table 1, undercoat paints B-2 to B-20 were prepared in the same manner as undercoat paint B-1.
＜製造例３＞活性エネルギー線硬化型インク−１〜４の調製
表２に活性エネルギー線硬化型インク１〜インク４の組成を示す。表１に示す処方にて、各原料を混合、攪拌して均一にした後、ビーズミルにて５時間練合し、活性エネルギー線硬化型インク−１〜４を調製した。調製したインク組成物をろ過し、不純物を取り除いた。
<Production Example 3> Preparation of active energy ray curable inks 1 to 4 Table 2 shows compositions of active energy ray curable inks 1 to 4. In the formulation shown in Table 1, each raw material was mixed and stirred to be uniform, and then kneaded in a bead mill for 5 hours to prepare active energy ray-curable inks 1 to 4. The prepared ink composition was filtered to remove impurities.
２）光重合開始剤、ＢＡＳＦ社製
＜製造例４＞上塗り塗料Ａの調製
攪拌条件下、アクリロイルモルホリン２０部に、ジペンタエリスリトールヘキサアクリレート２０部、アルコキシ化ヘキサンジオールジアクリレート１８．５部、２−ヒドロキシエチルアクリレート５部、脂肪族ウレタンアクリレートオリゴマー（商品名：ＣＮ９８３、サートマー社製）３０部、顔料分散剤（商品名：フローレンＧ７００、共栄社製）１部、レオロジーコントロール剤（商品名：ＢＹＫ４１０、ビックケミー社製）０．４部、開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（商品名：ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦ社製）５部、及び消泡剤（商品名：フローレンＡＣ−３２６Ｆ、共栄社製）０．１部を添加し、活性エネルギー線硬化型クリヤー塗料である上塗り塗料Ａを調製した。
<Production Example 4> Preparation of topcoat A Under stirring conditions, 20 parts of acryloylmorpholine, 20 parts of dipentaerythritol hexaacrylate, 18.5 parts of alkoxylated hexanediol diacrylate, 5 parts of 2-hydroxyethyl acrylate, aliphatic urethane 30 parts of acrylate oligomer (trade name: CN983, manufactured by Sartomer), 1 part of pigment dispersant (trade name: Floren G700, manufactured by Kyoeisha), 0.4 part of rheology control agent (trade name: BYK410, manufactured by Big Chemie), start 1 part of 1-hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF) and 0.1 part of antifoaming agent (trade name: Floren AC-326F, manufactured by Kyoei Co., Ltd.) as active agents Top coating that is a line curable clear coating A was prepared.
＜製造例５＞上塗り塗料Ｂの調製
攪拌条件下、アクリロイルモルホリン２５部に、アルコキシ化ヘキサンジオールジアクリレート１３．５部、２−ヒドロキシエチルアクリレート５部、エポキシアクリレートオリゴマー（商品名：ＥＢＥＣＲＹＬ３５００、ダイセル・オルネクス社製）４０部、マイカ１０部、顔料分散剤（商品名：フローレンＧ７００、共栄社製）１部、レオロジーコントロール剤（商品名：ＢＹＫ４１０、ビックケミー社製）０．４部、開始剤として１−ヒドロキシ−シクロヘキシル−フェニル−ケトン（商品名：ＩＲＧＡＣＵＲＥ１８４、ＢＡＳＦ社製）５部、及び消泡剤（商品名：フローレンＡＣ−３２６Ｆ、共栄社製）０．１部を添加し、活性エネルギー線硬化型クリヤー塗料である上塗り塗料Ｂを調製した。
<Production Example 5> Preparation of top coat B Under stirring conditions, 25 parts of acryloylmorpholine, 13.5 parts of alkoxylated hexanediol diacrylate, 5 parts of 2-hydroxyethyl acrylate, epoxy acrylate oligomer (trade names: EBECRYL3500, Daicel 40 parts by Ornex), 10 parts by mica, 1 part by pigment dispersant (trade name: Floren G700, by Kyoeisha), 0.4 part by rheology control agent (trade name: BYK410, by Big Chemie), 1- 5 parts of hydroxy-cyclohexyl-phenyl-ketone (trade name: IRGACURE 184, manufactured by BASF) and 0.1 part of antifoaming agent (trade name: Floren AC-326F, manufactured by Kyoei Co., Ltd.) were added, and the active energy ray-curable clear was added. A top coat B, which is a paint, was prepared.
＜製造例６＞上塗り塗料Ｃの調製
攪拌条件下、シリコーン・アクリル共重合物水系分散体（商品名：ポリデュレックスＧ６２０、旭化成製）６５部に、ブチルセロソルブ２０部、増粘剤（商品名：アデカノールＵＨ−４２０、アデカ製）５部及び艶消し剤（商品名：サイシリア３５０、フジシリシア製）１０部を添加した。調製した塗料をろ過して不純物を取り除き、水系クリヤー塗料である上塗り塗料Ｃを調製した。
<Production Example 6> Preparation of Topcoat C Under stirring conditions, 65 parts of silicone / acrylic copolymer aqueous dispersion (trade name: Polydurex G620, manufactured by Asahi Kasei), 20 parts of butyl cellosolve, thickener (trade name: Adecanol) 5 parts of UH-420 (manufactured by Adeka) and 10 parts of matting agent (trade name: Cicilia 350, manufactured by Fuji Silysia) were added. The prepared coating material was filtered to remove impurities, and a top coating material C that was a water-based clear coating material was prepared.
＜製造例７＞上塗り塗料Ｄの調製
撹拌条件下、イソシアネート硬化型アクリル樹脂（商品名：ユピカコートＡＣ３５２５、日本ユピカ製）５５部に、表面調製剤（商品名：ＴＥＧＯ Ｇｌｉｄｅ１１０、エボニックインダストリー製）３部、艶消し剤（商品名：サイシリア３５０、フジシリシア製）１０部、酢酸ブチル２５部及びキシレン５部を添加し、溶剤系クリヤー塗料である上塗り塗料Ｄの主剤を調製した。塗装直前に、硬化剤としてポリイソシアネート（商品名：コロネートＨＸ、日本ポリウレタン製）を２部添加した。
<Production Example 7> Preparation of top coat D Under stirring conditions, 55 parts of isocyanate curable acrylic resin (trade name: Iupika Coat AC3525, manufactured by Nippon Iupika) and 3 parts of surface preparation agent (trade name: TEGO Glide 110, manufactured by Evonik Industries) Then, 10 parts of a matting agent (trade name: Cicilia 350, manufactured by Fuji Silysia), 25 parts of butyl acetate and 5 parts of xylene were added to prepare a main component of a top coating material D which is a solvent-based clear coating material. Immediately before coating, 2 parts of polyisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane) was added as a curing agent.
＜実施例１〜２４＞
厚さ１２ｍｍの木質板を、５０℃に設定した乾燥炉内において、塗装面の表面温度が４０℃になるまで加温した。その後、ロールコーターにて製造例１にて調製した下塗り塗料Ａを塗布量２５ｇ／ｍ２となるように塗布した。その後、水銀ランプ８０Ｗ、積算光量１５０ｍＪ／ｃｍ２、ピーク強度１８０ｍＷ／ｃｍ２の条件にて硬化させ、下塗り塗膜層Ａを形成した。
<Examples 1 to 24>
A wood board having a thickness of 12 mm was heated in a drying furnace set to 50 ° C. until the surface temperature of the painted surface reached 40 ° C. Thereafter, the undercoat paint A prepared in Production Example 1 was applied by a roll coater so that the application amount was 25 g / m2. Thereafter, curing was performed under the conditions of a mercury lamp 80 W, an integrated light amount of 150 mJ / cm 2, and a peak intensity of 180 mW / cm 2 to form an undercoat coating film layer A.
前記下塗り塗膜層Ａ上に、製造例２にて調製した活性エネルギー線硬化型塗料Ｂ１〜Ｂ１７を塗布量３５ｇ／ｍ２となるように塗布した。その後、水銀ランプ８０Ｗ、積算光量２００ｍＪ／ｃｍ２、ピーク強度１８０ｍＷ／ｃｍ２の条件にて硬化させ、インクの受容層となる下塗り塗膜層Ｂを形成した。その後、下塗り塗膜層Ｂ上に、製造例３にて調製した活性エネルギー線硬化型インク−１〜４を用いてインクジェットプリンター（ＨＥＫ−１、コニカミノルタ社製）にて塗装し、木質調模様を形成し、メタルハライドランプにより波長３６５ｎｍのＵＶ光を積算光量が３００ｍＪ／ｃｍ２となるように照射した。 On the undercoat coating film layer A, the active energy ray-curable coating materials B1 to B17 prepared in Production Example 2 were applied so that the application amount was 35 g / m2. Thereafter, curing was performed under the conditions of a mercury lamp 80 W, an integrated light amount of 200 mJ / cm 2, and a peak intensity of 180 mW / cm 2, thereby forming an undercoat coating layer B serving as an ink receiving layer. Then, it coats with the ink jet printer (HEK-1, the product made by Konica Minolta Co., Ltd.) using the active energy ray hardening-type ink -1-4 prepared by manufacture example 3 on the undercoat coating-film layer B, and a woody pattern Then, UV light having a wavelength of 365 nm was irradiated with a metal halide lamp so that the integrated light amount was 300 mJ / cm 2.
前記活性エネルギー線硬化型インクを塗装し、硬化させた塗装物上に、製造例４にて調製した上塗り塗料Ａをロールコーターにて塗布量３０ｇ／ｍ２となるように塗布した。その後、水銀ランプ８０Ｗ、積算光量３００ｍＪ／ｃｍ２、ピーク強度２５０ｍＷ／ｃｍ２の条件にて硬化させ、上塗り塗料層Ａを形成した。 The top coating material A prepared in Production Example 4 was applied on the coated product obtained by coating the active energy ray-curable ink and cured with a roll coater so that the coating amount was 30 g / m 2. Then, it hardened | cured on the conditions of mercury lamp 80W, integrated light quantity 300mJ / cm2, and peak intensity 250mW / cm2, and formed the top coat layer A.
前記活性エネルギー線硬化型インクを塗装し、硬化させた塗装物上に、製造例５にて調製した上塗り塗料Ｂをロールコーターにて塗布量３０ｇ／ｍ２となるように塗布した。その後、水銀ランプ８０Ｗ、積算光量２００ｍＪ／ｃｍ２、ピーク強度１８０ｍＷ／ｃｍ２の条件にて硬化させ、上塗り塗料層Ｂを形成した。 The top coating material B prepared in Production Example 5 was applied to the coated product obtained by applying the active energy ray-curable ink and cured with a roll coater so that the coating amount was 30 g / m 2. Then, it hardened | cured on the conditions of the mercury lamp 80W, the integrated light quantity 200mJ / cm2, and the peak intensity 180mW / cm2, and formed the top coat layer B.
前記活性エネルギー線硬化型インクを塗装し、硬化させた塗装物上に、製造例６〜７にて調製した上塗り塗料Ｃ、Ｄを固形分の塗布量３０ｇ／ｍ２となるようにエアスプレーにより塗装した。その後、５分間静置し、１００℃に設定した乾燥炉中にて３０分間乾燥し、硬化させて上塗り塗膜層Ｃ、Ｄを形成した。 The top coating materials C and D prepared in Production Examples 6 to 7 are applied by air spray so that the applied amount of the solid content is 30 g / m 2 on the coated material obtained by applying and curing the active energy ray-curable ink. did. Then, it left still for 5 minutes, it dried for 30 minutes in the drying furnace set to 100 degreeC, it was made to harden, and the top coat film layers C and D were formed.
＜比較例１〜９＞
受容層の塗料を下塗り塗料Ｂ−１８〜Ｂ−２０とした以外は、実施例１と同様にして複層塗膜を形成させた。
<Comparative Examples 1-9>
A multilayer coating film was formed in the same manner as in Example 1 except that the coating material for the receiving layer was changed to the undercoat paints B-18 to B-20.
＜発色性＞
複層塗膜を形成させた塗装物の外観を目視により観察し、発色性を評価した。
［評価基準］
◎：インクの滲み、ハジキ等が全く無いとともに、基材由来の模様等が見られず、インク層が綺麗に発色して明確な模様が形成されている。
○：インクの滲み又はハジキ等が無く、明確な模様が形成されている。
△：多少のインクの滲みはあるが、実用上問題ない程度に模様が形成されている。
×：インクの滲み又はハジキが認められ、明確な模様が形成されていない。
<Color development>
The appearance of the coated material on which the multilayer coating film was formed was visually observed to evaluate the color developability.
[Evaluation criteria]
A: There is no ink bleeding or repellency, no pattern derived from the substrate, and the ink layer is clearly colored to form a clear pattern.
◯: There is no ink bleeding or repellency, and a clear pattern is formed.
Δ: There is some ink bleeding, but the pattern is formed to the extent that there is no practical problem.
X: Ink bleeding or repellency was observed, and a clear pattern was not formed.
＜インクの乾燥性及び硬化性＞
活性エネルギー線照射後、６０秒後のインク塗膜表面のタック感を指触及びセロテープ（登録商標）剥離により評価した。
［評価基準］
○：指触によるタック感がなく、剥離後のテープに未硬化インクの付着が確認されない。
△：指触によるタック感はないが、剥離後のテープに未硬化インクの付着が確認できる。
×：指触によるタック感があり、剥離後のテープに未硬化インクの付着が確認できる。
<Ink drying and curability>
Tackiness on the surface of the ink coating 60 seconds after irradiation with active energy rays was evaluated by finger touch and cellophane (registered trademark) peeling.
[Evaluation criteria]
○: There is no tactile sensation due to finger touch, and adhesion of uncured ink to the tape after peeling is not confirmed.
Δ: There is no tactile sensation due to finger touch, but adhesion of uncured ink to the tape after peeling can be confirmed.
X: There is a tactile sensation due to finger touch, and adhesion of uncured ink to the tape after peeling can be confirmed.
＜付着性＞
ＪＩＳ Ｋ−５６００−５−６に準拠して評価した。
［評価基準］
◎：塗膜外観及び形成された模様等に変化無く、層間剥離無し。
○：塗膜外観又は形成された模様等に変化軽微にあるが、層間剥離は認められず実用上問題ないレベルであった。
△：塗膜外観又は形成された模様等に変化軽微にあり、僅かに層間剥離が認められる。
×：塗膜外観又は形成された模様等に変化激しく、層間剥離が認められる。
<Adhesiveness>
Evaluation was performed according to JIS K-5600-5-6.
[Evaluation criteria]
A: There is no change in the appearance of the coating film and the pattern formed, and there is no delamination.
◯: Although the coating film appearance or the pattern formed was slight, delamination was not observed, and there was no practical problem.
Δ: The coating film appearance or the formed pattern is slightly changed, and slight delamination is observed.
X: The appearance of the coating film or the pattern formed is drastically changed, and delamination is observed.
＜耐温水性＞
各試験体を５０℃に設定した水浴中に１０日間浸漬させ、浸漬後の塗膜外観を目視評価及びＪＩＳ−Ｋ−５６００−５−６に準拠した付着性試験により評価した。
［評価基準］
◎：塗膜外観及び形成された模様等に変化無く、層間剥離無し。
○：塗膜外観又は形成された模様等に変化軽微にあるが、層間剥離は認められず実用上問題ないレベルであった。
△：塗膜外観又は形成された模様等に変化軽微にあり、僅かに層間剥離が認められる。
×：塗膜外観又は形成された模様等に変化激しく、層間剥離が認められる。
<Hot water resistance>
Each specimen was immersed in a water bath set at 50 ° C. for 10 days, and the appearance of the coating film after immersion was evaluated by visual evaluation and an adhesion test based on JIS-K-5600-5-6.
[Evaluation criteria]
A: There is no change in the appearance of the coating film and the pattern formed, and there is no delamination.
◯: Although the coating film appearance or the pattern formed was slight, delamination was not observed, and there was no practical problem.
Δ: The coating film appearance or the formed pattern is slightly changed, and slight delamination is observed.
X: The appearance of the coating film or the pattern formed is drastically changed, and delamination is observed.
＜耐摩耗性＞
上記で得られた木質板について、摩耗試験（ＪＡＳ）により、耐摩耗性を評価した。
試験片を摩耗試験装置の回転盤に水平に固定し、研摩紙を巻き付けたゴム製円板２個を取り付け、５００回の回転を行い、５００回転後における試験片の表面の変化及び１００回転当たりの摩耗減量を求めた。この場合、試験片面上に加わる総荷重量に相当する質量は、ゴム製円板の質量を含め１０００ｇとした。
［評価基準］
◎：インク層に形成された模様等に変化が認められず、１００回転当たりの摩耗減量が０．１５ｇ以下であった。
○：インク層に形成された模様等に変化軽微にあるが、１００回転当たりの摩耗減量が０．１５ｇ以下で実用上問題ないレベルであった。
△：インク層に形成された模様等に変化軽微にあり、僅かに素地露出が認められる。
×：インク層に形成された模様等に変化激しく、素地露出が認められる。
<Abrasion resistance>
About the wood board obtained above, abrasion resistance was evaluated by the abrasion test (JAS).
Fix the test piece horizontally on the rotating disk of the abrasion tester, attach two rubber discs wrapped with abrasive paper, rotate 500 times, change the surface of the test piece after 500 rotations and per 100 rotations The weight loss of wear was determined. In this case, the mass corresponding to the total load applied on the test piece surface was 1000 g including the mass of the rubber disk.
[Evaluation criteria]
A: No change was observed in the pattern or the like formed on the ink layer, and the wear loss per 100 revolutions was 0.15 g or less.
A: The pattern formed on the ink layer is slightly changed, but the wear loss per 100 revolutions is 0.15 g or less, which is a practically acceptable level.
Δ: The pattern formed on the ink layer is slightly changed, and the substrate is slightly exposed.
X: The pattern formed on the ink layer changes drastically, and the substrate exposure is recognized.
表３、４に、実施例の結果を示す。実施例１〜２４は、いずれも発色性、付着性及び耐摩性に優れていた。 Tables 3 and 4 show the results of the examples. Examples 1 to 24 were all excellent in color development, adhesion and abrasion resistance.
表５に比較例の結果を示す。比較例１〜６はともにインク受容層が十分に硬化されず、発色性、硬化性、付着性、耐温水性、耐摩耗性ともに不十分であった。また、顔料を含まない比較例７〜９では塗膜性能は優れるものの発色性が悪かった。 Table 5 shows the results of the comparative example. In each of Comparative Examples 1 to 6, the ink receiving layer was not sufficiently cured, and the color developability, curability, adhesion, hot water resistance, and abrasion resistance were insufficient. In Comparative Examples 7 to 9 containing no pigment, although the coating film performance was excellent, the color developability was poor.
上記結果から、本発明により、発色性が良く、付着性、耐摩耗性に優れる複層塗膜が得られた。 From the above results, according to the present invention, a multilayer coating film having good color developability and excellent adhesion and abrasion resistance was obtained.
１ 建築板
２ 基材
３ 下塗り層（介在層）
４ インク受容層（介在層）
５ 着色インク層
６ 表面保護層
1 Building board 2 Base material 3 Undercoat layer (intervening layer)
4 Ink receiving layer (intervening layer)
5 Colored ink layer 6 Surface protective layer
Claims (6)
候補白色顔料の、前記介在層よりも基材側の層の模様を隠蔽する機能及び前記活性エネルギー線の吸収能に基づき、前記候補白色顔料を選抜する工程を有する方法。 A building board comprising a base material, a colored ink layer, and an intervening layer interposed between the base material and the colored ink layer, wherein the colored ink layer and the intervening layer are formed of an active energy ray-curable composition A screening method for white pigment used in the intervening layer in
A method comprising a step of selecting the candidate white pigment based on the function of concealing the pattern of the layer on the substrate side of the intervening layer of the candidate white pigment and the ability to absorb the active energy ray.
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