JP5439546B2 - Laminated body - Google Patents
Laminated body Download PDFInfo
- Publication number
- JP5439546B2 JP5439546B2 JP2012147338A JP2012147338A JP5439546B2 JP 5439546 B2 JP5439546 B2 JP 5439546B2 JP 2012147338 A JP2012147338 A JP 2012147338A JP 2012147338 A JP2012147338 A JP 2012147338A JP 5439546 B2 JP5439546 B2 JP 5439546B2
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- Prior art keywords
- colored
- weight
- layer
- component
- colored layer
- Prior art date
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- 239000002245 particle Substances 0.000 claims description 95
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000377 silicon dioxide Substances 0.000 claims description 27
- 229910044991 metal oxide Inorganic materials 0.000 claims description 24
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- 239000000057 synthetic resin Substances 0.000 claims description 19
- 239000011164 primary particle Substances 0.000 claims description 15
- 239000010954 inorganic particle Substances 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 5
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- 230000009471 action Effects 0.000 description 10
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 6
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
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- RSOILICUEWXSLA-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 RSOILICUEWXSLA-UHFFFAOYSA-N 0.000 description 2
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- DOTYDHBOKPPXRB-UHFFFAOYSA-N 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioic acid Chemical compound CCCCC(C(O)=O)(C(O)=O)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 DOTYDHBOKPPXRB-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004986 Cholesteric liquid crystals (ChLC) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000951471 Citrus junos Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
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- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
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- 150000001298 alcohols Chemical class 0.000 description 1
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- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 230000003373 anti-fouling effect Effects 0.000 description 1
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- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
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- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
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- 239000011324 bead Substances 0.000 description 1
- OSIVCXJNIBEGCL-UHFFFAOYSA-N bis(2,2,6,6-tetramethyl-1-octoxypiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)N(OCCCCCCCC)C(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(OCCCCCCCC)C(C)(C)C1 OSIVCXJNIBEGCL-UHFFFAOYSA-N 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
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- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
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- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
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- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- 238000007873 sieving Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OQTSOKXAWXRIAC-UHFFFAOYSA-N tetrabutan-2-yl silicate Chemical compound CCC(C)O[Si](OC(C)CC)(OC(C)CC)OC(C)CC OQTSOKXAWXRIAC-UHFFFAOYSA-N 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ADLSSRLDGACTEX-UHFFFAOYSA-N tetraphenyl silicate Chemical compound C=1C=CC=CC=1O[Si](OC=1C=CC=CC=1)(OC=1C=CC=CC=1)OC1=CC=CC=C1 ADLSSRLDGACTEX-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
Description
本発明は、新規な積層体に関する。本発明積層体は、例えば、建築物の外壁面等に適用する建材として使用できる。 The present invention relates to a novel laminate. The laminate of the present invention can be used as, for example, a building material applied to an outer wall surface of a building.
建築物外装等に用いる建材には、景観上の観点から美観性が求められている。近年、このような建材としては、例えば天然石をイメージしたもの等が注目されており、比較的厚みがあり、様々な凹凸パターンによって重厚感が付与されたもの等も採用されている。
一方、近年、都市部においては、コンクリート建造物や冷房等から排出される人工放射熱等によって、都市部独特の気候が作り出されている。特に、夏期の都市部における屋外の温度上昇は著しく、ヒートアイランド現象と呼ばれる問題を引き起こしている。このような問題に対して、建築物外装面の温度上昇を抑制するために種々の材料が提案されている。
From the viewpoint of landscape, aesthetics are required for building materials used for building exteriors and the like. In recent years, as a building material, for example, an image of natural stone has been attracting attention, and a material having a relatively thick thickness and being given a heavy feeling by various uneven patterns has been adopted.
On the other hand, in recent years, in urban areas, a climate unique to urban areas has been created by artificial radiant heat discharged from concrete buildings and cooling. In particular, the outdoor temperature rise in urban areas in summer is significant, causing a problem called the heat island phenomenon. For such problems, various materials have been proposed in order to suppress the temperature rise of the building exterior surface.
このような背景の下、例えば特許文献１では、遮熱骨材を含有する塗材が基材上に塗布された材料が提案されている。この材料では、骨材の表面に熱反射顔料を付着させた遮熱骨材が採用されており、熱反射顔料が近赤外線反射作用を発揮することよって、温度低減効果が奏される。 Under such a background, for example, Patent Document 1 proposes a material in which a coating material containing a heat shielding aggregate is applied on a base material. In this material, a heat shielding aggregate in which a heat reflecting pigment is adhered to the surface of the aggregate is adopted, and the temperature reducing effect is exerted by the heat reflecting pigment exhibiting a near-infrared reflecting action.
しかし、特許文献１記載の材料の表面は、骨材に由来する微細な凹凸形状を有するものであり、この凹部には汚染物質が付着しやすい。特に都市部においては、自動車等からの排出ガスにより、大気中に油性の汚染物質が浮遊しているため、汚染が進行しやすい状況にある。このような汚染物質は、美観性低下を引き起こすだけでなく、太陽光中の赤外線の吸収能が非常に高いため、蓄熱場として作用し、温度上昇を助長するおそれがある。さらに、このような汚染物質に起因する過度の温度上昇は、材料劣化等の原因となるおそれもある。 However, the surface of the material described in Patent Document 1 has a fine concavo-convex shape derived from the aggregate, and contaminants are likely to adhere to the concave portion. Especially in urban areas, pollution is likely to proceed because oily pollutants are floating in the atmosphere due to exhaust gases from automobiles and the like. Such pollutants not only cause a decrease in aesthetics, but also have a very high ability to absorb infrared rays in sunlight, so that they act as a heat storage field and may promote a temperature rise. Furthermore, an excessive temperature rise caused by such contaminants may cause material deterioration and the like.
本発明は、このような問題点に鑑みなされたものであり、優れた美観性を有すると共に、太陽光照射時の温度上昇を効果的に抑制し、それを維持することができる積層体を得ることを目的とするものである。
This invention is made | formed in view of such a problem, and while obtaining the outstanding aesthetics, the temperature rise at the time of sunlight irradiation is suppressed effectively, and the laminated body which can maintain it is obtained. It is for the purpose.
本発明者は、上記目的を達成するため鋭意検討を行った結果、特定の着色粒子及び合成樹脂を特定重量比で含む着色層の上に、特定のシリカ及び合成樹脂を特定重量比で含む透明層を有する積層体に想到し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above object, the present inventor has found that a transparent layer containing specific silica and synthetic resin at a specific weight ratio on a colored layer containing specific colored particles and synthetic resin at a specific weight ratio. The inventors have come up with a laminate having layers and have completed the present invention.
すなわち、本発明の積層体は、下記の特徴を有するものである。
１．着色層の上に透明層が積層された積層体であって、
前記着色層は、着色粒子１００重量部に対し、合成樹脂を固形分重量比率で３〜５０重量部含み、その層の表面が前記着色粒子に由来する微視的な凹凸形状を有しており、
前記着色粒子は、無機質粒子の表面に金属酸化物が付着してなるものであり、
前記透明層は、平均一次粒子径１〜２００ｎｍのシリカ１００重量部に対し、合成樹脂を固形分重量比率で５〜５００重量部含むことを特徴とする積層体。
２．着色層の上に透明層が積層された積層体であって、
前記着色層は、着色粒子１００重量部に対し、合成樹脂を固形分重量比率で３〜５０重量部含み、その層の表面が前記着色粒子に由来する微視的な凹凸形状を有し、且つ巨視的な凹凸模様を有しており、
前記着色粒子は、無機質粒子の表面に、金属酸化物が付着してなるものであり、
前記透明層は、平均一次粒子径１〜２００ｎｍのシリカ１００重量部に対し、合成樹脂を固形分重量比率で５〜５００重量部含むことを特徴とする積層体。
That is, the laminate of the present invention has the following characteristics.
1. A laminate in which a transparent layer is laminated on a colored layer,
The colored layer includes 3 to 50 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles, and the surface of the layer has a microscopic uneven shape derived from the colored particles. ,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles,
The said transparent layer is a laminated body characterized by including 5-500 weight part of synthetic resins by solid content weight ratio with respect to 100 weight part of silica with an average primary particle diameter of 1-200 nm.
2. A laminate in which a transparent layer is laminated on a colored layer,
The colored layer contains 3 to 50 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles, the surface of the layer has a microscopic uneven shape derived from the colored particles, and It has a macroscopic uneven pattern,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles,
The said transparent layer is a laminated body characterized by including 5-500 weight part of synthetic resins by solid content weight ratio with respect to 100 weight part of silica with an average primary particle diameter of 1-200 nm.
本発明の積層体は、特定の着色粒子を含む着色層の上に、特定のシリカを含む透明層を有するものである。本発明では、着色層の色彩によって、美観性が付与される。さらに、着色層の赤外線反射性、透明層の汚染防止性等の相乗作用によって、太陽光照射時の温度上昇が効果的に抑制される。 The laminate of the present invention has a transparent layer containing specific silica on a colored layer containing specific colored particles. In the present invention, aesthetics are imparted by the color of the colored layer. Furthermore, the temperature rise at the time of sunlight irradiation is effectively suppressed by synergistic actions such as the infrared reflectivity of the colored layer and the anti-contamination property of the transparent layer.
このような作用に加え、本発明では着色層の赤外線反射作用により、透明層の温度上昇も抑えられる。もし透明層が過度に温度上昇すると、透明層に含まれる合成樹脂の軟化によって本来の汚染防止作用が発揮されなかったり、耐久性低下によって汚染防止作用が早期に損なわれたりするおそれがある。これに対し、本発明では、着色層の作用によって、透明層の温度上昇が抑制され、十分な汚染防止効果が長期にわたり発揮される。これにより、着色層の色彩等に基づく美観性が長期にわたり保持され、汚染物質の付着に起因する温度上昇も長期間回避できる。 In addition to such an action, in the present invention, an increase in the temperature of the transparent layer can be suppressed by the infrared reflecting action of the colored layer. If the temperature of the transparent layer rises excessively, there is a possibility that the original anti-contamination action may not be exhibited due to the softening of the synthetic resin contained in the transparent layer, or the anti-contamination action may be impaired early due to a decrease in durability. On the other hand, in this invention, the temperature rise of a transparent layer is suppressed by the effect | action of a colored layer, and sufficient pollution prevention effect is exhibited over a long period of time. Thereby, the aesthetics based on the color etc. of a colored layer are maintained over a long period of time, and the temperature rise resulting from adhesion of a contaminant can also be avoided for a long period of time.
以下、本発明を実施するための形態について説明する。
（着色層）
本発明の着色層は、着色粒子（Ａ）および合成樹脂（Ｂ）を必須成分として含むものであり、積層体に意匠性を付与する層である。
Hereinafter, modes for carrying out the present invention will be described.
(Colored layer)
The colored layer of the present invention contains colored particles (A) and a synthetic resin (B) as essential components, and is a layer that imparts design properties to the laminate.
本発明における（Ａ）着色粒子（以下「（Ａ）成分」ともいう）は、（ａ１）無機質粒子（以下「（ａ１）成分」ともいう）の表面に、（ａ２）金属酸化物（以下「（ａ２）成分」ともいう）が付着してなるものである。この（Ａ）成分は、粒子径の小さい一般的な着色顔料等を使用した場合と異なり、（Ａ）成分の小点が多彩模様として視認され、優れた色調や質感を付与するものである。また（Ａ）成分は、着色層表面に微視的な凹凸を形成し、立体的な意匠の付与にも寄与するものである。 In the present invention, (A) colored particles (hereinafter also referred to as “component (A)”) are formed on the surface of (a1) inorganic particles (hereinafter also referred to as “component (a1)”), and (a2) metal oxide (hereinafter referred to as “component”). (Also referred to as “component (a2)”). The component (A) is different from the case of using a general coloring pigment having a small particle diameter, and the small dot of the component (A) is visually recognized as a multicolored pattern, and gives excellent color tone and texture. Moreover, (A) component forms microscopic unevenness | corrugation in the colored layer surface, and contributes also to provision of a three-dimensional design.
このような（Ａ）成分を構成する（ａ１）成分としては、その材質が無機質であれば特に限定されず、天然品、人工品のいずれも使用することができる。具体的には、例えば、マイカ、カオリン、クレー、陶土、チャイナクレー、タルク、水酸化アルミニウム、水酸化マグネシウム、炭酸カルシウム、貝殻、バライト粉、大理石、御影石、蛇紋岩、花崗岩、蛍石、寒水石、長石、珪石、珪砂等の粉砕物、陶磁器粉砕物、セラミック粉砕物、ガラスビーズ、ガラス粉砕物、金属類等が挙げられる。 The component (a1) constituting the component (A) is not particularly limited as long as the material is inorganic, and any of natural products and artificial products can be used. Specifically, for example, mica, kaolin, clay, porcelain clay, china clay, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, shells, barite powder, marble, granite, serpentine, granite, fluorite, cold water stone , Pulverized materials such as feldspar, silica stone, and silica sand, ceramic pulverized materials, ceramic pulverized materials, glass beads, glass pulverized materials, and metals.
上記（ａ１）成分の表面に付着してなる（ａ２）成分は、（ａ１）成分の表面を着色するものである。（ａ２）成分としては、例えば、スカンジウム、チタン、バナジウム、クロム、マンガン、鉄、コバルト、ニッケル、銅等の遷移金属元素；ホロミウム、プラセオジウム、ネオジウム、エルビウム等の希土類元素；金、白金、銀、パラジウム、ロジウム等の貴金属元素；から選ばれる少なくとも１種の金属元素を含む金属酸化物、あるいはこれらの金属酸化物の複合酸化物が使用できる。複合酸化物としては、上記金属酸化物から選ばれる少なくとも１種と、ケイ素、アルミニウム、ジルコニウム、亜鉛、鉛、アンチモン及びスズ等の金属酸化物；マグネシウム、カルシウム、ストロンチウム、及びバリウム等のアルカリ土類金属酸化物；ホウ素、リン等の無機酸化物；から選ばれる少なくとも１種の酸化物との複合酸化物が挙げられる。 The component (a2) attached to the surface of the component (a1) is for coloring the surface of the component (a1). Examples of the component (a2) include transition metal elements such as scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, and copper; rare earth elements such as holmium, praseodymium, neodymium, and erbium; gold, platinum, silver, A metal oxide containing at least one metal element selected from noble metal elements such as palladium and rhodium, or a composite oxide of these metal oxides can be used. The composite oxide includes at least one selected from the above metal oxides and metal oxides such as silicon, aluminum, zirconium, zinc, lead, antimony and tin; alkaline earths such as magnesium, calcium, strontium and barium Examples thereof include composite oxides with at least one oxide selected from metal oxides; inorganic oxides such as boron and phosphorus.
上記（ａ２）成分を有することによって、（Ａ）成分は美観性に優れた色調を長期にわたり維持することができ、優れた赤外線反射作用を発揮することもできる。 By having the component (a2), the component (A) can maintain a color tone with excellent aesthetics over a long period of time, and can also exhibit an excellent infrared reflection effect.
本発明の（Ａ）成分は、上記（ａ１）成分の表面に、上記（ａ２）成分が付着されていればよい。このとき、上記（ａ１）成分と上記（ａ２）成分が直接付着したものであっても、バインダー成分を介して付着されたものであってもよい。バインダー成分としては、有機系、無機系、有機‐無機複合系等、公知のものが使用できる。本発明では特に、ケイ酸塩、アルミニウム塩、リン酸塩等から選ばれる１種以上を含む無機系バインダーが好ましい。 In the component (A) of the present invention, the component (a2) may be attached to the surface of the component (a1). At this time, the component (a1) and the component (a2) may be directly attached or may be attached via a binder component. As the binder component, known ones such as organic, inorganic and organic-inorganic composites can be used. In the present invention, an inorganic binder containing at least one selected from silicate, aluminum salt, phosphate and the like is particularly preferable.
（Ａ）成分は、平均粒子径２２〜６００μｍの着色粒子を含むことが好ましい。特に本発明では、（Ａ）成分中に、平均粒子径２２μｍ以上１５０μｍ未満の着色粒子（Ａ１）が１０重量％以上含まれることが好ましい。（Ａ）成分中の上記着色粒子（Ａ１）の比率は、より好ましくは１０〜８０重量％、さらに好ましくは２０〜７０重量％、最も好ましくは３０〜６０重量％である。
また、（Ａ）成分中に、平均粒子径１５０μｍ以上２１２μｍ未満の着色粒子（Ａ２）が１０〜４５重量％含まれることが好ましい。（Ａ）成分中の上記着色粒子（Ａ２）の比率は、より好ましくは１５〜４０重量％、さらに好ましくは２０〜３５重量％である。
さらに、（Ａ）成分中に、平均粒子径２１２μｍ以上６００μｍ未満の着色粒子（Ａ３）が１０〜４５重量％含まれることが好ましい。（Ａ）成分中の上記着色粒子（Ａ３）の比率は、より好ましくは１５〜４０重量％、さらに好ましくは２０〜３５重量％である。
The component (A) preferably contains colored particles having an average particle size of 22 to 600 μm. Particularly in the present invention, the component (A) preferably contains 10% by weight or more of colored particles (A1) having an average particle size of 22 μm or more and less than 150 μm. The ratio of the colored particles (A1) in the component (A) is more preferably 10 to 80% by weight, still more preferably 20 to 70% by weight, and most preferably 30 to 60% by weight.
Moreover, it is preferable that 10-45 weight% of colored particles (A2) with an average particle diameter of 150 micrometers or more and less than 212 micrometers are contained in (A) component. The ratio of the colored particles (A2) in the component (A) is more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight.
Further, the component (A) preferably contains 10 to 45% by weight of colored particles (A3) having an average particle diameter of 212 μm or more and less than 600 μm. The ratio of the colored particles (A3) in the component (A) is more preferably 15 to 40% by weight, still more preferably 20 to 35% by weight.
このような粒度分布を有する（Ａ）成分は、平均粒子径の異なる少なくとも２種以上、好ましくは３種以上の着色粒子を組み合せることによって得ることができる。好適な態様としては、平均粒子径５３μｍ以上１２５μｍ未満の着色粒子と、平均粒子径１２５μｍ以上５００μｍ未満の着色粒子との組み合わせが挙げられる。より好適な態様としては、平均粒子径５３μｍ以上１２５μｍ未満の着色粒子と、平均粒子径１２５μｍ以上２１２μｍ未満の着色粒子と、平均粒子径２１２μｍ以上５００μｍ未満の着色粒子との組み合わせが挙げられる。なお（Ａ）成分の平均粒子径は、ＪＩＳ Ｚ８８０１−１：２０００に規定される金属製網ふるいを用いてふるい分けを行い、その重量分布の平均値を算出することによって得られる値である。 The component (A) having such a particle size distribution can be obtained by combining at least two kinds, preferably three or more kinds of colored particles having different average particle diameters. A preferred embodiment includes a combination of colored particles having an average particle size of 53 μm or more and less than 125 μm and colored particles having an average particle size of 125 μm or more and less than 500 μm. As a more preferred embodiment, a combination of colored particles having an average particle diameter of 53 μm or more and less than 125 μm, colored particles having an average particle diameter of 125 μm or more and less than 212 μm, and colored particles having an average particle diameter of 212 μm or more and less than 500 μm can be mentioned. In addition, the average particle diameter of (A) component is a value obtained by sieving using the metal net sieve prescribed | regulated to JISZ8801-1: 2000, and calculating the average value of the weight distribution.
本発明では、上述のような（Ａ）成分の粒度構成によって、美観性を一層高めることができ、さらに、積層体の温度上昇抑制、劣化防止（膨れ等の防止）等の点でも有利である。この作用機構は明確ではないが、着色層において（Ａ）成分が密に凝集し、（Ａ）成分同士の間隙が減少した態様となり、その結果以下のような作用が生じるものと推定される。
・着色層の表面付近における光の拡散反射作用が高まる。
・着色層表面における凹凸の程度が緩和され、蓄熱源となる汚染物質が一層付着し難くなる。
・（Ａ）成分の熱伝導性によって、着色層の熱拡散作用が高まり、局所的な温度上昇が抑制される。
In the present invention, the aesthetics can be further enhanced by the particle size constitution of the component (A) as described above, and further advantageous in terms of suppressing temperature rise of the laminate, preventing deterioration (preventing swelling, etc.) and the like. . Although the mechanism of this action is not clear, it is presumed that the (A) component is densely aggregated in the colored layer and the gap between the (A) components is reduced, resulting in the following actions.
-The light diffuse reflection effect near the surface of the colored layer is enhanced.
-The degree of unevenness on the surface of the colored layer is alleviated, and contaminants serving as a heat storage source are more difficult to adhere.
-The thermal diffusion effect of the colored layer is increased by the thermal conductivity of the component (A), and the local temperature rise is suppressed.
着色層における（Ｂ）合成樹脂（以下、「（Ｂ）成分」ともいう）は、上記（Ａ）成分を固定化する役割を担う。このような（Ｂ）成分としては、例えば、アクリル樹脂、シリコーン樹脂、アクリルシリコーン樹脂、フッ素樹脂、酢酸ビニル樹脂、アクリル・酢酸ビニル樹脂、塩化ビニル樹脂、ウレタン樹脂、アクリルウレタン樹脂、エポキシ樹脂、アルキッド樹脂、ポリビニルアルコール樹脂、ポリエステル樹脂、エチレン樹脂、ポリビニルアルコール、セルロース及びその誘導体等が挙げられる。（Ｂ）成分の形態としては、水分散型、水可溶型、非水分散型、溶剤可溶型、無溶剤型等が挙げられ、これらは１液型、２液型等のいずれであってもよい。 The (B) synthetic resin (hereinafter also referred to as “component (B)”) in the colored layer plays a role of immobilizing the component (A). Examples of such component (B) include acrylic resin, silicone resin, acrylic silicone resin, fluorine resin, vinyl acetate resin, acrylic / vinyl acetate resin, vinyl chloride resin, urethane resin, acrylic urethane resin, epoxy resin, and alkyd. Examples include resins, polyvinyl alcohol resins, polyester resins, ethylene resins, polyvinyl alcohol, cellulose, and derivatives thereof. Examples of the form of component (B) include water-dispersed, water-soluble, non-water-dispersed, solvent-soluble, and solvent-free types, which are either one-component type or two-component type. May be.
（Ｂ）成分のガラス転移温度は、好ましくは−６０℃〜６０℃、より好ましくは−４０℃〜３０℃、さらに好ましくは−３０℃〜２０℃である。（Ｂ）成分のガラス転移温度がこのような範囲の場合、適度な可とう性を付与することが可能となる。また、本発明では（Ｂ）成分としてガラス転移温度が比較的低いものを使用しても、透明層の作用により十分な汚染防止効果が得られる。なお、ガラス転移温度はＦｏｘの計算式により求められる値である。 The glass transition temperature of (B) component becomes like this. Preferably it is -60 degreeC-60 degreeC, More preferably, it is -40 degreeC-30 degreeC, More preferably, it is -30 degreeC-20 degreeC. When the glass transition temperature of the component (B) is in such a range, it is possible to impart moderate flexibility. In the present invention, even if a component having a relatively low glass transition temperature is used as the component (B), a sufficient anti-contamination effect can be obtained by the action of the transparent layer. The glass transition temperature is a value determined by the Fox formula.
（Ｂ）成分の比率は、固形分換算で、（Ａ）成分１００重量部に対し、通常３重量部以上５０重量部以下、好ましくは４重量部以上３０重量部以下、より好ましくは５重量部以上２０重量部未満、さらに好ましくは６重量部以上１９重量部以下である。このような比率であれば、（Ａ）成分の質感を活かした意匠性が付与され、さらには温度上昇が効果的に抑制できる。また、着色層が十分な水蒸気透過性を有するため、着色層の膨れ等も防止できる。 The ratio of the component (B) is usually 3 parts by weight or more and 50 parts by weight or less, preferably 4 parts by weight or more and 30 parts by weight or less, more preferably 5 parts by weight with respect to 100 parts by weight of the component (A) in terms of solid content. More than 20 parts by weight, more preferably 6 parts by weight or more and 19 parts by weight or less. If it is such a ratio, the design property which utilized the texture of (A) component will be provided, and also a temperature rise can be suppressed effectively. Further, since the colored layer has sufficient water vapor permeability, swelling of the colored layer can be prevented.
着色層においては、上記成分に加え、（Ｃ）光安定剤（以下「（Ｃ）成分」ともいう）を使用することもできる。このような（Ｃ）成分を含むことにより、長期にわたり、後述の透明層と優れた密着性を維持することができ、本発明の効果を十分に発揮することができる。
このような（Ｃ）成分としては、ヒンダードアミン系光安定剤が挙げられる。具体的には、例えば、ビス（２，２，６−テトラメチル−４−ピペリジル）セバケート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、ビス（１−オクトキシ−２，２，６，６−テトラメチル−４−ピペリジル）セバケート、２−（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２−ｎ−ブチルマロン酸ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート、テトラキス（１，２，２，６，６−ペンタメチル−４−ピペリジル）−１，２，３，４−ブタンテトラカルボキシレート等が挙げられる。
（Ｃ）成分の比率は、（Ａ）成分１００重量部に対し、好ましくは０．０１〜１０重量部、より好ましくは０．０５〜５重量部、より好ましくは０．１〜３重量部である。
In the colored layer, in addition to the above components, (C) a light stabilizer (hereinafter also referred to as “component (C)”) may be used. By including such a component (C), it is possible to maintain excellent adhesion with a transparent layer described later over a long period of time, and the effects of the present invention can be sufficiently exhibited.
Examples of such component (C) include hindered amine light stabilizers. Specifically, for example, bis (2,2,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octoxy- 2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate , 6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2) , 6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like.
The ratio of the component (C) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the component (A). is there.
また、着色層は本発明の効果を著しく損なわない限り、必要に応じ、その他の成分を含むことができる。このような成分としては、例えば、可塑剤、防藻剤、抗菌剤、消臭剤、吸着剤、難燃剤、着色顔料、光輝性顔料、蛍光顔料、体質顔料、骨材、繊維、紫外線吸収剤、酸化防止剤、触媒等が挙げられる。なお、本発明においては、前記無機質粒子の表面に金属酸化物が付着した着色粒子以外の着色粒子（有機質着色粒子、着色骨材等）を、本発明の効果を損なわない程度に含むこともできる。 Moreover, unless the effect of this invention is impaired remarkably, a colored layer can contain another component as needed. Examples of such components include plasticizers, algae inhibitors, antibacterial agents, deodorants, adsorbents, flame retardants, colored pigments, bright pigments, fluorescent pigments, extender pigments, aggregates, fibers, and UV absorbers. , Antioxidants, catalysts and the like. In the present invention, colored particles (organic colored particles, colored aggregates, etc.) other than the colored particles having a metal oxide adhered to the surface of the inorganic particles can be included to such an extent that the effects of the present invention are not impaired. .
本発明の着色層は、その表面に、上記（Ａ）成分に由来する微視的な凹凸形状を有する。この微視的な凹凸は、（Ａ）成分の粒子径や凝集具合等に起因するもので、好ましくは１．５ｍｍ以下（より好ましくは０．００５ｍｍ以上１．２ｍｍ以下、さらに好ましくは０．０１ｍｍ以上１ｍｍ以下、最も好ましくは０．０２ｍｍ以上０．８ｍｍ以下）の高低差を有するものである。 The colored layer of the present invention has a microscopic uneven shape derived from the component (A) on the surface. This microscopic unevenness is caused by the particle size, aggregation state, etc. of the component (A), preferably 1.5 mm or less (more preferably 0.005 mm or more and 1.2 mm or less, more preferably 0.01 mm). 1 mm or less, most preferably 0.02 mm or more and 0.8 mm or less).
本発明の着色層としては、上述の微視的な凹凸に加え、さらに巨視的な凹凸模様を有するものが使用できる。本発明では、着色層がこのような態様である場合に、特に有利な効果が得られる。
巨視的な凹凸模様は、着色層に立体感を付与する。この巨視的な凹凸模様は、上述の微視的な凹凸よりも大きく、好ましくは１ｍｍ以上１０ｍｍ（より好ましくは１．５ｍｍ以上８ｍｍ以下）の高低差を有するものである。このような高低差を有する凹凸模様としては、例えば、ゆず肌模様、さざ波模様、スタッコ模様、砂壁模様、石材模様、岩肌模様、砂岩模様、吹放し模様、月面模様、櫛引模様、虫喰模様、等が挙げられる。
As the colored layer of the present invention, a layer having a macroscopic concavo-convex pattern in addition to the above microscopic concavo-convex can be used. In the present invention, particularly advantageous effects can be obtained when the colored layer has such an embodiment.
The macroscopic concavo-convex pattern imparts a stereoscopic effect to the colored layer. This macroscopic concavo-convex pattern is larger than the above-mentioned microscopic concavo-convex pattern, and preferably has a height difference of 1 mm to 10 mm (more preferably 1.5 mm to 8 mm). Examples of the uneven pattern having such a height difference include, for example, a yuzu skin pattern, a ripple pattern, a stucco pattern, a sand wall pattern, a stone pattern, a rock texture pattern, a sandstone pattern, a blown pattern, a moon pattern, a comb pattern, and an insect pattern , Etc.
着色層の厚みは、目的に応じて適宜設定すればよいが、好ましくは０．５ｍｍ〜１０ｍｍ、より好ましくは１ｍｍ〜８ｍｍである。このような範囲の場合、彫りの深い凹凸模様（巨視的な凹凸模様）の形成に有利であり、立体感のある優れた意匠性が得られやすい。 The thickness of the colored layer may be appropriately set according to the purpose, but is preferably 0.5 mm to 10 mm, more preferably 1 mm to 8 mm. In such a range, it is advantageous for the formation of a deeply carved uneven pattern (macroscopic uneven pattern), and an excellent design with a three-dimensional effect is easily obtained.
（透明層）
本発明の透明層は、積層体の最表面に設けられるものであり、（Ｅ）平均一次粒子径１〜２００ｎｍのシリカ（以下「（Ｅ）成分」ともいう）が（Ｆ）合成樹脂（以下「（Ｆ）成分」ともいう）で固定化されたものである。
(Transparent layer)
The transparent layer of the present invention is provided on the outermost surface of the laminate, and (E) silica having an average primary particle diameter of 1 to 200 nm (hereinafter also referred to as “(E) component”) is (F) a synthetic resin (hereinafter referred to as “F”). (Also referred to as “component (F)”).
透明層における（Ｅ）成分は、粒子自体の硬度が高く、さらに粒子表面にシラノール基を多く有する等によって、優れた汚染防止効果を発揮するものである。
（Ｅ）成分の平均一次粒子径は、通常１〜２００ｎｍ、好ましくは３〜１００ｎｍ、より好ましくは５〜６０ｎｍである。この範囲内であれば、平均一次粒子径が異なる複数のシリカを併用することもできる。（Ｅ）成分の平均一次粒子径が２００ｎｍよりも大きい場合は、比表面積が小さくなり、シラノール基も減るため汚染防止性が不十分となる。平均一次粒子径が１ｎｍよりも小さい場合は、シリカ自体が不安定化するため、実用的でない。なお、ここで言う平均一次粒子径は、光散乱法によって測定される値である。
The component (E) in the transparent layer exhibits an excellent antifouling effect due to the high hardness of the particles themselves and the fact that they have many silanol groups on the surface of the particles.
(E) The average primary particle diameter of a component is 1-200 nm normally, Preferably it is 3-100 nm, More preferably, it is 5-60 nm. Within this range, a plurality of silicas having different average primary particle sizes can be used in combination. When the average primary particle size of the component (E) is larger than 200 nm, the specific surface area becomes small, and silanol groups are reduced, so that the anti-contamination property becomes insufficient. When the average primary particle diameter is smaller than 1 nm, the silica itself becomes unstable, so it is not practical. In addition, the average primary particle diameter said here is a value measured by the light-scattering method.
このような（Ｅ）成分としては、シリカゾルに由来するものが好ましく、さらにはｐＨ５以上１２以下（好ましくは６以上１０以下、より好ましくは６以上９以下）の水分散性シリカゾルに由来するものが好ましい。
このような水分散性シリカゾルは、例えば、珪酸ソーダ、珪酸リチウム、珪酸カリウム、シリケート化合物等を原料として製造できる。このうち、シリケート化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラｎ−プロポキシシラン、テトライソプロポキシシラン、テトラｎ−ブトキシシラン、テトライソブトキシシラン、テトラｓｅｃ−ブトキシシラン、テトラｔ−ブトキシシラン、テトラフェノキシシラン等、あるいはこれらの縮合物等が挙げられる。この他、上記シリケート化合物以外のアルコキシシラン化合物や、アルコール類、グリコール類、グリコールエーテル類、フッ素アルコール、シランカップリング剤、ポリオキシアルキレン基含有化合物等を併せて使用することもできる。
As such component (E), those derived from silica sol are preferable, and those derived from water-dispersible silica sol having a pH of 5 or more and 12 or less (preferably 6 or more and 10 or less, more preferably 6 or more and 9 or less). preferable.
Such a water-dispersible silica sol can be produced using, for example, sodium silicate, lithium silicate, potassium silicate, a silicate compound or the like as a raw material. Among these, as silicate compounds, for example, tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetrasec-butoxysilane, tetra-t-butoxy Examples thereof include silane, tetraphenoxysilane, and their condensates. In addition, alkoxysilane compounds other than the silicate compounds, alcohols, glycols, glycol ethers, fluoroalcohols, silane coupling agents, polyoxyalkylene group-containing compounds, and the like can also be used.
上記（Ｅ）成分を固定化する（Ｆ）成分としては、各種樹脂が使用できる。具体的には上記（Ｂ）成分と同様のものが挙げられ、これらの１種または２種以上が使用できる。このような樹脂としては、水溶性樹脂及び／または水分散性樹脂が好ましい。 Various resins can be used as the component (F) for immobilizing the component (E). Specifically, the same thing as said (B) component is mentioned, These 1 type (s) or 2 or more types can be used. Such a resin is preferably a water-soluble resin and / or a water-dispersible resin.
（Ｆ）成分の比率は、（Ｅ）成分の固形分１００重量部に対し、通常５〜５００重量部、好ましくは１０〜１００重量部、より好ましくは２０〜８０重量部である。このような比率であることにより、着色層への密着性に優れると共に、十分な汚染防止効果が得られ、温度上昇抑制の点でも有利である。しかも、このような効果が長期間にわたり発揮される。また、着色層の水蒸気透過性が阻害されず、膨れ防止等の点でも有利である。（Ｅ）成分の熱伝導性に基づく熱拡散作用によって、局所的な温度上昇も抑制されると考えられる。 The ratio of the component (F) is usually 5 to 500 parts by weight, preferably 10 to 100 parts by weight, and more preferably 20 to 80 parts by weight with respect to 100 parts by weight of the solid content of the component (E). By being such a ratio, while being excellent in the adhesiveness to a colored layer, the sufficient contamination prevention effect is acquired and it is advantageous also at the point of temperature rise suppression. And such an effect is exhibited over a long period of time. Further, the water vapor permeability of the colored layer is not hindered, which is advantageous in terms of preventing swelling. It is considered that the local temperature rise is also suppressed by the thermal diffusion action based on the thermal conductivity of the component (E).
また、透明層においては、上記成分に加え、本発明の効果を損なわない程度に、１μｍ未満のガラス粉末を使用することもできる。このような１μｍ未満のガラス粉末を含むことにより、太陽光照射時の温度上昇をより効果的に抑制することができる。 Moreover, in a transparent layer, in addition to the said component, glass powder below 1 micrometer can also be used to such an extent that the effect of this invention is not impaired. By including such glass powder of less than 1 μm, it is possible to more effectively suppress the temperature rise during sunlight irradiation.
本発明の透明層は、上記、（Ｅ）成分、（Ｆ）成分等の他に、本発明の効果を損なわない程度に、必要に応じ、その他の成分を含むことができる。このような成分としては、例えば、可塑剤、防藻剤、抗菌剤、消臭剤、吸着剤、難燃剤、繊維、紫外線吸収剤、光安定剤、酸化防止剤、触媒、光輝性顔料、蛍光顔料等が挙げられる。 The transparent layer of the present invention can contain other components as needed, in addition to the above-mentioned (E) component, (F) component, etc., to the extent that the effects of the present invention are not impaired. Such components include, for example, plasticizers, algae inhibitors, antibacterial agents, deodorants, adsorbents, flame retardants, fibers, UV absorbers, light stabilizers, antioxidants, catalysts, glitter pigments, fluorescent And pigments.
本発明では特に、透明層に、光輝性顔料を含むが好ましい。透明層に光輝性顔料を含むことによって着色層の意匠性とあいまって、高級感のある優れた意匠性を得ることができる。
光輝性顔料としては、例えば、アルミニウムフレーク顔料、蒸着アルミニウムフレーク顔料、金属酸化物被覆アルミニウムフレーク顔料、着色アルミニウムフレーク顔料、金属酸化物被覆マイカ顔料、金属酸化物被覆合成マイカ顔料、金属酸化物被覆アルミナフレーク顔料、金属酸化物被覆シリカフレーク顔料、金属被覆ガラスフレーク顔料、金属酸化物被覆ガラスフレーク顔料、金属酸化物被覆板状酸化鉄、グラファイト、ステンレスフレーク、金属チタンフレーク顔料、板状硫化モリブデン、板状塩化ビスマス、ホログラム顔料、コレステリック液晶ポリマー、金属蒸着高分子フィルムの破砕品等が挙げられる。このような光輝性顔料の平均粒子径は、通常０．１μｍ以上０．３ｍｍ未満であるものを使用すればよい。
光輝性顔料の比率は、特に限定されないが、（Ｅ）成分の固形分１００重量部に対し、通常０．１〜１００重量部、好ましくは０．２〜５０重量部である。このような範囲であることにより、着色層の意匠性を有しつつ、光輝性顔料のキラキラ感が現れ、優れた意匠性を得ることができる。
In the present invention, it is particularly preferable that the transparent layer contains a bright pigment. By including the glitter pigment in the transparent layer, it is possible to obtain a high-quality and excellent design property combined with the design property of the colored layer.
Examples of glitter pigments include aluminum flake pigments, vapor-deposited aluminum flake pigments, metal oxide-coated aluminum flake pigments, colored aluminum flake pigments, metal oxide-coated mica pigments, metal oxide-coated synthetic mica pigments, and metal oxide-coated alumina. Flake pigment, metal oxide coated silica flake pigment, metal coated glass flake pigment, metal oxide coated glass flake pigment, metal oxide coated plate iron oxide, graphite, stainless steel flake, metal titanium flake pigment, plate molybdenum sulfide, plate Bismuth chloride, holographic pigment, cholesteric liquid crystal polymer, crushed product of metal-deposited polymer film, and the like. What is necessary is just to use what the average particle diameter of such a luster pigment is 0.1 micrometer or more and less than 0.3 mm normally.
The ratio of the glitter pigment is not particularly limited, but is usually 0.1 to 100 parts by weight, preferably 0.2 to 50 parts by weight with respect to 100 parts by weight of the solid content of the component (E). By being in such a range, while having the designability of a colored layer, the glittering feeling of a glittering pigment appears and the excellent designability can be obtained.
透明層は、着色層の全面を被覆する形態であればよい。透明層の単位面積当たりの重量は、固形分換算で、好ましくは０．１〜５０ｇ／ｍ２、より好ましくは０．５〜２０ｇ／ｍ２である。このような透明層は、着色層上部における個々の着色粒子の表面、着色粒子の近傍、着色粒子同士の間隙等を含む着色層全体を覆うことができる。 The transparent layer may be in a form that covers the entire surface of the colored layer. Weight per unit area of the transparent layer, in terms of solid content, preferably 0.1 to 50 g / m 2, more preferably 0.5 to 20 g / m 2. Such a transparent layer can cover the entire colored layer including the surface of the individual colored particles above the colored layer, the vicinity of the colored particles, the gap between the colored particles, and the like.
本発明において、透明層は、微視的な凹凸形状の凹部に偏在した態様とすることができる。このような態様では、着色層の美観性を阻害することなく、汚染防止、温度上昇抑制等の効果を一層高めることができる。しかも、その効果を長期間にわたり発揮することができる。その作用機構は明確ではないが、以下のような点が関与しているものと推定される。
・着色層表面の凹凸が緩和され、汚染物質等の付着が抑制される。
・着色層表面における着色粒子と合成樹脂の界面が補強される。
・凹部では、膜厚が厚くなるため、侵食等の影響を受け難くなる。
In the present invention, the transparent layer may be unevenly distributed in a concave portion having a microscopic uneven shape. In such an embodiment, effects such as contamination prevention and temperature rise suppression can be further enhanced without impairing the aesthetics of the colored layer. And the effect can be exhibited over a long period of time. The mechanism of action is not clear, but it is presumed that the following points are involved.
-Unevenness on the surface of the colored layer is alleviated and adhesion of contaminants and the like is suppressed.
-The interface between the colored particles and the synthetic resin on the colored layer surface is reinforced.
-Since the thickness of the recess is increased, it is less susceptible to erosion and the like.
（基層）
本発明では、本発明効果を阻害しない限り、例えば、着色層の内部乃至裏面に基層を積層することができる。基層に用いる材料としては、可とう性、水蒸気透過性等を有するものが好ましい。このような材料としては、織布、不織布、メッシュ、クロス等の繊維質材料が挙げられる。具体的に、繊維質材料としては、厚さ０．０５〜１．５ｍｍ（より好ましくは０．１〜１．２ｍｍ、さらに好ましくは０．２〜１ｍｍ）、坪量５〜３００ｇ／ｍ２、（より好ましくは１０〜２５０ｇ／ｍ２、さらに好ましくは２０〜２００ｇ／ｍ２）の無機繊維を含むもの等が挙げられる。このような繊維質材料を用いることにより、積層体の割れ防止性等を高めることができる。また、積層体を外壁面等へ施工した際、積層体を安定的に支えることができる。
(Base layer)
In the present invention, as long as the effects of the present invention are not impaired, for example, a base layer can be laminated on the inside or the back surface of the colored layer. As the material used for the base layer, a material having flexibility, water vapor permeability and the like is preferable. Examples of such a material include fibrous materials such as woven fabric, non-woven fabric, mesh, and cloth. Specifically, the fibrous material has a thickness of 0.05 to 1.5 mm (more preferably 0.1 to 1.2 mm, more preferably 0.2 to 1 mm), a basis weight of 5 to 300 g / m 2 , Examples include those containing inorganic fibers (more preferably 10 to 250 g / m 2 , and still more preferably 20 to 200 g / m 2 ). By using such a fibrous material, it is possible to improve the crack prevention property of the laminate. Moreover, when constructing a laminated body to an outer wall surface etc., a laminated body can be supported stably.
（積層体の製造方法）
本発明では、上記着色層の上に上記透明層が積層される限り、その製造方法は特に限定されないが、特に下記（１）または（２）のように、着色層を形成した後、着色層の上に透明層を形成する製造方法が好ましい。この方法によれば、透明層が着色層の全面を被覆すると共に、微視的な凹凸形状の凹部に偏在した態様が得られやすく、本発明の効果発現の点でも好適である。なお、下記（２）では、基層上に着色層及び透明層が順に積層された積層体が得られる。
(Laminate manufacturing method)
In the present invention, the production method is not particularly limited as long as the transparent layer is laminated on the colored layer, but the colored layer is formed after the colored layer is formed as in the following (1) or (2). The manufacturing method which forms a transparent layer on this is preferable. According to this method, it is easy to obtain a mode in which the transparent layer covers the entire surface of the colored layer and is unevenly distributed in the concave portion having a microscopic uneven shape, which is also preferable from the viewpoint of the effect of the present invention. In the following (2), a laminate in which a colored layer and a transparent layer are sequentially laminated on the base layer is obtained.
（１）離型性下地の上に、（Ａ）着色粒子及び（Ｂ）合成樹脂を含む着色層用組成物を塗付して着色層を形成した後、（Ｅ）シリカ及び（Ｆ）合成樹脂を含む透明層用組成物を塗付して透明層を形成し、硬化後に離型性下地を除去する方法。
（２）基層上に、（Ａ）着色粒子及び（Ｂ）合成樹脂を含む着色層用組成物を塗付して着色層を形成した後、（Ｅ）シリカ及び（Ｆ）合成樹脂を含む透明層用組成物を塗付し透明層を形成する方法。
(1) A colored layer composition containing (A) colored particles and (B) synthetic resin is applied on a releasable substrate to form a colored layer, and then (E) silica and (F) synthesis A method of forming a transparent layer by applying a composition for a transparent layer containing a resin, and removing the releasable substrate after curing.
(2) After applying a colored layer composition containing (A) colored particles and (B) synthetic resin on the base layer to form a colored layer, (E) transparent containing silica and (F) synthetic resin A method of forming a transparent layer by applying a layer composition.
上記（１）における離型性下地としては、硬化後に除去できるものであればよく、例えば、シリコン樹脂製、ウレタン樹脂製、金属製等の型枠、あるいは離型紙等が使用できる。
また、上記（１）、（２）では、離型性下地または基層を水平に設置し、その上に着色層用組成物及び透明層用組成物を積層することが望ましい。
The releasable substrate in (1) may be any substrate that can be removed after curing. For example, a mold made of silicon resin, urethane resin, metal, or release paper may be used.
Moreover, in said (1) and (2), it is desirable to install a mold release base | substrate or base layer horizontally, and to laminate | stack the composition for colored layers, and the composition for transparent layers on it.
上記（１）、（２）において、着色層用組成物、透明層用組成物は、本発明の効果を著しく損なわない限り、必要に応じ、公知の添加剤を含むことができる。このような添加剤としては、例えば、増粘剤、造膜助剤、レベリング剤、湿潤剤、可塑剤、凍結防止剤、ｐＨ調整剤、防腐剤、防黴剤、防藻剤、抗菌剤、消臭剤、分散剤、消泡剤、吸着剤、難燃剤、着色顔料、体質顔料、繊維、撥水剤、架橋剤、紫外線吸収剤、酸化防止剤、触媒等が挙げられる。 In said (1) and (2), the composition for colored layers and the composition for transparent layers can contain a well-known additive as needed, unless the effect of this invention is impaired remarkably. Examples of such additives include thickeners, film-forming aids, leveling agents, wetting agents, plasticizers, antifreezing agents, pH adjusting agents, antiseptics, antifungal agents, algaeproofing agents, antibacterial agents, Examples include deodorants, dispersants, antifoaming agents, adsorbents, flame retardants, color pigments, extender pigments, fibers, water repellents, crosslinking agents, ultraviolet absorbers, antioxidants, and catalysts.
上記（１）、（２）において、着色層用組成物を塗付する際には、例えば、スプレー、ローラー、鏝、レシプロ、コーター、流し込み等の公知の塗付器具が使用できる。透明層用組成物を塗付する際には、例えば、スプレー、ローラー等の公知の塗付器具が使用できる。 In the above (1) and (2), when applying the composition for the colored layer, for example, a known application device such as spray, roller, scissors, reciprocator, coater, and pouring can be used. When applying the composition for transparent layer, well-known applicators, such as a spray and a roller, can be used, for example.
上記（１）、（２）において、着色層用組成物、透明層用組成物の乾燥は、それぞれ別に行ってもよいし、着色層用組成物が未乾燥の状態で透明層用組成物を塗付し同時に行ってもよい。乾燥は、常温で行うこともできるが、本発明では加熱することが好ましい。加熱温度としては４０℃以上１７０℃未満程度とすることが好ましい。 In the above (1) and (2), the colored layer composition and the transparent layer composition may be dried separately, or the transparent layer composition may be dried in an undried state. It may be applied at the same time. Although drying can also be performed at normal temperature, it is preferable to heat in this invention. The heating temperature is preferably about 40 ° C. or more and less than 170 ° C.
着色層に巨視的な凹凸模様を形成する方法としては、例えば以下の方法が採用できる。
（イ）着色層用組成物を塗付する際に、模様塗りを行う。
（ロ）着色層用組成物を均一に塗付後、未硬化の状態でその一部を除去したり、押圧したりする。
（ハ）着色層用組成物の硬化後、その表面を部分的に切削する。
As a method for forming a macroscopic uneven pattern on the colored layer, for example, the following method can be employed.
(A) When applying the colored layer composition, a pattern is applied.
(B) After uniformly applying the colored layer composition, a part thereof is removed or pressed in an uncured state.
(C) The surface of the colored layer composition is partially cut after curing.
上記（イ）では、塗付器具の種類とその使用方法を適宜選定したり、着色層用組成物の粘性を調整したりすることで、種々の凹凸模様が得られる。
上記（ロ）では、着色層用組成物が乾燥するまでに、その塗面をデザインローラー、鏝、刷毛、櫛、へら、スタンプ、エンボス等の器具を用いて除去または押圧処理することで、種々の凹凸模様が得られる。
上記（ハ）では、研磨具、切削具等を用いることができる。
In said (I), various uneven | corrugated patterns are obtained by selecting suitably the kind of application tool, its usage, or adjusting the viscosity of the composition for colored layers.
In the above (b), before the colored layer composition is dried, the coated surface is removed or pressed by using a tool such as a design roller, scissors, brush, comb, spatula, stamp, emboss, etc. An uneven pattern is obtained.
In (c) above, a polishing tool, a cutting tool, or the like can be used.
このうち本発明では、上記（イ）及び／または（ロ）の方法が好ましい。
特に上記（イ）では、着色層用組成物の玉状物を加速させて塗付する方法が好ましい。このような方法としては、遠心力、風圧等を用いて着色層用組成物を玉状に吹付ける方法等が挙げられる。
また上記（ロ）では、着色層用組成物の塗面を押圧する方法が好ましい。このような方法としては、着色層用組成物を塗付後、その塗面をエンボス加工する方法等が挙げられる。
このような方法によれば、（Ａ）成分が密に凝集しやすく、本発明の効果が得られやすい。
Among these, in the present invention, the above methods (a) and / or (b) are preferable.
In the case of (i) above, a method of applying the ball-shaped product of the colored layer composition by accelerating it is preferable. Examples of such a method include a method of spraying the colored layer composition in a ball shape using centrifugal force, wind pressure, or the like.
In (b) above, a method of pressing the coating surface of the colored layer composition is preferred. Examples of such a method include a method of embossing the coated surface after applying the colored layer composition.
According to such a method, the component (A) tends to agglomerate densely, and the effects of the present invention can be easily obtained.
（積層体の施工方法）
本発明積層体は、主に建築物の外装建材として適用できる。すなわち、本発明積層体の施工においては、建築物外装面（下地）に対し積層体を貼着すればよい。このような下地としては、コンクリート、モルタル、繊維混入セメント板、セメント珪酸カルシウム板、スラグセメントパーライト板、石膏ボード、タイル、ＡＬＣ板、サイディング板、押出成形板、鋼板、プラスチック板、木質板等が挙げられる。これら下地は、フィラー、パテ、シーラー等で処理されたものであってもよい。
(Laminate construction method)
The laminate of the present invention can be applied mainly as an exterior building material for buildings. That is, in the construction of the laminate of the present invention, the laminate may be attached to the building exterior surface (base). Such bases include concrete, mortar, fiber-mixed cement board, cement calcium silicate board, slag cement pearlite board, gypsum board, tile, ALC board, siding board, extrusion board, steel sheet, plastic board, wood board, etc. Can be mentioned. These foundations may be treated with a filler, putty, sealer or the like.
本発明積層体を下地に貼着する際には、例えば、接着剤、粘着剤、粘着テープ、釘、鋲等を用いればよい。その他、ピン、ファスナー、レール等を用いて固定化することもできる。中でも、接着剤を介して下地に貼着することが好ましい。本発明積層体は、適度な水蒸気透過性を有するため、接着剤を介して下地に貼着した場合、接着剤の乾燥性を促進させる効果を発揮する。 When the laminate of the present invention is attached to the base, for example, an adhesive, a pressure-sensitive adhesive, a pressure-sensitive adhesive tape, a nail, a heel or the like may be used. In addition, it can also be fixed using pins, fasteners, rails or the like. Especially, it is preferable to stick to the base | substrate through an adhesive agent. Since this invention laminated body has moderate water vapor permeability, when it sticks to the foundation | substrate via an adhesive agent, the effect which accelerates | stimulates the drying property of an adhesive agent is exhibited.
また、積層体を接着剤で貼着する際には、隣接する積層体同士を突き合わせて貼着したり、積層体を所定の間隔で貼着して目地を設けたりすることができる。本発明では、接着剤が積層体の間で露出するように、積層体を貼着することによって、容易に目地部を形成することができる。この場合、積層体を貼着する間隔（目地幅）は、好ましくは１〜３０ｍｍ程度であればよい。このような範囲であれば、目地模様を活かした装飾仕上げが得られる。目地部の接着剤は、必要に応じ、へら等で平滑処理しても良い。なお、接着剤を硬化させる際の雰囲気温度は、適宜設定することができるが、通常は常温でよい。 Moreover, when sticking a laminated body with an adhesive agent, adjacent laminated bodies can be stuck and stuck, or a laminated body can be stuck at a predetermined | prescribed space | interval and a joint can be provided. In this invention, a joint part can be easily formed by sticking a laminated body so that an adhesive agent may be exposed between laminated bodies. In this case, the interval (joint width) for adhering the laminate is preferably about 1 to 30 mm. Within such a range, a decorative finish utilizing the joint pattern can be obtained. The adhesive at the joint may be smoothed with a spatula or the like as necessary. In addition, although the atmospheric temperature at the time of hardening an adhesive agent can be set suitably, it may be normal temperature normally.
以下に実施例を示し、本発明の特徴をより明確にする。 Examples are given below to clarify the features of the present invention.
（着色層用組成物１〜９）
表１に示す配合に従い、各原料を常法により混合・攪拌することによって着色層用組成物１〜９を製造した。なお、原料としては以下のものを使用した。
(Colored layer compositions 1 to 9)
According to the composition shown in Table 1, colored layers Compositions 1 to 9 were produced by mixing and stirring each raw material by a conventional method. In addition, the following were used as a raw material.
・着色粒子１：珪石の表面に複合酸化物（酸化マンガン・酸化コバルト・酸化鉄）が付着した黒色粒子（平均粒子径９０μｍ）
・着色粒子２：珪石の表面に複合酸化物（酸化マンガン・酸化コバルト・酸化鉄）が付着した黒色粒子（平均粒子径１６０μｍ）
・着色粒子３：珪石の表面に複合酸化物（酸化マンガン・酸化コバルト・酸化鉄）が付着した黒色粒子（平均粒子径３００μｍ）
・着色粒子４：珪石の表面に酸化鉄を含む金属酸化物が付着した茶色粒子（平均粒子径８０μｍ）
・着色粒子５：珪石の表面に酸化鉄を含む金属酸化物が付着した茶色粒子（平均粒子径１７０μｍ）
・着色粒子６：珪石の表面に酸化鉄を含む金属酸化物が付着した茶色粒子（平均粒子径２８０μｍ）
・着色粒子７：珪石の表面に酸化チタンを含む金属酸化物が付着した白色粒子（平均粒子径９５μｍ）
・着色粒子８：珪石の表面に酸化チタンを含む金属酸化物が付着した白色粒子（平均粒子径１４０μｍ）
・着色粒子９：珪石の表面に酸化チタンを含む金属酸化物が付着した白色粒子（平均粒子径３５０μｍ）
・合成樹脂１（アクリル樹脂エマルション、固形分５０重量％、ガラス転移温度０℃）
・光安定剤（ビス（１，２，２，６，６‐ペンタメチル‐４‐ピペリジル）セバケート）
Colored particles 1: Black particles (average particle size 90 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica
Colored particles 2: Black particles (average particle size 160 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica stone
Colored particles 3: Black particles (average particle size 300 μm) with complex oxide (manganese oxide, cobalt oxide, iron oxide) attached to the surface of silica stone
Colored particles 4: Brown particles (average particle size 80 μm) with metal oxides containing iron oxide attached to the surface of silica
-Colored particles 5: Brown particles (average particle size 170 μm) with a metal oxide containing iron oxide attached to the surface of silica stone
Colored particle 6: Brown particle (average particle size 280 μm) with a metal oxide containing iron oxide attached to the surface of silica
Colored particles 7: White particles (average particle size 95 μm) in which a metal oxide containing titanium oxide is adhered to the surface of silica
-Colored particles 8: White particles (average particle size 140 μm) in which a metal oxide containing titanium oxide adheres to the surface of silica
Colored particle 9: White particle (average particle diameter 350 μm) in which a metal oxide containing titanium oxide adheres to the surface of silica
Synthetic resin 1 (acrylic resin emulsion, solid content 50% by weight, glass transition temperature 0 ° C.)
・ Light stabilizer (bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate)
なお、着色層用組成物５の着色粒子中、平均粒子径２２μｍ以上１５０μｍ未満の着色粒子（Ａ１）は４０重量％、平均粒子径１５０μｍ以上２１２μｍ未満の着色粒子（Ａ２）は３０重量％、平均粒子径２１２μｍ以上６００μｍ未満の着色粒子（Ａ３）は３０重量％であった。
着色層用組成物６の着色粒子中、（Ａ１）は４５重量％、（Ａ２）は３１重量％、（Ａ３）は２４重量％であった。
着色層用組成物７中の着色粒子中、（Ａ１）は５２重量％、（Ａ２）は２２重量％、（Ａ３）は２６重量％であった。
着色層用組成物８及び９は、着色層用組成物５と同様であった。
In the colored particles of the colored layer composition 5, the colored particles (A1) having an average particle diameter of 22 μm or more and less than 150 μm are 40% by weight, and the colored particles (A2) having an average particle diameter of 150 μm or more and less than 212 μm are 30% by weight, average. The colored particles (A3) having a particle diameter of 212 μm or more and less than 600 μm were 30% by weight.
In the colored particles of the colored layer composition 6, (A1) was 45% by weight, (A2) was 31% by weight, and (A3) was 24% by weight.
In the colored particles in the colored layer composition 7, (A1) was 52% by weight, (A2) was 22% by weight, and (A3) was 26% by weight.
The colored layer compositions 8 and 9 were the same as the colored layer composition 5.
（透明層用組成物）
透明層用組成物としては、以下のものを用意した。
・透明層用組成物１
シリカ（水分散性シリカゾル、ｐＨ７．６、平均一次粒子径２７ｎｍ）：アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）＝１００：６０（固形分重量比）の水分散液。
・透明層用組成物２
シリカ（水分散性シリカゾル、ｐＨ７．３、平均一次粒子径４３ｎｍ）：アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）＝１００：３８（固形分重量比）の水分散液。
・透明層用組成物３
シリカ（水分散性シリカゾル、ｐＨ７．８、平均一次粒子径１２ｎｍ）：アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）＝１００：７２（固形分重量比）の水分散液。
・透明層用組成物４
シリカ（水分散性シリカゾル、ｐＨ７．６、平均一次粒子径２７ｎｍ）：アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）＝１００：３２０（固形分重量比）の水分散液。
・透明層用組成物５
アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）の水分散液。
・透明層用組成物６
シリカ（水分散性シリカゾル、ｐＨ７．６、平均一次粒子径２７ｎｍ）：アクリルシリコンポリマー（メチルメタクリレート‐ｎ‐ブチルアクリレート‐２‐エチルヘキシルアクリレート‐γ‐メタクリロイルオキシプロピルトリメトキシシラン共重合樹脂、ガラス転移温度１８℃）：光輝性顔料（蒸着アルミニウムフレーク顔料、平均粒子径１５０μｍ）＝１００：６０：０．８（固形分重量比）の水分散液。
(Transparent layer composition)
As the composition for transparent layer, the following were prepared.
-Composition 1 for transparent layer
Silica (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 60 (solid weight ratio) aqueous dispersion.
・ Transparent layer composition 2
Silica (water-dispersible silica sol, pH 7.3, average primary particle size 43 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 38 (solid weight ratio) aqueous dispersion.
-Composition 3 for transparent layer
Silica (water-dispersible silica sol, pH 7.8, average primary particle size 12 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 72 (solid weight ratio) aqueous dispersion.
-Composition 4 for transparent layer
Silica (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.) = 100: 320 (solid weight ratio) aqueous dispersion.
-Composition 5 for transparent layer
An aqueous dispersion of an acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature 18 ° C.).
-Composition 6 for transparent layer
Silica (water-dispersible silica sol, pH 7.6, average primary particle size 27 nm): acrylic silicon polymer (methyl methacrylate-n-butyl acrylate-2-ethylhexyl acrylate-γ-methacryloyloxypropyltrimethoxysilane copolymer resin, glass transition temperature) 18 ° C.): Bright pigment (evaporated aluminum flake pigment, average particle size 150 μm) = 100: 60: 0.8 (solid content weight ratio) aqueous dispersion.
（試験例１）
基層（ガラス不織布：厚み０．４ｍｍ、坪量５０ｇ／ｍ２）上に、着色層用組成物１を、乾燥厚みが２ｍｍとなるようにコーターで塗付し、６０℃下で６０分間乾燥した。次いで、透明層用組成物１を、乾燥後の固形分重量が５ｇ／ｍ２となるようにスプレー塗装後、８０℃下で６０分間乾燥し、積層体１を得た。着色層における微視的凹凸の高低差は０．２ｍｍであった。
得られた積層体１について以下の試験を行った。結果は表２に示す。
(Test Example 1)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m 2 ), the colored layer composition 1 was applied with a coater so as to have a dry thickness of 2 mm, and dried at 60 ° C. for 60 minutes. . Subsequently, the composition 1 for transparent layers was spray-coated so that the solid content weight after drying might be 5 g / m < 2 >, Then, it dried at 80 degreeC for 60 minutes, and the laminated body 1 was obtained. The height difference of the microscopic unevenness in the colored layer was 0.2 mm.
The obtained laminate 1 was subjected to the following test. The results are shown in Table 2.
（試験方法）
上述の方法で得られた積層体を、汚染物質懸濁液（濃度１重量％）に２時間浸漬し、引き上げて標準状態で２４時間放置した後、水洗・乾燥した。以上の処理を行った積層体に対し、赤外線ランプを５０ｃｍの距離から照射し、温度上昇が平衡に達したときの試験体の裏面温度を測定し、温度上昇抑制性を評価した。評価は、温度が５５．０℃未満であったものを「Ａ」、５５．０℃以上５７．５℃未満であったものを「Ａ’」、５７．５℃以上６０．０℃未満であったものを「Ｂ」、６０．０℃以上６２．５℃未満であったものを「Ｂ’」、６２．５℃以上６５．０℃未満であったものを「Ｃ」、６５．０℃以上であったものを「Ｃ’」とした。
(Test method)
The laminate obtained by the above-described method was immersed in a contaminant suspension (concentration: 1% by weight) for 2 hours, pulled up and allowed to stand for 24 hours in a standard state, and then washed and dried. The laminated body subjected to the above treatment was irradiated with an infrared lamp from a distance of 50 cm, and the back surface temperature of the test body when the temperature rise reached equilibrium was measured to evaluate the temperature rise inhibitory property. The evaluation was “A” when the temperature was lower than 55.0 ° C., and “A ′” when the temperature was higher than 55.0 ° C. and lower than 57.5 ° C. “B” for what was 60.0 ° C. or more and less than 62.5 ° C., “C” for what was 62.5 ° C. or more and less than 65.0 ° C., 65.0 What was more than degree C was set to "C '".
（試験例２〜５）
着色層用組成物１を着色層用組成物２〜５に代えた以外は、試験例１と同様の方法で、それぞれ積層体２〜５を作製した（着色層における微視的凹凸の高低差０．２ｍｍ）。
得られた積層体につき、試験例１と同様の試験を行った。結果は表２に示す。
(Test Examples 2 to 5)
Laminates 2 to 5 were produced in the same manner as in Test Example 1 except that the colored layer composition 1 was replaced with the colored layer compositions 2 to 5 (the difference in level of microscopic unevenness in the colored layer) 0.2 mm).
About the obtained laminated body, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例６〜７）
透明層用組成物１を透明層用組成物２〜３に代えた以外は、試験例１と同様の方法で、それぞれ積層体６〜７を作製した（着色層における微視的凹凸の高低差０．２ｍｍ）。
得られた積層体につき、試験例１と同様の試験を行った。結果は表２に示す。
(Test Examples 6 to 7)
Except having replaced the composition 1 for transparent layers with the compositions 2-3 for transparent layers, the laminated bodies 6-7 were produced by the method similar to the test example 1, respectively (the height difference of the microscopic unevenness | corrugation in a colored layer) 0.2 mm).
About the obtained laminated body, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例８）
基層（ガラス不織布：厚み０．４ｍｍ、坪量５０ｇ／ｍ２）上に、着色層用組成物５を、乾燥厚みが４ｍｍとなるようにコーターで塗付し、６０℃下で１０分間乾燥した後、エンボス加工し表面に砂岩調の凹凸模様（高低差３ｍｍ）を形成した（微視的凹凸の高低差０．１ｍｍ）。次いで、透明層用組成物１を、乾燥後の固形分重量が５ｇ／ｍ２となるようにスプレー塗装後、８０℃下で６０分間乾燥し、積層体８を得た。
得られた積層体８について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 8)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m 2 ), the colored layer composition 5 was applied with a coater so as to have a dry thickness of 4 mm, and dried at 60 ° C. for 10 minutes. Thereafter, it was embossed to form a sandstone-like uneven pattern (3 mm height difference) on the surface (0.1 mm height difference of microscopic unevenness). Subsequently, the composition 1 for transparent layers was spray-coated so that the solid content weight after drying might be 5 g / m < 2 >, Then, it dried at 80 degreeC for 60 minutes, and the laminated body 8 was obtained.
About the obtained laminated body 8, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例９）
着色層用組成物５を着色層用組成物８に代えた以外は、試験例８と同様の方法で積層体９を作製した（凹凸模様の高低差３ｍｍ、微視的凹凸の高低差０．１ｍｍ）。
得られた積層体９について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 9)
A laminate 9 was produced in the same manner as in Test Example 8 except that the colored layer composition 5 was replaced with the colored layer composition 8 (3 mm height difference of the concavo-convex pattern, 0. 1 mm).
About the obtained laminated body 9, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１０）
基層（ガラス不織布：厚み０．４ｍｍ、坪量５０ｇ／ｍ２）上に、着色層用組成物５を、風圧を用いて玉状に吹付け、乾燥厚み１〜３ｍｍ（高低差２ｍｍ）の凹凸模様を形成し、６０℃下で６０分間乾燥した（微視的凹凸の高低差０．１ｍｍ）。次いで、透明層用組成物１を、乾燥後の固形分重量が５ｇ／ｍ２となるようにスプレー塗装後、８０℃下で６０分間乾燥し、積層体１０を得た。
得られた積層体１０について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 10)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m 2 ), the colored layer composition 5 is sprayed into a ball shape using wind pressure, and the dry thickness is 1 to 3 mm (height difference 2 mm). A pattern was formed and dried at 60 ° C. for 60 minutes (microscopic unevenness difference 0.1 mm). Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m 2, and then dried at 80 ° C. for 60 minutes to obtain a laminate 10.
About the obtained laminated body 10, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１１）
着色層用組成物５を着色層用組成物９に代えた以外は、試験例１０と同様の方法で積層体１１を作製した（凹凸模様の高低差２ｍｍ、微視的凹凸の高低差０．１ｍｍ）。
得られた積層体１１について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 11)
A laminate 11 was prepared in the same manner as in Test Example 10 except that the colored layer composition 5 was replaced with the colored layer composition 9 (the height difference of the uneven pattern was 2 mm, the height difference of the microscopic unevenness was 0.00. 1 mm).
About the obtained laminated body 11, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１２）
透明層用組成物１を透明層用組成物４に代えた以外は、試験例１０と同様の方法で積層体１２を作製した（凹凸模様の高低差２ｍｍ、微視的凹凸の高低差０．１ｍｍ）。
得られた積層体１２について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 12)
A laminate 12 was produced in the same manner as in Test Example 10 except that the transparent layer composition 1 was replaced with the transparent layer composition 4 (the height difference of the concavo-convex pattern was 2 mm, the height difference of the microscopic unevenness was 0.00. 1 mm).
About the obtained laminated body 12, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１３）
基層（ガラス不織布：厚み０．４ｍｍ、坪量５０ｇ／ｍ２）上に、着色層用組成物５、６、７をそれぞれ風圧を用いて玉状に吹付け、乾燥厚み１〜３ｍｍ（高低差２ｍｍ）の凹凸模様を形成し、６０℃下で６０分間乾燥した（微視的凹凸の高低差０．１ｍｍ）。次いで、透明層用組成物１を、乾燥後の固形分重量が５ｇ／ｍ２となるようにスプレー塗装後、８０℃下で６０分間乾燥し、積層体１３を得た。
得られた積層体１３について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 13)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m 2 ), the colored layer compositions 5, 6, and 7 are each sprayed into a ball shape using wind pressure, and the dry thickness is 1 to 3 mm (height difference) 2 mm) uneven pattern was formed, and dried at 60 ° C. for 60 minutes (microscopic unevenness difference 0.1 mm). Next, the transparent layer composition 1 was spray-coated so that the solid content weight after drying was 5 g / m 2, and then dried at 80 ° C. for 60 minutes to obtain a laminate 13.
About the obtained laminated body 13, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１４）
基層（ガラス不織布：厚み０．４ｍｍ、坪量５０ｇ／ｍ２）上に、着色層用組成物１を、乾燥厚みが２ｍｍとなるようにコーターで塗付し、６０℃下で６０分間乾燥後、さらに８０℃下で６０分間乾燥し、積層体１４を得た（着色層における凹凸の微視的高低差０．２ｍｍ）。
得られた積層体１４について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 14)
On the base layer (glass nonwoven fabric: thickness 0.4 mm, basis weight 50 g / m 2 ), the colored layer composition 1 is applied with a coater so that the dry thickness is 2 mm, and dried at 60 ° C. for 60 minutes. Furthermore, it dried at 80 degreeC for 60 minute (s), and the laminated body 14 was obtained (microscopic height difference of the unevenness | corrugation in a colored layer 0.2mm).
About the obtained laminated body 14, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１５）
透明層用組成物１を透明層用組成物５に代えた以外は、試験例１と同様の方法で積層体１５を作製した（着色層における凹凸の微視的高低差０．２ｍｍ）。得られた積層体１５について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 15)
Except having replaced the composition 1 for transparent layers with the composition 5 for transparent layers, the laminated body 15 was produced by the method similar to Test Example 1 (microscopic height difference of the unevenness | corrugation in a colored layer 0.2mm). About the obtained laminated body 15, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１６）
透明層用組成物１を透明層用組成物６に代えた以外は、試験例１と同様の方法で積層体１６を作製した（着色層における凹凸の微視的高低差０．２ｍｍ）。得られた積層体１６は、優れた高級感のある意匠性を有していた。得られた積層体１６について、試験例１と同様の試験を行った。結果は表２に示す。
(Test Example 16)
A laminate 16 was produced in the same manner as in Test Example 1 except that the transparent layer composition 1 was replaced with the transparent layer composition 6 (microscopic height difference of unevenness in the colored layer 0.2 mm). The obtained laminate 16 had an excellent high-quality design. About the obtained laminated body 16, the test similar to Test Example 1 was done. The results are shown in Table 2.
（試験例１７）
上述の積層体１０及び積層体１１を、促進耐候性試験機にて１２００時間曝露後、試験例１と同様の試験を実施した。その結果、曝露後の積層体１０は「Ｂ」、曝露後の積層体１１は「Ａ」の評価となった。
(Test Example 17)
After the laminated body 10 and the laminated body 11 were exposed for 1200 hours with an accelerated weather resistance tester, the same test as in Test Example 1 was performed. As a result, the laminate 10 after the exposure was evaluated as “B”, and the laminate 11 after the exposure was evaluated as “A”.
Claims (4)
前記着色層は、着色粒子１００重量部に対し、合成樹脂を固形分重量比率で３〜３０重量部含み、その層の表面が前記着色粒子に由来する微視的な凹凸形状を有しており、
前記着色粒子は、無機質粒子の表面に金属酸化物が付着してなるものであり、
前記透明層は、平均一次粒子径１〜２００ｎｍのシリカ１００重量部に対し、合成樹脂を固形分重量比率で５〜５００重量部含むことを特徴とする積層体。 A laminate in which a transparent layer is laminated on a colored layer,
The colored layer contains 3 to 30 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles, and the surface of the layer has a microscopic uneven shape derived from the colored particles. ,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles,
The said transparent layer is a laminated body characterized by including 5-500 weight part of synthetic resins by solid content weight ratio with respect to 100 weight part of silica with an average primary particle diameter of 1-200 nm.
前記着色層は、着色粒子１００重量部に対し、合成樹脂を固形分重量比率で３〜３０重量部含み、その層の表面が前記着色粒子に由来する微視的な凹凸形状を有し、且つ巨視的な凹凸模様を有しており、
前記着色粒子は、無機質粒子の表面に、金属酸化物が付着してなるものであり、
前記透明層は、平均一次粒子径１〜２００ｎｍのシリカ１００重量部に対し、合成樹脂を固形分重量比率で５〜５００重量部含むことを特徴とする積層体。 A laminate in which a transparent layer is laminated on a colored layer,
The colored layer contains 3 to 30 parts by weight of a synthetic resin in a solid weight ratio with respect to 100 parts by weight of the colored particles, and the surface of the layer has a microscopic uneven shape derived from the colored particles, and It has a macroscopic uneven pattern,
The colored particles are formed by attaching a metal oxide to the surface of inorganic particles,
The said transparent layer is a laminated body characterized by including 5-500 weight part of synthetic resins by solid content weight ratio with respect to 100 weight part of silica with an average primary particle diameter of 1-200 nm.
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