JP6010315B2 - Matting multilayer film forming method for ceramics building materials - Google Patents
Matting multilayer film forming method for ceramics building materials Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims description 98
- 239000004566 building material Substances 0.000 title claims description 94
- 238000000034 method Methods 0.000 title claims description 44
- 238000000576 coating method Methods 0.000 claims description 96
- 239000008187 granular material Substances 0.000 claims description 94
- 239000011248 coating agent Substances 0.000 claims description 93
- 230000008439 repair process Effects 0.000 claims description 76
- 239000003973 paint Substances 0.000 claims description 72
- 210000003298 dental enamel Anatomy 0.000 claims description 47
- 239000002320 enamel (paints) Substances 0.000 claims description 46
- 239000000049 pigment Substances 0.000 claims description 44
- 239000011347 resin Substances 0.000 claims description 42
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011230 binding agent Substances 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 23
- 239000011324 bead Substances 0.000 claims description 20
- 239000004925 Acrylic resin Substances 0.000 claims description 18
- 229920000178 Acrylic resin Polymers 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 13
- 239000004576 sand Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- 238000002834 transmittance Methods 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 239000010436 fluorite Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 description 43
- 230000000052 comparative effect Effects 0.000 description 15
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- 239000004606 Fillers/Extenders Substances 0.000 description 8
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 4
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
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- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- UJRDRFZCRQNLJM-UHFFFAOYSA-N methyl 3-[3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl]propanoate Chemical compound CC(C)(C)C1=CC(CCC(=O)OC)=CC(N2N=C3C=CC=CC3=N2)=C1O UJRDRFZCRQNLJM-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 210000002966 serum Anatomy 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910014314 BYK190 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- NYGZLYXAPMMJTE-UHFFFAOYSA-M metanil yellow Chemical group [Na+].[O-]S(=O)(=O)C1=CC=CC(N=NC=2C=CC(NC=3C=CC=CC=3)=CC=2)=C1 NYGZLYXAPMMJTE-UHFFFAOYSA-M 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- FYNROBRQIVCIQF-UHFFFAOYSA-N pyrrolo[3,2-b]pyrrole-5,6-dione Chemical compound C1=CN=C2C(=O)C(=O)N=C21 FYNROBRQIVCIQF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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Landscapes
- Application Of Or Painting With Fluid Materials (AREA)
- Paints Or Removers (AREA)
Description
本発明は、窯業建材上に形成する艶消しクリヤー塗膜を含む艶消し複層膜の形成方法、及び、艶消し複層膜の補修方法に関する。 The present invention relates to a method for forming a matte multilayer film including a matte clear coating film formed on a ceramic building material, and a method for repairing the matte multilayer film.
近年、６０度光沢値が３０以下である窯業建材の艶消し意匠として、透明感と艶消し意匠を両立させる高意匠のニーズがあり、窯業建材上にクリヤー塗膜と艶消しクリヤー塗膜とからなる複層膜を形成することが主流となっている。この艶消しクリヤー塗膜の形成には、艶消し材を含んだクリヤー塗料が用いられる。艶消し材としては、透明性の高い透明樹脂ビーズ等が用いられる。 In recent years, there is a need for a high-quality design that achieves both transparency and matte design as a matte design for ceramics building materials with a 60 ° gloss value of 30 or less. It is the mainstream to form a multilayer film. For the formation of the matte clear coating film, a clear paint containing a matte material is used. As the matting material, transparent resin beads having high transparency are used.
ここで、複層膜を形成した窯業建材は重量があるため、保管、運搬等で積載する際、自重によりブロッキングという複層膜が破壊される現象が起こり、それが原因により艶等の意匠のムラが発生することがあった。そのため、比較的粒子径の大きい透明樹脂ビーズを用い、複層膜の表面にやや大きい凹凸を形成して、ブロッキングの発生を抑制していた。 Here, ceramic building materials that have a multilayer film are heavy, so when loading them in storage, transportation, etc., a phenomenon occurs in which the multilayer film called blocking occurs due to its own weight. Unevenness may occur. For this reason, transparent resin beads having a relatively large particle diameter are used, and slightly large irregularities are formed on the surface of the multilayer film, thereby suppressing the occurrence of blocking.
特許文献１には、窯業建材上に形成したクリヤー塗膜の膜厚の２〜１０倍の平均粒子径を有する樹脂ビーズを含むクリヤー塗料、さらにクリヤー塗膜の膜厚の０．５〜２倍の平均粒子径を有する樹脂ビーズを含むクリヤー塗料が開示されている。 Patent Document 1 discloses a clear paint containing resin beads having an average particle diameter of 2 to 10 times the film thickness of a clear coating film formed on a ceramic building material, and further 0.5 to 2 times the film thickness of the clear coating film. A clear coating comprising resin beads having an average particle size of is disclosed.
一方、窯業建材の複層膜の補修方法として、エナメル塗料と艶消しクリヤー塗料との２種類が用いられていたが、近年では工数を削減するために、エナメル塗料のみで補修することが求められている。しかしながら、エナメル塗料のみによる補修では、例えば、調色によって窯業建材の補修部分の周囲の色相に合わせても、見る角度によって補修部分と周囲との艶の差異が目立ったり、光の入射角によっては、補修部分が周囲から際立って目立つという問題があった。 On the other hand, two methods of enamel paint and matte clear paint were used as repair methods for multilayer films in ceramic building materials. In recent years, repair with only enamel paint is required in order to reduce man-hours. ing. However, in repairs using only enamel paint, for example, even when matching the hue around the repaired part of ceramic building materials by toning, the difference in gloss between the repaired part and the surroundings depends on the viewing angle, and depending on the incident angle of light There was a problem that the repaired part stood out from the surroundings.
したがって、本発明の課題は、透明感を損なうことなくブロッキングを抑制でき、かつ、補修時に補修部分が目立たない窯業建材用艶消し複層膜の形成方法を提供することである。 Therefore, the subject of this invention is providing the formation method of the mat | matte multilayer film for ceramics building materials which can suppress blocking, without impairing transparency, and a repair part is not conspicuous at the time of repair.
本発明は、
窯業建材上に、エナメル塗料を塗布してエナメル塗膜を形成する工程（１）、上記工程（１）で得られたエナメル塗膜上に、窯業建材用艶消しクリヤー塗料を、乾燥膜厚が１０〜４０μｍとなるように塗布して艶消しクリヤー塗膜を形成する工程（２）を含む窯業建材用艶消し複層膜形成方法であって、
上記窯業建材用艶消しクリヤー塗料は、
メジアン径（Ｄ５０）が２〜１０μｍの光透過性粒状物（ａ）、
メジアン径（Ｄ５０）が５０〜２００μｍの光非透過性粒状物（ｂ）、及び、
バインダー樹脂（ｃ）、
を含み、上記バインダー樹脂（ｃ）の固形分質量に対する上記光透過性粒状物（ａ）の含有量が５〜７０質量％であり、かつ、上記バインダー樹脂（ｃ）の固形分質量に対する上記光非透過性粒状物（ｂ）の含有量が０．３〜１０質量％である窯業建材用艶消し複層膜形成方法、を提供するものであり、これにより課題が解決される。
The present invention
Step (1) of applying enamel paint on ceramic building material to form an enamel coating, and matte clear paint for ceramic building material on the enamel coating obtained in the above step (1). A matting multilayer film forming method for ceramic building materials comprising a step (2) of forming a matte clear coating film by applying to 10 to 40 μm,
The matte clear paint for ceramic building materials
A light transmissive granular material (a) having a median diameter (D50) of 2 to 10 μm,
A light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm, and
Binder resin (c),
The light-transparent granular material (a) content is 5 to 70% by mass with respect to the solid content mass of the binder resin (c), and the light with respect to the solid mass of the binder resin (c) The present invention provides a matting multilayer film forming method for ceramic building materials in which the content of the non-permeable granular material (b) is 0.3 to 10% by mass, thereby solving the problem.
また、上記光透過性粒状物（ａ）は、透明アクリル樹脂ビーズ及び／又は透明ガラスビーズであることが好ましい。 Moreover, it is preferable that the said light transmissive granular material (a) is a transparent acrylic resin bead and / or a transparent glass bead.
また、窯業建材用艶消し複層膜形成方法によって得られる窯業建材用艶消し複層膜であって、上記クリヤー塗膜の乾燥膜厚に対する上記光透過性粒状物（ａ）のメジアン径（Ｄ５０）の比が、０．０５〜０．５であり、かつ、上記クリヤー塗膜の乾燥膜厚に対する上記光非透過性粒状物（ｂ）のメジアン径（Ｄ５０）の比が、２．０〜１０．０であることが好ましい。 Further, a matting multilayer film for ceramics building materials obtained by a method for forming a matting multilayer film for ceramics building materials, wherein the median diameter (D50) of the light-transmitting granular material (a) with respect to the dry film thickness of the clear coating film ) Ratio of 0.05 to 0.5, and the ratio of the median diameter (D50) of the light-impermeable granular material (b) to the dry film thickness of the clear coating film is 2.0 to It is preferable that it is 10.0.
また、上記窯業建材用艶消し複層膜は、６０度光沢値に対する８５度光沢値の比が０．７〜１．２であることが好ましい。 Moreover, it is preferable that the ratio of the 85 degree gloss value with respect to the 60 degree gloss value is 0.7 to 1.2 in the matting multilayer film for ceramic building materials.
本発明の別の形態として、
クリヤー塗膜を有する窯業建材上に艶消しクリヤー塗膜を形成するために用いる窯業建材用艶消しクリヤー塗料であって、
上記窯業建材用艶消しクリヤー塗料は、
メジアン径（Ｄ５０）が２〜１０μｍの光透過性粒状物（ａ）、
メジアン径（Ｄ５０）が５０〜２００μｍの光非透過性粒状物（ｂ）、及び、
バインダー樹脂（ｃ）、
を含み、上記光透過性粒状物（ａ）の含有量が、上記バインダー樹脂（ｃ）の固形分に対して５〜７０質量％であり、かつ、上記光非透過性粒状物（ｂ）の含有量が、上記バインダー樹脂（ｃ）の固形分に対して０．３〜１０質量％である窯業建材用艶消しクリヤー塗料、を提供するものである。
As another form of the present invention,
A matte clear paint for ceramics building materials used to form a matte clear paint film on a ceramics building material having a clear paint film,
The matte clear paint for ceramic building materials
A light transmissive granular material (a) having a median diameter (D50) of 2 to 10 μm,
A light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm, and
Binder resin (c),
The content of the light transmissive granular material (a) is 5 to 70% by mass with respect to the solid content of the binder resin (c), and the light non-transparent granular material (b) The present invention provides a matte clear coating material for ceramic building materials having a content of 0.3 to 10% by mass based on the solid content of the binder resin (c).
本発明の別の形態として、
窯業建材用艶消し複層膜の補修部に対して、エナメル補修用塗料を塗布してエナメル補修塗膜を形成する窯業建材用艶消し複層膜補修方法であって、
上記エナメル補修用塗料は顔料を含み、また、メジアン径（Ｄ５０）が５０〜２００μｍである光非透過性粒状物（ｂ）を含んでも良く、かつ、塗料固形分体積に対する上記顔料と上記光非透過性粒状物（ｂ）との総量の含有量が２〜１０％である窯業建材用艶消し複層膜補修方法、を提供するものである。
As another form of the present invention,
A matte multilayer coating repair method for ceramic building materials in which an enamel repair coating is applied to a repair portion of a matting multilayer coating for ceramics building materials,
The enamel repair coating material may include a pigment, and may include a light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm. A matting multilayer film repair method for ceramic building materials, in which the total content with the permeable granular material (b) is 2 to 10%, is provided.
本発明の別の形態として、
窯業建材用艶消し複層膜補修方法によって得られるエナメル補修塗膜を有する窯業建材用艶消し複層膜、を提供するものである。
As another form of the present invention,
The present invention provides a matting multilayer film for ceramics building materials having an enamel repair coating film obtained by the method of repairing a matting multilayer film for ceramics building materials.
本発明の窯業建材用艶消し複層膜形成方法は、所定のメジアン径を有する光透過性粒状物と光非透過性粒状物とを、それぞれ所定量含む窯業建材用艶消しクリヤー塗料を用いているので、透明感を損なうことなくブロッキングを抑制できる。これは、粒子径が小さく膜に内包される光透過性粒状物に光散乱させ透明感のある艶消し機能を、また、粒子径が大きく複層膜の表面に凹凸を形成する光非透過性粒状物によってブロッキング抑制の機能をそれぞれ分担させることができたことによる。また、艶消し機能を分担させる光透過性粒状物が膜に内包されることにより、複層膜の表面で光散乱しないため、補修時にも補修部分が目立たない。 The matting multilayer film forming method for ceramic building materials according to the present invention uses a matte clear coating material for ceramics building materials containing a predetermined amount of a light-transmitting granular material and a light-impermeable granular material each having a predetermined median diameter. Therefore, blocking can be suppressed without impairing transparency. It has a transparent matte function by scattering light on light-transmitting granular materials contained in a film with a small particle diameter, and light non-transmission that forms irregularities on the surface of a multilayer film with a large particle diameter This is because the blocking function can be shared by the granular materials. In addition, since the light-transmitting granular material that shares the matte function is included in the film, light is not scattered on the surface of the multilayer film, so that the repaired portion is not noticeable even during repair.
また、本発明の窯業建材用複層膜補修方法は、上記窯業建材用艶消し複層膜形成方法によって得られた複層膜に対して所定のメジアン径を有する光非透過性粒状物を所定量含むエナメル補修用塗料を用いるので、補修時にも補修部分が目立たなくなった。 Further, the multilayer film repair method for ceramic building materials according to the present invention provides a light non-transparent granular material having a predetermined median diameter with respect to the multilayer film obtained by the matting multilayer film forming method for ceramic building materials. Since the enamel repair paint that includes a fixed amount is used, the repair part is not noticeable even during repair.
本発明の窯業建材用艶消し複層膜形成方法は、窯業建材上に、エナメル塗料を塗布してエナメル塗膜を形成する工程（１）、上記工程（１）で得られたエナメル塗膜上に、窯業建材用艶消しクリヤー塗料を、乾燥膜厚が１０〜４０μｍとなるように塗布して艶消しクリヤー塗膜を形成する工程（２）を含む。 The matting multilayer film forming method for ceramic building materials according to the present invention includes a step (1) of forming an enamel coating film by applying an enamel coating on a ceramic building material, and the enamel coating film obtained in the above step (1). And a step (2) of forming a matte clear coating film by applying a matte clear coating material for ceramic building materials so that the dry film thickness is 10 to 40 μm.
工程（１）
本発明の第１の工程は窯業建材上に、エナメル塗料を塗布してエナメル塗膜を形成する工程（１）である。
Process (1)
The first step of the present invention is a step (1) of applying an enamel paint on a ceramic building material to form an enamel coating film.
窯業建材
上記窯業建材としては外壁仕上げ材として用いられるものであり、具体的には、窯業系サイディング及び屋根スレート材が挙げられる。窯業系サイディング及び屋根スレート材としては、例えば、ＪＩＳ Ａ５４２２によって規定される建材、ＪＩＳ Ａ５４２３によって規定される化粧スレート、および、硬質木質セメント板、押出成型セメント板及び軽量発泡コンクリート等のセメント板が挙げられる。
Ceramic Industry Building Materials The ceramic industry building materials are those used as exterior wall finishing materials, and specifically include ceramic industry siding and roof slate materials. Examples of ceramic siding and roof slate materials include building materials defined by JIS A5422, decorative slate defined by JIS A5423, and cement boards such as hard wood cement boards, extruded cement boards, and lightweight foamed concrete. It is done.
上記窯業建材は、次工程（１）で得られるエナメル塗膜との密着性や防水性付与のために、下塗り塗膜を備えていることが好ましい。また、エナメル塗膜を形成しない部分には裏面用塗膜を形成していてもよい。これら下塗り塗膜を形成するための下塗り塗料や裏面用塗膜を形成するための裏面用塗料は、当業者によってよく知られているものを用いることができる。 It is preferable that the ceramic building material includes an undercoat coating film in order to provide adhesion and waterproofness with the enamel coating film obtained in the next step (1). Moreover, you may form the coating film for back surfaces in the part which does not form an enamel coating film. As the undercoat paint for forming these undercoat films and the back coat for forming the back coat film, those well known by those skilled in the art can be used.
エナメル塗料
本発明の窯業建材用艶消し複層膜形成方法の工程（１）に用いられるエナメル塗料は、バインダー樹脂及び着色顔料を含んでいる。
Enamel paint The enamel paint used in the step (1) of the matting multilayer film forming method for ceramic building materials of the present invention contains a binder resin and a color pigment.
バインダー樹脂
上記バインダー樹脂としては特に限定されず、例えば、アクリル樹脂、アクリルウレタン樹脂、フッ素樹脂、ポリエステル樹脂、エポキシ樹脂、アクリルエマルション樹脂、シリコン変性アクリルエマルション樹脂等が挙げられる。得られる複層膜の耐候性の観点から、アクリル樹脂、アクリルウレタン樹脂、アクリルエマルション樹脂及びシリコン変性アクリルエマルション樹脂が好ましい。
Binder resin The binder resin is not particularly limited, and examples thereof include acrylic resins, acrylic urethane resins, fluororesins, polyester resins, epoxy resins, acrylic emulsion resins, and silicone-modified acrylic emulsion resins. From the viewpoint of the weather resistance of the resulting multilayer film, an acrylic resin, an acrylic urethane resin, an acrylic emulsion resin, and a silicon-modified acrylic emulsion resin are preferable.
着色顔料
上記エマルション塗料に含まれる着色顔料としては特に限定されず、モノアゾ系顔料、ジケトピロロピロール系顔料、フタロシアニン系顔料、キナクリドン系顔料等の有機系着色顔料、黄色酸化鉄、ベンガラ、チタンイエロー、カーボンブラック、二酸化チタン等の無機系着色顔料、グラファイト系顔料、アルミナフレーク顔料等の着色扁平顔料が挙げられる。
Color pigments The color pigments contained in the emulsion paint are not particularly limited, and organic color pigments such as monoazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinacridone pigments, yellow iron oxide, bengara, titanium yellow Inorganic colored pigments such as carbon black and titanium dioxide, and colored flat pigments such as graphite pigments and alumina flake pigments.
体質顔料
上記エマルション塗料には体質顔料が含まれても良い。体質顔料としては特に限定されず、炭酸カルシウム、硫酸バリウム、炭酸バリウム、ケイ酸マグネシウム、クレー、タルク、焼成カオリン等が挙げられる。
Extender Pigment The extender paint may contain extender pigments. The extender is not particularly limited, and examples thereof include calcium carbonate, barium sulfate, barium carbonate, magnesium silicate, clay, talc, and calcined kaolin.
その他の成分
上記エナメル塗料は、その他の成分として、必要に応じて、例えば、意匠剤、造膜助剤、顔料分散剤、表面調整剤、防腐剤、防かび剤、消泡剤、光安定剤、紫外線吸収剤、酸化防止剤、ｐＨ調整剤、粘性調整剤等を含むことができる。上記意匠剤としては、後述の光透過性粒状物（ａ）や光非透過性粒状物（ｂ）が挙げられる。
Other components The above-mentioned enamel paint is, as necessary, other components such as a design agent, a film-forming aid, a pigment dispersant, a surface conditioner, an antiseptic, an antifungal agent, an antifoaming agent, and a light stabilizer. , UV absorbers, antioxidants, pH adjusters, viscosity adjusters, and the like. Examples of the design agent include a light transmissive granular material (a) and a light non-transmissive granular material (b) described later.
調製
上記エナメル塗料は、上記バインダー樹脂、着色顔料および必要に応じてその他の成分を攪拌、混合することにより調製することができる。
Preparation The enamel paint can be prepared by stirring and mixing the binder resin, the color pigment and other components as required.
エナメル塗料の塗布
上記エナメル塗料の塗布方法としては特に限定されず、例えば、浸漬、刷毛、ローラー、ロールコーター、エアスプレー、エアレススプレー、カーテンフローコーター、ローラーカーテンコーター、ダイコーター等、当業者によってよく知られているものが挙げられる。また、上記塗布方法による塗布膜厚は特に限定されず、例えば、乾燥膜厚で２０〜３００μｍとなるように塗布する。
Application of enamel paint The application method of the enamel paint is not particularly limited. For example, immersion, brush, roller, roll coater, air spray, airless spray, curtain flow coater, roller curtain coater, die coater, etc. What is known is mentioned. Moreover, the coating film thickness by the said coating method is not specifically limited, For example, it apply | coats so that it may become 20-300 micrometers in a dry film thickness.
乾燥
上記塗布後、得られたエナメル塗膜を加熱して強制乾燥させてもよい。上記加熱条件は特に限定されず、例えば、６０〜１５０℃で３０秒〜１０分間である。
Drying After the application, the enamel coating film obtained may be heated and forced to dry. The said heating conditions are not specifically limited, For example, it is 30 seconds-10 minutes at 60-150 degreeC.
工程（２）
本発明の第２の工程は、上記工程（１）で得られたエナメル塗膜上に、窯業建材用艶消しクリヤー塗料を、乾燥膜厚が１０〜４０μｍとなるように塗布して艶消しクリヤー塗膜を形成する工程（２）である。
Step (2)
In the second step of the present invention, the matte clear coating for ceramic industry building material is applied on the enamel coating film obtained in the above step (1) so that the dry film thickness is 10 to 40 μm. Step (2) for forming a coating film.
窯業建材用艶消しクリヤー塗料
本発明の窯業建材用艶消し複層膜形成方法の工程（２）に用いられる窯業建材用艶消しクリヤー塗料は、光透過性粒状物（ａ）、光非透過性粒状物（ｂ）及びバインダー樹脂（ｃ）を含んでいる。
Matting clear paint for ceramics building materials The matting clear paint for ceramics building materials used in the step (2) of the method for forming a matting multilayer film for ceramics building materials of the present invention is a light-transmitting granular material (a), light-impermeable. The granular material (b) and the binder resin (c) are included.
光透過性粒状物（ａ）
上記光透過性粒状物（ａ）は、高い透明感を維持しつつ、艶消し効果を発現する。また、複層膜の表面の凹凸を形成しないので、得られた複層膜を補修時にも補修部が目立たなくする機能を発現する。
Light transmissive granular material (a)
The light transmissive granular material (a) exhibits a matte effect while maintaining high transparency. Moreover, since the unevenness | corrugation of the surface of a multilayer film is not formed, the function which makes a repair part inconspicuous also at the time of repairing the obtained multilayer film is expressed.
上記光透過性粒状物（ａ）とは可視光における平均光透過率が５０％以上の透明の粒状物であり、透明樹脂ビーズ及び／又は透明ガラスビーズであることが好ましい。 The light transmissive granular material (a) is a transparent granular material having an average light transmittance of 50% or more in visible light, and is preferably transparent resin beads and / or transparent glass beads.
上記光透過性粒状物（ａ）のメジアン径（Ｄ５０）は２〜１０μｍである。メジアン径（Ｄ５０）が２μｍ未満の場合は艶消し効果が小さくなり、１０μｍを超える場合は複層膜の表面の凹凸に影響を与えてしまい、補修時に補修部が目立ってしまう。好ましくは３〜８μｍである。
なお、本明細書におけるメジアン径（Ｄ５０）は、レーザー回折式粒度分布計によって測定される体積換算の積算５０％となる粒子径をいう。
The median diameter (D50) of the light transmissive granular material (a) is 2 to 10 μm. When the median diameter (D50) is less than 2 μm, the matting effect is small, and when it exceeds 10 μm, the unevenness of the surface of the multilayer film is affected, and the repaired portion becomes conspicuous during repair. Preferably it is 3-8 micrometers.
In addition, the median diameter (D50) in this specification means the particle diameter used as the volume conversion integrated 50% measured by the laser diffraction type particle size distribution meter.
上記透明樹脂ビーズとしては、具体的には、タフチックＦ−２００（東洋紡社製、メジアン径（Ｄ５０）３μｍ）、タフチックＦＨ−Ｓ００５（東洋紡社製、メジアン径（Ｄ５０）５μｍ）、タフチックＦＨ−Ｓ００８（東洋紡社製、メジアン径（Ｄ５０）８μｍ）等の透明アクリル樹脂ビーズ、透明アクリロニトリル樹脂ビーズ、ＳＰ−５００（東レ社製、メジアン径（Ｄ５０）５μｍ）等の透明ナイロン樹脂ビーズ等が挙げられる。また、上記透明ガラスビーズとしては、ＳＰＬ−５（ユニチカ社製、メジアン径（Ｄ５０）５μｍ）等が挙げられる。複層膜の耐候性の観点から、透明アクリル樹脂ビーズ及び／又は透明ガラスビーズであることがさらに好ましい。 As the transparent resin beads, specifically, Tafuchikku F-200 (manufactured by Toyobo Co., Ltd., median diameter (D50) 3 [mu] m), Tafuchikku FH-S005 (manufactured by Toyobo Co., Ltd., median diameter (D50) 5 [mu] m), Tafuchikku FH-S008 Examples thereof include transparent acrylic resin beads such as Toyobo Co., Ltd., median diameter (D50) 8 μm), transparent acrylonitrile resin beads, transparent nylon resin beads such as SP-500 (manufactured by Toray Industries Inc., median diameter (D50) 5 μm), and the like. Examples of the transparent glass beads include SPL-5 (manufactured by Unitika Ltd., median diameter (D50) 5 μm). From the viewpoint of the weather resistance of the multilayer film, transparent acrylic resin beads and / or transparent glass beads are more preferable.
光非透過性粒状物（ｂ）
上記窯業建材用艶消しクリヤー塗料に含まれる光非透過性粒状物（ｂ）は、複層膜の表面に凹凸を付与し、ブロッキングを抑制する機能を有する。
Light-impermeable granular material (b)
The light-impermeable granular material (b) contained in the matte clear paint for ceramic building materials has a function of imparting irregularities to the surface of the multilayer film and suppressing blocking.
上記光非透過性粒状物（ｂ）とは、顔料を除く、可視光における平均光透過率が５０％未満の非透過性の粒状物である。 The light-impermeable granular material (b) is a non-transparent granular material having an average light transmittance in visible light of less than 50%, excluding pigments.
上記光非透過性粒状物（ｂ）のメジアン径（Ｄ５０）は５０〜２００μｍである。メジアン径（５０）が５０μｍ未満の場合は複層膜の表面の凹凸の付与が小さくなり、ブロッキングの抑制が不充分になる。２００μｍを超える場合はクリヤー塗膜の透明性が低下し、また、塗装作業性が低下する。好ましくは６０〜１５０μｍであり、さらに好ましくは８０〜１３０μｍである。なお、上記光非透過性粒状物（ｂ）は上記光透過性粒状物（ａ）とは異なり光散乱は発生しないため、補修時に補修部が目立つことはない。 The median diameter (D50) of the light-impermeable granular material (b) is 50 to 200 μm. When the median diameter (50) is less than 50 μm, the unevenness on the surface of the multilayer film is reduced, and the suppression of blocking becomes insufficient. When it exceeds 200 μm, the transparency of the clear coating film is lowered, and the coating workability is also lowered. Preferably it is 60-150 micrometers, More preferably, it is 80-130 micrometers. In addition, since the said light-impermeable granular material (b) does not generate light scattering unlike the said light-transmissive granular material (a), a repair part does not stand out at the time of repair.
上記光非透過性粒状物（ｂ）としては、具体的には、着色顔料による着色や焼成によって光を透過しないようにした着色樹脂ビーズ、着色樹脂フレーク等の着色樹脂、ホタル石、ケイ砂、石英等の天然石、陶磁器粉砕粒子、炭酸カルシウム粒子、雲母片等が挙げられる。
上記着色顔料としては、上記エナメル塗料のところで述べた着色顔料のうちの、有機系着色顔料および無機系着色顔料が挙げられる。
Specific examples of the light-impermeable granular material (b) include colored resin beads that are prevented from transmitting light by coloring or baking with a coloring pigment, colored resin flakes and other colored resins, fluorite, silica sand, Examples thereof include natural stones such as quartz, ceramic ground particles, calcium carbonate particles, mica pieces and the like.
Examples of the color pigment include organic color pigments and inorganic color pigments among the color pigments described in the enamel paint.
上記着色樹脂ビーズとしては、タフチックＡＲ６５０ＭＺ（東洋紡社製、メジアン径（Ｄ５０）６０μｍ）、タフチックＡＲ６５０ＭＬ（東洋紡社製、メジアン径（Ｄ５０）８０μｍ）、タフチックＡＲ６５０Ｌ（東洋紡社製、メジアン径（Ｄ５０）１００μｍ）、タフチックＡＲ６５０ＬＣ（東洋紡社製、メジアン径（Ｄ５０）１３０μｍ）等の着色アクリル樹脂ビーズ、セラチップＳＣ−３０（北斗産業社製、メジアン径（Ｄ５０）１５０μｍ）等の鱗片状雲母片、カラーサンドＮｏ．８（オクムラセラム社製、メジアン径（Ｄ５０）１００μｍ）等の焼成着色ケイ砂等が挙げられる。 As the colored resin beads, Tafuchikku AR650MZ (Toyobo Co., Ltd., median diameter (D50) 60 [mu] m), Tafuchikku AR650ML (Toyobo Co., Ltd., median diameter (D50) 80 [mu] m), Tafuchikku AR650L (Toyobo Co., Ltd., median diameter (D50) 100 [mu] m ), Colored acrylic resin beads such as Tuftic AR650LC ( manufactured by Toyobo Co., Ltd., median diameter (D50) 130 μm), scaly mica fragments such as Cerachip SC-30 (manufactured by Hokuto Sangyo Co., Ltd., median diameter (D50) 150 μm), color sand No. . 8 (Okumura Serum, median diameter (D50) 100 μm), etc.
バインダー樹脂（ｃ）
上記窯業建材用艶消しクリヤー塗料に含まれるバインダー樹脂（ｃ）としては特に限定されず、具体的には、上記エナメル塗料のところで述べたバインダー樹脂が挙げられる。得られる複層膜の耐候性の観点から、アクリル樹脂、アクリルウレタン樹脂、アクリルエマルション樹脂及びシリコン変性アクリルエマルション樹脂が好ましい。なお、必ずしも上記エナメル塗料と同一のものを使用する必要はない。
Binder resin (c)
The binder resin (c) contained in the matte clear paint for ceramics building materials is not particularly limited, and specific examples thereof include the binder resins described in the enamel paint. From the viewpoint of the weather resistance of the resulting multilayer film, an acrylic resin, an acrylic urethane resin, an acrylic emulsion resin, and a silicon-modified acrylic emulsion resin are preferable. It is not always necessary to use the same enamel paint.
ここで、上記バインダー樹脂（ｃ）の固形分質量に対する上記光透過性粒状物（ａ）の含有量が５〜７０質量％である。上記含有量が５質量％未満の場合、塗膜の６０度光沢値が３０より大きくなり、充分な艶消し効果を得られず、７０質量％を超える場合は得られる膜の物性が低下し、かつ、塗布作業性が低下する。好ましくは１０〜５０質量％であり、さらに好ましくは１０〜３５質量％である。 Here, content of the said light-transmitting granular material (a) with respect to solid content mass of the said binder resin (c) is 5-70 mass%. When the content is less than 5% by mass, the 60-degree gloss value of the coating film is greater than 30, a sufficient matting effect cannot be obtained, and when it exceeds 70% by mass, the physical properties of the resulting film are reduced, And application workability falls. Preferably it is 10-50 mass%, More preferably, it is 10-35 mass%.
また、上記バインダー樹脂（ｃ）の固形分質量に対する上記光非透過性粒状物（ｂ）の含有量が０．３〜１０質量％である。上記含有量が０．３質量％未満の場合、複層膜の表面の凹凸の形成が不充分になりブロッキングの抑制ができず、１０質量％を超える場合はクリヤー塗膜の透明性が低下する。好ましくは０．５〜８質量％であり、さらに好ましくは０．５〜７質量％である。 Moreover, content of the said light-impermeable granular material (b) with respect to solid content mass of the said binder resin (c) is 0.3-10 mass%. When the content is less than 0.3% by mass, the formation of irregularities on the surface of the multilayer film is insufficient and blocking cannot be suppressed, and when the content exceeds 10% by mass, the transparency of the clear coating film decreases. . Preferably it is 0.5-8 mass%, More preferably, it is 0.5-7 mass%.
その他の成分
上記窯業建材用艶消しクリヤー塗料は、その他の成分として、必要に応じて、上記エナメル塗料のところで述べたものを含むことができる。
Other Components The matte clear coating material for ceramic building materials may include, as necessary, those described for the enamel coating material as necessary.
調製
上記窯業建材用艶消しクリヤー塗料は、上記光透過性粒状物（ａ）、光非透過性粒状物（ｂ）、バインダー樹脂（ｃ）および必要に応じてその他の成分を攪拌、混合することにより調製することができる。
Preparation The matte clear paint for ceramic building materials is to stir and mix the light transmissive granular material (a), light non-transparent granular material (b), binder resin (c) and other components as required. Can be prepared.
窯業建材用艶消しクリヤー塗料の塗布
上記窯業建材用艶消しクリヤー塗料の塗布方法としては特に限定されず、上記エナメル塗料のところで述べたものが挙げられる。また、上記塗布方法による塗布膜厚は乾燥膜厚で１０〜４０μｍとなるように塗布する。
Application of Matte Clear Paint for Ceramic Industry Building Material The method for applying the matte clear paint for ceramic industry building material is not particularly limited, and examples thereof include those described in the enamel paint. Moreover, it apply | coats so that the coating film thickness by the said coating method may be 10-40 micrometers by a dry film thickness.
乾燥
上記塗布後、得られたクリヤー塗膜を加熱して強制乾燥させる。上記加熱条件は特に限定されず、例えば、６０〜１５０℃で３０秒〜１０分間である。なお、上記工程（１）において得られたエナメル塗膜を強制乾燥していない場合は、クリヤー塗膜を強制乾燥することによって先に塗布して形成したエナメル塗膜も同時に強制乾燥される。
このようにして本発明の窯業建材用艶消し複層膜形成方法によって、窯業建材上にエナメル塗膜とクリヤー塗膜とを備えた窯業建材用艶消し複層膜を形成することができる。
Drying After the application, the clear coating film obtained is heated and forcedly dried. The said heating conditions are not specifically limited, For example, it is 30 seconds-10 minutes at 60-150 degreeC. In addition, when the enamel coating film obtained in the above step (1) is not forcibly dried, the enamel coating film formed by applying the clear coating film forcibly is also forcibly dried at the same time.
Thus, the matting multilayer film for ceramics building materials provided with the enamel coating film and the clear coating film on the ceramics building material can be formed by the method for forming the matting multilayer film for ceramics building material of the present invention.
窯業建材用艶消し複層膜
本発明の窯業建材用艶消し複層膜は、上記窯業建材用艶消し複層膜形成方法によって得られ、６０度光沢値が３０以下であり極めて優れた艶消し複層膜である。具体的には、窯業建材上に、エナメル塗膜と、光透過性粒状物（ａ）および光非透過性粒状物（ｂ）を含んだ乾燥膜厚が１０〜４０μｍであるクリヤー塗膜とを備えるものである。上記窯業建材、エナメル塗膜及びクリヤー塗膜は、上記窯業建材用艶消し複層膜形成方法で述べたものである。
Matting multilayer film for ceramics building materials The matting multilayer film for ceramics building materials of the present invention is obtained by the above-described matting multilayer film forming method for ceramics building materials, and has a gloss value of 60 or less and an extremely excellent matting film. It is a multilayer film. Specifically, on a ceramic building material, an enamel coating, and a clear coating having a dry film thickness of 10 to 40 μm including the light transmissive granular material (a) and the light non-transparent granular material (b). It is to be prepared. The ceramic building material, the enamel coating film and the clear coating film are those described in the matting multilayer film forming method for a ceramic building material.
乾燥膜厚とメジアン径との比
ここで、上記クリヤー塗膜の乾燥膜厚に対する上記光透過性粒状物（ａ）のメジアン径（Ｄ５０）の比が、０．０５〜０．５である。上記比が０．０５未満である場合、艶消し効果が小さくなり、０．５を超える場合、複層膜の表面に上記光透過性粒状物（ａ）による凹凸が生じ、補修時に補修部が目立つようになる。好ましくは０．１〜０．４である。
Ratio of dry film thickness to median diameter Here, the ratio of the median diameter (D50) of the light transmissive granular material (a) to the dry film thickness of the clear coating film is 0.05 to 0.5. When the ratio is less than 0.05, the matte effect is reduced, and when it exceeds 0.5, irregularities due to the light-transmitting granular material (a) are generated on the surface of the multilayer film, and the repaired part is repaired at the time of repair. Become prominent. Preferably it is 0.1-0.4.
また、上記クリヤー塗膜の乾燥膜厚に対する上記光非透過性粒状物（ｂ）のメジアン径（Ｄ５０）の比が、２．０〜１０．０である。上記比が２．０未満である場合、複層膜の表面の凹凸が小さくなって艶消し効果が小さくなり、１０．０を超える場合、クリヤー塗膜の透明性が低下する。好ましくは３．０〜８．０である。 Moreover, ratio of the median diameter (D50) of the said light-impermeable granular material (b) with respect to the dry film thickness of the said clear coating film is 2.0-10.0. When the above ratio is less than 2.0, the unevenness of the surface of the multilayer film becomes small and the matting effect becomes small, and when it exceeds 10.0, the transparency of the clear coating film decreases. Preferably it is 3.0-8.0.
光沢値の比
本発明の窯業建材用艶消し複層膜は、６０度光沢値が３０以下である。さらに、６０度光沢値に対する８５度光沢値の比が０．７〜１．２であることが好ましい。上記比が０．７未満である場合、１．２を超える場合、補修時に補修部が目立つおそれがある。好ましくは０．９〜１．１である。
なお、本明細書における６０度光沢値及び８５度光沢値は、複層膜の表面を光沢計により測定することができる。
Gloss value ratio The matte multilayer film for ceramic building materials of the present invention has a 60 degree gloss value of 30 or less. Furthermore, the ratio of the 85 ° gloss value to the 60 ° gloss value is preferably 0.7 to 1.2. When the above ratio is less than 0.7, when the ratio exceeds 1.2, there is a possibility that the repaired part is noticeable during repair. Preferably it is 0.9-1.1.
In addition, the 60 degree gloss value and the 85 degree gloss value in this specification can measure the surface of the multilayer film with a gloss meter.
窯業建材用艶消しクリヤー塗料
本発明の窯業建材用艶消しクリヤー塗料は、クリヤー塗膜を有する窯業建材上に艶消しクリヤー塗膜を形成するために用いる窯業建材用艶消しクリヤー塗料であって、光透過性粒状物（ａ）、光非透過性粒状物（ｂ）及びバインダー樹脂（ｃ）を含むものである。上記窯業建材用艶消しクリヤー塗料は、上記窯業建材用艶消し複層膜形成方法の窯業建材用艶消しクリヤー塗料のところで述べたものである。
Matting clear paint for ceramics building materials Matting clear paint for ceramics building materials of the present invention is a matting clear paint for ceramics building materials used to form a matte clear coating film on ceramic building materials having a clear coating film, It contains a light transmissive granular material (a), a light non-transparent granular material (b), and a binder resin (c). The matte clear paint for ceramic industry building materials is the same as that described for the matte clear paint for ceramic industry building materials in the method for forming a matte multilayer film for ceramic industry building materials.
窯業建材用艶消し複層膜補修方法
本発明の窯業建材用艶消し複層膜補修方法は、上記窯業建材用艶消し複層膜の補修部に対して、エナメル補修用塗料を塗布してエナメル補修塗膜を形成するものである。
Method of repairing matte multilayer film for ceramics building materials The method of repairing matte multilayer film for ceramics building materials according to the present invention is to apply an enamel repair coating to the repair part of the matte multilayer film for ceramics building materials. A repair coating film is formed.
上記窯業建材用艶消し複層膜の補修部は、上記窯業建材用艶消し複層膜のうち、傷つき等によって複層膜に欠陥が生じた部分をいう。上記補修部はエナメル補修用塗料を塗布する前に付着している汚れ等を洗浄し、必要に応じて研磨をしておいてもよい。 The repaired portion of the matting multilayer film for ceramic building materials refers to a portion of the matting multilayer film for ceramics building materials in which a defect has occurred in the multilayer film due to scratches or the like. The repairing part may be cleaned before being applied with the enamel repair coating, and may be polished if necessary.
エナメル補修用塗料
上記エナメル補修用塗料は顔料を含み、また、メジアン径（Ｄ５０）が５０〜２００μｍである光非透過性粒状物（ｂ）とを含んでも良い。上記顔料としては、上記エナメル塗料のところで述べた着色顔料および体質顔料が挙げられる。また、上記光非透過性粒状物（ｂ）も、同様に上記エナメル塗料のところで述べたものが挙げられる。
Enamel Repair Paint The enamel repair paint contains a pigment, and may contain a light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm. Examples of the pigment include the color pigments and extender pigments described in the enamel paint. Further, the light non-transparent granular material (b) may be the same as described in the enamel paint.
顔料と光非透過性粒状物（ｂ）との総量の含有量
塗料固形分体積に対する上記顔料と上記光非透過性粒状物（ｂ）との総量の含有量は２〜１０％である。上記含有量が２％未満の場合は、エナメル補修用塗膜の透明性が強くなり過ぎ、上記含有量が１０％を超える場合は、エナメル補修用塗膜のソリッド感が強くなり過ぎ、艶消し複層膜の補修が充分にできない。好ましくは３〜９％であり、そのようにすることによって、得られるエナメル補修塗膜のソリッド感と透明感を両立させた本発明の窯業建材用複層膜の意匠を、上記エナメル用補修塗料だけで補修することができる。つまりエナメル補修用塗料１つのみを用いる場合であっても、補修前の艶消し複層膜に対して、シェードでの補修跡が目立たない補修が可能となる。なお、上記含有量の算出する際に必要となる顔料の比重は、「塗料原料便覧第７版」（社団法人日本塗料工業会）によるものであり、また、樹脂固形分の比重は１と近似するものとする。
Content of the total amount of the pigment and the light-impermeable granular material (b) The content of the total amount of the pigment and the light-impermeable granular material (b) with respect to the solid volume of the paint is 2 to 10%. When the content is less than 2%, the transparency of the enamel repair coating becomes too strong. When the content exceeds 10%, the solid feeling of the enamel repair coating becomes too strong and matte. The repair of the multilayer film is not enough. Preferably, it is 3 to 9%. By doing so, the design of the multilayer film for ceramic building materials of the present invention in which the solid feeling and transparency of the obtained enamel repair coating film are both compatible with each other is used as the repair paint for enamel. Can only be repaired. In other words, even when only one enamel repair coating is used, it is possible to repair the matte multilayer film before the repair with less noticeable repair marks on the shade. The specific gravity of the pigment required for calculating the content is according to the “Paint Raw Material Handbook 7th Edition” (Japan Paint Manufacturers Association), and the specific gravity of the resin solid is approximately 1. It shall be.
なお、上記エナメル補修用塗料の塗料固形分体積に対する顔料と光非透過性粒状物との総量の含有量は、上記艶消し複層膜形成方法のエナメル塗料の含有量よりも５〜１５％低いことが好ましい。５％未満の場合は、得られるエナメル補修塗膜のソリッド感が強くなるおそれがあり、また、１５％を超える場合は、得られるエナメル補修塗膜の透明性が強くなりすぎて、艶消し複層膜の補修が充分にできないおそれがある。 In addition, the content of the total amount of the pigment and the light-impermeable granular material with respect to the solid content volume of the enamel repair paint is 5 to 15% lower than the content of the enamel paint in the matting multilayer film forming method. It is preferable. If it is less than 5%, the resulting enamel repair coating may become solid, and if it exceeds 15%, the resulting enamel repair coating will become too transparent, resulting in a matte composite. There is a possibility that the repair of the layer film cannot be sufficiently performed.
バインダー樹脂
上記エナメル補修用塗料は、通常、バインダー樹脂を含んでいる。上記バインダー樹脂としては、上記エナメル塗料のところで述べたものが挙げられる。
Binder resin The enamel repair coating usually contains a binder resin. Examples of the binder resin include those described in the enamel paint.
艶消し材
上記エナメル補修用塗料は、得られる補修膜の艶を調整するために、艶消し材を含むことができる。上記艶消し材としては、例えば、メジアン径（Ｄ５０）が２〜１０μｍの光透過性粒状物（ａ）、シリカ化合物及び体質顔料等が挙げられる。上記光透過性粒状物（ａ）は上記窯業建材用艶消し複層膜形成方法の艶消しクリヤー塗料のところで述べたものが挙げられる。上記シリカ化合物としては、例えば、サイリシア４４６（富士シリシア化学社製）などの疎水性シリカが挙げられる。上記体質顔料としては、上記顔料のところで述べたように、上記エナメル塗料のところで述べた体質顔料が挙げられる。
Matting Material The above-mentioned enamel repair coating material may contain a matting material in order to adjust the gloss of the resulting repaired film. Examples of the matting material include light transmissive granular materials (a) having a median diameter (D50) of 2 to 10 μm, silica compounds, and extender pigments. Examples of the light transmissive granular material (a) include those described in the matte clear coating material of the matting multilayer film forming method for ceramic building materials. Examples of the silica compound include hydrophobic silica such as silicia 446 (manufactured by Fuji Silysia Chemical Ltd.). Examples of the extender pigment include extender pigments described in the enamel paint, as described in the pigment section.
上記エナメル補修用塗料における艶消し材の含有量は、塗料固形分１００質量部に対して５〜４０質量部であることが好ましい。５質量部未満の場合は、艶消しの効果が不充分になるおそれがあり、また、４０質量部を超える場合は、塗膜の透過性が低下し、塗膜の粗度が大きくなるため、艶消し複層膜の意匠を補修が充分にできないおそれがある。さらに好ましくは５〜３０質量部である。 The content of the matte material in the enamel repair coating is preferably 5 to 40 parts by mass with respect to 100 parts by mass of the solid content of the paint. If the amount is less than 5 parts by mass, the matting effect may be insufficient, and if it exceeds 40 parts by mass, the permeability of the coating film decreases and the roughness of the coating film increases. There is a possibility that the design of the matte multilayer film cannot be sufficiently repaired. More preferably, it is 5-30 mass parts.
その他の成分
上記エナメル補修用塗料は、その他の成分として、必要に応じて、上記エナメル塗料のところで述べたものが挙げられる。
Other components The above-mentioned enamel repair coating may include those described in the enamel coating as other components, if necessary.
調製
上記エナメル補修用塗料は、顔料、光非透過性粒状物（ｂ）、バインダー樹脂及び必要に応じて、艶消し材やその他の成分を攪拌、混合することにより調製することができる。
Preparation The enamel repair coating can be prepared by stirring and mixing a pigment, a light-impermeable granular material (b), a binder resin and, if necessary, a matting material and other components.
エナメル補修用塗料の塗布
上記エナメル補修用塗料の塗布方法としては特に限定されず、上記エナメル塗料のところで述べたものが挙げられる。また、上記塗布方法による塗布膜厚は乾燥膜厚で１０〜８０μｍとなるように塗布することが好ましい。
Application of Enamel Repair Paint The method for applying the enamel repair paint is not particularly limited, and examples thereof include those described for the enamel paint. Moreover, it is preferable to apply | coat so that the coating film thickness by the said coating method may be 10-80 micrometers by a dry film thickness.
乾燥
塗装されたエナメル補修塗膜の乾燥は、常温で放置して乾燥しても良いし、６０〜１５０℃の加熱による強制乾燥を行なっても良い。屋外で塗装されることが多いため、好ましくは常温で、３０分〜２４時間程度、放置して乾燥することができる。
The dried enamel repair coating film may be dried by leaving it at room temperature or by forced drying by heating at 60 to 150 ° C. Since it is often painted outdoors, it can be dried by leaving it at room temperature for about 30 minutes to 24 hours.
エナメル補修塗膜を有する窯業建材用艶消し複層膜
本発明のエナメル補修塗膜を有する窯業建材用艶消し複層膜は、窯業建材用艶消し複層膜形成方法によって形成される艶消し複層膜を、上記エナメル補修用塗料を用いて補修することによって得られるものである。得られたエナメル補修塗膜を有する窯業建材用艶消し複層膜は、補修部が目立たず、周囲から際立つことを抑制できる。
Ceramic building material matte Fukusomaku with enamel repair coating ceramic building material matte multilayer film present invention having the enamel repair coating, matte double formed by matte multilayer film forming method for ceramic building materials It is obtained by repairing the layer film with the enamel repair paint. The matted multilayer film for ceramics building materials having the obtained enamel repair coating film can prevent the repaired portion from being noticeable and stand out from the surroundings.
以下、実施例により本発明をさらに具体的に説明するが、本発明はこれら実施例によって限定されるものではない。実施例中、「部」および「％」は、ことわりのない限り、質量基準による。 EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited by these Examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.
［ 製造例１ 白色エナメル塗料の製造 ］
ＢＹＫ１９０（ビックケミー社製顔料分散剤、固形分濃度４０．０％）２部、チタンＣＲ−９５（石原産業社製二酸化チタン）１５部、沈降性硫酸バリウム＃１００（堺化学社製沈降性硫酸バリウム）５部、脱イオン水５部からなる顔料分散ペーストにバインダー樹脂としてＶＯＮＣＯＡＴ ＳＡ−６３６０（ＤＩＣ社製アクリルエマルジョン、固形分濃度５０．０％）４０部、揮発性塩基化合物として２５％アンモニア水溶液 ０．３部順次混合した。さらに、サノールＬＳ２９２（三共社製ヒンダードアミン系安定剤）０．５部、テキサノール（イーストマン社製造膜助剤）３部及び脱イオン水 ２５部を混合した。最後に、ストーマー粘度計にて７５ＫＵとなるようＡＳＥ−６０（ローム＆ハース社製増粘剤）を添加して、白色エナメル塗料を得た。白色エナメル塗料における塗料固形分体積に対する顔料と光非透過性粒状物との総量の含有量は１８％であった。なお、この含有量の計算に用いた比重の値は、チタンＣＲ−９５が４．２、沈降性硫酸バリウム＃１００が４．３、樹脂は全て１．０とした。
[Production Example 1 Production of white enamel paint]
BYK190 (pig dispersant manufactured by Big Chemie, solid content concentration 40.0%) 2 parts, titanium CR-95 (titanium dioxide manufactured by Ishihara Sangyo Co., Ltd.), precipitated barium sulfate # 100 (precipitated barium sulfate manufactured by Sakai Chemical Co., Ltd.) ) 5 parts of deionized water 5 parts of pigment dispersion paste VONCOAT SA-6360 (DIC Corporation acrylic emulsion, solid concentration 50.0%) as binder resin 40 parts, volatile base compound 25% ammonia aqueous solution 0 3 parts were mixed sequentially. Furthermore, 0.5 part of SANOL LS292 (Hyadodamine stabilizer manufactured by Sankyo Co., Ltd.), 3 parts of Texanol (manufactured by Eastman Co., Ltd.) and 25 parts of deionized water were mixed. Finally, ASE-60 (a thickener manufactured by Rohm & Haas) was added with a Stormer viscometer to obtain 75 KU to obtain a white enamel paint. The total content of the pigment and the non-light-transmitting granular material with respect to the solid content volume of the white enamel paint was 18%. The specific gravity used for calculating the content was 4.2 for titanium CR-95, 4.3 for precipitated barium sulfate # 100, and 1.0 for all resins.
［ 製造例２ 艶消しクリヤー塗料１の製造 ］
ＶＯＮＣＯＡＴ ＳＡ−６３６０を６０部、テキサノール５部、チヌビン１１３０（チバスペシャリティーケミカルズ社製紫外線吸収剤）０．５部、サノールＬＳ２９２０．５部、光透過粒状物であるタフチックＦＨ−Ｓ００５（東洋紡社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）５μｍ、）４．８部、光非透過粒状物であるタフチックＡＲ６５０ＬＣ（東洋紡社製カーボンブラック着色アクリル樹脂ビーズ、メジアン径（Ｄ５０）１００μｍ）０．５部、サイリシア４４６（富士シリシア化学社製シリカ化合物）１．５部及び脱イオン水２０部を混合し、さらに、ストーマー粘度計にて６５ＫＵとなるようＡＳＥ−６０を添加して艶消しクリヤー塗料１を得た。
[Production Example 2 Production of Matte Clear Paint 1]
60 parts VONCOAT SA-6360, 5 parts texanol, 0.5 parts Tinuvin 1130 (UV absorber manufactured by Ciba Specialty Chemicals), 2920.5 parts Sanol LS, Tuftic FH-S005 ( manufactured by Toyobo Co., Ltd.) Transparent acrylic resin beads, median diameter (D50) 5 μm, 4.8 parts), Toughtic AR650LC (Toyobo Co., Ltd. carbon black colored acrylic resin beads, median diameter (D50) 100 μm) 0.5 parts, which is a light non-transparent granular material, Mix 1.5 parts of Silicia 446 (silica compound manufactured by Fuji Silysia Chemical Co., Ltd.) and 20 parts of deionized water, and then add ASE-60 so that it becomes 65 KU with a Stormer viscometer to obtain a matte clear coating material 1. It was.
［ 製造例３ 艶消しクリヤー塗料２の製造 ］
タフチックＦＨ−Ｓ００５の配合量を１０．５部とした以外は、製造例２と同様にしてで、艶消しクリヤー塗料２を得た。
[Production Example 3 Production of Matte Clear Paint 2]
A matte clear paint 2 was obtained in the same manner as in Production Example 2 except that the amount of Tuftic FH-S005 was changed to 10.5 parts.
［ 製造例４ 艶消しクリヤー塗料３の製造 ］
光透過粒状物であるタフチックＦＨ−Ｓ００５ ４．８部に代えて、ＳＰＬ−５（ユニチカ社製透明ガラスビーズ、メジアン径（Ｄ５０）５μｍ）４．８部とした以外は、製造例２と同様にして、艶消しクリヤー塗料３を得た。
[Production Example 4 Production of Matte Clear Paint 3]
It is the same as that of Production Example 2 except that 4.8 parts of SPL-5 (transparent glass beads manufactured by Unitika Ltd., median diameter (D50) 5 μm) is used instead of 4.8 parts of tuftic FH-S005 which is a light transmitting granular material. Thus, a matte clear paint 3 was obtained.
［ 製造例５ 艶消しクリヤー塗料４の製造 ］
光非透過粒状物であるタフチックＡＲ６５０ＬＣ ０．５部に代えて、カラーサンドＮｏ．８（オクムラセラム社製硅砂、メジアン径（Ｄ５０）１００μｍ）０．５部とした以外は、製造例２と同様にして、艶消しクリヤー塗料４を得た。
[Production Example 5 Production of Matte Clear Paint 4]
Instead of 0.5 part of tuftic AR650LC which is a light non-transparent granular material, color sand No. A matte clear paint 4 was obtained in the same manner as in Production Example 2 except that 0.5 parts of 8 (Okumura Serum's cinnabar sand, median diameter (D50) 100 μm) was used.
［ 製造例６ 艶消しクリヤー塗料５の製造 ］
光透過粒状物であるタフチックＦＨ−Ｓ００５ ４．８部に代えて、タフチックＦ−２００（東洋紡社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）３μｍ）４．８部とした以外は、製造例２と同様にして、艶消しクリヤー塗料５を得た。
[Production Example 6 Production of Matte Clear Paint 5]
Production Example 2 except that 4.8 parts of tuftic FH-S005, which is a light-transmitting granular material, was replaced with 4.8 parts of tuftic F-200 (transparent acrylic resin beads produced by Toyobo Co., Ltd., median diameter (D50) 3 μm). In the same manner, a mat clear paint 5 was obtained.
［ 製造例７ 艶消しクリヤー塗料６の製造 ］
光透過粒状物であるタフチックＦＨ−Ｓ００５ ４．８部に代えて、タフチックＦＨ−Ｓ００８（東洋紡社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）８μｍ）４．８部とした以外は、製造例２と同様にして、艶消しクリヤー塗料６を得た。
[Production Example 7 Production of matte clear paint 6]
Production Example 2 except that 4.8 parts of tuftic FH-S005 (transparent acrylic resin beads, median diameter (D50) 8 μm, manufactured by Toyobo Co., Ltd.) was used instead of 4.8 parts of tuftic FH-S005 which is a light transmitting granular material. In the same manner, a mat clear paint 6 was obtained.
［ 製造例８ 艶消しクリヤー塗料７の製造 ］
光非透過粒状物であるタフチックＡＲ６５０ＬＣ ０．５部に代えて、タフチックＡＲ６５０ＭＺ（東洋紡社製カーボンブラック着色アクリル樹脂ビーズ、メジアン径（Ｄ５０）６０μｍ）０．５部とした以外は、製造例２と同様にして、艶消しクリヤー塗料７を得た。
[Production Example 8 Production of Matte Clear Paint 7]
Production Example 2 except that 0.5 part of tuftic AR650LC, which is a light non-transparent granular material, was replaced with 0.5 part of tuftic AR650MZ (carbon black colored acrylic resin beads manufactured by Toyobo Co., Ltd., median diameter (D50) 60 μm). Similarly, a mat clear paint 7 was obtained.
［ 比較製造例１ 艶消しクリヤー塗料８の製造 ］
ＶＯＮＣＯＡＴ ＳＡ−６３６０を６０部、テキサノール５部、チヌビン１１３０を０．５部、サノールＬＳ２９２を０．５部、光透過粒状物であるタフチックＦＨ−Ｓ００５を４．８部、サイリシア４４６を１．５部及び脱イオン水２０部を混合し、さらに、ストーマー粘度計にて６５ＫＵとなるようＡＳＥ−６０を添加して艶消しクリヤー塗料８を得た。
[Comparative Production Example 1 Production of Matte Clear Paint 8]
60 parts VONCOAT SA-6360, 5 parts Texanol, 0.5 parts Tinuvin 1130, 0.5 parts Sanol LS292, 4.8 parts Tuftic FH-S005, which is a light transmitting granule, 1.5 parts Silicia 446 Parts and 20 parts of deionized water were mixed, and further, ASE-60 was added to 65 KU with a Stormer viscometer to obtain a matte clear paint 8.
［ 比較製造例２ 艶消しクリヤー塗料９の製造 ］
光透過粒状物であるタフチックＦＨ−Ｓ００５ ４．８部に代えて、タフチックＡＲ６５０Ｌ（東洋紡績社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）１００μｍ）４．８部とした以外は、比較製造例１と同様にして、艶消しクリヤー塗料９を得た。
[Comparative Production Example 2 Production of Matte Clear Paint 9]
Comparative Production Example 1 except that 4.8 parts of tuftic FH-S005, which is a light-transmitting granular material, was replaced with 4.8 parts of tuftic AR650L (transparent acrylic resin beads produced by Toyobo Co., Ltd., median diameter (D50) 100 μm). In the same manner, a mat clear paint 9 was obtained.
［ 比較製造例３ 艶消しクリヤー塗料１０の製造 ］
光非透過粒状物であるタフチックＡＲ６５０ＬＣ ０．５部に代えて、タフチックＡＲ６５０Ｍ（東洋紡社製カーボンブラック着色アクリル樹脂ビーズ、メジアン径（Ｄ５０）３０μｍ）０．５部とした以外は、製造例２と同様にして、艶消しクリヤー塗料１０を得た。
[Comparative Production Example 3 Production of Matte Clear Paint 10]
Production Example 2 except that 0.5 part of tuftic AR650LC, which is a light non-transparent granular material, was replaced with 0.5 part of tuftic AR650M (carbon black colored acrylic resin beads manufactured by Toyobo Co., Ltd., median diameter (D50) 30 μm). Similarly, a matte clear paint 10 was obtained.
［ 比較製造例４ 艶消しクリヤー塗料１１の製造 ］
光透過粒状物であるタフチックＦＨ−Ｓ００５ ４．８部に代えて、タフチックＡＲ６５０ＭＸ（東洋紡社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）４０μｍ）４．８部とした以外は、製造例２と同様にして、艶消しクリヤー塗料１１を得た。
[Comparative Production Example 4 Production of Matte Clear Paint 11]
The same as Production Example 2 except that 4.8 parts of tuftic AR650MX (transparent acrylic resin beads, median diameter (D50) 40 μm) manufactured by Toyobo Co., Ltd. was used instead of 4.8 parts of tuftic FH-S005 which is a light transmitting granular material. Thus, a matte clear paint 11 was obtained.
上記製造例によって得られた艶消し塗料１〜１１に含まれる粒状物の内容および配合量について、下記表１および２にまとめる。 The contents and blending amounts of the granular materials contained in the matte paints 1 to 11 obtained by the above production examples are summarized in Tables 1 and 2 below.
［ 製造例９ 白色エナメル補修用塗料１の製造 ］
ＢＹＫ１０８を４部、チタンＣＲ−９５１５部、キシレン５部、酢酸ブチル５部、ダイヤナールＢＲ１１２（三菱レイヨン社製アクリル樹脂、固形分濃度４０．０％）６０部をサンドミルにより分散し、顔料分散ペーストを得た。該顔料分散ペーストにダイヤナールＢＲ１１２を２０部、キシレン１０部、酢酸ブチル１０部を順次混合した。さらに、サノールＬＳ２９２を０．５部、光透過性粒状物であるタフチックＡＲ６５０Ｓ（東洋紡社製透明アクリル樹脂ビーズ、メジアン径（Ｄ５０）１８μｍ）５．０部、サイリシア４４６を５．０部、光非透過性粒状物であるタフチックＡＲ６５０ＬＣを０．０１部を混合し、さらに、ストーマー粘度計にて７０ＫＵとなるようにキシレン、酢酸ブチル＝１／１混合品を添加し、白色エナメル補修用塗料１を得た。エナメル補修用塗料１における塗料固形分体積に対する顔料と光非透過性粒状物との総量の含有量は６．０％であった。なお、この含有量の計算に用いた比重の値は、チタンＣＲ−９５が４．２、サイリシア４４６が１．０、樹脂およびタフチックＡＲ６５０Ｓは１．０、タフチックＡＲ６５０ＬＣは１．２とした。
[Production Example 9 Production of white enamel repair paint 1]
Disperse 4 parts of BYK108, 5 parts of titanium CR-9515, 5 parts of xylene, 5 parts of butyl acetate, and 60 parts of Dianal BR112 (acrylic resin manufactured by Mitsubishi Rayon Co., Ltd., solid content concentration 40.0%) with a sand mill, and a pigment dispersion paste Got. 20 parts of Dianal BR112, 10 parts of xylene and 10 parts of butyl acetate were sequentially mixed with the pigment dispersion paste. Furthermore, 0.5 parts of Sanol LS292, Toughtic AR650S (transparent acrylic resin beads made by Toyobo Co., Ltd., median diameter (D50) 18 μm) 5.0 parts, 5.0 parts of Silicia 446, light non-transparent granular material Mix 0.01 parts of Tuftic AR650LC, which is a permeable granular material, and add a mixture of xylene and butyl acetate = 1/1 so as to be 70 KU with a Stormer viscometer. Obtained. In the enamel repair coating 1, the total content of the pigment and the light-impermeable granular material with respect to the solid content volume of the paint was 6.0%. The specific gravity values used for calculating the content were 4.2 for titanium CR-95, 1.0 for silicia 446, 1.0 for resin and tuftic AR650S, and 1.2 for tuftic AR650LC.
[ 製造例１０ エナメル補修用塗料２の製造 ]
サイリシア４４６の量を７．０部とした以外は、製造例９と同様にして、エナメル補修用塗料２を得た。エナメル補修用塗料２における塗料固形分体積に対する顔料と光非透過性粒状物との総量の含有量は５．７％である。
[Production Example 10 Production of Enamel Repair Paint 2]
An enamel repair coating 2 was obtained in the same manner as in Production Example 9, except that the amount of silicia 446 was 7.0 parts. In the enamel repair coating 2, the total content of the pigment and the light-impermeable granular material with respect to the volume of the solid content of the coating is 5.7%.
［ 実施例１ ］
窯業系建材軽量発泡セメント板上に、オーデタイト１２８シーラー（日本ペイント社製シーラー）を塗布し乾燥させ、乾燥膜厚４０μｍのシーラー塗膜を形成して被塗物を作成した。
被塗物の表面温度が６０℃となるように加熱した後、製造例１で得られた白色エナメル塗料を乾燥膜厚４０μｍとなるように塗布した後、１００℃×３分間加熱して、被塗物上にエナメル塗膜を得た。次いで実施例２で得られた艶消しクリヤー塗料１を乾燥膜厚２０μｍとなるようにスプレーによって塗布した後、１００℃で１０分間加熱して、複層膜１を形成した。
[Example 1]
On the ceramic building material lightweight foamed cement board, an Odetite 128 sealer (Nippon Paint Co., Ltd. sealer) was applied and dried to form a sealer coating film having a dry film thickness of 40 μm to prepare an article to be coated.
After heating so that the surface temperature of the object to be coated is 60 ° C., the white enamel paint obtained in Production Example 1 is applied to a dry film thickness of 40 μm, and then heated at 100 ° C. for 3 minutes. An enamel coating was obtained on the coating. Next, the matte clear coating material 1 obtained in Example 2 was applied by spraying to a dry film thickness of 20 μm, and then heated at 100 ° C. for 10 minutes to form a multilayer film 1.
［ 実施例２〜７、比較例１〜４ ］
艶消しクリヤー塗料１に代えて、製造例３〜８及び比較製造例１〜４で得られた艶消しクリヤー塗料２〜１１を用いた以外は、実施例１と同様にして、複層膜２〜１１を形成した。得られた複層膜は以下に示す試験を行った。結果は表３および表４に示した。
[Examples 2-7, Comparative Examples 1-4]
In place of the matte clear paint 1, the multilayer film 2 was obtained in the same manner as in Example 1 except that the matte clear paints 2 to 11 obtained in Production Examples 3 to 8 and Comparative Production Examples 1 to 4 were used. ~ 11 were formed. The obtained multilayer film was subjected to the following tests. The results are shown in Tables 3 and 4.
複層膜の光沢値測定方法
得られた複層膜の表面をマイクロトリグロス（ＢＹＫ Ｇａｒｄｎｅｒ社製光沢計）にて、６０度および８５度の光沢値を測定した。６０度光沢値が３〜３０であれば、艶消し意匠として合格レベルであり、さらに３〜１５であればより好ましい。
Method for Measuring Gloss Value of Multilayer Film Gloss values of 60 degrees and 85 degrees were measured on the surface of the obtained multilayer film with a micro trigloss (Gloss meter manufactured by BYK Gardner). If the 60 degree gloss value is 3-30, it is a pass level as a matte design, and more preferably 3-15.
また、６０度光沢値に対する８５度光沢値の比率が０．７〜１．２であれば合格であり、０．９〜１．１であればより好ましい。 Moreover, it is a pass if the ratio of the 85-degree gloss value to the 60-degree gloss value is 0.7 to 1.2, and more preferably 0.9 to 1.1.
複層膜の耐ブロッキング性評価方法
得られた複層膜の耐ブロッキング性について評価を行った。上記複層膜を形成した窯業系建材軽量発泡セメント板上を１０ｃｍ×１０ｃｍに切断したものを作成し、厚さ３０μｍのポリエチレンフィルムを試験板の塗装面を向かい合わせ、５０℃の雰囲気下で５．０ｋｇ／ｃｍ２の荷重をかけて１０分間静置した。ポリエチレンフィルムを剥がした際の状態を以下の基準により評価した。
５・・圧着なし、かつ、合紙跡なし
４・・少し圧着あり、かつ、合紙跡５％以下
３・・少し圧着あり、かつ、合紙跡１０％以下
２・・圧着あり、かつ、合紙跡面積３０％以下
１・・圧着あり、かつ、合紙跡面積３０％以上
Method for evaluating blocking resistance of multilayer film The blocking resistance of the obtained multilayer film was evaluated. A ceramic building material lightweight foamed cement board on which the multilayer film is formed is cut to 10 cm × 10 cm, and a polyethylene film with a thickness of 30 μm is faced with the painted surface of the test board facing each other in an atmosphere of 50 ° C. It was left to stand for 10 minutes under a load of 0.0 kg / cm 2 . The state when the polyethylene film was peeled was evaluated according to the following criteria.
5 ・ ・ No crimping and no slippage 4 ・ ・ Slight crimping and 5% or less slippage 3 ・ ・ Slightly crimping and 10% or less slippage 2 ・ ・ Crimping and Interleaving paper trace area 30% or less 1. ・ There is crimping and interleaving paper trace area 30% or more
本発明に係る実施例１〜７の複層膜は６０度光沢値が１５以下であり、艶消し意匠としては良好である。また、６０度光沢値に対する８５度光沢値の比率も０．７〜１．２であり、複層膜に光沢値の角度依存性が生じておらず、補修性が良好であると予想できた。さらに、耐ブロッキング性も全ての実施例で良好であった。
一方、メジアン径が５０〜２００μｍの光非透過性粒状物をクリヤー塗料に有しない比較例１および３は、クリヤー塗膜面に対して十分な凹凸を有していないため、耐ブロッキング性が劣った。また、比較例２〜４は６０度光沢値に対する８５度光沢値の比率が０．７未満であり、補修性に問題があると予想できた。
The multilayer films of Examples 1 to 7 according to the present invention have a 60 ° gloss value of 15 or less, and are good as a matte design. Moreover, the ratio of the 85 degree gloss value to the 60 degree gloss value is also 0.7 to 1.2, and the angle dependency of the gloss value does not occur in the multilayer film, and it can be expected that the repairability is good. . Furthermore, the blocking resistance was also good in all examples.
On the other hand, Comparative Examples 1 and 3, which do not have a light-impermeable granular material having a median diameter of 50 to 200 μm in the clear coating, do not have sufficient unevenness with respect to the clear coating surface, and therefore have poor blocking resistance. It was. In Comparative Examples 2 to 4, the ratio of the 85 ° gloss value to the 60 ° gloss value was less than 0.7, and it was predicted that there was a problem in repairability.
［ 実施例８ ］
エナメル補修塗膜を有する複層膜
実施例１で得られた複層膜１の一部分に対して、製造例１０で得られたエナメル補修用塗料をハケ塗りした後、常温で１２時間放置して乾燥し、乾燥膜厚が３０μｍのエナメル補修塗膜を有する複層膜を得た。エナメル補修塗膜の６０度光沢値は９．９で、８５度光沢値は９．６であった。
[Example 8]
Multilayer film having an enamel repair coating film A part of the multilayer film 1 obtained in Example 1 was brushed with the enamel repair paint obtained in Production Example 10 and then allowed to stand at room temperature for 12 hours. It dried and the multilayer film which has an enamel repair coating film with a dry film thickness of 30 micrometers was obtained. The 60-degree gloss value of the enamel repair coating film was 9.9, and the 85-degree gloss value was 9.6.
［ 実施例９〜１４、比較例５〜８ ］
実施例１で得られた複層膜１に代えて、実施例３で得られた複層膜３、実施例４で得られた複層膜４、実施例５で得られた複層膜５、実施例６で得られた複層膜６、実施例７で得られた複層膜７、比較例１で得られた複層膜８、比較例２で得られた複層膜９、比較例３で得られた複層膜１０、比較例４で得られた複層膜１１それぞれの上にエナメル補修用塗料１を用いて、実施例８と同様にしてエナメル補修塗膜を有する複層膜を得た。また、実施例２で得られた複層膜２の上には、エナメル補修用塗料２で、実施例８と同様にしてエナメル補修塗膜を有する複層膜を得た。なお、比較例６におけるエナメル補修塗膜の６０度光沢値は９．８で、８５度光沢値は１８．２であった。
[Examples 9-14, Comparative Examples 5-8]
Instead of the multilayer film 1 obtained in Example 1, the multilayer film 3 obtained in Example 3, the multilayer film 4 obtained in Example 4, and the multilayer film 5 obtained in Example 5 are used. The multilayer film 6 obtained in Example 6, the multilayer film 7 obtained in Example 7, the multilayer film 8 obtained in Comparative Example 1, the multilayer film 9 obtained in Comparative Example 2, and the comparison Using the enamel repair coating 1 on each of the multilayer film 10 obtained in Example 3 and the multilayer film 11 obtained in Comparative Example 4, a multilayer having an enamel repair coating film in the same manner as in Example 8. A membrane was obtained. Further, on the multilayer film 2 obtained in Example 2, the multilayer film having the enamel repair coating film was obtained with the enamel repair coating 2 in the same manner as in Example 8. The 60-degree gloss value of the enamel repair coating film in Comparative Example 6 was 9.8, and the 85-degree gloss value was 18.2.
スポットライトによる補修塗膜の目視評価
得られたエナメル補修塗膜を有する複層膜に対して、スポットライト（ＳＥＲＩＣ社製昼光光源）を垂直方向から照射し、スポットライトの照射光に対して４５度（正面）及び７５度（シェード）から、複層膜の補修部分とその周辺の塗膜の艶に差異があるかを目視で評価した。
３・・正面及びシェード評価どちらでも差異を確認できず
２・・正面では差異を確認できないが、シェードでは僅かに差異を確認できる
１・・正面では差異を僅かに確認でき、かつ、シェードでは差異を明らかに確認できる
Visual evaluation of the repair coating film by spotlight The multi-layer film having the enamel repair coating film obtained was irradiated with a spotlight (daylight source manufactured by SERIC) from the vertical direction, and the spotlight irradiation light From 45 degrees (front) and 75 degrees (shade), it was visually evaluated whether there was a difference in gloss between the repaired portion of the multilayer film and the coating film around it.
3. ・ No difference can be confirmed by either front or shade evaluation. 2. ・ No difference can be confirmed at the front, but a slight difference can be confirmed at the shade. ・ ・ A slight difference can be confirmed at the front, and there is a difference at the shade. Can be clearly confirmed
本発明に係る実施例８〜１４で得られたエナメル補修塗膜を有する複層膜はスポットライト照射での試験において、見る角度に関わらず、補修部分とその周辺の塗膜での艶に差異は確認できず、補修部分が目立たなかった。
一方、メジアン径が１０μｍより大きい光透過性粒状物をクリヤー塗膜中に有する比較例６および８は、太陽光およびスポットライト照射での試験において、補修部分とその周辺の塗膜で正面の艶の差異は僅かであるが、シェードでの艶には差異が明らかに視認でき、補修部分が非常に目立つものであった。
The multilayer film having the enamel repair coating obtained in Examples 8 to 14 according to the present invention has a difference in gloss between the repaired portion and the surrounding coating in the spotlight irradiation test regardless of the viewing angle. Was not confirmed, and the repaired part was not noticeable.
On the other hand, in Comparative Examples 6 and 8 having a light-transmitting granular material having a median diameter larger than 10 μm in the clear coating film, the front surface gloss of the repaired part and the surrounding coating film in the test with sunlight and spotlight irradiation. Although the difference was slight, the difference in the gloss on the shade was clearly visible, and the repaired part was very conspicuous.
本発明の複層膜の形成方法、艶消し塗料及び複層膜の補修方法は、窯業建材を基材にして、艶消しの高意匠塗膜を形成する分野に好適に用いられる。 The method for forming a multilayer film, the matting paint and the method for repairing the multilayer film of the present invention are suitably used in the field of forming a matte high-design coating film using a ceramic building material as a base material.
Claims (6)
前記窯業建材用艶消しクリヤー塗料は、
メジアン径（Ｄ５０）が２〜１０μｍの光透過性粒状物（ａ）、
メジアン径（Ｄ５０）が５０〜２００μｍの光非透過性粒状物（ｂ）、及び、
バインダー樹脂（ｃ）、
を含み、前記バインダー樹脂（ｃ）の固形分質量に対する前記光透過性粒状物（ａ）の含有量が５〜７０質量％であり、かつ、前記バインダー樹脂（ｃ）の固形分質量に対する前記光非透過性粒状物（ｂ）の含有量が０．３〜１０質量％であり、および、
前記光非透過性粒状物（ｂ）は、着色樹脂粒状物、ホタル石、ケイ砂、焼成着色ケイ砂、石英、陶磁器粉砕粒子および炭酸カルシウム粒子からなる群から選択される１種またはそれ以上であり、
前記光非透過性粒状物（ｂ）は、可視光における平均光透過率が５０％未満の非透過性の粒状物である、
窯業建材用艶消し複層膜形成方法。 Step (1) for forming an enamel coating by applying an enamel coating on ceramic building materials, and a matte clear coating for ceramic building materials on the enamel coating obtained in the step (1). A matting multilayer film forming method for ceramic building materials comprising a step (2) of forming a matte clear coating film by applying to 10 to 40 μm,
The matte clear paint for ceramic building materials is
A light transmissive granular material (a) having a median diameter (D50) of 2 to 10 μm,
A light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm, and
Binder resin (c),
The light-transparent granular material (a) content is 5 to 70% by mass with respect to the solid content mass of the binder resin (c), and the light with respect to the solid mass of the binder resin (c) The content of the non-permeable granular material (b) is 0.3 to 10% by mass, and
The light-impermeable granular material (b) is one or more selected from the group consisting of colored resin granular material, fluorite, silica sand, calcined colored silica sand, quartz, ceramic ground particles and calcium carbonate particles. Oh it is,
The light-impermeable granular material (b) is a non-transparent granular material having an average light transmittance in visible light of less than 50%.
Matting multilayer film forming method for ceramics building materials.
請求項１または２記載の窯業建材用艶消し複層膜形成方法。 The ratio of the median diameter (D50) of the light transmissive granular material (a) to the dry film thickness of the clear coating film is 0.05 to 0.5, and the dry film thickness of the clear coating film is The ratio of the median diameter (D50) of the light-impermeable granular material (b) is 2.0 to 10.0.
The matte multilayer film forming method for ceramics building materials according to claim 1 or 2.
請求項１〜３いずれかに記載の窯業建材用艶消し複層膜形成方法。 The matte multilayer film for ceramics building materials formed by the method has a ratio of 85 degree gloss value to 60 degree gloss value of 0.7 to 1.2. Matte multilayer film formation method.
前記窯業建材用艶消しクリヤー塗料は、
メジアン径（Ｄ５０）が２〜１０μｍの光透過性粒状物（ａ）、
メジアン径（Ｄ５０）が５０〜２００μｍの光非透過性粒状物（ｂ）、及び、
バインダー樹脂（ｃ）、
を含み、前記光透過性粒状物（ａ）の含有量が、前記バインダー樹脂（ｃ）の固形分に対して５〜７０質量％であり、かつ、前記光非透過性粒状物（ｂ）の含有量が、前記バインダー樹脂（ｃ）の固形分に対して０．３〜１０質量％であり、および、
前記光非透過性粒状物（ｂ）は、着色樹脂粒状物、ホタル石、ケイ砂、焼成着色ケイ砂、石英、陶磁器粉砕粒子および炭酸カルシウム粒子からなる群から選択される１種またはそれ以上であり、
前記光非透過性粒状物（ｂ）は、可視光における平均光透過率が５０％未満の非透過性の粒状物である、
窯業建材用艶消しクリヤー塗料。 A matte clear paint for ceramics building materials used to form a matte clear paint film on a ceramics building material having a clear paint film,
The matte clear paint for ceramic building materials is
A light transmissive granular material (a) having a median diameter (D50) of 2 to 10 μm,
A light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm, and
Binder resin (c),
And the content of the light transmissive granular material (a) is 5 to 70% by mass with respect to the solid content of the binder resin (c), and the light nontransparent granular material (b) Content is 0.3-10 mass% with respect to solid content of the said binder resin (c), and
The light-impermeable granular material (b) is one or more selected from the group consisting of colored resin granular material, fluorite, silica sand, calcined colored silica sand, quartz, ceramic ground particles and calcium carbonate particles. Yes,
The light-impermeable granular material (b) is a non-transparent granular material having an average light transmittance in visible light of less than 50%.
Matte clear paint for ceramics building materials.
前記エナメル補修用塗料は顔料を含み、また、メジアン径（Ｄ５０）が５０〜２００μｍである光非透過性粒状物（ｂ）を含んでもよく、かつ、
塗料固形分体積に対する前記顔料と前記光非透過性粒状物（ｂ）との総量の含有量が２〜１０％である窯業建材用艶消し複層膜補修方法。 The ceramic industry which applies an enamel repair coating material and forms an enamel repair coating film on the repair part of the multilayer film formed by the matte multilayer film forming method for ceramics building materials according to any one of claims 1 to 4 A matte multilayer film repair method for building materials,
The enamel repair coating material may include a pigment, and may include a light-impermeable granular material (b) having a median diameter (D50) of 50 to 200 μm, and
A matting multilayer film repair method for ceramic building materials, wherein the total content of the pigment and the light-impermeable granular material (b) with respect to the solid content volume of the paint is 2 to 10%.
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