JP2009196874A - 窯業系建材 - Google Patents
窯業系建材 Download PDFInfo
- Publication number
- JP2009196874A JP2009196874A JP2008043362A JP2008043362A JP2009196874A JP 2009196874 A JP2009196874 A JP 2009196874A JP 2008043362 A JP2008043362 A JP 2008043362A JP 2008043362 A JP2008043362 A JP 2008043362A JP 2009196874 A JP2009196874 A JP 2009196874A
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- JP
- Japan
- Prior art keywords
- group
- component
- coating film
- weight
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000919 ceramic Substances 0.000 title claims abstract description 34
- 239000004566 building material Substances 0.000 title claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 223
- 238000000576 coating method Methods 0.000 claims abstract description 153
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 96
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 86
- 239000011941 photocatalyst Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 41
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- 239000000463 material Substances 0.000 claims description 19
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- 239000003973 paint Substances 0.000 claims description 6
- 238000010422 painting Methods 0.000 claims description 2
- 238000005524 ceramic coating Methods 0.000 claims 1
- 241000195493 Cryptophyta Species 0.000 abstract description 10
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 2
- 230000008021 deposition Effects 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 95
- -1 pulp Substances 0.000 description 80
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- 150000001282 organosilanes Chemical class 0.000 description 43
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- 239000002904 solvent Substances 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
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- 238000006482 condensation reaction Methods 0.000 description 8
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- 239000000945 filler Substances 0.000 description 8
- 230000007774 longterm Effects 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
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- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 150000004756 silanes Chemical class 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 6
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- 125000003342 alkenyl group Chemical group 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
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- 230000007423 decrease Effects 0.000 description 6
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- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 6
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- 239000003995 emulsifying agent Substances 0.000 description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000005055 methyl trichlorosilane Substances 0.000 description 6
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 6
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 6
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- 150000003839 salts Chemical class 0.000 description 6
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- IJOOHPMOJXWVHK-UHFFFAOYSA-N trimethylsilyl-trifluoromethansulfonate Natural products C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 6
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
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- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 5
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- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 4
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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Abstract
【解決手段】窯業系基材1の表面に塗装塗膜を施して形成される窯業系建材に関する。塗装塗膜の最表面は光触媒含有無機塗膜2によって形成されており、光触媒含有無機塗膜2に含有される光触媒は平均粒子径が20〜30nmの酸化チタンであることを特徴とする。
【選択図】図1
Description
(1)有機溶剤に対する有機塗膜のゲル分率が30%以下であること。
(2)有機塗膜3のTg(ガラス転移温度)が50℃以下であること。
(3)上塗りの無機塗膜4の無機コーティング剤との接触角が40度以下であること。
(A):一般式R1 nSiX4−n (1)
(式(1)中、R1は同一または異種の、アルキル基、シクロアルキル基、アルケニル基、ハロゲン置換炭化水素基、γ−メタクリロキシプロピル基、γ−グリシドキシプロピル基、3,4−エポキシシクロヘキシルエチル基およびγ−メルカプトプロピル基からなる群より選ばれる、炭素数1〜8の1価炭化水素基を示し、nは0〜3の整数、Xはアルコキシ基、アセトキシ基、オキシム基、エノキシ基、アミノ基、アミノキシ基およびアミド基からなる群より選ばれる加水分解性基を示す。)
で表わされる加水分解性オルガノシランを有機溶媒または水に分散されたコロイダルシリカ中で、X1モルに対し水0.001〜0.5モルを使用する条件下で部分加水分解してなる、オルガノシランのシリカ分散オリゴマー溶液、
(B):平均組成式R2 aSi (OH)bO(4−a−b)/2 (2)
(式(2)中、R2は同一または異種の、アルキル基、シクロアルキル基、アルケニル基、ハロゲン置換炭化水素基、γ−メタクリロキシプロピル基、γ−グリシドキシプロピル基、3,4−エポキシシクロヘキシルエチル基およびγ−メルカプトプロピル基からなる群より選ばれる、炭素数1〜8の1価炭化水素基を示し、aおよびbはそれぞれ0.2≦a≦2、0.0001≦b≦3、a+b<4の関係を満たす数である。)
で表わされ、成分中のR2にフェニル基を全R2基に対して1〜30モル%含有するポリオルガノシロキサン、および、
(C):(A)成分と(B)成分との縮合反応を促進する触媒
を必須成分とし、(A)成分においてシリカを固形分として5〜95重量%含有し、加水分解性オルガノシランの少なくとも50モル%がn=1のオルガノシランで、(A)成分1〜99重量部に対して(B)成分99〜1重量部が配合されているものである。
一般式 R1 nSiX4−n (3)
(式(3)中、R1は同一又は異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、nは0〜3の整数、Xは加水分解性基を示す)
で表される加水分解性オルガノシランを、微粒子酸化物を微粒子径0.2〜3μmに分散させた状態で、X1モルに対して水0.001〜0.5モルを使用する条件下で部分加水分解させて得られたものに、
一般式 OH(R2 2SiO)mH (4)
(式(4)中、R2は同一又は異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、mは1以上を示す)
で表される重量平均分子量10000以下のシリコーンジオール成分を5〜30重量%配合した、シリコーンジオール含有微粒子酸化物分散オリゴマー(D成分)と、
平均組成式 R3 aSi(OH)bO(4−a−b)/2 (5)
(式(5)中、R3は同一又は異種の置換もしくは非置換の炭素数1〜8の1価炭化水素基を示し、aおよびbはそれぞれ0.2≦a<2.0、0.0001≦b≦3、a+b<4の関係を満たす数である)
で表される、分子中にシラノール基を含有するポリオルガノシロキサン(E成分)と、
触媒(F成分)の各成分を含有するものである。
一般式 (R1)mSi(OR2)4−m (6)
(式(6)中、R1は各々メチル基、エチル基又はフェニル基を表し、R2は各々炭素数1〜8のアルキル基を表す。mは0,1又は2である。)
で表されるケイ素化合物及び/又はその部分加水分解物を主成分とするケイ素アルコキシド系コーティング剤に、紫外線吸収剤を配合したものである。
(i):一般式(6)においてm=0で示されるケイ素化合物及びコロイド状シリカ20〜200重量部
(ii):一般式(6)においてm=1で示されるケイ素化合物100重量部
(iii):一般式(6)においてm=2で示されるケイ素化合物0〜80重量部
これらのケイ素化合物としては後述の(7)式におけるアルコキシシラン類を用いることができる。また成分(i)のコロイド状シリカ(コロイダルシリカ)は微粒子シリカ成分を水、メタノール等の有機溶剤またはこれらの混合溶剤中に分散して使用するが、それらがコロイド状である限り、その粒径や溶剤種等は特に制限されるものではない。尚、成分(i)のコロイド状シリカの配合量は分散媒も含む重量部である。
一般式 (R3)nSiX4−n (7)
(式(7)中、R3は各々置換もしくは非置換の炭素数1〜8の1価の炭化水素基を表し、Xは加水分解性基を表す。nは0〜3の整数である。)
で表される加水分解性オルガノシランを、有機溶媒及び/又は水に分散されたコロイド状シリカ中で部分加水分解してなる、オルガノシランのシリカ分散オリゴマー溶液(G)と、
平均組成式 (R4)dSi(OH)eO(4−d−e)/2 (8)
(式(8)中、R4は各々置換もしくは非置換の炭素数1〜8の1価の炭化水素基を表し、dおよびeはそれぞれ0.2≦d≦2.0、0.0001≦e≦3、d+e<4の関係を満たす数である。)
で表される、分子中にシラノール基を含有するポリオルガノシロキサン(H)と、
硬化触媒(I)の、
(G),(H),(I)の3成分を必須成分として含有するケイ素アルコキシド系コーティング剤に、紫外線吸収剤を配合したものである。
一般式:Si(OR1)4 (9)
で表されるケイ素化合物、および/または、コロイド状シリカが、非水系の有機溶媒に分散した有機溶媒分散性であるコロイダルシリカを20〜200重量部、
一般式:R2Si(OR1)3 (10)
で表されるケイ素化合物を100重量部、
一般式:R2 2Si(OR1)2 (11)
で表されるケイ素化合物を0〜60重量部の割合で含有すると共に(上記式(9)〜(11)においてR1、R2は1価の炭化水素基を示す)、光触媒を含有するコーティング剤を用いることができる。
一般式:R2 nSi(OR1)4−n (12)
(式(12)中、n=0〜3を示し、R1、R2は1価の炭化水素基を示す。)
前式(12)のR1、R2は1価の炭化水素基を示す限り限定はされないが、R2として炭素数1〜8の置換または非置換の炭化水素基を示す。例えば、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等のアルキル基、シクロペンチル基、シクロヘキシル基等のシクロアルキル基、2−フェニルエチル基、3−フェニルプロピル基等のアラルキル基、フェニル基、トリル基等のアリール基、ビニル基、アリル基等のアニケニル基、クロロメチル基、γ−クロロプロピル基、3,3,3−トリフルオロプロピル基等のハロゲン置換炭化水素基、及び、γ−メタクリロキシプロピル基、γ−グリシドキシプロピル基、3,4−エポキシシクロヘキシルエチル基、γ−メルカプトプロピル基等の置換炭化水素基が挙げられる。なかでも合成の容易さ、または、入手の容易さから炭素数1〜4のアルキル基、及び、フェニル基が好ましい。
・有機コーティング剤
有機コーティング剤として、コアシェル型アクリルエマルジョン塗料(関西ペイント社製)を用いた。
メチルトリメトキシシラン100重量部、テトラエトシキシラン20重量部、イソプロピルアルコールオルガノシリカゾル(触媒化学化成工業株式会社製「OSCAL1432」、SiO2含有量30重量%)150重量部、ジメチルジメトキシシラン40重量部及びイソプロピルアルコール100重量部を混合し、さらに水200重量部を添加して攪拌し、これを60℃の恒温槽中で重量平均分子量Mwを1200に調整することによって、ケイ素アルコキシドを調製した。
メチルトリメトキシシラン100重量部に、テトラエトキシシラン10重量部、IPAオルガノシリカゾルを90重量部、ジメチルジメトキシシラン30重量部、イソプロピルアルコール(IPA)100重量部を混合した後に、水90重量部を添加し、攪拌した。これを、60℃の恒温槽中で重量平均分子量Mwを1500に調製した。
酸化チタンを、アクリル系分散剤を1質量%含有する酸化チタン水分散体の状態で用いるようにした他は、実施例1と同様にして光触媒含有シリコーン系コーティング剤を調製した。その他は実施例1と同様にして塗装塗膜を施した窯業系建材を得た。
酸化チタンを、アクリル系分散剤を2質量%含有する酸化チタン水分散体の状態で用いるようにした他は、実施例1と同様にして光触媒含有シリコーン系コーティング剤を調製した。その他は実施例1と同様にして塗装塗膜を施した窯業系建材を得た。
酸化チタンとして平均粒子径が7nmであり、DTA測定において400〜500℃の範囲に発熱のピークを有しアナタース型の結晶化が低いものを用いた。またこの酸化チタンを酸化チタンゾルの状態で用い、酸化チタンゾルをコーティング液に配合することによって、酸化チタンをコーティング液に分散させるようにした他は、実施例1と同様にして光触媒含有シリコーン系コーティング剤を調製した。その他は実施例1と同様にして塗装塗膜を施した窯業系建材を得た。
酸化チタンとして平均粒子径が31nmであり、DTA測定において400〜500℃の範囲に発熱のピークがなくアナタース型の結晶化が高いものを用いるようにした他は、実施例1と同様にして光触媒含有シリコーン系コーティング剤を調製した。その他は実施例1と同様にして塗装塗膜を施した窯業系建材を得た。
JIS A1445に準拠して、サンシャインウェザオメーターで測定した。そして5000時間経過後の色差ΔEが3以下を「◎」、3を超える場合を「×」と評価した。
試験サンプルを北面に垂直に設置し、2日間暴露した後に、5質量%濃度のカーボン液をスプレーし、拭いて汚れが落ちるかどうかを試験した。そして汚れが全く残らない場合を「◎」、汚れが5%以下の割合で残る場合を「○」、汚れが5%を超え10%以下で残る場合を「△」、汚れが10%を越えて残る場合を「×」と評価した。
3リットルのテドラーバックに100ppmのNOガスを充填し、この中に100mm×100mmの試験サンプルを入れ、これにブラックライトで1mW/cm2の紫外線を1時間照射した後の、NOガス濃度の減少量を測定した。そして減少率が90%以上の場合を「◎」、50%以上90%未満の場合を「○」、減少率が30%以上50%未満の場合を「△」、減少率が30%未満の場合を「×」と評価した。
JIS Z2911に準拠して、ブラックライトで2mW/cm2の紫外線を照射しながら、試験サンプルの表面にカビが生えたかどうかを試験した。そしてカビが生えない場合を「◎」、カビが5%以下の面積で生えた場合を「○」、カビが5%を超える面積で生えた場合を「×」と評価した。
2 光触媒含有無機塗膜
3 有機塗膜
4 無機塗膜
Claims (4)
- 窯業系基材の表面に塗装塗膜を施して形成される窯業系建材であって、塗装塗膜の最表面は光触媒含有無機塗膜によって形成されており、光触媒含有無機塗膜に含有される光触媒は平均粒子径が20〜30nmの酸化チタンであることを特徴とする窯業系建材。
- 酸化チタンは、DTA測定において400〜500℃の範囲に発熱のピークがなく、アナタース型の結晶化度が高いものであることを特徴とする請求項1に記載の窯業系建材。
- 塗装塗膜は、窯業系基材の表面に、有機塗膜、無機塗膜、光触媒含有無機塗膜をこの順に設けて形成されていることを特徴とする請求項1又は2に記載の窯業系建材。
- 光触媒含有無機塗膜は、光触媒を含有するシリコーン系コーティング剤の塗装によって形成されていることを特徴とする請求項1乃至3のいずれかに記載の窯業系建材。
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