JP2621427C - - Google Patents
Info
- Publication number
- JP2621427C JP2621427C JP2621427C JP 2621427 C JP2621427 C JP 2621427C JP 2621427 C JP2621427 C JP 2621427C
- Authority
- JP
- Japan
- Prior art keywords
- water
- silane compound
- weight
- fluorine
- cement
- 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.)
- Expired - Lifetime
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- -1 silane compound Chemical class 0.000 claims description 26
- 229910000077 silane Inorganic materials 0.000 claims description 22
- 229910052731 fluorine Inorganic materials 0.000 claims description 18
- 239000011737 fluorine Substances 0.000 claims description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 239000004566 building material Substances 0.000 claims description 11
- 239000004568 cement Substances 0.000 claims description 11
- 239000010454 slate Substances 0.000 claims description 10
- 210000001565 ALC Anatomy 0.000 claims description 8
- 239000005871 repellent Substances 0.000 claims description 8
- 230000002940 repellent Effects 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 239000004567 concrete Substances 0.000 claims description 5
- 239000011083 cement mortar Substances 0.000 claims description 4
- JHLNERQLKQQLRZ-UHFFFAOYSA-N Calcium silicate Chemical compound [Ca+2].[Ca+2].[O-][Si]([O-])([O-])[O-] JHLNERQLKQQLRZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2R,3R,4S,5R,6S)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2S,3R,4S,5R,6R)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2R,3R,4S,5R,6R)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N Iron(III) oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 206010037844 Rash Diseases 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001929 titanium oxide Inorganic materials 0.000 description 2
- UOCLRXFKRLRMKV-UHFFFAOYSA-N 2-[bis(2-nitrooxyethyl)amino]ethyl nitrate;phosphoric acid Chemical compound OP(O)(O)=O.OP(O)(O)=O.[O-][N+](=O)OCCN(CCO[N+]([O-])=O)CCO[N+]([O-])=O UOCLRXFKRLRMKV-UHFFFAOYSA-N 0.000 description 1
- 229960003563 Calcium Carbonate Drugs 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 125000002340 chlorooxy group Chemical group ClO[*] 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000000855 fungicidal Effects 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic Secondary and tertiary amines Drugs 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 201000002674 obstructive nephropathy Diseases 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N oxo-oxoalumanyloxy-[oxo(oxoalumanyloxy)silyl]oxysilane;dihydrate Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 1
- 238000011041 water permeability test Methods 0.000 description 1
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は含フッ素シラン化合物からなる撥水撥油剤で処理された耐候性、耐汚
染性、耐水性、耐凍害性等耐久性及び防カビ性に優れた建築用材料に関する。さ
らに詳しくは、撥水撥油性のセメント系目地材、ALC板、スレート板、ケイ酸カ
ルシウム板、スレート抜、セメント系成形体、セメントモルタル、コンクリート
下地およびこれらに塗布する塗料に関する。
〔従来の技術と問題点〕
一般に建築用下地材、例えばALC板、セメントモルタル面、コンクリート面、
スレート板、珪カル板は、吸水率が高く、吸水によりしみ、汚れを生じ易い。特
にALC板、スレート板等は吸水により強度が低下するため意匠上あるいは基板保
護のため塗装されることが多く未塗装で使用されることは少ない。この塗装面に
ついて塗膜の耐久性が不十分であると劣化により、剥離、ふくれ等を生じ、塗膜
だけでなく下地の欠け、脱落、脆弱化を
引き起こす。
〔発明が解決しようとする課題〕
上記のような建築材料の劣化を引き起こす原因は何れも水が介在しており、多
くの場合水を介して劣化が生ずる。従って建築材料に撥水性を付与すれば材料自
体の成分を変更せずに、耐久性を要求される箇所に使用可能な材料を得ることが
できる。
〔課題を解決するための手段〕
本発明は一般式Rf(CH2)nY(CH2)mSiX3(I)〔式中RfはC1〜20のペルフルオロア
ルキル基、nおよびmは0〜3の整数、Yは-CH2-、-CH2O-、-NR-、-CO2-、-CON
R-、-S-、-SO3-、-SO2NR-(RはHまたはC1〜5のアルキル基)、XはCl、Br、OC
H3、OC2H5〕で表わされる含フッ素シラン化合物からなる撥水撥油剤で処理され
た撥水撥油処理建築材料を提供する。
本発明において対象とする建築材料は、セメント系目地材、ALC板、スレート
板、ケイ酸カルシウム板、セメント系成形体、セメン
トモルタル、コンクリート下地およびこれらに塗膜を施した材料等多くの建築材
料が含まれる。
本発明において撥水撥油剤の主剤をなす含フッ素シラン化合物は一般式(I)で
表わされる化合物であり、好ましくは一般式C5F17SO2NR(CH2)3SiX3(II)(式中R
はHまたはC1〜5のアルキル基、XはCl、Br,OCH3、OC2H5)で表わされる含フッ
素シラン化合物である。一般式(II)で表わされる化合物は直鎖のスルホニル基と
側鎖のアルキル基により、溶剤との相溶性が高く、建築材料に塗布した場合の塗
布膜の均一性が高い。さらにパーフルオロアルキル基が均一に外表面に配向して
優れた疎水性を示し、少量で水の浸透を防ぐ作用を有する。
本発明において、一般式(I)もしくは(II)で表わされる含フッ素シラン化合物
の塗布量は0.001〜20重量%の範囲が好適である。0.001重量%以下であると撥水
撥油性の効果が小さく、20重量%で効果が飽和し処理剤の無駄となる。
本発明に用いられる含フッ素シラン化合物は、通常溶剤で希釈して塗布する希
釈濃度は0.01〜20
重量%好ましくは0.1〜10重量%の溶液で用いられる。含フッ素シランカップリ
ング剤の濃度が0.01重量%以下でも数回重ね塗りすることにより十分な撥水、撥
油効果を得ることができる。20重量%以上であると塗りむらが生じたり、乾燥に
長時間を必要とする。また吸水率の高い建築用材料例えば無機系材料に塗布する
場合はより優れた吸水防止効果を付与するため、重ね塗りを繰返すのが好ましい
。溶剤としてはハロゲン化炭化水素、アルコール、エーテル等の有機溶媒が好ま
しく、無水かまたは必要に応じてアミンまたは酸の水溶液を少量添加したものが
使用される。ここで用いられるアミンは一級、二級および三級アミンのいずれで
もよいが特に一級アミンが有効である。これらのアミンまたは酸の水溶液の中で
、含フッ素シラン化合物のトリハロゲノシリル基またはトリアルコキシシリル基
が水によって加水分解されトリヒドロキシル基を形成し材料の表面附近に存在す
る極性基(例えば水酸基、カルボキシル基等)との間で水素結合もしくは脱水縮
合して化学結合
を生じ強い吸着作用を示す。
本発明において含フッ素シラン化合物からなる撥水撥油剤による建築材料の処
理方法は、含フッ素シラン化合物の溶液を材料の表面に塗布するかまたは溶液中
に材料を浸漬した後乾燥することにより行なわれる。
〔発明の効果〕
本発明による含フッ素シラン化合物で表面処理された建築用材料は防カビ性、
耐汚染性、耐水性、耐凍害性、耐白華性等に優れる。特にスルホニル基と側鎖に
アルキル基をもった(II)式で表わされる含フッ素シラン化合物は優れた特性を発
揮する。
〔実施例〕
以下、本発明の実施例を示す。
実施例1
陶器タイル、磁器タイルの目地材としてセメント100重量部、砂300重量部、水
60重量部、メチルセルロース0.2重量部を混練して、コンクリートブロック(30
×30×5cm)に5mmの厚さでコテ塗りし、2週間湿空養生後含フッ素シラン化合
物
C8F17SO2N(CH3)(CH2)3Si(OCH3)3をエタノールで5%に希釈して塗布し乾燥して
試験体とした。その試験体の下5cmを水に浸漬して湿度95%、室温35℃にてカビ
、コケの発生を観察した。その結果3ケ月を経過してもカビ、コケは発生しなか
った。
比較例1
実施例1で作成したセメント下地をシラン化合物としてCH3Si(OCH3)3をエタノ
ールで5%に希釈して塗布し、乾燥後実施例1と同条件で、試験したところ3ケ
月後にカビを発生した。
実施例2
アクリル系エマルション(大日本インキ工業(株)製EC720)40重量部、酸化チタ
ン25重量部、オレイン酸ナトリウム0.2重量部、メチルセルロース0.3重量部、水
35重量部を混合してエマルション系塗料を作成し、この塗料を150×50×3mmの
スレート板に塗布し、乾燥後含フッ素シラン化合物C8F17SO2N(C2H5)(CH2)3Si(OC
H3)3をエタノールで0.1%に希釈して1回塗布し試験体とした。
その試験体の表面、側面をシールして屋外曝露
して塗装面のふくれ、剥離、汚れ等を観察した。その結果1ケ年経過しても塗装
面のふくれ、剥離、汚れ等の変化はみられなかった。
比較例2
実施例2で作成した塗装面にシラン化合物としてCH3CONHC3H6Si(OCH3)3をエタ
ノールで5%に希釈して塗布し、乾燥後、実施例2と同条件で1ケ年屋外曝露を
行ったところ塗装面のふくれ、剥離等はみられなかったが、著しく汚染されてい
た。
実施例3(参考例)
実施例2で作成した塗装面にC7F15-COO-CH2CH2CH2Si(OCH3)3で表わされる含フ
ッ素シラン化合物をニタノールで5%に希釈し塗布し乾燥後、実施例2と同条件
で1ケ年屋外曝露を行ったところ塗装面のふくれ、剥離等はみられなかったが、
わずかに汚染された程度であった。
実施例4
コロイダルシリカ(日産化学(株)製スノーテックスC)20重量部、酸化チタン
10重量部、炭酸カルシウム20重量部、オレイン酸ナトリウム0.2重
量部、メチルセルロース0.4重量部、水50重量部、赤色酸化鉄1.0重量部を混合し
てシリカ系塗料を作成し、この塗料を150×150×3mmのスレート板に塗布し、乾
燥後含フッ素シラン化合物C8F17SO2N(C3H7)(CH2)3Si(OCH3)3をエタノールで5%
に希釈して1回塗布して試験体とした。その試験体の裏面、側面をシールして下
半分を水に浸漬して塗装面のふくれ、剥離等を観察した。その結果3ケ月を経過
しても塗膜にふくれ、剥離等の変化はなく、また境界面での汚れもほとんどなか
った。
比較例3
実施例4で作成した塗装面にシラン化合物とし
に希釈して塗布し乾燥後実施例4と同条件で水に半分浸漬したところ3ケ月後に
は水と境界面付近で剥離した。
実施例5
ALC板(150×40×40mm)を含フッ素シラン化合物
C8F17SO2NH(CH2)3Si(OC2H5)3の10%エタノール溶液に全面浸漬し、含浸させた後
乾燥して試験体とした。その試験体を水に全面浸漬して−20℃2時間、30℃2時
間、1日2サイクルで凍結融解試験を行ない試験体の割れ、欠け等を観察した。
その結果20サイクルでは割れ、欠げ等の変化はみられず、50サイクルで一部欠け
を生じた。
比較例4
実施例5で用いたALC板をC8F17CH2CH2CH2Si(OCH3)3Si(OCH3)3で表わされる含
フッ素シラン化合物をエタノールで10%に希釈した液に浸漬し、含浸させた後、
乾燥して実施例5と同条件で試験を行ったところ凍結融解20サイクルでは割れ欠
け等の変化はみられなかったが40サイクルで一部亀裂を生じ、50サイクルで破壊
した。
比較例5
実施例5で用いたALC板をシラン化合物C3H7Si(OCH3)3の10%エタノール溶液に
全面浸漬し、実施例5と同じ試験を行なったところ、凍結
融解20サイクルで欠けを生じ、30サイクルで破壊した。
実施例6
スレート板(300×300×5mm)に含フッ素シラン化合物C8F17SO2N(C3H7)(CH2)3S
i(OCl)3の10%エタノール溶液を1回塗布し、乾燥後JISA6910に準じて透水試験
を行った。その結果24時間経ても吸水量は0で変化がなかった。
比較例6
実施例6で用いたものと同じスレート板について含フッ素シラン化合物による
処理を行なわずに実施例6と同じ試験を行なったところ、1時間で吸水量が30cc
を越えた。
実施例7
セメント100重量部、砂200重量部、水40重量部を混練して200×100×10mmの
セメント成形体を作製し、室温で1日養生後、含フッ素シラン化合物C8F17SO2N(
CH3)(CH2)3Si(OCH3)3の5%エタノール溶液を1回塗布し、乾燥後裏面側面をシ
ールして温度5℃、湿度95%の条件で表面の自華現象に
ついて観察した結果1ケ月を経過してもみられなかった。
比較例7
実施例7で作成したセメント成形体について含フッ素シラン化合物による処理
をしないで実施例7と同一の試験を行なったところ、1週間後に表面が白くなり
白華現象がみられた。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to durability, such as weather resistance, stain resistance, water resistance, and frost resistance, treated with a water- and oil-repellent agent comprising a fluorine-containing silane compound, and mold resistance. To building materials with excellent properties. More specifically, the present invention relates to a water- and oil-repellent cement joint material, an ALC plate, a slate plate, a calcium silicate plate, a slate, a cement molding, a cement mortar, a concrete base, and a paint applied to these. [Conventional technology and problems] In general, building base materials, such as ALC boards, cement mortar surfaces, concrete surfaces,
The slate plate and the silica plate have a high water absorption rate, and are easily stained and stained by water absorption. In particular, ALC plates, slate plates, and the like are often coated on a design or for protection of a substrate because the strength is reduced by water absorption, and are rarely used without being coated. If the durability of the coating film on the coated surface is insufficient, deterioration, peeling, blistering, etc., occur, and not only the coating film but also the underlayer is chipped, dropped off, and weakened. [Problems to be Solved by the Invention] Water causes any of the causes of the deterioration of building materials as described above, and in many cases, deterioration occurs through water. Therefore, if water repellency is imparted to a building material, it is possible to obtain a material that can be used in places where durability is required without changing the components of the material itself. [Means for Solving the Problems] The present invention relates to a compound represented by the general formula R f (CH 2 ) n Y (CH 2 ) m SiX 3 (I) wherein R f is a C 1-20 perfluoroalkyl group, n and m is an integer of 0 to 3, Y is -CH 2 -, - CH 2 O -, - NR -, - CO 2 -, - CON
R -, - S -, - SO 3 -, - SO 2 NR- (R is H or an alkyl group C 1 to 5), X is Cl, Br, OC
H 3 , OC 2 H 5 ] and a water / oil repellent treated building material treated with a water / oil repellent comprising a fluorinated silane compound. The building materials targeted in the present invention are many building materials such as cement-based jointing materials, ALC plates, slate plates, calcium silicate plates, cement-based moldings, cement mortars, concrete bases, and materials coated with these. Is included. In the present invention, the fluorine-containing silane compound which is the main component of the water / oil repellent is a compound represented by the general formula (I), and is preferably a general formula C 5 F 17 SO 2 NR (CH 2 ) 3 SiX 3 (II) ( Where R
Alkyl group, X of H or C 1 to 5 is a fluorine-containing silane compound represented Cl, Br, with OCH 3, OC 2 H 5) . The compound represented by the general formula (II) has high compatibility with a solvent due to a linear sulfonyl group and a side chain alkyl group, and has high uniformity of a coating film when applied to a building material. Further, the perfluoroalkyl group is uniformly oriented on the outer surface, exhibits excellent hydrophobicity, and has a function of preventing permeation of water with a small amount. In the present invention, the coating amount of the fluorine-containing silane compound represented by the general formula (I) or (II) is preferably in the range of 0.001 to 20% by weight. If it is 0.001% by weight or less, the effect of water / oil repellency is small, and if it is 20% by weight, the effect is saturated and the treatment agent is wasted. The fluorine-containing silane compound used in the present invention is usually used as a solution having a dilution concentration of 0.01 to 20% by weight, preferably 0.1 to 10% by weight, which is applied by diluting with a solvent. Even when the concentration of the fluorinated silane coupling agent is 0.01% by weight or less, sufficient water repellency and oil repellency can be obtained by coating several times. If the content is more than 20% by weight, uneven coating may occur or a long time is required for drying. When applied to a building material having a high water absorption rate, for example, an inorganic material, it is preferable to repeat the recoating in order to impart a better water absorption prevention effect. As the solvent, organic solvents such as halogenated hydrocarbons, alcohols, ethers and the like are preferable, and those which are anhydrous or to which a small amount of an aqueous solution of an amine or an acid is added as necessary are used. The amine used here may be any of primary, secondary and tertiary amines, but primary amines are particularly effective. In an aqueous solution of these amines or acids, a polar group present near the surface of the material (for example, a hydroxyl group, a hydroxyl group, a trihalogenosilyl group or a trialkoxysilyl group of a fluorinated silane compound) is hydrolyzed by water to form a trihydroxyl group. Hydrogen bond or dehydration-condensation with a carboxyl group or the like to form a chemical bond and exhibit a strong adsorption action. In the present invention, a method of treating a building material with a water / oil repellent comprising a fluorine-containing silane compound is performed by applying a solution of the fluorine-containing silane compound to the surface of the material or by immersing the material in the solution and then drying. . [Effects of the Invention] Architectural materials surface-treated with the fluorine-containing silane compound according to the present invention have fungicidal properties,
Excellent in stain resistance, water resistance, frost damage resistance, efflorescence resistance, etc. Particularly, a fluorine-containing silane compound represented by the formula (II) having a sulfonyl group and an alkyl group in a side chain exhibits excellent properties. EXAMPLES Examples of the present invention will be described below. Example 1 100 parts by weight of cement, 300 parts by weight of sand, water as a joint material for ceramic tiles and porcelain tiles
60 parts by weight and 0.2 parts by weight of methylcellulose are kneaded and mixed in a concrete block (30
× 30 × 5cm) with a thickness of 5mm and after curing for 2 weeks in wet air, fluorinated silane compound C 8 F 17 SO 2 N (CH 3 ) (CH 2 ) 3 Si (OCH 3 ) 3 with ethanol It was diluted to 5%, applied and dried to obtain a test specimen. The lower 5 cm of the test specimen was immersed in water, and the occurrence of mold and moss was observed at a humidity of 95% and a room temperature of 35 ° C. As a result, no mold or moss was generated even after 3 months. Comparative Example 1 Using the cement base prepared in Example 1 as a silane compound, CH 3 Si (OCH 3 ) 3 was diluted to 5% with ethanol, applied, dried, and tested under the same conditions as in Example 1 to obtain 3 months. Later mold developed. Example 2 40 parts by weight of an acrylic emulsion (EC720 manufactured by Dainippon Ink and Chemicals, Inc.), 25 parts by weight of titanium oxide, 0.2 parts by weight of sodium oleate, 0.3 parts by weight of methylcellulose, water
An emulsion paint was prepared by mixing 35 parts by weight, this paint was applied to a slate plate of 150 × 50 × 3 mm, dried, and dried to obtain a fluorine-containing silane compound C 8 F 17 SO 2 N (C 2 H 5 ) (CH 2 2 ) 3 Si (OC
H 3 ) 3 was diluted to 0.1% with ethanol and applied once to obtain a test sample. The surface and side surfaces of the test specimen were sealed and exposed outdoors to observe the coating surface for blistering, peeling, dirt, and the like. As a result, no change such as blistering, peeling, and dirt on the painted surface was observed even after one year. Comparative Example 2 CH 3 CONHC 3 H 6 Si (OCH 3 ) 3 as a silane compound was diluted to 5% with ethanol, applied to the painted surface prepared in Example 2, dried, and dried under the same conditions as in Example 2. When exposed outdoors for 1 year, there was no blistering or peeling of the painted surface, but it was significantly contaminated. Example 3 (Reference Example) A fluorine-containing silane compound represented by C 7 F 15 —COO—CH 2 CH 2 CH 2 Si (OCH 3 ) 3 was diluted to 5% with nitranol on the painted surface prepared in Example 2. After coating and drying, the coated surface was exposed outdoors for one year under the same conditions as in Example 2, but no blistering or peeling of the painted surface was observed.
Slightly contaminated. Example 4 20 parts by weight of colloidal silica (Snowtex C manufactured by Nissan Chemical Industries, Ltd.), titanium oxide
10 parts by weight, 20 parts by weight of calcium carbonate, 0.2 parts by weight of sodium oleate, 0.4 parts by weight of methylcellulose, 50 parts by weight of water, 1.0 part by weight of red iron oxide were mixed to prepare a silica-based paint, and this paint was 150 × 150 Apply to a × 3 mm slate plate and after drying, fluorinated silane compound C 8 F 17 SO 2 N (C 3 H 7 ) (CH 2 ) 3 Si (OCH 3 ) 3 with ethanol at 5%
And applied once to obtain a test specimen. The back and side surfaces of the test body were sealed, and the lower half was immersed in water to observe blistering and peeling of the painted surface. As a result, there was no change such as blistering or peeling of the coating film even after 3 months, and there was almost no stain on the boundary surface. Comparative Example 3 A silane compound was applied to the painted surface prepared in Example 4. After diluting, drying and half-immersing in water under the same conditions as in Example 4, the film peeled off near the boundary surface with water after 3 months. Example 5 An ALC plate (150 × 40 × 40 mm) was entirely immersed and impregnated in a 10% ethanol solution of a fluorine-containing silane compound C 8 F 17 SO 2 NH (CH 2 ) 3 Si (OC 2 H 5 ) 3 . After drying, the specimen was obtained. The specimen was completely immersed in water and subjected to a freeze-thaw test at -20 ° C. for 2 hours and 30 ° C. for 2 hours, two cycles a day, to observe cracks, chipping and the like of the specimen.
As a result, no change such as cracking or chipping was observed in 20 cycles, and partial chipping occurred in 50 cycles. Comparative Example 4 A liquid obtained by diluting a fluorine-containing silane compound represented by C 8 F 17 CH 2 CH 2 CH 2 Si (OCH 3 ) 3 Si (OCH 3 ) 3 to 10% with ethanol using the ALC plate used in Example 5 After immersion in impregnation,
After drying and conducting a test under the same conditions as in Example 5, no change such as cracking was observed in 20 cycles of freezing and thawing, but some cracks occurred in 40 cycles, and fracture occurred in 50 cycles. Comparative Example 5 The ALC plate used in Example 5 was completely immersed in a 10% ethanol solution of the silane compound C 3 H 7 Si (OCH 3 ) 3 , and the same test as in Example 5 was performed. Chipped and destroyed in 30 cycles. Example 6 Fluorine-containing silane compound C 8 F 17 SO 2 N (C 3 H 7 ) (CH 2 ) 3 S was placed on a slate plate (300 × 300 × 5 mm).
A 10% ethanol solution of i (OCl) 3 was applied once, dried, and subjected to a water permeability test according to JISA6910. As a result, even after 24 hours, the water absorption was 0 and did not change. Comparative Example 6 The same test as in Example 6 was performed on the same slate plate as that used in Example 6 without performing the treatment with the fluorine-containing silane compound.
Crossed. Example 7 100 parts by weight of cement, 200 parts by weight of sand, and 40 parts by weight of water were kneaded to prepare a cement molded body of 200 × 100 × 10 mm, which was cured at room temperature for one day, and then a fluorine-containing silane compound C 8 F 17 SO 2 N (
A 5% ethanol solution of CH 3 ) (CH 2 ) 3 Si (OCH 3 ) 3 is applied once, dried, sealed on the back side, and observed at the temperature of 5 ° C. and 95% humidity for the self-phenomena on the surface. As a result, it was not observed after one month. Comparative Example 7 The same test as in Example 7 was performed on the cement molded article prepared in Example 7 without performing treatment with the fluorine-containing silane compound. As a result, the surface became white one week later, and a efflorescence phenomenon was observed.
Claims (1)
系成形体、セメントモルタル、またはコンクリート下地である建築材料であって
、一般式Rf(CH2)nY(CH2)mSiX3(I)[式中、RfはC1〜20のペルフルオロアルキル
基、nおよびmは0〜3の整数、Yは-SO2NR-(RはHまたはC1〜8のアルキル基
)、XはCl、Br、OCH3、またはOC2H5]で表わされる含フッ素シラン化合物からな
る撥水撥油剤で処理された撥水撥油処理建築材料。 [Claims] 1. A cement-based joint material, an ALC board, a slate board, a calcium silicate board, a cement-based molded product, a cement mortar, or a building material that is a concrete base, and has a general formula R f (CH 2 ) n Y (CH 2 ) m SiX 3 (I) wherein R f is a C 1-20 perfluoroalkyl group, n and m are integers of 0 to 3, Y is —SO 2 NR— (R is H or an alkyl group of C 1-8 ) ), X is a water / oil repellent treated building material treated with a water / oil repellent comprising a fluorine-containing silane compound represented by Cl, Br, OCH 3 or OC 2 H 5 ].
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