JP6917024B2 - Fluorine-containing diol / triazine derivative composite - Google Patents
Fluorine-containing diol / triazine derivative composite Download PDFInfo
- Publication number
- JP6917024B2 JP6917024B2 JP2017039456A JP2017039456A JP6917024B2 JP 6917024 B2 JP6917024 B2 JP 6917024B2 JP 2017039456 A JP2017039456 A JP 2017039456A JP 2017039456 A JP2017039456 A JP 2017039456A JP 6917024 B2 JP6917024 B2 JP 6917024B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- fluorine
- triazine
- containing diol
- triazine derivative
- 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.)
- Active
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims description 31
- 239000011737 fluorine Substances 0.000 title claims description 31
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 30
- 150000002009 diols Chemical class 0.000 title claims description 28
- 150000003918 triazines Chemical class 0.000 title claims description 25
- 239000002131 composite material Substances 0.000 title claims description 21
- 239000006185 dispersion Substances 0.000 claims description 9
- 239000012756 surface treatment agent Substances 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims description 2
- OMRXVBREYFZQHU-UHFFFAOYSA-N 2,4-dichloro-1,3,5-triazine Chemical compound ClC1=NC=NC(Cl)=N1 OMRXVBREYFZQHU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 13
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 13
- 239000000758 substrate Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 9
- 239000005871 repellent Substances 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000004744 fabric Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000002940 repellent Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- SYWDUFAVIVYDMX-UHFFFAOYSA-M sodium;4,6-dichloro-1,3,5-triazin-2-olate Chemical compound [Na+].[O-]C1=NC(Cl)=NC(Cl)=N1 SYWDUFAVIVYDMX-UHFFFAOYSA-M 0.000 description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical class C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FIDRAVVQGKNYQK-UHFFFAOYSA-N 1,2,3,4-tetrahydrotriazine Chemical compound C1NNNC=C1 FIDRAVVQGKNYQK-UHFFFAOYSA-N 0.000 description 1
- JJUBFBTUBACDHW-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluoro-1-decanol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JJUBFBTUBACDHW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008568 cell cell communication Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical group C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Landscapes
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Polyethers (AREA)
- Paints Or Removers (AREA)
Description
本発明は、含フッ素ジオール／トリアジン誘導体コンポジットに関する。さらに詳しくは、表面処理剤として有効に用いられる含フッ素ジオール／トリアジン誘導体コンポジットに関する。 The present invention relates to a fluorine-containing diol / triazine derivative composite. More specifically, the present invention relates to a fluorine-containing diol / triazine derivative composite that is effectively used as a surface treatment agent.
無機材料表面を各種の化合物やポリマーでコーティングすることにより、様々な表面特性を発現させることが知られている。中でも、フッ素系化合物を表面処理に使用した場合には、フッ素原子の有する特性から、撥水性だけではなく撥油性の点でも表面改質できるので、様々な基材へのコーティングに利用されている。 It is known that various surface properties are exhibited by coating the surface of an inorganic material with various compounds and polymers. Above all, when a fluorine-based compound is used for surface treatment, it can be surface-modified not only in terms of water repellency but also in terms of oil repellency due to the characteristics of fluorine atoms, so it is used for coating various substrates. ..
特に、C8のパーフルオロアルキル基を有する表面処理剤を基質に塗布するとことで、高い撥水撥油性を示すコーティングが可能であるが、近年C7以上のパーフルオロアルキル基を有する化合物が、細胞株を用いた試験管内試験において、発がん因子と考えられている細胞間コミュニケーション阻害をひき起すこと、かつこの阻害は官能基ではなく、フッ素化された炭素鎖長に依存し、炭素鎖が長いもの程阻害力が高いことが報告されており、フッ素化された炭素数の長い化合物を使用したモノマーの製造が制限されるようになってきている。 In particular, a surface treatment agent having a perfluoroalkyl group of C 8 By when applied to the substrate, although it is possible coatings exhibit high water and oil repellency, compounds in recent years have a C 7 or more perfluoroalkyl groups, In an in vitro test using a cell line, it causes inhibition of cell-cell communication, which is considered to be a carcinogenic factor, and this inhibition depends on the fluorinated carbon chain length, not the functional group, and the carbon chain is long. It has been reported that the higher the inhibitory power is, and the production of monomers using fluorinated compounds having a long carbon number has been restricted.
また、炭素数が6以下のパーフルオロアルキル基を有する含フッ素アルコールにあっては、ガラス、金属、石材等の無機質基材への密着性に欠けるという問題もみられる。 Further, the fluorotelomer alcohol having a perfluoroalkyl group having 6 or less carbon atoms has a problem that it lacks adhesion to an inorganic base material such as glass, metal or stone.
本発明の目的は、環境中に放出されてもパーフルオロオクタン酸等を生成させず、しかも短鎖の化合物に分解され易いユニットを有する含フッ素アルコールを用い、無機質基材等に撥水性および／または撥油性を付与する含フッ素ジオール／トリアジン誘導体コンポジットを提供することにある。 An object of the present invention is to use a fluorine-containing alcohol having a unit that does not generate perfluorooctanoic acid or the like even when released into the environment and is easily decomposed into a short-chain compound, and is water-repellent and / or water-repellent on an inorganic substrate or the like. Alternatively, it is an object of the present invention to provide a fluorine-containing diol / triazine derivative composite that imparts oil repellency.
かかる本発明の目的は、一般式
HO(CH 2 ) a CF(CF 3 )〔OCF 2 CF(CF 3 )〕 b O(CF 2 ) c O〔CF(CF 3 )CF 2 O〕 d CF(CF 3 )(CH 2 ) a OH 〔I〕
(ここで、aは1〜6であり、cは1〜6であり、b+dは0〜50の整数である)で表される含フッ素ジオールおよび2,4-ジクロロ-6-ソジオオキシ-1,3,5-トリアジン、1,3,5-s-トリアジン、2,4-ジクロロ-1,3,5-トリアジンまたは2-アルキル-4,6-ジクロロ-1,3,5-トリアジンであるトリアジン誘導体の縮合反応生成物からなる含フッ素ジオール／トリアジン誘導体コンポジットによって達成される。
An object of the present invention is a general formula.
HO (CH 2 ) a CF (CF 3 ) [OCF 2 CF (CF 3 )] b O (CF 2 ) c O [CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) a OH [I]
(Here, a is 1 to 6, c is 1 to 6, b + d is an integer of 0 to 50), and the fluorine-containing diol and 2,4-dichloro-6-sodiooxy- With 1,3,5-triazine, 1,3,5-s-triazine, 2,4-dichloro-1,3,5-triazine or 2-alkyl-4,6-dichloro-1,3,5-triazine It is achieved by a fluorine-containing diol / triazine derivative composite consisting of a condensation reaction product of a triazine derivative.
本発明で用いられた含フッ素アルコールは、パーフルオロアルキレンエーテル基中のパーフルオロアルキレン鎖の炭素数が６以下のものであり、短鎖の含フッ素化合物に分解され易いユニットを有しているため、環境汚染につながらない。 The fluorine-containing alcohol used in the present invention has a perfluoroalkylene chain having 6 or less carbon atoms in the perfluoroalkylene ether group, and has a unit that is easily decomposed into a short-chain fluorine-containing compound. , Does not lead to environmental pollution.
得られた含フッ素ジオール／トリアジン誘導体コンポジットは、ガラス表面に撥水撥油性を、ろ紙表面には撥油性を、またPET布表面には撥水性をそれぞれ付与することができる。 The obtained fluorine-containing diol / triazine derivative composite can impart water and oil repellency to the glass surface, oil repellency to the filter paper surface, and water repellency to the PET cloth surface.
本発明の親水撥油性コンポジットは、含フッ素ジオールおよびトリアジン誘導体の縮合物からなる。 The hydrophilic oil-repellent composite of the present invention comprises a condensate of a fluorine-containing diol and a triazine derivative.
含フッ素ジオールとしては、一般式
HO(CH 2 ) a CF(CF 3 )〔OCF 2 CF(CF 3 )〕 b O(CF 2 ) c O〔CF(CF 3 )CF 2 O〕 d CF(CF 3 )(CH 2 ) a OH 〔I〕
a：1〜6、好ましくは1〜3、特に好ましくは1
b+d：0〜50、好ましくは1〜20
b+dの値に関しては、分布を有する混合物であってもよい
c：1〜6、好ましくは2〜4
で表される化合物等が用いられる。
As a fluorine-containing diol, a general formula
HO (CH 2 ) a CF (CF 3 ) [OCF 2 CF (CF 3 )] b O (CF 2 ) c O [CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) a OH [I]
a: 1 to 6, preferably 1 to 3, particularly preferably 1
b + d: 0 to 50, preferably 1 to 20
With respect to the value of b + d, it may be a mixture having a distribution.
c: 1-6, preferably 2-4
A compound represented by is used.
一般式〔I〕で表される含フッ素ジオールにおいて、a＝1の化合物は特許文献１〜２に記載されており、次のような一連の工程を経て合成される。
FOCRfCOF → H3COOCRfCOOCH3 → HOCH2RfCH2OH
Rf：-CF(CF3)〔OCF2CF(CF3)〕bO(CF2)cO〔CF(CF3)CF2O〕dCF(CF3)-
In the fluorine-containing diol represented by the general formula [I] , the compound with a = 1 is described in Patent Documents 1 and 2, and is synthesized through a series of steps as follows.
FOCRfCOF → H 3 COOCRfCOOCH 3 → HOCH 2 RfCH 2 OH
Rf: -CF (CF 3 ) [OCF 2 CF (CF 3 )] b O (CF 2 ) c O [CF (CF 3 ) CF 2 O] d CF (CF 3 )-
一般式〔I〕で表される、ポリフルオロアルキレン基を有する含フッ素ジオールとしては、例えば一般式
HOCH 2 CF 2 (OCF 2 CF 2 ) q (OCF 2 ) r OCF 2 CH 2 OH 〔II〕
q+r：1〜50、好ましくは10〜40
で表される化合物等が用いられる。
Examples of the fluorine-containing diol having a polyfluoroalkylene group represented by the general formula [I] include the general formula.
HOCH 2 CF 2 (OCF 2 CF 2 ) q (OCF 2 ) r OCF 2 CH 2 OH [II]
q + r: 1 to 50, preferably 10 to 40
A compound represented by is used.
パーフルオロアルキレンジオール等と縮合反応されるトリアジン誘導体としては、2,4-ジクロロ-6-ソジオオキシ-1,3,5-トリアジン、1,3,5-s-トリアジン、2,4-ジクロロ-1,3,5-トリアジンまたは2-アルキル-4,6-ジクロロ-1,3,5-トリアジンが用いられ、好ましくは2,4-ジクロロ-6-ソジオオキシ-1,3,5-トリアジンが用いられる。 Triazine derivatives that undergo a condensation reaction with perfluoroalkylene diol, etc. include 2,4-dichloro-6-sodiooxy-1,3,5-triazine, 1,3,5-s-triazine, and 2,4-dichloro-1. , 3,5-Triazine or 2-alkyl-4,6-dichloro-1,3,5-triazine is used, preferably 2,4-dichloro-6-sodiooxy-1,3,5-triazine. ..
含フッ素ジオールとトリアジン誘導体との反応に際しては、含フッ素ジオール100重量部に対して1.4〜60重量部のトリアジン誘導体が用いられる。モル比的には、一般に含フッ素ジオール 1モル(水酸基として2当量)に対し、約0.106〜5モル、好ましくは約1〜4.5モルのトリアジン誘導体が用いられる。 In the reaction between the fluorine-containing diol and the triazine derivative, 1.4 to 60 parts by weight of the triazine derivative is used with respect to 100 parts by weight of the fluorine-containing diol. In terms of molar ratio, a triazine derivative of about 0.106 to 5 mol, preferably about 1 to 4.5 mol, is generally used with respect to 1 mol of fluorine-containing diol (2 equivalents as a hydroxyl group).
反応は、含フッ素ジオールとそれを溶解し得る有機溶媒、例えばメタノールの溶液を約5〜10℃の温度で攪拌し、そこにトリアジン誘導体の約5〜10重量％水溶液と0.1M水酸化ナトリウム水溶液の混合水溶液を徐々に滴下し、約5〜10℃で約5〜6時間攪拌することにより行われる。水酸化ナトリウムに代えて、水酸化カルシウム等も用いられる。 In the reaction, a solution of fluorine-containing diol and an organic solvent capable of dissolving it, such as methanol, is stirred at a temperature of about 5 to 10 ° C., and an aqueous solution of about 5 to 10% by weight of a triazine derivative and a 0.1 M aqueous sodium hydroxide solution are added thereto. It is carried out by gradually dropping the mixed aqueous solution of the above and stirring at about 5 to 10 ° C. for about 5 to 6 hours. Instead of sodium hydroxide, calcium hydroxide or the like is also used.
生成物は、含フッ素ジオールとトリアジン誘導体との縮合反応生成物と考えられる含フッ素ジオール／トリアジン誘導体コンポジットであり、水性分散液として得られる。 The product is a fluorine-containing diol / triazine derivative composite considered to be a condensation reaction product of a fluorine-containing diol and a triazine derivative, and is obtained as an aqueous dispersion.
含フッ素ジオール／トリアジン誘導体コンポジットは、それ自体で撥水性、撥油性または撥水撥油性を示すが、それを水洗浄、水洗浄-メタノール洗浄することによって、撥油性の向上あるいは撥水性の経時的な低下の抑制に有効である。 The fluorine-containing diol / triazine derivative composite exhibits water repellency, oil repellency or water repellency by itself, but by washing it with water, water washing-methanol washing, the oil repellency is improved or the water repellency over time. It is effective in suppressing the decrease.
具体的には、基質としてガラスに適用した場合には、水洗浄による撥油性の向上、水洗浄-メタノール洗浄による撥水性の経時的な低下の抑制に有効であり、ろ紙に適用した場合には、水洗浄、水洗浄-メタノール洗浄による撥油性の向上に有効であり、またPET布の場合には撥水性の経時的な低下の抑制に有効である。 Specifically, when applied to glass as a substrate, it is effective in improving oil repellency by washing with water and suppressing a decrease in water repellency over time by washing with water-washing with methanol. When applied to filter paper, it is effective. , Water washing, water washing-Effective in improving oil repellency by washing with methanol, and in the case of PET cloth, it is effective in suppressing a decrease in water repellency over time.
各種無機質基質、有機質基質への含フッ素ジオール／トリアジン誘導体コンポジットの適用は、例えば固形分濃度(含フッ素ジオールおよびトリアジン誘導体の重量割合)約0.05〜50重量％のコンポジット水性分散液を基質にディッピング法、キャスティング法、スプレー法、コーティング法など一般的に用いられている適用方法によって適用し、室温条件下で乾燥させた後、約70〜80℃で約5〜7時間程度加熱することにより行われる。なお、コンポジット水性分散液の固形分濃度は、含フッ素ジオール／トリアジン誘導体コンポジットが溶媒に分散可能な範囲であれば特に限定されない。 The application of the fluorine-containing diol / triazine derivative composite to various inorganic substrates and organic substrates is, for example, a dipping method using a composite aqueous dispersion having a solid content concentration (weight ratio of fluorine-containing diol and triazine derivative) of about 0.05 to 50% by weight as a substrate. It is applied by a commonly used application method such as a casting method, a spray method, and a coating method, dried under room temperature conditions, and then heated at about 70 to 80 ° C. for about 5 to 7 hours. .. The solid content concentration of the aqueous composite dispersion is not particularly limited as long as the fluorine-containing diol / triazine derivative composite can be dispersed in the solvent.
本発明の含フッ素ジオール／トリアジン誘導体コンポジットは、特に水性分散液の形で、撥水剤、撥油剤、撥水撥油剤、離型剤、防汚剤等の各種基材への表面処理剤として有効に用いられる。 The fluorine-containing diol / triazine derivative composite of the present invention, particularly in the form of an aqueous dispersion, can be used as a surface treatment agent for various substrates such as water repellents, oil repellents, water repellent oil repellents, mold release agents, and antifouling agents. It is used effectively.
次に、実施例について本発明を説明する。 Next, the present invention will be described with respect to Examples.
実施例１
容量30mlの反応容器に、
HOCH2CF(CF3)[OCF2CF(CF3)]bOCF2CF2O[CF(CF3)CF2O]dCF(CF3)CH2OH
［OXF8PO-OH(b+d=6)］
21mgおよびメタノール5mlを仕込み、5〜10℃で攪拌を開始した。その後、2,4-ジクロロ-6-ソジオオキシ-1,3,5-トリアジン(トリアジン誘導体)0.3mg(OXF8PO-OH 100重量部に対して1.4重量部、モル比0.106)の10重量％水溶液および0.1M水酸化ナトリウム水溶液5mlの混合水溶液を徐々に滴下させて加え、5〜10℃で5時間攪拌することにより、目的とする含フッ素ジオール／トリアジン誘導体コンポジット水性分散液を得た。
Example 1
In a reaction vessel with a capacity of 30 ml
HOCH 2 CF (CF 3 ) [OCF 2 CF (CF 3 )] b OCF 2 CF 2 O [CF (CF 3 ) CF 2 O] d CF (CF 3 ) CH 2 OH
[OXF8PO-OH (b + d = 6)]
21 mg and 5 ml of methanol were charged, and stirring was started at 5 to 10 ° C. Then, a 10 wt% aqueous solution of 2,4-dichloro-6-sodiooxy-1,3,5-triazine (triazine derivative) 0.3 mg (1.4 parts by weight with respect to 100 parts by weight of OXF8PO-OH, molar ratio 0.106) and 0.1. A mixed aqueous solution of 5 ml of M sodium hydroxide aqueous solution was gradually added dropwise, and the mixture was stirred at 5 to 10 ° C. for 5 hours to obtain the desired fluorine-containing diol / triazine derivative composite aqueous dispersion.
得られたコンポジット水性分散液(固形分濃度0.24重量％)について、液滴の接触角の測定を行った。
液滴の接触角（単位：°）の測定：
コンポジット分散液に、カバーガラス(松浪ガラス工業製品硼ケイ酸ガラス；18×18mm)、ろ紙(アドバンテック社製品定性濾紙No.131)またはPET布(ユニチカ製品ポリエステルトロピカル13001)をそれぞれ1分間ディッピングし、室温条件下で乾燥させた後、75℃のホットプレート上で6時間加熱した。得られた表面改質基材に、必要に応じて水洗浄または水洗浄-メタノール洗浄を行った後、n-ドデカンまたは水の液滴4μｌを静かに接触させ、付着した液滴の接触角をθ/2法により、接触角計(協和界面化学製Drop Master 300)を用いて測定した。なお、水については、経時的な測定が行われた。
The contact angle of the droplets was measured for the obtained composite aqueous dispersion (solid content concentration 0.24% by weight).
Measurement of droplet contact angle (unit: °):
Dip the cover glass (Matsunami Glass Industry product borosilicate glass; 18 x 18 mm), filter paper (Advantech product qualitative filter paper No. 131) or PET cloth (Unitika product polyester tropical 13001) for 1 minute each into the composite dispersion. After drying under room temperature conditions, it was heated on a hot plate at 75 ° C. for 6 hours. The obtained surface-modified substrate is washed with water or water-methanol as necessary, and then 4 μl of n-dodecane or water droplets are gently contacted to adjust the contact angle of the adhered droplets. The water was measured by the θ / 2 method using a contact angle meter (Drop Master 300 manufactured by Kyowa Surface Chemical Co., Ltd.). Water was measured over time.
実施例２〜４
実施例１において、トリアジン誘導体量が6mg、9mgまたは12mg(OXF8PO-OH 100重量部に対して29重量部、43重量部または57重量部、モル比2.16、3.20または4.24)に変更されて用いられた。得られたコンポジット分散液の固形分濃度は、それぞれ0.24、0.24、0.25重量％であった。
Examples 2-4
In Example 1, the amount of triazine derivative was changed to 6 mg, 9 mg or 12 mg (29 parts by weight, 43 parts by weight or 57 parts by weight, molar ratio 2.16, 3.20 or 4.24 with respect to 100 parts by weight of OXF8PO-OH). rice field. The solid content concentrations of the obtained composite dispersion were 0.24, 0.24, and 0.25% by weight, respectively.
比較例１〜３
カバーガラス、ろ紙またはPET布について、実施例１と同様にして接触角の測定が行われた。
Comparative Examples 1 to 3
For the cover glass, filter paper or PET cloth, the contact angle was measured in the same manner as in Example 1.
得られた結果は、次の表に示される。
表
接触角(°)
水
基材 例 洗浄方法 C 12 H 26 ０分 ５分 10分 15分 20分 25分 30分
ガラス 実１ なし 55 83 45 38 24 13 0 0
水 59 83 75 74 74 72 72 72
水-MeOH 53 75 71 68 66 64 62 59
実２ なし 60 75 71 71 69 68 65 60
水 62 86 78 76 75 73 71 69
水-MeOH 53 85 82 81 79 77 75 72
実３ なし 56 73 60 58 55 53 48 44
水 52 86 80 77 74 73 71 69
水-MeOH 55 91 76 76 72 71 71 68
実４ なし 53 65 63 61 61 61 59 54
水 56 87 79 76 75 74 72 67
水-MeOH 51 84 80 78 76 74 72 70
ろ紙 実１ なし 83 0 0 0 0 0 0 0
水 87 0 0 0 0 0 0 0
水-MeOH 88 0 0 0 0 0 0 0
実２ なし 89 0 0 0 0 0 0 0
水 91 0 0 0 0 0 0 0
水-MeOH 73 0 0 0 0 0 0 0
実３ なし 90 0 0 0 0 0 0 0
水 81 0 0 0 0 0 0 0
水-MeOH 69 0 0 0 0 0 0 0
実４ なし 57 0 0 0 0 0 0 0
水 94 0 0 0 0 0 0 0
水-MeOH 84 0 0 0 0 0 0 0
PET布 実１ なし 0 120 103 76 0 0 0 0
水 0 107 101 101 98 98 96 95
水-MeOH 0 116 109 104 104 102 100 93
実２ なし 0 125 0 0 0 0 0 0
水 0 108 103 101 101 98 95 91
水-MeOH 0 106 103 102 99 96 92 92
実３ なし 0 123 78 0 0 0 0 0
水 0 114 111 105 104 104 102 102
水-MeOH 0 115 112 111 111 105 105 103
実４ なし 0 122 120 107 104 96 88 74
水 0 112 104 102 101 99 98 96
水-MeOH 0 93 92 90 83 83 78 77
ガラス 比１ 水 0 54 42 35 24 20 20 20
ろ紙 比２ 水 0 0 0 0 0 0 0 0
PET布 比３ 水 0 113 0 0 0 0 0 0
The results obtained are shown in the following table.
table
Contact angle (°)
water
Substrate example Cleaning method C 12 H 26 0 minutes 5 minutes 10 minutes 15 minutes 20 minutes 25 minutes 30 minutes <br /> No glass fruit 1 55 83 45 38 24 13 0 0
Water 59 83 75 74 74 72 72 72
Water-MeOH 53 75 71 68 66 64 62 59
Real 2 None 60 75 71 71 69 68 65 60
Water 62 86 78 76 75 73 71 69
Water-MeOH 53 85 82 81 79 77 75 72
Real 3 None 56 73 60 58 55 53 48 44
Water 52 86 80 77 74 73 71 69
Water-MeOH 55 91 76 76 72 71 71 68
Real 4 None 53 65 63 61 61 61 59 54
Water 56 87 79 76 75 74 72 67
Water-MeOH 51 84 80 78 76 74 72 70
Filter paper 1 None 83 0 0 0 0 0 0 0
Water 87 0 0 0 0 0 0 0
Water-MeOH 88 0 0 0 0 0 0 0
Real 2 None 89 0 0 0 0 0 0 0
Water 91 0 0 0 0 0 0 0
Water-MeOH 73 0 0 0 0 0 0 0
Real 3 None 90 0 0 0 0 0 0 0
Water 81 0 0 0 0 0 0 0
Water-MeOH 69 0 0 0 0 0 0 0
Real 4 None 57 0 0 0 0 0 0 0
Water 94 0 0 0 0 0 0 0
Water-MeOH 84 0 0 0 0 0 0 0
PET cloth 1 None 0 120 103 76 0 0 0 0
Water 0 107 101 101 98 98 96 95
Water-MeOH 0 116 109 104 104 102 100 93
Real 2 None 0 125 0 0 0 0 0 0
Water 0 108 103 101 101 98 95 91
Water-MeOH 0 106 103 102 99 96 92 92
Real 3 None 0 123 78 0 0 0 0 0
Water 0 114 111 105 104 104 102 102
Water-MeOH 0 115 112 111 111 105 105 103
Real 4 None 0 122 120 107 104 96 88 74
Water 0 112 104 102 101 99 98 96
Water-MeOH 0 93 92 90 83 83 78 77
Glass ratio 1 water 0 54 42 35 24 20 20 20
Filter paper ratio 2 Water 0 0 0 0 0 0 0 0
PET cloth ratio 3 water 0 113 0 0 0 0 0 0
Claims (3)
HO(CH 2 ) a CF(CF 3 )〔OCF 2 CF(CF 3 )〕 b O(CF 2 ) c O〔CF(CF 3 )CF 2 O〕 d CF(CF 3 )(CH 2 ) a OH 〔I〕
(ここで、aは1〜6であり、cは1〜6であり、b+dは0〜50の整数である)で表される含フッ素ジオールおよび2,4-ジクロロ-6-ソジオオキシ-1,3,5-トリアジン、1,3,5-s-トリアジン、2,4-ジクロロ-1,3,5-トリアジンまたは2-アルキル-4,6-ジクロロ-1,3,5-トリアジンであるトリアジン誘導体の縮合反応生成物からなる含フッ素ジオール／トリアジン誘導体コンポジット。 General formula
HO (CH 2 ) a CF (CF 3 ) [OCF 2 CF (CF 3 )] b O (CF 2 ) c O [CF (CF 3 ) CF 2 O] d CF (CF 3 ) (CH 2 ) a OH [I]
(Here, a is 1 to 6, c is 1 to 6, b + d is an integer of 0 to 50), and the fluorine-containing diol and 2,4-dichloro-6-sodiooxy- With 1,3,5-triazine, 1,3,5-s-triazine, 2,4-dichloro-1,3,5-triazine or 2-alkyl-4,6-dichloro-1,3,5-triazine A fluorine-containing diol / triazine derivative composite consisting of a condensation reaction product of a triazine derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017039456A JP6917024B2 (en) | 2017-03-02 | 2017-03-02 | Fluorine-containing diol / triazine derivative composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017039456A JP6917024B2 (en) | 2017-03-02 | 2017-03-02 | Fluorine-containing diol / triazine derivative composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018145250A JP2018145250A (en) | 2018-09-20 |
| JP6917024B2 true JP6917024B2 (en) | 2021-08-11 |
Family
ID=63589424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017039456A Active JP6917024B2 (en) | 2017-03-02 | 2017-03-02 | Fluorine-containing diol / triazine derivative composite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6917024B2 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1007029B (en) * | 1974-01-23 | 1976-10-30 | Montedison Spa | FLUORINATED ELASTOMERIC POLYMERS CONTAINING THE RING OF 1.3.5 TRIAZINE AND PROCEDURE FOR THE PREPARATION |
| IT1308639B1 (en) * | 1999-03-03 | 2002-01-09 | Ausimont Spa | FLUORINATED TRIAZINIC COMPOUNDS. |
| EP2646491B1 (en) * | 2010-12-03 | 2016-01-27 | Solvay Specialty Polymers Italy S.p.A. | Triazine derivative |
| US9017834B2 (en) * | 2012-10-05 | 2015-04-28 | Seagate Technology Llc | Lubricants for data storage |
| JP6204132B2 (en) * | 2013-09-24 | 2017-09-27 | リンテック株式会社 | Release sheet and adhesive sheet |
-
2017
- 2017-03-02 JP JP2017039456A patent/JP6917024B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| JP2018145250A (en) | 2018-09-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1844116B1 (en) | Compositions of monomeric fluoro-surfactants | |
| TWI558678B (en) | Oleophobic coatings | |
| TWI723964B (en) | Water and oil repellent coating composition and transparent film | |
| EP1831234A1 (en) | Compositions containing c4-swallow tail silanes | |
| KR20060135791A (en) | Perfluoropolyether benzotriazole derivatives and use thereof as coatings | |
| CN111511802B (en) | Fluorine-containing ether compound, fluorine-containing ether composition, coating liquid, article, and method for producing same | |
| EP3368617A1 (en) | Solvent-based repellent coating compositions and coated substrates | |
| CN109071935B (en) | Composition comprising a metal oxide and a metal oxide | |
| KR102365803B1 (en) | Fluorine-containing polymers | |
| KR20110081845A (en) | Silanes blend | |
| CN114957646B (en) | Perfluoro polyether amino compound and preparation method and application thereof | |
| WO2016076274A1 (en) | Transparent film | |
| JPS58172244A (en) | Surface treating agent for glass | |
| JPS58172243A (en) | Treating agent for glass surface | |
| JPS58142958A (en) | Water and oil repellent for glass surface | |
| JP6917024B2 (en) | Fluorine-containing diol / triazine derivative composite | |
| CN115210295B (en) | Fluorine-containing alcohol complex | |
| JP2019073727A (en) | Non-aqueous crosslinkable composition, method of producing the same, and coatings and articles comprising the same | |
| JP7325730B2 (en) | Fluoroether alcohol/triazine derivative/polyalkylene glycol composite | |
| JP5955468B2 (en) | Fluorine-containing boric acid composite particles | |
| JP6573278B2 (en) | Fluorinated cellulose ether composite | |
| JP7165017B2 (en) | Perfluoroether-containing compound and nonionic fluorine-containing surfactant | |
| JP6917023B2 (en) | Hydrophilic oil repellent composite | |
| US20070031678A1 (en) | Use of fluorinated compounds for the protective treatment of titanium surfaces | |
| CN106062128B (en) | The particle of composition capsule containing fluoboric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200130 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210108 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210202 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210305 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210629 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210708 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6917024 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |