JP2020105417A - Ptfe aqueous dispersion, and dust inhibiting agent composition made of the aqueous dispersion - Google Patents
Ptfe aqueous dispersion, and dust inhibiting agent composition made of the aqueous dispersion Download PDFInfo
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- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 120
- 239000006185 dispersion Substances 0.000 title claims abstract description 87
- 239000000428 dust Substances 0.000 title claims abstract description 77
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 230000002401 inhibitory effect Effects 0.000 title abstract 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 119
- 239000002253 acid Substances 0.000 claims abstract description 38
- 239000000126 substance Substances 0.000 claims abstract description 32
- 238000010494 dissociation reaction Methods 0.000 claims abstract description 14
- 230000005593 dissociations Effects 0.000 claims abstract description 14
- 150000007513 acids Chemical class 0.000 claims abstract description 5
- 230000001629 suppression Effects 0.000 claims description 27
- 239000003995 emulsifying agent Substances 0.000 claims description 25
- -1 polytetrafluoroethylene Polymers 0.000 claims description 22
- 238000010410 dusting Methods 0.000 claims description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 239000001384 succinic acid Substances 0.000 claims description 3
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical group FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 9
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 40
- 239000000292 calcium oxide Substances 0.000 description 20
- 235000012255 calcium oxide Nutrition 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- 239000007787 solid Substances 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 14
- 239000011737 fluorine Substances 0.000 description 14
- 229910052731 fluorine Inorganic materials 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 239000000920 calcium hydroxide Substances 0.000 description 10
- 235000011116 calcium hydroxide Nutrition 0.000 description 10
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- 239000003945 anionic surfactant Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 238000010556 emulsion polymerization method Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920001519 homopolymer Polymers 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000006703 hydration reaction Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000239290 Araneae Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical class OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- OVYQSRKFHNKIBM-UHFFFAOYSA-N butanedioic acid Chemical compound OC(=O)CCC(O)=O.OC(=O)CCC(O)=O OVYQSRKFHNKIBM-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- ZWBAMYVPMDSJGQ-UHFFFAOYSA-N perfluoroheptanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F ZWBAMYVPMDSJGQ-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012255 powdered metal Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003583 soil stabilizing agent Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、防塵効果が高く、分散安定性及び再分散性に優れたポリテトラフルオロエチレン（以下ＰＴＦＥという）の水性分散液に関し、より詳細には、分散安定剤として水中の酸解離定数（ｐＫａ）が１〜６である酸を含むＰＴＦＥ水性分散液からなる塵埃抑制処理剤組成物に関する。 TECHNICAL FIELD The present invention relates to an aqueous dispersion of polytetrafluoroethylene (hereinafter referred to as PTFE) having a high dustproof effect and excellent dispersion stability and redispersibility, and more specifically, an acid dissociation constant (pKa) in water as a dispersion stabilizer. The present invention relates to a dust suppressing treatment agent composition comprising a PTFE aqueous dispersion liquid containing an acid having 1 to 6).
塵埃を出す物質の塵埃を抑制する技術は、健康上、安全上、環境上その他の要請から、生活のためにまた産業のために重要な技術である。
このような塵埃抑制技術としては、下記特許文献１において、ＰＴＦＥを粉末状物質と混合し、該混合物に約２０〜２００℃の温度で圧縮−剪断作用を施すことによりＰＴＦＥをフィブリル化して粉末状物質の塵埃発生を抑制する方法が提案されている。
A technique for suppressing dust of a substance that emits dust is an important technique for life and industry because of health, safety, environmental and other requirements.
As such a dust control technique, in Patent Document 1 below, PTFE is mixed with a powdered substance, and the mixture is subjected to compression-shearing at a temperature of about 20 to 200° C. to fibrillate the PTFE to form a powdery form. A method for suppressing dust generation of a substance has been proposed.
同提案に記載されているＰＴＦＥは、組成としてはテトラフルオロエチレンのホモポリマーで形態としてはファインパウダー又はエマルジョンであるテフロン（登録商標）６又はテフロン（登録商標）３０、並びに組成としてはテトラフルオロエチレンの変性ポリマーで形態としては同じくファインンパウダーであるテフロン（登録商標）６Ｃなどである。 The PTFE described in the proposal is Teflon (registered trademark) 6 or Teflon (registered trademark) 30 which is a homopolymer of tetrafluoroethylene as a composition and is a fine powder or emulsion as a form, and tetrafluoroethylene as a composition. The modified polymer of Teflon (registered trademark) 6C, which is also a fine powder, is used as the form.
また、下記特許文献２には、ＰＴＦＥに対して１．０質量％以上の炭化水素系アニオン界面活性剤を含有する水性エマルジョンを使用する安定性のよい塵埃抑制方法が提案されており、粉末状物質について塵埃抑制効果があることが示されている。同公報によれば、ＰＴＦＥの粒子は、下記特許文献３に開示されている乳化重合法、即ちテトラフルオロエチレンを水溶性重合開始剤及びフルオロアルキル基を疎水基とするアニオン系界面活性剤（以下、含フッ素乳化剤という）を乳化剤として含む水性媒体中に圧入、重合させることにより、水性エマルジョンの形態で製造されるが、安定性を増すためにさらに乳化安定剤が添加されている。 Further, Patent Document 2 below proposes a stable dust control method using an aqueous emulsion containing 1.0% by mass or more of a hydrocarbon-based anionic surfactant with respect to PTFE, which is powdery. It has been shown that substances have a dust control effect. According to the publication, the particles of PTFE are produced by an emulsion polymerization method disclosed in Patent Document 3 below, that is, a water-soluble polymerization initiator of tetrafluoroethylene and an anionic surfactant having a fluoroalkyl group as a hydrophobic group (hereinafter , A fluorine-containing emulsifier) as an emulsifier, and then polymerized in the form of an aqueous emulsion by press-fitting and polymerizing, but an emulsion stabilizer is further added to increase stability.
更に、下記特許文献４には、含フッ素乳化剤の含有率が５０ｐｐｍ以下である含フッ素重合体水性分散液からなる塵埃抑制処理剤組成物を用いることにより、塵埃抑制効果があって、環境への影響を懸念することなく塵埃を抑制できる方法が記載されている。 Furthermore, in Patent Document 4 below, by using a dust suppressing treatment agent composition comprising a fluoropolymer aqueous dispersion having a content of a fluorine-containing emulsifier of 50 ppm or less, there is a dust suppressing effect, and environmental protection is achieved. A method that can suppress dust without concern about the influence is described.
しかしながら、これらの方法に塵埃抑制処理剤組成物として用いられるＰＴＦＥは高分子量であり、その水性分散液は長期間静置された場合には沈降し易く、一度沈降したＰＴＦＥは強固に固まり再分散し難いという問題が有り、ＰＴＦＥ水性分散液中のＰＴＦＥ濃度の低下を引き起こすなど、使用条件によっては本来ＰＴＦＥが備えている塵埃抑制効果を十分に発揮できなくなるおそれがあった。
そこで本発明者らは、分散安定性及び再分散性に優れ、塵埃抑制効果が有り且つ環境への影響を懸念することなく塵埃を抑制できる方法の開発に鋭意注力した結果、本発明に到達したものである。
However, PTFE used as a dust control treatment composition in these methods has a high molecular weight, and its aqueous dispersion easily settles when left standing for a long time, and once settled PTFE solidifies and redisperses firmly. There is a problem in that it is difficult to do, and there is a possibility that the dust suppressing effect originally possessed by PTFE may not be sufficiently exhibited depending on the use conditions, such as a decrease in the PTFE concentration in the PTFE aqueous dispersion.
Therefore, the present inventors have achieved the present invention as a result of diligently focusing on the development of a method that is excellent in dispersion stability and redispersibility, has a dust suppressing effect, and can suppress dust without concern about the influence on the environment. It is a thing.
本発明者らは、ＰＴＦＥ水性分散液中の高分子量ＰＴＦＥが、長期間静置された場合には沈降し易く、一度沈降したＰＴＦＥは強固に固まり再分散し難いという問題に着目して、分散安定性及び再分散性に優れたＰＴＦＥ水性分散液の開発を進めた。
すなわち、本発明は、分散安定性及び再分散性に優れ且つ環境問題の可能性が低いＰＴＦＥ水性分散液、及び該ＰＴＦＥ水性分散液を用いた塵埃抑制処理剤組成物を提供することを目的とする。
The present inventors focused on the problem that the high-molecular-weight PTFE in the aqueous PTFE dispersion is likely to settle when left standing for a long period of time, and the once settled PTFE is firmly solidified and difficult to re-disperse. We proceeded with the development of an aqueous PTFE dispersion having excellent stability and redispersibility.
That is, an object of the present invention is to provide a PTFE aqueous dispersion having excellent dispersion stability and redispersibility and a low possibility of environmental problems, and a dust suppressing treatment agent composition using the PTFE aqueous dispersion. To do.
本発明は、水中の酸解離定数（ｐＫａ）が１〜６である酸から選択される少なくとも１種を含有するＰＴＦＥ水性分散液を提供する。 The present invention provides an aqueous PTFE dispersion containing at least one selected from acids having an acid dissociation constant (pKa) of 1 to 6 in water.
本発明のＰＴＦＥ水性分散液においては、
１．前記酸が、ＨＯ２Ｃ−（ＣＨ２）ｎ−ＣＯ２Ｈ（ｎ＝０〜４）で示されるジカルボン酸から選択される少なくとも１種或いはそれらの混合物であること、
２．前記酸が、アルキルジカルボン酸であること、
３．前記酸が、コハク酸であること、
４．前記酸をＰＴＦＥに対し０．５〜２．０質量％含んでいること、
５．ｐＨが５〜８であること、
６．含フッ素乳化剤の含有率が５０ｐｐｍ以下であること、
が好適な態様である。
In the PTFE aqueous dispersion of the present invention,
1. The acid is at least one selected from dicarboxylic acids represented by HO 2 C-(CH 2 )n-CO 2 H (n=0 to 4) or a mixture thereof.
2. The acid is an alkyldicarboxylic acid,
3. The acid is succinic acid,
4. Containing 0.5 to 2.0 mass% of the acid with respect to PTFE,
5. pH is 5-8,
6. The content of the fluorinated emulsifier is 50 ppm or less,
Is the preferred embodiment.
本発明はまた、前記ＰＴＦＥの水性分散液を用いた発塵性物質の塵埃抑制処理剤組成物を提供する。
本発明の塵埃抑制処理剤組成物は、前記発塵性物質として、発塵性粉末状物質に好適に使用することができる。
The present invention also provides a dust suppressing treatment agent composition of a dusting substance using the aqueous PTFE dispersion.
The dust suppression treatment agent composition of the present invention can be suitably used as a dusting powdery substance as the dusting substance.
本発明により、分散安定性及び再分散性に優れ且つ環境問題の可能性が低いＰＴＦＥ水性分散液、及び発塵が抑制され、かつ環境問題の可能性が低い発塵性物質の塵埃抑制処理剤組成物が提供される。 According to the present invention, a PTFE aqueous dispersion having excellent dispersion stability and redispersibility and having a low possibility of environmental problems, and a dust suppressing treatment agent of a dusting substance that suppresses dust generation and has a low possibility of environmental problems A composition is provided.
本発明は、酸解離定数（ｐＫａ）が１〜６である酸から選択される少なくとも１種を含有するＰＴＦＥの水性分散液、及びこのＰＴＦの水性分散液からなる塵埃抑制処理剤組成物を提供するものであり、この塵埃抑制処理剤組成物を発塵性物質と混合し、該混合物に約２０〜２００℃の温度で圧縮−剪断作用を施すことにより、ＰＴＦＥをフィブリル化して発塵性物質の塵埃を抑制することが可能である。 The present invention provides an aqueous dispersion of PTFE containing at least one selected from acids having an acid dissociation constant (pKa) of 1 to 6, and a dust suppressing agent composition comprising the aqueous dispersion of PTF. This dust suppression treatment agent composition is mixed with a dust-generating substance, and the mixture is subjected to compression-shearing at a temperature of about 20 to 200° C. to fibrillate PTFE to generate a dust-generating substance. It is possible to suppress the dust.
本発明のＰＴＦＥ水性分散液におけるＰＴＦＥとしては、ホモポリマーと呼ばれるテトラフルオロエチレンの単独重合体（ＰＴＦＥ）と、変性ポリマーと呼ばれる１％以下のコモノマーを含むテトラフルオロエチレンの共重合体（変性ＰＴＦＥ）が挙げられる。ＰＴＦＥはＴＦＥのホモポリマーであることが好ましい。
変性ＰＴＦＥ水性分散液からなる塵埃抑制処理剤組成物は、ＰＴＦＥ水性分散液からなる塵埃抑制処理剤組成物に比べ塵埃抑制効果が低く、同じ塵埃抑制効果を出すためにしばしば５０％以上多い量の処理剤を使用しなければならないことがある。
Examples of PTFE in the PTFE aqueous dispersion of the present invention include a homopolymer of tetrafluoroethylene called a homopolymer (PTFE) and a copolymer of tetrafluoroethylene containing 1% or less of a comonomer called a modified polymer (modified PTFE). Are listed. PTFE is preferably a homopolymer of TFE.
The dust suppression treatment agent composition composed of the modified PTFE aqueous dispersion has a lower dust suppression effect than the dust suppression treatment agent composition composed of the PTFE aqueous dispersion, and is often in an amount of 50% or more in order to exhibit the same dust suppression effect. Treatment agents may have to be used.
本発明のＰＴＦＥ水性分散液中のＰＴＦＥは、平均粒径０．１〜０．５μｍ程度、好ましくは０．１〜０．３μｍ程度のコロイド粒子であることが望ましい。平均粒径が０．１μｍ未満のコロイド粒子は防塵効果が低く、一方平均粒径が０．５μｍを越えるコロイド粒子の水性分散液は安定性が低いという欠点がある。
また、比重は２．２７以下、好ましくは２．２２以下、より好ましくは２．２０以下であることが望ましい。比重が２．２７を越えるＰＴＦＥも防塵効果が低いという欠点がある。
The PTFE in the aqueous PTFE dispersion of the present invention is preferably colloidal particles having an average particle size of about 0.1 to 0.5 μm, preferably about 0.1 to 0.3 μm. Colloidal particles having an average particle size of less than 0.1 μm have a low dustproof effect, while colloidal particles having an average particle size of more than 0.5 μm have a drawback of low stability.
Further, it is desirable that the specific gravity is 2.27 or less, preferably 2.22 or less, and more preferably 2.20 or less. PTFE having a specific gravity of more than 2.27 also has a drawback that the dustproof effect is low.
本発明のＰＴＦＥ水性分散液中のＰＴＦＥ濃度は特に限定されないが、塵埃発生物質へのＰＴＦＥの分散効果を高めるためには、その濃度が低いほど好ましい。一方、ＰＴＦＥ水性分散液を輸送する際にはその濃度が高いほど輸送コストを節約できるため、通常１０質量％以上、好ましくは２０〜７０質量％の範囲であることが望ましい。更に高い濃度はＰＴＦＥ水性分散液の安定性を損ねるため好ましくない。従って、製品として販売される塵埃抑制処理剤組成物中のＰＴＦＥ濃度は、２０〜７０質量％であり、塵埃発生物質へ混合するときはそれを水で希釈して５質量％以下のＰＴＦＥ濃度として使用することも可能である。 The concentration of PTFE in the aqueous PTFE dispersion of the present invention is not particularly limited, but in order to enhance the effect of dispersing PTFE in the dust generating substance, the lower the concentration, the better. On the other hand, when the PTFE aqueous dispersion is transported, the higher the concentration thereof, the more the transportation cost can be saved. Higher concentrations are not preferable because they impair the stability of the PTFE aqueous dispersion. Therefore, the concentration of PTFE in the dust suppression treatment agent composition sold as a product is 20 to 70% by mass, and when mixed with the dust generating substance, it is diluted with water to obtain a PTFE concentration of 5% by mass or less. It is also possible to use.
本発明の酸は、酸解離定数（ｐＫａ）が１〜６、好ましくは２〜６、より好ましくは４〜６である酸から選択される少なくとも１種であることが望ましい。
酸解離定数（ｐＫａ）は、水溶液中での解離し易さ（水素イオンの放出し易さ）を示し、酸解離定数が大きいほど弱酸（弱酸性）であることを示している。
この様な酸は、ＰＴＦＥ水性分散液中のＰＴＦＥの分散性及び再分散性を向上させることが可能となる。従って、酸解離定数が１未満の場合にはＰＴＦＥの凝集を引き起こしやすくなるため好ましくなく、酸解離定数が６を超える場合には分散安定効果が低くなるため好ましくない。
The acid of the present invention is preferably at least one selected from the acids having an acid dissociation constant (pKa) of 1 to 6, preferably 2 to 6, and more preferably 4 to 6.
The acid dissociation constant (pKa) indicates the ease of dissociation in an aqueous solution (ease of release of hydrogen ions), and the larger the acid dissociation constant, the weaker the acid (weakly acidic).
Such an acid can improve the dispersibility and redispersibility of PTFE in the PTFE aqueous dispersion. Therefore, when the acid dissociation constant is less than 1, it tends to cause aggregation of PTFE, which is not preferable, and when the acid dissociation constant exceeds 6, the dispersion stabilizing effect becomes unfavorable.
この様な酸としては、ＨＯ２Ｃ−（ＣＨ２）ｎ−ＣＯ２Ｈ（ｎ＝０〜４）で示されるジカルボン酸である、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸から選択される少なくとも一種或いはそれらの混合物を好適に使用できる。より好ましくはアルキルジカルボン酸であり、より好ましくはエチレンジカルボン酸（コハク酸）が挙げられる。ジカルボン酸の場合、酸解離定数（ｐＫａ）として２つの値が得られるが、本発明においてはこれら２つの値の何れも１〜６、好ましくは２〜６、より好ましくは４〜６の範囲であることが望ましい。
この様な酸の添加量は、ＰＴＦＥの質量あたり０．５質量％以上であり、好ましくは０．５〜２．０質量％、より好ましくは１．０〜２．０質量％の範囲である。添加量が０．５質量％未満の場合にはＰＴＦＥ水性分散液の分散安定効果が低く、また２質量％を超える場合にはＰＴＦＥの凝集を引き起こすため好ましくない。
Examples of such an acid include carboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid, which are dicarboxylic acids represented by HO 2 C-(CH 2 )n-CO 2 H (n=0 to 4). At least one selected from the above or a mixture thereof can be preferably used. Alkyldicarboxylic acid is more preferable, and ethylenedicarboxylic acid (succinic acid) is more preferable. In the case of dicarboxylic acid, two values are obtained as the acid dissociation constant (pKa), but in the present invention, both of these two values are in the range of 1 to 6, preferably 2 to 6, and more preferably 4 to 6. Is desirable.
The amount of such an acid added is 0.5% by mass or more based on the mass of PTFE, preferably 0.5 to 2.0% by mass, and more preferably 1.0 to 2.0% by mass. .. If the added amount is less than 0.5% by mass, the dispersion stabilizing effect of the PTFE aqueous dispersion is low, and if it exceeds 2% by mass, PTFE agglomeration is caused, which is not preferable.
本発明の塵埃抑制処理剤組成物のｐＨは５〜８、好ましくは５〜７であることが望ましい。従来の塵埃抑制処理剤組成物のｐＨは、そのｐＨは９〜１０のアルカリ性を示すが、ｐＨが９〜１０の場合、分散安定性が低いため好ましくない。また、ｐＨが１〜４の酸性の場合はＰＴＦＥが凝集を引き起こし易くなるため好ましくない。 It is desirable that the dust suppression treatment agent composition of the present invention has a pH of 5 to 8, preferably 5 to 7. Regarding the pH of the conventional dust suppression treatment agent composition, the pH shows an alkalinity of 9 to 10. However, when the pH is 9 to 10, the dispersion stability is low, which is not preferable. Further, when the pH is acidic from 1 to 4, PTFE tends to cause aggregation, which is not preferable.
本発明のＰＴＦＥ水性分散液に含まれる含フッ素乳化剤は、難分解性であり環境への蓄積が懸念されるので含有率は低い事が望まれ、実用的な除去方法で含フッ素乳化剤の安定した含有率での製造が可能な５０ｐｐｍ以下であることが好ましい。 The fluorine-containing emulsifier contained in the PTFE aqueous dispersion of the present invention is difficult to decompose and may be accumulated in the environment. Therefore, it is desirable that the content is low, and the fluorine-containing emulsifier is stabilized by a practical removal method. The content is preferably 50 ppm or less, which enables production at a content rate.
含フッ素乳化剤の含有率が５０ｐｐｍ以下であるＰＴＦＥ水性分散を得る方法には特に制限がないが、例えば前述した特許文献３に開示されているような乳化重合法、即ちテトラフルオロエチレンを水溶性重合開始剤及び乳化剤としてフルオロアルキル基を疎水基とするアニオン系界面活性剤（含フッ素乳化剤）を含む水性媒体中に圧入、重合して得られる、含フッ素乳化剤（アンモニウム塩及び／又はアルカリ塩の形のパーフルオロオクタン酸）を含フッ素重合体の重量に対し約０．０２〜１質量％含む水性分散液から、含フッ素乳化剤を公知の除去方法、例えば特表２００５−５０１９５６号（ＷＯ２００３／０２０８３６）及び特表２００２−５３２５８３号（ＷＯ００／３５９７１）に記載される有効量の陰イオン交換体と接触させ分離して除去する方法、或いは米国特許第４，３６９，２２６号に記載される含フッ素重合体水性分散液の限外ろ過により除去する方法、にて除去することにより得ることができる。含フッ素乳化剤の除去方法はこれらに限定されるものではない。 There is no particular limitation on the method for obtaining the PTFE aqueous dispersion having a content of the fluorinated emulsifier of 50 ppm or less, but for example, the emulsion polymerization method as disclosed in Patent Document 3 described above, that is, tetrafluoroethylene is water-soluble polymerized. Fluorine-containing emulsifier (in the form of ammonium salt and/or alkali salt) obtained by press-fitting and polymerizing in an aqueous medium containing an anionic surfactant (fluorine-containing emulsifier) having a fluoroalkyl group as a hydrophobic group as an initiator and an emulsifier. Perfluorooctanoic acid) of about 0.02 to 1% by mass based on the weight of the fluoropolymer, a known method for removing the fluorinated emulsifier, for example, Japanese Patent Publication No. 2005-501956 (WO2003/020836). And a method of separating by contacting with an effective amount of anion exchanger described in JP-A-2002-532583 (WO00/35971), or a fluorine-containing polymer described in US Pat. No. 4,369,226. It can be obtained by removing the combined aqueous dispersion by ultrafiltration. The method for removing the fluorinated emulsifier is not limited to these.
ＰＴＦＥ水性分散液に乳化剤として含まれる界面活性剤（含フッ素乳化剤）は、重合における反応不活性の故に不可欠のものではあるが難分解性で環境への影響が懸念されるため、塵埃抑制処理剤組成物から出来るだけ除去されることが望ましい。また、含フッ素乳化剤は高価であるため回収され再利用されることが望ましい。 The surfactant (fluorine-containing emulsifier) contained in the PTFE aqueous dispersion as an emulsifier is indispensable because it is inactive in the reaction in the polymerization, but it is difficult to decompose and may affect the environment. It is desirable to remove as much as possible from the composition. Further, since the fluorine-containing emulsifier is expensive, it is desirable to collect and reuse it.
前記した本発明のＰＴＦＥ水性分散液を得る乳化重合法において、乳化剤としては前述した特許文献３に開示されている乳化剤を選択して使用することができるが、本発明の目的のためには、特に非テロゲン性乳化剤と呼ばれることがある乳化剤が好ましく、たとえば炭素数６〜２０程度、好ましくは炭素数６〜１２程度のＦ（ＣＦ２）ｎ（ＣＨ２）ｍＣＯＯＨ（ｍ：０または１、ｎ：６〜２０）で表されるフッ素含有アルカン酸またはその塩、フッ素含有アルキルスルホン酸またはその塩などを挙げることができる。塩としては、アルカリ金属塩、アンモニウム塩、アミン塩などを挙げることができる。具体的には、パーフルオロヘプタン酸、パーフルオロオクタン酸、及びそれらの塩、２−パーフルオロヘキシルエタンスルホン酸及びその塩などを挙げることができるがこれに限られるものではない。 In the emulsion polymerization method for obtaining the above-mentioned PTFE aqueous dispersion of the present invention, the emulsifier disclosed in Patent Document 3 described above can be selected and used as an emulsifier, but for the purpose of the present invention, In particular, an emulsifier sometimes called a non-telogenic emulsifier is preferable. For example, F(CF 2 )n(CH 2 )mCOOH (m:0 or 1, n having about 6 to 20 carbon atoms, preferably about 6 to 12 carbon atoms). : 6-20), a fluorine-containing alkanoic acid or salt thereof, a fluorine-containing alkylsulfonic acid or salt thereof, and the like. Examples of the salt include alkali metal salts, ammonium salts, amine salts and the like. Specific examples thereof include, but are not limited to, perfluoroheptanoic acid, perfluorooctanoic acid, salts thereof, 2-perfluorohexylethanesulfonic acid and salts thereof, and the like.
更に、本発明のＰＴＦＥ水性分散液は、ＰＴＦＥ水性分散液の安定性を高めるため乳化安定剤を含んでいてもよい。乳化安定剤としては、炭化水素系アニオン系界面活性剤が好ましい。この界面活性剤は本質的に土中成分であるカルシウム、アルミニウム及び鉄分と水に不溶性又は難溶性の塩を形成するため、界面活性剤に起因する河川、湖沼及び地下水汚染を回避することが出来る。 Further, the aqueous PTFE dispersion of the present invention may contain an emulsion stabilizer in order to enhance the stability of the aqueous PTFE dispersion. As the emulsion stabilizer, a hydrocarbon-based anionic surfactant is preferable. This surfactant essentially forms insoluble or sparingly soluble salts in water with the soil components calcium, aluminum and iron, thus avoiding river, lake and groundwater contamination due to the surfactant. ..
このような炭化水素系アニオン系界面活性剤としては、高級脂肪酸塩類、高級アルコール硫酸エステル塩類、液体脂肪油硫酸エステル塩類、脂肪族アルコールリン酸エステル塩類、二塩基性脂肪酸エステルスルホン酸塩類、アルキルアリルスルホン酸塩類などがあるが、特にポリオキシエチレンアルキルフェニルエーテルエチレンスルホン酸（ポリオキシエチレンのｎは１〜６、アルキルの炭素数は８〜１１）、アルキルベンゼンスルホン酸（アルキルの炭素数は１０〜１２）及び、ジアルキルスルホコハク酸エステル（アルキルの炭素数は８〜１０）などのＮａ，Ｋ，Ｌｉ，及びＮＨ４塩はＰＴＦＥ水性分散液に高い機械的安定性を与えるため、好ましいものとして例示することができる。 Such hydrocarbon-based anionic surfactants include higher fatty acid salts, higher alcohol sulfate ester salts, liquid fatty oil sulfate ester salts, aliphatic alcohol phosphate ester salts, dibasic fatty acid ester sulfonates, alkyl allyls. There are sulfonates, but especially polyoxyethylene alkylphenyl ether ethylene sulfonic acid (n of polyoxyethylene is 1 to 6, carbon number of alkyl is 8 to 11), alkylbenzene sulfonic acid (carbon number of alkyl is 10 to 10). 12) and Na, K, Li, and NH 4 salts such as dialkyl sulfosuccinic acid esters (wherein the alkyl has 8 to 10 carbon atoms) give high mechanical stability to the PTFE aqueous dispersion, and are preferred examples. be able to.
乳化安定剤の添加量はＰＴＦＥの重量当り１．０質量％以上であり、好ましくは１．５〜５質量％の範囲である。１．０質量％未満の添加量ではＰＴＦＥ水性分散液の安定効果が低く、また１０質量％以上の添加量では経済的に不利である。 The addition amount of the emulsion stabilizer is 1.0% by mass or more, preferably 1.5 to 5% by mass, based on the weight of PTFE. If the added amount is less than 1.0% by mass, the stabilizing effect of the PTFE aqueous dispersion is low, and if the added amount is 10% by mass or more, it is economically disadvantageous.
本発明の塵埃抑制処理剤組成物を用いた塵埃抑制処理方法は、ＰＴＦＥを発塵性物質と混合し、該混合物に２０〜２００℃の温度で圧縮−剪断作用を施すことによりＰＴＦＥをフィブリル化して発塵性物質の塵埃を抑制する方法、例えば特許第２８２７１５２号、特許第２５３８７８３号等の方法において、酸解離定数が１〜６の範囲にある安定化剤を含むであるＰＴＦＥ水性分散液からなる塵埃抑制処理剤組成物を用いることが好ましい。 A dust suppression treatment method using the dust suppression treatment agent composition of the present invention comprises mixing PTFE with a dust-generating substance and subjecting the mixture to compression-shearing at a temperature of 20 to 200° C. to fibrillate the PTFE. A method of suppressing dust of a dust-generating substance, for example, a method of Japanese Patent No. 2827152, Japanese Patent No. 2538783, etc., from a PTFE aqueous dispersion liquid containing a stabilizer having an acid dissociation constant in the range of 1 to 6. It is preferable to use the following dust suppressing treatment composition.
特定のＰＴＦＥは、上記したような適度な条件下で圧縮−剪断作用を施すとフィブリル化したクモの巣状に超微細繊維化するが、本発明の塵埃抑制処理剤組成物を用いて処理された発塵性物質の塵埃抑制処理物は、発塵性物質がクモの巣状の微細繊維に捕捉凝集されて塵埃抑制されると考えられる。 The specific PTFE becomes ultrafine fibers in the form of a fibrillated spider web when subjected to compression-shearing under the appropriate conditions as described above, but it is treated with the dust control composition of the present invention. It is considered that the dust-suppressed processed dusty substance is dust-suppressed by the dust-generating substance being captured and aggregated by the spiderweb-shaped fine fibers.
本発明の塵埃抑制処理剤組成物を用いて塵埃抑制処理される発塵性物質は、無機及び／または有機の発塵性物質であって、物質、形状などには特に限定はない。本発明は、発塵性物質として発塵性粉末状物質にも効果的に適用できる。特に好適に処理可能な発塵性物質としては、例えば、ポルトランドセメント、アルミナセメントなどのセメント類、消石灰、生石灰粉末、炭酸カルシウム、ドロマイト、マグネサイト、タルク、珪石、蛍石などの鉱産物粉末、カオリン、ベントナイト等の粘土鉱物粉、鉄鋼等の金属、非鉄金属の製造工程で副生されるスラグ粉末、石炭、ゴミ等の燃焼灰粉末、石膏粉末、粉末状金属、カーボンブラック、活性炭粉、金属酸化物等のセラッミックス粉、顔料等が挙げられ、すなわち固体粒子状物質が空気中に飛散し浮遊し、塵埃を発生する全ての発塵性物質が挙げられる。 The dust-generating substance that is dust-reduced by using the dust-suppressing treatment composition of the present invention is an inorganic and/or organic dust-generating substance, and there is no particular limitation on the substance, shape, or the like. The present invention can be effectively applied to dusty powdery substances as dusting substances. Examples of dusting substances that can be preferably processed include, for example, cements such as Portland cement and alumina cement, slaked lime, quicklime powder, calcium carbonate, dolomite, magnesite, talc, silica stone, mineral powder such as fluorite, Clay mineral powder such as kaolin and bentonite, metal such as iron and steel, slag powder by-produced in the manufacturing process of non-ferrous metal, combustion ash powder such as coal and dust, gypsum powder, powdered metal, carbon black, activated carbon powder, metal Examples include ceramic powders such as oxides, pigments, and the like, that is, all dusting substances that generate dust by causing solid particulate matter to be scattered and suspended in the air.
本発明の塵埃抑制処理剤組成物を用いた塵埃抑制処理方法は、建材分野、土壌安定材分野、固化材分野、肥料分野、焼却灰及び有害物質の埋立処分分野、防爆分野、化粧品分野、各種プラスチックス類への充填材分野等において塵埃抑制処理し、発塵性物質の塵埃抑制処理物を得るのに好適に用いられる。 Dust suppression treatment method using the dust suppression treatment agent composition of the present invention, building materials field, soil stabilizer field, solidification material field, fertilizer field, landfill disposal field of incineration ash and harmful substances, explosion-proof field, cosmetic field, various. It is suitable for use in the field of fillers for plastics and the like to obtain dust-suppressed substances of dust-generating substances by performing dust-suppression treatment.
以下に本発明を、実施例および比較例を挙げてさらに具体的に説明するが、この説明が本発明を限定するものではない。
本発明において各物性の測定は、下記の方法によって行った。
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples, but the description does not limit the present invention.
In the present invention, each physical property was measured by the following methods.
（１）ＰＴＦＥ粒子の平均粒子径
ＰＴＦＥ粒子の平均粒径は、マイクロトラックＵＰＡ１５０ Ｍｏｄｅｌ Ｎｏ．９３４０（日機装社製）を用いて測定した。
（２）発塵性粉体の粒子径
（株）堀場製作所製レーザー回折／散乱式粒度分布測定器にて、エタノールを分散媒として測定した。
(1) Average Particle Diameter of PTFE Particles The average particle diameter of the PTFE particles is Microtrac UPA150 Model No. It measured using 9340 (made by Nikkiso Co., Ltd.).
(2) Particle size of dust generating powder It was measured with ethanol as a dispersion medium using a laser diffraction/scattering type particle size distribution analyzer manufactured by Horiba Ltd.
（３）ＰＴＦＥの標準比重
ＡＳＴＭ Ｄ−４８９４により測定した。
乳化重合により得られるＰＴＦＥ水性分散体を、純水を用いて１５質量％濃度に調整する。その後ポリエチレン容器（１０００ｍｌ容量）に約７５０ｍｌ入れ手で激しく振蕩して重合体を凝集させる。水から分離した重合体のパウダーを１５０℃で１６時間乾燥する。乾燥した樹脂粉末１２．０ｇを直径２．８５ｃｍの円筒形型中に入れてならし、３０秒後に最終圧力が３５０ｋｇ／ｃｍ２となるよう圧力を次第に増加し、３５０ｋｇ／ｃｍ２の最終圧力で２分間保持する。このようにして得られた予備成形体を３０分間３８０℃の空気炉中で焼成した後、１分間１℃の割合で２９４℃まで冷却し、２９４℃で１分間保持した後、空気炉中から取り出し室温（２３±１℃）で冷却して標準試料とする。室温（２３℃±１℃）における同体積の水の重量に対する標準試料の重量比を標準比重とする。
この標準比重は平均分子量の目安となり、一般に標準比重が低い程分子量は大きい。
(3) Standard specific gravity of PTFE It was measured by ASTM D-4894.
The PTFE aqueous dispersion obtained by emulsion polymerization is adjusted to a concentration of 15 mass% with pure water. Then, about 750 ml is put into a polyethylene container (1000 ml capacity) and shaken vigorously to aggregate the polymer. The polymer powder separated from the water is dried at 150° C. for 16 hours. 12.0 g of dried resin powder was placed in a cylindrical mold having a diameter of 2.85 cm, and the pressure was gradually increased to a final pressure of 350 kg/cm 2 after 30 seconds, and a final pressure of 350 kg/cm 2 was applied. Hold for 2 minutes. The preform thus obtained was fired in an air oven at 380° C. for 30 minutes, cooled to 294° C. at a rate of 1° C. for 1 minute, and held at 294° C. for 1 minute. It is taken out and cooled at room temperature (23±1° C.) to obtain a standard sample. The standard specific gravity is the weight ratio of the standard sample to the weight of water of the same volume at room temperature (23°C ± 1°C).
This standard specific gravity is a measure of the average molecular weight, and generally, the lower the standard specific gravity, the higher the molecular weight.
（４）ＰＴＦＥ水性分散液中の含フッ素乳化剤濃度
ＰＴＦＥ水性分散液を−２０℃の冷凍庫に入れ凍らせ、ＰＴＦＥを凝集し水と分離した。ポリ容器の中身を全てソックスレーの抽出器に移し、約８０ｍｌのメタノールで７時間抽出を行う。メスアップしたサンプル液を液体クロマトグラフで測定を行い、ＰＴＦＥ水性分散液中の含フッ素乳化剤濃度を算出する。
(4) Concentration of Fluorine-Containing Emulsifier in PTFE Aqueous Dispersion The PTFE aqueous dispersion was put in a freezer at −20° C. and frozen, and PTFE was aggregated and separated from water. All the contents of the poly container are transferred to a Soxhlet extractor and extracted with about 80 ml of methanol for 7 hours. The sample liquid thus measured is measured with a liquid chromatograph, and the concentration of the fluorinated emulsifier in the PTFE aqueous dispersion is calculated.
（５）落下粉塵量
内径３９ｃｍ、高さ５９ｃｍの円筒容器の頂部投入口より試料２００ｇを自然落下させ、底面より高さ４５ｃｍの位置の容器内の浮遊粉塵量（相対濃度（ＣＰＭ：Ｃｏｕｎｔ ｐｅｒ Ｍｉｎｕｔｅ）を散乱光式デジタル粉塵計により測定する。浮遊粉塵量の測定は、試料投入後１分間計測を連続し５回行い、試料投入前の測定値（ダークカウント）を差し引いた値の幾何平均値を当該試料の「落下粉塵量」とする。幾何平均値ｘは次の式により求める。
Ｌｏｇ ｘ＝１／５・Σｌｏｇ（ｘI‐ｄ）
ここで、ｘI：個々の浮遊粉塵量、ｄ：ダークカウントである。
(5) Falling dust amount 200 g of the sample is naturally dropped from the top inlet of a cylindrical container having an inner diameter of 39 cm and a height of 59 cm, and the amount of floating dust (relative concentration (CPM: Count per Minute) in the container at a height of 45 cm from the bottom is dropped. ) Is measured by a scattered light type digital dust meter.The amount of suspended dust is measured 5 times continuously for 1 minute after sample loading, and the geometric mean value of the values obtained by subtracting the measured value (dark count) before sample loading Is the “falling dust amount” of the sample.The geometric mean value x is calculated by the following formula.
Log x=1/5・Σlog(xI-d)
Here, xI: the amount of each suspended dust, d: dark count.
（実施例１）
乳化重合法により得られた樹脂固形分濃度３０質量％のＰＴＦＥの水性分散液（平均粒径０．２μｍ、含フッ素乳化剤含有量２１ｐｐｍ、比重２．１９、アニオン系界面活性剤をＰＴＦＥの重量に対して３．０質量％含む）５００ｍｌを容量１０００ｍｌのビーカー中でスターラーを回転（１００ｒｐｍ）させながら、６．０質量％のコハク酸水溶液（水中の酸解離定数がｐＫａ１が４．２、ｐＫａ２が５．６）をＰＴＦＥの重量に対するコハク酸濃度１．６質量％分を加え、５分間緩やかに撹拌し、ＰＴＦＥ水性分散液（I）を得た。得られたＰＴＦＥ水性分散液（I）はｐＨ７．２であった。
このＰＴＦＥ水性分散液（I）を試験管に１８ｇ入れ、室温にて３０日静置後及び７０日静置後の沈降量を測定し分散安定性とした。
また、同様に３０日静置後及び７０日静置後、試験管を上下に１０回手で振とうした後の沈降量を測定し再分散沈降量を測定した。結果を表１に示す。
(Example 1)
An aqueous dispersion of PTFE having a resin solid content concentration of 30 mass% obtained by an emulsion polymerization method (average particle diameter 0.2 μm, content of fluorine-containing emulsifier 21 ppm, specific gravity 2.19, anionic surfactant in weight of PTFE) While stirring a stirrer (100 rpm) in a beaker having a capacity of 1000 ml, 500 ml of 500 ml (containing 3.0 mass%), a 6.0 mass% succinic acid aqueous solution (acid dissociation constant in water, pKa1 of 4.2, pKa2 of 5.6) was added with a succinic acid concentration of 1.6 mass% based on the weight of PTFE, and gently stirred for 5 minutes to obtain a PTFE aqueous dispersion (I). The obtained PTFE aqueous dispersion (I) had a pH of 7.2.
18 g of this PTFE aqueous dispersion (I) was placed in a test tube, and the amount of sedimentation after standing for 30 days and 70 days at room temperature was measured to obtain dispersion stability.
Similarly, after standing still for 30 days and 70 days, the sedimentation amount after shaking the test tube by hand 10 times was measured to measure the redispersion sedimentation amount. The results are shown in Table 1.
（実施例２）
乳化重合法により得られた樹脂固形分濃度３０質量％のＰＴＦＥの水性分散液（平均粒径０．２μｍ、含フッ素乳化剤含有量２１ｐｐｍ、比重２．１４、アニオン系界面活性剤をＰＴＦＥの重量に対して３．０質量％含む）を用いた以外は、実施例１と同様にしてＰＴＦＥの水性分散液（II）を得た。得られたＰＴＦＥの水性分散液（II）はｐＨ６．９であった。
このＰＴＦＥ水性分散液（II）を用い、実施例１と同様にして分散安定性及び再分散沈降量を測定した。結果を表１に示す。
(Example 2)
An aqueous dispersion of PTFE having a resin solid content concentration of 30 mass% obtained by an emulsion polymerization method (average particle diameter 0.2 μm, content of fluorine-containing emulsifier 21 ppm, specific gravity 2.14, anionic surfactant in weight of PTFE). Aqueous dispersion (II) of PTFE was obtained in the same manner as in Example 1 except that 3.0% by mass was used. The obtained PTFE aqueous dispersion (II) had a pH of 6.9.
Using this PTFE aqueous dispersion (II), dispersion stability and redispersion sedimentation amount were measured in the same manner as in Example 1. The results are shown in Table 1.
（比較例１）
乳化重合法により得られた樹脂固形分濃度３０質量％のＰＴＦＥの水性分散液（平均粒径０．２μｍ、含フッ素乳化剤含有量２１ｐｐｍ、比重２．１９、アニオン系界面活性剤をＰＴＦＥの重量に対して３．０質量％含む）をＰＴＦＥの水性分散液（III）とした。ＰＴＦＥの水性分散液（III）はｐＨ９．０であった。
このＰＴＦＥ水性分散液（III）を用い、実施例１と同様にして分散安定性及び再分散沈降量を測定した。結果を表１に示す。
(Comparative Example 1)
An aqueous dispersion of PTFE having a resin solid content concentration of 30 mass% obtained by an emulsion polymerization method (average particle diameter 0.2 μm, content of fluorine-containing emulsifier 21 ppm, specific gravity 2.19, anionic surfactant in weight of PTFE) (Containing 3.0% by mass) was used as an aqueous dispersion (III) of PTFE. The aqueous dispersion (III) of PTFE had a pH of 9.0.
Using this PTFE aqueous dispersion (III), the dispersion stability and redispersion sedimentation amount were measured in the same manner as in Example 1. The results are shown in Table 1.
（実施例３）
ＣａＯ９３．７％及びＭｇＯ１．０６％含有する粉末生石灰（２．０ｍｍの標準網フルイを全通、６００μｍの標準網フルイ残分７．８６％、３００μｍの標準網フルイ残分２５．１９％、１５０μｍの標準網フルイ残分１８．８０％、１５０μｍの標準網フルイ通過分４８．１５％の粉末生石灰）１，０００ｇを容積５リットルの小型ソイルミキサーに投入し、回転数１４０ｒ．ｐ．ｍ．で攪拌しながら、ＰＴＦＥ水性分散液（I）０．３３ｇ（ＰＴＦＥ樹脂固形分０．１０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０１質量％に相当）を清水９９．７７ｇに分散した分散液を徐々に投入した。
投入開始より約１分後には生石灰の水和反応熱による水蒸気を発生し始め、その後約２分で水分のすべてが生石灰の水和により消石灰の生成のため使用され尽くし水蒸気の発生が無くなった。攪拌開始より３分後にミキサーの攪拌を止めた。このときの温度を温度計で計測すると１０３℃であった。この塵埃抑制処理された生石灰は、水和反応により新たに生成した消石灰約３０％を含む生石灰と消石灰の混合物であった。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Example 3)
Powdered quick lime containing 93.7% CaO and 1.06% MgO (whole standard mesh sieve of 2.0 mm, standard mesh residue of 600 μm 7.86%, standard mesh sieve residue of 300 μm 25.19%, 150 μm 1.80 g of powdered quick lime (80.80% of standard mesh sieve residue and 48.15% of 150 .mu.m standard mesh sieve passed) was charged into a small soil mixer having a volume of 5 liters, and the rotation speed was 140 r.p.m. p. m. A dispersion in which 0.33 g of PTFE aqueous dispersion (I) (0.10 g of PTFE resin solid content, corresponding to 0.01% by mass of PTFE resin solid content with respect to quicklime) was dispersed in 99.77 g of clear water while being stirred. Was gradually added.
Approximately 1 minute after the start of charging, steam started to be generated due to the heat of hydration reaction of quick lime, and in about 2 minutes thereafter, all of the water was exhausted to generate slaked lime due to hydration of quick lime, and steam was not generated. After 3 minutes from the start of stirring, stirring of the mixer was stopped. The temperature at this time was 103° C. when measured with a thermometer. The dust-suppressing quick lime was a mixture of quick lime and slaked lime containing about 30% of slaked lime newly generated by the hydration reaction. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（実施例４）
ＰＴＦＥ水性分散液（I）０．６７ｇ（ＰＴＦＥ樹脂固形分０．２０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０２質量％に相当）を清水９９．５３ｇに分散した分散液を用いた以外は、実施例１と同様にして塵埃抑制処理された生石灰と消石灰の混合物を得た。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Example 4)
Except that a dispersion of 0.67 g of PTFE aqueous dispersion (I) (0.20 g of PTFE resin solid content, corresponding to 0.02% by mass of PTFE resin solid content with respect to quicklime) in 99.53 g of clear water was used. A mixture of quick lime and slaked lime that had been subjected to the dust suppression treatment was obtained in the same manner as in Example 1. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（実施例５）
ＰＴＦＥ水性分散液（II）０．３３ｇ（ＰＴＦＥ樹脂固形分０．１０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０１質量％に相当）を清水９９．７７ｇに分散した分散液を用いた以外は、実施例１と同様にして塵埃抑制処理された生石灰と消石灰の混合物を得た。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Example 5)
Except that 0.33 g of PTFE aqueous dispersion (II) (0.10 g of PTFE resin solid content, corresponding to 0.01% by mass of PTFE resin solid content with respect to quicklime) was dispersed in 99.77 g of clear water. A mixture of quick lime and slaked lime that had been subjected to the dust suppression treatment was obtained in the same manner as in Example 1. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（実施例６）
ＰＴＦＥ水性分散液（II）０．６７ｇＰＴＦＥ樹脂固形分０．２０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０２質量％に相当）を清水９９．５３ｇに分散した分散液を用いた以外は、実施例１と同様にして塵埃抑制処理された生石灰と消石灰の混合物を得た。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Example 6)
PTFE aqueous dispersion (II) 0.67 g PTFE resin solid content 0.20 g, equivalent to 0.02 mass% of PTFE resin solid content with respect to quick lime) 99.53 g of clear water In the same manner as in Example 1, a mixture of quick lime and slaked lime that had been subjected to the dust suppression treatment was obtained. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（比較例２）
ＰＴＦＥ水性分散液（III）０．３３ｇ（ＰＴＦＥ樹脂固形分０．１０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０１質量％に相当）に分散した分散液を用いた以外は、実施例１と同様にして塵埃抑制処理された生石灰と消石灰の混合物を得た。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Comparative example 2)
Example 1 was repeated except that 0.33 g of PTFE aqueous dispersion (III) (0.10 g of PTFE resin solid content, equivalent to 0.01% by mass of PTFE resin solid content in quicklime) was used. Similarly, a mixture of quick lime and slaked lime that had been subjected to dust suppression treatment was obtained. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（比較例３）
ＰＴＦＥ水性分散液（III）０．６７ｇ（ＰＴＦＥ樹脂固形分０．２０ｇ、生石灰に対しＰＴＦＥ樹脂固形分で０．０２質量％に相当）を清水９９．５３ｇに分散した分散液を用いた以外は、実施例１と同様にして塵埃抑制処理された生石灰と消石灰の混合物を得た。得られた塵埃抑制処理物の落下発塵量を測定した。結果を表２に示す。
(Comparative example 3)
Except that 0.67 g of PTFE aqueous dispersion (III) (0.20 g of PTFE resin solid content, corresponding to 0.02% by mass of PTFE resin solid content relative to quicklime) was dispersed in 99.53 g of clear water. A mixture of quick lime and slaked lime that had been subjected to the dust suppression treatment was obtained in the same manner as in Example 1. The amount of dust generated by falling of the obtained dust suppression treated product was measured. The results are shown in Table 2.
（比較例４）
ＰＴＦＥ水性分散液を使用せず清水１００ｇを用いた以外は、実施例１と同様にして、得られた生石灰と消石灰の混合物の落下発塵量を測定した。結果を表２に示す。
(Comparative Example 4)
The falling dust generation amount of the obtained mixture of quick lime and slaked lime was measured in the same manner as in Example 1 except that 100 g of fresh water was used without using the PTFE aqueous dispersion. The results are shown in Table 2.
本発明により、分散安定性及び再分散性に優れ且つ環境問題の可能性が低いＰＴＦＥの水性分散液、及び発塵が抑制され、かつ環境問題の可能性が低い発塵性物質の塵埃抑制処理剤組成物が提供される。 According to the present invention, an aqueous dispersion of PTFE which is excellent in dispersion stability and redispersibility and has a low possibility of environmental problems, and dust suppression treatment of dust-generating substances which suppress dust generation and have a low possibility of environmental problems An agent composition is provided.
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| JP7317307B2 (en) | 2018-12-28 | 2023-07-31 | 株式会社Nippo | Dust suppression treatment method |
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