JP4430458B2 - Low foaming spreading agent composition - Google Patents
Low foaming spreading agent composition Download PDFInfo
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- JP4430458B2 JP4430458B2 JP2004155148A JP2004155148A JP4430458B2 JP 4430458 B2 JP4430458 B2 JP 4430458B2 JP 2004155148 A JP2004155148 A JP 2004155148A JP 2004155148 A JP2004155148 A JP 2004155148A JP 4430458 B2 JP4430458 B2 JP 4430458B2
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- 239000000203 mixture Substances 0.000 title claims description 13
- 238000005187 foaming Methods 0.000 title claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 16
- 125000000962 organic group Chemical group 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 7
- 230000000694 effects Effects 0.000 description 16
- -1 polyoxyethylene Polymers 0.000 description 13
- 239000003905 agrochemical Substances 0.000 description 12
- 239000002518 antifoaming agent Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 150000002430 hydrocarbons Chemical group 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 238000007259 addition reaction Methods 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 230000006806 disease prevention Effects 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- ZQTYRTSKQFQYPQ-UHFFFAOYSA-N trisiloxane Chemical group [SiH3]O[SiH2]O[SiH3] ZQTYRTSKQFQYPQ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は特定の構造を有するオルガノポリシロキサンを含む低起泡性の展着剤組成物に関するものである。 The present invention relates to a low-foaming spreader composition containing an organopolysiloxane having a specific structure.
除草、害虫駆除、病害予防等の目的で農作物へ農薬を散布する際に、農作物への農薬の付着状態が不均一であると薬効が低下してしまう。そして、散布してからできるだけ短時間のうちに、かつ均一に農薬を農作物に付着させ、雨が降る前に薬効成分を葉等の内部へ浸透させることを目的として、農薬水溶液、水性分散液等に界面活性剤を添加して、農薬水溶液、水性分散液等の表面張力を低下させる方法が一般に採用されている。 When agricultural chemicals are sprayed on crops for the purposes of weeding, pest control, disease prevention, etc., the efficacy of the agricultural chemicals on the crops will be reduced. And in the shortest possible time after spraying, the agricultural chemicals are uniformly attached to the crops, and the aqueous solution of the agricultural chemicals, aqueous dispersions, etc. for the purpose of allowing the medicinal ingredients to penetrate into the leaves before raining. In general, a method of reducing the surface tension of an agrochemical aqueous solution, an aqueous dispersion, or the like by adding a surfactant to is generally employed.
前記界面活性剤としては、通常、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン高級脂肪酸エステル等の非イオン系界面活性剤が使用され、また、低毒性であり界面活性力が高いという特性からシリコーン系界面活性剤が使用されている。これらの中でも、トリシロキサン骨格の主鎖を有する特定構造のポリエーテル変性シリコーンが最も界面活性力が高く、既に農薬用展着剤として実用化されている（特許文献１）。更に、該ポリエーテル変性シリコーンはｐＨが酸性あるいは塩基性である条件では界面活性力が低下するという欠点があったが、この欠点はシロキサン鎖の構造を変更することで改良されている（特許文献２）。 As the surfactant, nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene higher fatty acid ester and the like are usually used, and they have low toxicity and surface activity. Silicone surfactants are used because of their high properties. Among these, a polyether-modified silicone having a specific structure having a main chain of a trisiloxane skeleton has the highest surface activity and has already been put into practical use as a spreading agent for agricultural chemicals (Patent Document 1). Furthermore, the polyether-modified silicone has a drawback that the surface activity is lowered under the condition that the pH is acidic or basic, but this disadvantage is improved by changing the structure of the siloxane chain (Patent Document). 2).
しかし、これらの展着剤を添加した農薬水溶液、水性分散液等は表面張力が低下するため泡立ちやすくなる。そのため、農薬水溶液、水性分散液等を調製する際には、更に、泡立ち防止の目的で消泡剤が添加されているが、これらの農薬用展着剤、特にポリエーテル変性シリコーンは界面活性力が高いため、消泡剤を添加しても泡立ちを完全に抑えることは困難であった。 However, agrochemical aqueous solutions, aqueous dispersions, and the like to which these spreading agents are added tend to foam because the surface tension is lowered. Therefore, when preparing an agrochemical aqueous solution, an aqueous dispersion, etc., an antifoaming agent is further added for the purpose of preventing foaming, but these spreading agents for agricultural chemicals, particularly polyether-modified silicones, have surface activity. Therefore, it was difficult to completely suppress foaming even when an antifoaming agent was added.
さらに、十分な効果を発揮するまで消泡剤を多量に添加すると、展着剤や農薬自体の効果を阻害するおそれがあるため好ましくない。このため、界面活性力が高く泡立ちの少ない農薬用展着剤が求められていた。 Furthermore, it is not preferable to add a large amount of an antifoaming agent until a sufficient effect is exhibited, since the effects of the spreading agent and the agricultural chemical itself may be hindered. For this reason, a spreading agent for agricultural chemicals having high surface activity and less foaming has been demanded.
本発明は、高い界面活性力を有し、かつ低起泡性である、農薬用の展着剤組成物を提供することにある。 An object of the present invention is to provide a spreading agent composition for agricultural chemicals having high surface activity and low foaming property.
本発明者らは上記課題を達成するため鋭意検討を行った結果本発明を完成した。
即ち、本発明は、
(Ａ)下記一般式(1)：
The inventors of the present invention have completed the present invention as a result of intensive studies to achieve the above-mentioned problems.
That is, the present invention
(A) The following general formula (1):
［式中、Ｒ1は独立に水酸基または非置換もしくは置換の炭素原子数１〜18の１価炭化水素基であり、
Ｒ2は独立に下記一般式(2)：
[Wherein R 1 is independently a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms;
R 2 is independently the following general formula (2):
（式中、Ｒ4は独立に非置換または置換の炭素原子数２〜８の２価炭化水素基であり、Ｒ5は独立に水素原子、非置換もしくは置換の炭素原子数１〜６の１価炭化水素基またはアセチル基（-ＣＯＣＨ3）であり、ｘは４〜15の整数、ｙは０〜10の整数であり、ｙが０ではないとき、式中の式：(Ｃ2Ｈ4Ｏ)で表される繰り返し単位と式：(Ｃ3Ｈ6Ｏ)で表される繰り返し単位との配列はランダム状またはブロック状である）
で表される有機基であり、
(In the formula, R 4 is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms, and R 5 is independently a hydrogen atom, an unsubstituted or substituted carbon atom having 1 to 6 carbon atoms. A valent hydrocarbon group or an acetyl group (—COCH 3 ), x is an integer of 4 to 15, y is an integer of 0 to 10, and when y is not 0, the formula in the formula: (C 2 H 4 The arrangement of the repeating unit represented by O) and the repeating unit represented by the formula: (C 3 H 6 O) is random or block)
An organic group represented by
Ｒ3は独立に水酸基または非置換もしくは置換の炭素原子数１〜18の１価炭化水素基、或いは前記一般式(2)で表される有機基であり、
ｍは０〜10の整数、ｎは０〜10の整数であり、かつｍ＋ｎの和は１〜20の整数であり、
但し、ｎ＝０であるとき、式中の２個のＲ3のうち少なくとも１個は前記一般式(2)で表される有機基である。］
で表されるポリオキシアルキレン変性オルガノポリシロキサン： 51〜99.9質量部、および
(Ｂ)下記一般式(3)：
R 3 is independently a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, or an organic group represented by the general formula (2),
m is an integer of 0 to 10, n is an integer of 0 to 10, and the sum of m + n is an integer of 1 to 20,
However, when n = 0, at least one of the two R 3 in the formula is an organic group represented by the general formula (2). ]
A polyoxyalkylene-modified organopolysiloxane represented by: 51-99.9 parts by weight, and
(B) The following general formula (3):
［式中、Ｒ6は独立に非置換または置換の炭素原子数１〜１８の１価炭化水素基であり、
Ｒ7は独立に下記一般式(4)：
[Wherein, R 6 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms,
R 7 is independently the following general formula (4):
（式中、Ｒ9は独立に非置換または置換の炭素原子数２〜８の２価炭化水素基である）
で表される有機基であり、
Ｒ8は独立に非置換または置換の炭素原子数１〜１８の１価炭化水素基、或いは前記一般式(4)で表される有機基であり、
ｏは０〜６の整数、ｐは０〜２の整数であり、
但し、ｐ＝０であるとき、式中の２個のＲ8のうち少なくとも１個は前記一般式(4)で表される有機基である。］
で表されるグリセリン変性オルガノポリシロキサン： 0.1〜49質量部
（但し、上記(Ａ)成分と上記(Ｂ)成分との合計量は、100質量部である）
を含有する低起泡性展着剤組成物を提供する。
(Wherein R 9 is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms)
An organic group represented by
R 8 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, or an organic group represented by the general formula (4),
o is an integer from 0 to 6, p is an integer from 0 to 2,
However, when p = 0, at least one of the two R 8 in the formula is an organic group represented by the general formula (4). ]
Glycerin-modified organopolysiloxane represented by: 0.1 to 49 parts by mass (provided that the total amount of component (A) and component (B) is 100 parts by mass)
There is provided a low-foaming spreading agent composition containing
以下、本発明につき詳しく説明する。
［(Ａ)成分］
本発明における(Ａ)成分のポリオキシアルキレン変性オルガノポリシロキサンは、下記一般式(1)：
Hereinafter, the present invention will be described in detail.
[Component (A)]
The polyoxyalkylene-modified organopolysiloxane (A) in the present invention has the following general formula (1):
（式中、Ｒ1は、Ｒ2、Ｒ5、ｍおよびｎは上記と同じである）
で表される。
(Wherein R 1 is R 2 , R 5 , m and n are the same as above)
It is represented by
上記Ｒ1としては、例えば、水酸基；メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、トリデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基等のアルキル基；シクロペンチル基、シクロヘキシル基等のシクロアルキル基；ビニル基、アリル基等のアルケニル基；フェニル基、トリル基などのアリール基；ベンジル基等のアラルキル基；これらの炭化水素基の水素原子の一部または全部をハロゲン原子、シアノ基、アミノ基等で置換した基、例えば、クロロメチル基、3-クロロプロピル基、3,3,3,-トリフルオロプロピル基、シアノエチル基、3-アミノプロピル基、Ｎ-β(アミノエチル)γ-アミノプロピル基等；等が挙げられる。これらの中でも(Ａ)成分の界面活性力及び入手が容易であること等からメチル基が好ましく、全Ｒ1の80モル％以上がメチル基であることが好ましい。
上記Ｒ2は、下記一般式(2)：
Examples of R 1 include hydroxyl group; methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, hexadecyl group. Group, alkyl group such as octadecyl group; cycloalkyl group such as cyclopentyl group and cyclohexyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group and tolyl group; aralkyl group such as benzyl group; Groups in which part or all of the hydrogen atoms in the hydrogen group are substituted with halogen atoms, cyano groups, amino groups, etc., such as chloromethyl groups, 3-chloropropyl groups, 3,3,3-trifluoropropyl groups, cyanoethyl Group, 3-aminopropyl group, N-β (aminoethyl) γ-aminopropyl group, and the like. Among these, a methyl group is preferable because of the surface activity of the component (A) and availability, and 80 mol% or more of all R 1 is preferably a methyl group.
R 2 represents the following general formula (2):
（式中、Ｒ4、Ｒ5、ｘおよびｙ、並びに式：(Ｃ2Ｈ4Ｏ)で表される繰り返し単位と式：(Ｃ3Ｈ6Ｏ)で表される繰り返し単位との配列は上記と同じである）
で表される有機基である。
(Wherein R 4 , R 5, x and y and the sequence of the repeating unit represented by the formula: (C 2 H 4 O) and the repeating unit represented by the formula: (C 3 H 6 O) are the same as above. Is the same)
It is an organic group represented by.
上記Ｒ4としては、例えば、エチレン基、プロピレン基（トリメチレン基）、ブチレン基（テトラメチレン基）等が挙げられる。 Examples of R 4 include an ethylene group, a propylene group (trimethylene group), a butylene group (tetramethylene group), and the like.
上記Ｒ5はとしては、例えば、水素原子；メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基等のアルキル基；アセチル基が挙げられる。上記ｘが４未満であると(Ａ)成分の水溶性が低下し、15を超えると界面活性力が低下する。更に、ｘ／(ｘ＋ｙ)のモル比が0.4以上であることが好ましい。前記モル比が0.4未満であると(Ａ)成分の水溶性が乏しくなることがある。 Examples of R 5 include a hydrogen atom; an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; and an acetyl group. When x is less than 4, the water solubility of the component (A) decreases, and when it exceeds 15, the surface activity decreases. Furthermore, the molar ratio of x / (x + y) is preferably 0.4 or more. When the molar ratio is less than 0.4, the water solubility of the component (A) may be poor.
また、上記Ｒ3としては、上記Ｒ1について例示した基および上記Ｒ2について例示した基が挙げられ、ｎ＝０であるとき、上記一般式(1)中の２個のＲ3のうち少なくとも１個は上記Ｒ2について例示した基である。 Examples of R 3 include the groups exemplified for R 1 and the groups exemplified for R 2. When n = 0, at least two of R 3 in the general formula (1) are used. One is the group exemplified for R 2 above.
上記ｍが１０を越えると親水性が低くなりすぎて界面活性力が低下し、上記ｎが１０を越えると分子量が大きくなりすぎるため界面活性力が低下してしまう。
この(Ａ)成分の具体例としては、次のものが挙げられる。
When m exceeds 10, the hydrophilicity becomes too low and the surface activity decreases, and when n exceeds 10, the molecular weight becomes too large and the surface activity decreases.
Specific examples of the component (A) include the following.
この(Ａ)成分のポリオキシアルキレン変性オルガノポリシロキサンは、１種単独でも２種以上を組み合わせても使用することができる。
The polyoxyalkylene-modified organopolysiloxane of component (A) can be used alone or in combination of two or more.
［(Ｂ)成分］
本発明における(Ｂ)成分のグリセリン変性オルガノポリシロキサンは、下記一般式(3)：
[Component (B)]
The glycerin-modified organopolysiloxane (B) in the present invention is represented by the following general formula (3):
（式中、Ｒ6、Ｒ7、Ｒ8、ｏおよびｐは上記と同じである）
(Wherein R 6 , R 7 , R 8 , o and p are the same as above)
上記Ｒ6としては、上記一般式(1)の上記Ｒ1について例示したものと同じ基が挙げられる。また、上記Ｒ1と同じく、その80モル％以上がメチル基であることが好ましい。
上記Ｒ7は下記一般式(4)：
Examples of R 6 include the same groups as those exemplified for R 1 in the general formula (1). Further, like R 1 , 80 mol% or more of them is preferably a methyl group.
R 7 is the following general formula (4):
（式中、Ｒ9は上記と同じである）
で表される有機基であり、Ｒ9としては、上記一般式(2)の上記Ｒ4について例示したものと同じ基が挙げられる。
(Wherein R 9 is the same as above)
As R 9 , the same groups as those exemplified for R 4 in the general formula (2) can be mentioned.
また、上記Ｒ8としては、上記Ｒ6について例示した基および上記Ｒ７について例示した基が挙げられ、ｐ＝０であるとき、上記一般式(3)中の２個のＲ8のうち少なくとも１個は上記Ｒ７について例示した基である。
上記ｏが６を超えると親水性が低下し、ｐが２を超えると界面活性力が低下してしまう。
この(Ｂ)成分の具体例としては、次のものが挙げられる。
Examples of R 8 include the groups exemplified for R 6 and the groups exemplified for R 7. When p = 0, at least two of R 8 in the general formula (3) are used. One is the group exemplified for R 7 above.
When the above o exceeds 6, the hydrophilicity is lowered, and when p exceeds 2, the surface activity is reduced.
Specific examples of the component (B) include the following.
この(Ｂ)成分のグリセリン変性オルガノポリシロキサンは、１種単独でも２種以上を組み合わせても使用することができる。
The glycerin-modified organopolysiloxane of component (B) can be used singly or in combination of two or more.
［(Ａ)，(Ｂ)成分の調製］
上記(Ａ)成分のポリオキシアルキレン変性オルガノポリシロキサンは、ケイ素原子に結合した水素原子（ＳｉＨ）を有するオルガノハイドロジェンポリシロキサンと、ポリオキシアルキレン構造からなる主鎖を有し、分子鎖末端にアリル基等の付加反応性であるアルケニル基を有する化合物とを、白金またはロジウム等の白金族金属系ヒドロシリル化反応触媒の存在下、付加反応させることによって得ることができる。
[Preparation of components (A) and (B)]
The polyoxyalkylene-modified organopolysiloxane of the component (A) has an organohydrogenpolysiloxane having a hydrogen atom (SiH) bonded to a silicon atom, a main chain composed of a polyoxyalkylene structure, and has a molecular chain terminal. It can be obtained by subjecting a compound having an alkenyl group that is addition-reactive such as an allyl group to an addition reaction in the presence of a platinum group metal hydrosilylation reaction catalyst such as platinum or rhodium.
上記(Ｂ)成分のグリセリン変性オルガノポリシロキサンについても同様にして、オルガノハイドロジェンポリシロキサンとグリセリンモノアリルエーテル等のグリセリンアルケニルエーテル類とを付加反応させることによって得ることができる。 Similarly, the glycerin-modified organopolysiloxane (B) can be obtained by addition reaction of an organohydrogenpolysiloxane and a glycerin alkenyl ether such as glyceryl monoallyl ether.
上記ヒドロシリル化反応触媒としては、白金触媒が好ましく、例えば、塩化白金酸、アルコール変性塩化白金酸、塩化白金酸−ビニルシロキサン錯体等が挙げられる。また、助触媒として酢酸ナトリウム、クエン酸ナトリウム等を併用してもよい。 As the hydrosilylation reaction catalyst, a platinum catalyst is preferable, and examples thereof include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinylsiloxane complex. Moreover, you may use sodium acetate, sodium citrate, etc. together as a promoter.
なお、触媒の使用量は有効量であればよく特に制限されないが、白金、ロジウム等の白金族金属量として、オルガノハイドロジェンポリシロキサンとアルケニル基含有化合物の合計量に対し、重量基準で、通常、50 ppm以下であることが好ましく、特に20 ppm以下であることが好ましい。 The amount of the catalyst used is not particularly limited as long as it is an effective amount, but the platinum group metal amount such as platinum and rhodium is usually based on the weight based on the total amount of the organohydrogenpolysiloxane and the alkenyl group-containing compound. , 50 ppm or less, preferably 20 ppm or less.
上記付加反応は、必要に応じて有機溶剤中で行ってもよい。有機溶剤としては、例えばメタノール、エタノール、2-プロパノール、ブタノール等の脂肪族アルコール；トルエン、キシレン等の芳香族炭化水素；ｎ-ペンタン、ｎ-ヘキサン、シクロヘキサン等の脂肪族または脂環式炭化水素；ジクロロメタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素等が挙げられる。付加反応条件は特に限定されるものではないが、還流下で１〜10時間程度反応させることが好ましい。 You may perform the said addition reaction in an organic solvent as needed. Examples of the organic solvent include aliphatic alcohols such as methanol, ethanol, 2-propanol, and butanol; aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, and cyclohexane. Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and the like. The addition reaction conditions are not particularly limited, but it is preferable to carry out the reaction for about 1 to 10 hours under reflux.
［本発明組成物の調製］
本発明組成物は、上記(Ａ)成分51〜99.9質量部、好ましくは70〜99質量部と、上記(Ｂ)成分0.1〜49質量部、好ましくは１〜30質量部（但し、上記(Ａ)成分と上記(Ｂ)成分との合計量は、100質量部である）とを含有するものである。
[Preparation of composition of the present invention]
The composition of the present invention comprises (A) component 51 to 99.9 parts by mass, preferably 70 to 99 parts by mass, and (B) component 0.1 to 49 parts by mass, preferably 1 to 30 parts by mass (provided that (A The total amount of the component (B) and the component (B) is 100 parts by mass).
上記(Ａ)成分の量が、51質量部未満であると界面活性力が低下し、99.9質量部を越えると泡立ちが多くなる。上記(Ｂ)成分の量が、0.1質量部未満であると泡立ちが多くなり、49質量部を超えると界面活性力が低下する。 When the amount of the component (A) is less than 51 parts by mass, the surface activity decreases, and when it exceeds 99.9 parts by mass, foaming increases. When the amount of the component (B) is less than 0.1 parts by mass, foaming increases, and when it exceeds 49 parts by mass, the surface activity decreases.
次に本発明を、実施例および比較例を示して更に具体的に説明するが、下記実施例は本発明を何ら制限するものではない。なお、下記において「粘度」は、何れも25℃での測定値である。
・(Ａ)成分として、下記のものを使用した。
EXAMPLES Next, although an Example and a comparative example are shown and this invention is demonstrated more concretely, the following Example does not restrict | limit this invention at all. In the following, “viscosity” is a value measured at 25 ° C.
-The following were used as the component (A).
（粘度：50.9ｍｍ2／s，微黄色透明液体）
これを、「Ａ１」とする。
(Viscosity: 50.9 mm 2 / s, slightly yellow transparent liquid)
This is referred to as “A1”.
（粘度：19.6ｍｍ2／s，微黄色透明液体）
これを、「Ａ２」とする。
(Viscosity: 19.6 mm 2 / s, slightly yellow transparent liquid)
This is designated as “A2”.
（粘度：38.6ｍｍ2／s，微黄色透明液体）
これを、「Ａ３」とする。
・(Ｂ)成分として、下記のものを使用した。
(Viscosity: 38.6mm 2 / s, slightly yellow transparent liquid)
This is designated as “A3”.
-The following were used as the component (B).
（粘度：102ｍｍ2／s，微黄色透明液体）
これを、「Ｂ１」とする。
(Viscosity: 102mm 2 / s, slightly yellow transparent liquid)
This is designated as “B1”.
（粘度：58.6ｍｍ2／s，微黄色透明液体）
これを、「Ｂ２」とする。
(Viscosity: 58.6mm 2 / s, slightly yellow transparent liquid)
This is designated as “B2”.
（粘度：71.4ｍｍ2／s，微黄色透明液体）
これを、「Ｂ３」とする。
(Viscosity: 71.4 mm 2 / s, slightly yellow transparent liquid)
This is designated as “B3”.
［実施例１〜５］
上記(Ａ)成分および(Ｂ)成分を用い、表１に記載の量比で配合して組成物を調製した。
[Examples 1 to 5]
Using the components (A) and (B), the compositions were prepared by blending them in the quantitative ratios shown in Table 1.
［比較例１〜５］
上記(Ａ)成分を用い、表２に記載のとおり、上記(Ｂ)成分を使用せず、または、使用して、表２に記載の量比で配合して組成物を調製した。なお、比較例１は(Ｂ)成分を使用しない例である。
また、比較例２および比較例３は、上記(Ｂ)成分に代えて、消泡剤(1)として、ポリアルキレングリコール系消泡剤：ディスホームNKL-5450（商品名、日本油脂社製）、または消泡剤(2)として、シリコーン系消泡剤：FSアンチフォーム001（商品名、ダウコーニング社製）を用いた例である。
[Comparative Examples 1-5]
Using the above component (A), as described in Table 2, the above component (B) was not used, or was used and blended in the quantitative ratio described in Table 2 to prepare a composition. Comparative Example 1 is an example in which the component (B) is not used.
Further, in Comparative Example 2 and Comparative Example 3, in place of the component (B), as the antifoaming agent (1), a polyalkylene glycol-based antifoaming agent: Dishome NKL-5450 (trade name, manufactured by NOF Corporation) In this example, silicone antifoaming agent: FS Antifoam 001 (trade name, manufactured by Dow Corning) is used as antifoaming agent (2).
＜性能評価＞
上記各実施例および比較例の組成物の外観および性能を評価した。結果を表３に示す。
−泡立ち性−
各組成物の１質量％水性分散液をガラスびん（内径：4.5ｃｍ、高さ：8.0ｃｍ）に入れ、１分間に250回振とうした。振とう停止から30秒後の泡高さ（ｍｍ）を測定した。
−表面張力−
各組成物の0.1質量％水性分散液を用いて、ウィルヘルミー法に準じて25℃における表面張力（ｍＮ／ｍ）を測定した。
<Performance evaluation>
The appearance and performance of the compositions of the above Examples and Comparative Examples were evaluated. The results are shown in Table 3.
-Foaming-
A 1% by mass aqueous dispersion of each composition was placed in a glass bottle (inner diameter: 4.5 cm, height: 8.0 cm) and shaken 250 times per minute. The bubble height (mm) after 30 seconds from the shaking stop was measured.
-Surface tension-
Using a 0.1% by mass aqueous dispersion of each composition, the surface tension (mN / m) at 25 ° C. was measured according to the Wilhelmy method.
［評価］
表３の結果から明らかなように、本発明の展着剤組成物は泡立ちが少なく、さらに表面張力の値が低い（界面活性力が高い）ものである。
[Evaluation]
As is clear from the results in Table 3, the spreading agent composition of the present invention has less foaming and a low surface tension value (high surface activity).
Claims (1)
［式中、Ｒ1は独立に水酸基または非置換もしくは置換の炭素原子数１〜18の１価炭化水素基であり、
Ｒ2は独立に下記一般式(2)：
（式中、Ｒ4は独立に非置換または置換の炭素原子数２〜８の２価炭化水素基であり、Ｒ5は独立に水素原子、非置換もしくは置換の炭素原子数１〜６の１価炭化水素基またはアセチル基（-ＣＯＣＨ3）であり、ｘは４〜15の整数、ｙは０〜10の整数であり、ｙが０ではないとき、式中の式：(Ｃ2Ｈ4Ｏ)で表される繰り返し単位と式：(Ｃ3Ｈ6Ｏ)で表される繰り返し単位との配列はランダム状またはブロック状である）
で表される有機基であり、
Ｒ3は独立に水酸基または非置換もしくは置換の炭素原子数１〜18の１価炭化水素基、或いは前記一般式(2)で表される有機基であり、
ｍは０〜10の整数、ｎは０〜10の整数であり、かつｍ＋ｎの和は１〜20の整数であり、
但し、ｎ＝０であるとき、式中の２個のＲ3のうち少なくとも１個は前記一般式(2)で表される有機基である。］
で表されるポリオキシアルキレン変性オルガノポリシロキサン： 51〜99.9質量部、および
(Ｂ)下記一般式(3)：
［式中、Ｒ6は独立に非置換または置換の炭素原子数１〜１８の１価炭化水素基であり、
Ｒ7は独立に下記一般式(4)：
（式中、Ｒ9は独立に非置換または置換の炭素原子数２〜８の２価炭化水素基である）
で表される有機基であり、
Ｒ8は独立に非置換または置換の炭素原子数１〜１８の１価炭化水素基、或いは前記一般式(4)で表される有機基であり、
ｏは０〜６の整数、ｐは０〜２の整数であり、
但し、ｐ＝０であるとき、式中の２個のＲ8のうち少なくとも１個は前記一般式(4)で表される有機基である。］
で表されるグリセリン変性オルガノポリシロキサン： 0.1〜49質量部
（但し、上記(Ａ)成分と上記(Ｂ)成分との合計量は、100質量部である）
を含有する低起泡性展着剤組成物。 (A) The following general formula (1):
[Wherein R 1 is independently a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms;
R 2 is independently the following general formula (2):
(In the formula, R 4 is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms, and R 5 is independently a hydrogen atom, an unsubstituted or substituted carbon atom having 1 to 6 carbon atoms. A valent hydrocarbon group or an acetyl group (—COCH 3 ), x is an integer of 4 to 15, y is an integer of 0 to 10, and when y is not 0, the formula in the formula: (C 2 H 4 The arrangement of the repeating unit represented by O) and the repeating unit represented by the formula: (C 3 H 6 O) is random or block)
An organic group represented by
R 3 is independently a hydroxyl group or an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, or an organic group represented by the general formula (2),
m is an integer of 0 to 10, n is an integer of 0 to 10, and the sum of m + n is an integer of 1 to 20,
However, when n = 0, at least one of the two R 3 in the formula is an organic group represented by the general formula (2). ]
A polyoxyalkylene-modified organopolysiloxane represented by: 51-99.9 parts by weight, and
(B) The following general formula (3):
[Wherein, R 6 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms,
R 7 is independently the following general formula (4):
(Wherein R 9 is independently an unsubstituted or substituted divalent hydrocarbon group having 2 to 8 carbon atoms)
An organic group represented by
R 8 is independently an unsubstituted or substituted monovalent hydrocarbon group having 1 to 18 carbon atoms, or an organic group represented by the general formula (4),
o is an integer from 0 to 6, p is an integer from 0 to 2,
However, when p = 0, at least one of the two R 8 in the formula is an organic group represented by the general formula (4). ]
Glycerin-modified organopolysiloxane represented by: 0.1 to 49 parts by mass (provided that the total amount of component (A) and component (B) is 100 parts by mass)
A low-foaming spreading agent composition comprising:
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| JP4963065B2 (en) | 2007-01-15 | 2012-06-27 | 信越化学工業株式会社 | Low foaming silicone composition |
| JP5722304B2 (en) * | 2010-03-01 | 2015-05-20 | 日本化薬株式会社 | Pest control composition |
| JP5607211B2 (en) * | 2013-05-29 | 2014-10-15 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Hydrolysis-resistant organically modified trisiloxane surfactants |
| JP2013216898A (en) * | 2013-05-29 | 2013-10-24 | Momentive Performance Materials Inc | Hydrolysis-resistant organically modified trisiloxane surfactant |
| JP5785585B2 (en) * | 2013-05-29 | 2015-09-30 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Hydrolysis-resistant organically modified trisiloxane surfactants |
| US20220279780A1 (en) | 2019-08-05 | 2022-09-08 | Ishihara Sangyo Kaisha, Ltd. | Agricultural formulation |
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2004
- 2004-05-25 JP JP2004155148A patent/JP4430458B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10829718B2 (en) | 2016-04-27 | 2020-11-10 | Dow Silicones Corporation | Detergent composition comprising a carbinol functional trisiloxane |
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