JP4235809B2 - Surfactant composition - Google Patents
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- JP4235809B2 JP4235809B2 JP2003340981A JP2003340981A JP4235809B2 JP 4235809 B2 JP4235809 B2 JP 4235809B2 JP 2003340981 A JP2003340981 A JP 2003340981A JP 2003340981 A JP2003340981 A JP 2003340981A JP 4235809 B2 JP4235809 B2 JP 4235809B2
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- polyoxyalkylene
- surfactant
- surfactant composition
- modified silicone
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- 239000004094 surface-active agent Substances 0.000 title claims description 52
- 239000000203 mixture Substances 0.000 title claims description 41
- 229920001296 polysiloxane Polymers 0.000 claims description 45
- 239000011248 coating agent Substances 0.000 claims description 27
- -1 acetylene glycol Chemical compound 0.000 claims description 24
- 239000000049 pigment Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 5
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- 239000000976 ink Substances 0.000 description 32
- 239000006185 dispersion Substances 0.000 description 19
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000000576 coating method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 230000003254 anti-foaming effect Effects 0.000 description 8
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000013065 commercial product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 230000001846 repelling effect Effects 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- NUYADIDKTLPDGG-UHFFFAOYSA-N 3,6-dimethyloct-4-yne-3,6-diol Chemical compound CCC(C)(O)C#CC(C)(O)CC NUYADIDKTLPDGG-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 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
- 125000002091 cationic group Chemical group 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003945 anionic surfactant Substances 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
- 239000006229 carbon black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 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
- 239000003085 diluting agent Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- UZZFFIUHUDOYPS-UHFFFAOYSA-L disodium 4-amino-3,6-bis[[4-[(2,4-diaminophenyl)diazenyl]phenyl]diazenyl]-5-oxido-7-sulfonaphthalene-2-sulfonate Chemical compound [Na+].[Na+].Nc1ccc(N=Nc2ccc(cc2)N=Nc2c(N)c3c(O)c(N=Nc4ccc(cc4)N=Nc4ccc(N)cc4N)c(cc3cc2S([O-])(=O)=O)S([O-])(=O)=O)c(N)c1 UZZFFIUHUDOYPS-UHFFFAOYSA-L 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 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
- 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 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 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
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000011049 pearl Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Degasification And Air Bubble Elimination (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Paper (AREA)
Description
本発明は、界面活性剤組成物に関するものであり、特には、インキや紙コート剤などに配合した場合、動的表面張力や接触角が低いため、優れた濡れ性、浸透性、消泡性及び分散性を発揮し、高速印刷及び高速塗工にも対応でき、無機顔料、有機顔料などを短時間に分散させると共に、消泡効果による優れた減粘効果を発揮する界面活性剤組成物に関するものである。 The present invention relates to a surfactant composition, and in particular, when blended in an ink or paper coating agent, because of its low dynamic surface tension and contact angle, it has excellent wettability, permeability and antifoaming properties. And a surfactant composition that exhibits high dispersibility, can be used for high-speed printing and high-speed coating, disperses inorganic pigments, organic pigments, and the like in a short time, and also exhibits an excellent devising effect due to the defoaming effect. Is.
近年、パソコンなどのＯＡ機器用のプリンターに水性インキを用いた記録方式が使われる比率が高まっており、それに伴ってインキの需要も拡大しつつあるが、その一方で、プリントの品位、彩度、外観、画像を更によくするために、より高度な特性を持つインキが要求されるようになってきた。 In recent years, the ratio of printing methods using water-based inks has been increasing in printers for office automation equipment such as personal computers, and the demand for ink has been increasing along with this. In order to further improve the appearance and image, inks having higher properties have been demanded.
また、印刷業界や製紙業界においても、常に生産性向上に伴う高速化への対応が余儀なくされており、高速印刷や高速塗工に対応したインキや紙コート剤の性能向上が要求されている。 Also in the printing industry and the papermaking industry, it is always necessary to cope with the high speed accompanying the improvement of productivity, and the performance improvement of ink and paper coating agent corresponding to high speed printing and high speed coating is required.
このような背景から、インキや水性塗料業界においては、基材に対する湿潤化及び浸透性付与のため優れた表面張力低下能と低接触角性を付与する界面活性剤を必要としている。 Against this background, in the ink and water-based paint industries, a surfactant that imparts excellent surface tension lowering ability and low contact angle properties is required for wetting and penetrating the substrate.
２，４，７，９−テトラメチル−５−デシン−４，７−ジオール及びそのエトキシル化体のようなアセチレングリコール系界面活性剤は、静的表面張力と動的表面張力の低下能とのバランスがとれており、従来の非イオン及び陰イオン性界面活性剤のマイナス点をほとんど有しないこと、しかも消泡性も有することから、インキ、塗料用の湿潤剤、分散助剤などとして使用されてきた。しかし、性能向上や生産性向上の進歩に伴って、濡れ性、分散性等の更なる向上が期待されている。 Acetylene glycol-based surfactants such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethoxylated derivatives thereof have the ability to reduce static surface tension and dynamic surface tension. It is well-balanced, has almost no negative points of conventional nonionic and anionic surfactants, and has antifoaming properties, so it is used as a wetting agent for inks, paints, and dispersion aids. I came. However, with improvements in performance and productivity, further improvements in wettability and dispersibility are expected.
一方、シリコーン系界面活性剤は、その界面活性剤のもつ低表面張力性、低接触角性を利用して、塗料のレベリング剤や顔料分散時の分散助剤として実用化されている。しかしながら、シリコーン系界面活性剤は、高いレベリング性、湿潤性、分散性を有するものの起泡性が極めて高く、泡による実用上の弊害が多くみられる。すなわち、分散、混合時に発生する泡が原因と考えられる塗工液、分散液の粘度アップによる塗工不能や塗膜表面の塗工ムラ、ピンホールの発生などが起こっている。 On the other hand, silicone surfactants have been put to practical use as coating leveling agents and dispersion aids when dispersing pigments by utilizing the low surface tension and low contact angle properties of the surfactants. However, although the silicone-based surfactant has high leveling property, wettability and dispersibility, the foaming property is extremely high, and many practical problems due to foams are observed. That is, the coating liquid considered to be caused by bubbles generated during dispersion and mixing, coating inability due to increased viscosity of the dispersion, coating unevenness on the coating film surface, generation of pinholes, and the like have occurred.
なお、本発明に関連する公知文献としては、下記のものがある。
本発明は、上記事情を改善するためになされたもので、低い動的表面張力と静的表面張力及び低接触角性を有するため、印刷時あるいは塗工時の優れた基材への濡れ性、浸透性、消泡性を発揮し、かつ顔料分散の際、消泡効果を有するため分散時の減粘効果が得られ、しかも分散効果の優れた界面活性剤組成物を提供することを目的とする。 The present invention was made to improve the above circumstances, and has low dynamic surface tension, static surface tension, and low contact angle, so that it has excellent wettability to the substrate during printing or coating. An object of the present invention is to provide a surfactant composition that exerts penetrability and antifoaming properties and has a defoaming effect when pigments are dispersed, so that a thinning effect at the time of dispersion is obtained and an excellent dispersing effect. And
本発明者らは、上記目的を達成するため鋭意検討した結果、アセチレングリコール系界面活性剤とシリコーン系界面活性剤、好ましくはノニオン型シリコーン系界面活性剤、より好ましくは特定のポリオキシアルキレン変性シリコーンを用いることにより、インキや紙コート剤などの添加剤として使用した場合に、表面張力や接触角が低いため、優れた濡れ性、浸透性、消泡性及び分散性を発揮し、更には、顔料などを短時間に分散させると共に消泡効果による優れた減粘効果を示すものであり、この界面活性剤を用いることにより、上述した従来の問題点が解決し得ることを知見し、本発明をなすに至った。 As a result of intensive studies to achieve the above object, the present inventors have found that an acetylene glycol surfactant and a silicone surfactant, preferably a nonionic silicone surfactant, more preferably a specific polyoxyalkylene-modified silicone. When used as an additive such as ink or paper coating agent, the surface tension and contact angle are low, so that it exhibits excellent wettability, permeability, antifoaming and dispersibility. The present invention has been found to disperse pigments and the like in a short time and exhibits an excellent devising effect due to the defoaming effect. By using this surfactant, it has been found that the conventional problems described above can be solved, and the present invention. It came to make.
従って、本発明は、
（Ａ）下記一般式（２）
で表されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上
５〜９５質量％
（Ｂ）ポリオキシエチレンの含有量が４０〜６０質量％であるポリオキシアルキレン変性シリコーンからなるノニオン型シリコーン系界面活性剤 ５〜９５質量％
を含有し、イオン交換水及び水溶性有機溶剤が組成物全体の０質量％であることを特徴とする界面活性剤組成物を提供する。
Therefore, the present invention
(A) under following general formula (2)
1 type or 2 types or more chosen from the ethoxylated form of acetylene glycol represented by
5 to 95% by mass
(B) Nonionic silicone-based surfactant comprising polyoxyalkylene-modified silicone having a polyoxyethylene content of 40 to 60% by mass of 5 to 95% by mass
Contains, provides a surfactant composition that ion-exchanged water and a water-soluble organic solvent and wherein 0% by mass Rukoto of the total composition.
本発明の界面活性剤組成物は、滴下直後の接触角が低く、動的表面張力も低いため、インキや紙コート剤などに添加した際、基材への濡れ性、浸透性、消泡性及び分散性を与え、更に、無機又は有機粉末などの分散に使用した際には、低添加量で優れた分散性と消泡性を有し、優れた減粘効果を発揮するものである。この特性により、本発明の界面活性剤組成物は、実用的に極めて有利である。 Since the surfactant composition of the present invention has a low contact angle immediately after dropping and low dynamic surface tension, when added to an ink or paper coating agent, wettability to a substrate, permeability, antifoaming property Furthermore, when it is used for dispersing inorganic or organic powders, it has excellent dispersibility and antifoaming properties at a low addition amount, and exhibits an excellent viscosity reducing effect. Due to this characteristic, the surfactant composition of the present invention is extremely advantageous practically.
本発明の界面活性剤組成物の成分（Ａ）は、上述したように、下記一般式（２）で示されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上のアセチレングリコール類である。 Component of the surfactant composition of the present invention (A), as described above, with one or more acetylene glycols selected from ethoxylated body acetylene glycol represented by the following following general formula (2) is there.
上記一般式（２）のアセチレングリコールのエトキシル化体としては、例えば、
２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオールのエトキシル化体（エチレンオキサイド付加モル数：６）、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：１０）、
２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化体（エチレンオキサイド付加モル数：４）、
３，６−ジメチル−４−オクチン−３，６−ジオールのエトキシル化体（エチレンオキサイド付加モル数：４）
等の上記アセチレングリコールのエチレンオキサイド誘導体を挙げることができ、そのアセチレングリコール中のエチレンオキサイド単位の付加モル数は、それぞれ０．５〜２５モルであり、これらの付加モル総数は１〜４０モルである。エチレンオキサイドの付加モル総数が４０モルを超えた場合、水への溶解度がアップし、更には、起泡性がアップするため消泡効果が低下する。
Ethoxylated of acetylene glycol above following general formula (2), for example,
2,5,8,11-tetramethyl-6-dodecin-5,8-diol ethoxylated compound (ethylene oxide addition mole number: 6),
Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (number of moles of ethylene oxide added: 10),
2,4,7,9-tetramethyl-5-decyne-4,7-diol ethoxylated compound (ethylene oxide addition mole number: 4),
Ethoxylated product of 3,6-dimethyl-4-octyne-3,6-diol (number of moles of ethylene oxide added: 4)
The ethylene oxide derivative of the above acetylene glycol can be exemplified, and the number of moles of ethylene oxide units in the acetylene glycol is 0.5 to 25 moles, and the total number of moles of these added is 1 to 40 moles. is there. When the total number of added moles of ethylene oxide exceeds 40 moles, the solubility in water is increased, and furthermore, the foaming property is improved, so that the defoaming effect is lowered.
これらのアセチレングリコール類〔成分（Ａ）〕は、その１種を単独で又は２種以上を混合して使用することができ、本発明の界面活性剤組成物を調製する際に用いられる量は、組成物全体の５〜９５質量％であり、好ましくは２０〜８０質量％である。５質量％未満であると消泡効果が低下し、泡によるピンホールや十分な減粘効果が得られなくなるおそれがあるし、９５質量％を超えると水への溶解性が低下し、配合した際に凝集物が発生し、十分な表面張力低下効果が得られず白色顔料などの分散不良が発生したり、インキの吸収性にバラツキが生じ印刷ムラが発生する。 These acetylene glycols [component (A)] can be used singly or in combination of two or more, and the amount used when preparing the surfactant composition of the present invention is as follows. The total composition is 5 to 95% by mass, preferably 20 to 80% by mass. If the amount is less than 5% by mass, the defoaming effect is lowered, and there is a risk that pinholes due to foam and sufficient viscosity-reducing effect may not be obtained. If the amount exceeds 95% by mass, the solubility in water is lowered and blended. At the same time, agglomerates are generated, and a sufficient surface tension lowering effect cannot be obtained, resulting in poor dispersion of white pigments, etc., or variations in ink absorbability, resulting in uneven printing.
本発明で使用される成分（Ｂ）のシリコーン系界面活性剤としては、アニオン型シリコーン系界面活性剤、ノニオン型シリコーン系界面活性剤、カチオン型シリコーン系界面活性剤及び両性型シリコーン系界面活性剤が挙げられる。アニオン型シリコーン系界面活性剤としては、カルボン酸塩変性シリコーン、スルホン酸塩変性シリコーン、硫酸エステル塩変性シリコーン及びリン酸エステル塩変性シリコーンなどが挙げられ、ノニオン型シリコーン系界面活性剤としては、ポリオキシアルキレン変性シリコーン、（ポリ）グリセリン変性シリコーン、糖類変性シリコーンなどが挙げられ、カチオン型シリコーン系界面活性剤としては、４級アンモニウム変性シリコーンなどが挙げられ、両性型シリコーン系界面活性剤としては、ベタイン変性シリコーンなどを挙げることができるが、広範囲な用途に適合するという観点から、ノニオン型シリコーン系界面活性剤が好ましく、更には、原料の入手の容易さや経済性の観点から、ポリオキシアルキレン変性シリコーンがより好ましい。 Examples of the silicone surfactant of component (B) used in the present invention include anionic silicone surfactants, nonionic silicone surfactants, cationic silicone surfactants, and amphoteric silicone surfactants. Is mentioned. Examples of the anionic silicone surfactants include carboxylate-modified silicones, sulfonate-modified silicones, sulfate ester-modified silicones, and phosphate ester-modified silicones. Examples include oxyalkylene-modified silicones, (poly) glycerin-modified silicones, and sugar-modified silicones. Cationic silicone surfactants include quaternary ammonium-modified silicones. Amphoteric silicone surfactants include Examples include betaine-modified silicones, but nonionic silicone surfactants are preferable from the viewpoint of adapting to a wide range of applications, and further, polyoxyalkylene-modified from the viewpoint of availability of raw materials and economy. Silicone is more Masui.
ポリオキシアルキレン変性シリコーンは、構造中にポリオキシアルキレン鎖を有するシリコーン化合物であれば特に限定はされないが、下記平均組成式（３）で表されるポリオキシアルキレン変性シリコーンであることが好ましい。 The polyoxyalkylene-modified silicone is not particularly limited as long as it is a silicone compound having a polyoxyalkylene chain in the structure, but is preferably a polyoxyalkylene-modified silicone represented by the following average composition formula (3).
Ｒ3 pＲ4 qＳｉＯ(4-p-q)/2 （３）
（Ｒ3は脂肪族不飽和結合を有しない置換又は非置換の炭素数１〜１０、好ましくは１〜８の１価炭化水素基、Ｒ4は一般式−ＣfＨ2fＯ（ＣgＨ2gＯ）hＲ5で示される有機基、Ｒ5は水素原子もしくは脂肪族不飽和基を有しない置換又は非置換１価炭化水素基、又はアセチル基である。ｆは２〜１２の整数、ｇは２〜４の整数、ｈは１〜２００の整数である。ｐ及びｑはそれぞれ０≦ｐ＜３．０、０＜ｑ＜３．０、かつ０＜ｐ＋ｑ≦３．０を満たす正数である。）
R 3 p R 4 q SiO (4-pq) / 2 (3)
(R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms having no aliphatic unsaturated bond, and R 4 is a group represented by the general formula —C f H 2f O (C g H 2g O) h R an organic group represented by 5, R 5 is a hydrogen atom or an aliphatic-substituted or having no unsaturated group unsubstituted monovalent hydrocarbon group, or an acetyl group .f is an integer from 2 to 12, g is an integer of 2 to 4, and h is an integer of 1 to 200. p and q are positive values satisfying 0 ≦ p <3.0, 0 <q <3.0, and 0 <p + q ≦ 3.0, respectively. Number.)
Ｒ3の具体例としては、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；フェニル基、トリル基等のアリール基；ベンジル基、フェネチル基等のアラルキル基；トリフロロプロピル基、ヘプタデカフロロデシル基等のフッ素置換アルキル基などが挙げられるが、表面張力低下能の観点からメチル基が好ましい。Ｒ5は好ましくは水素、炭素数１〜４の１価炭化水素基で具体例としては水素原子、メチル基、エチル基、プロピル基、ブチル基、アセチル基などが挙げられる。 Specific examples of R 3 include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; cyclopentyl and cyclohexyl, etc. Alkyl groups; aryl groups such as phenyl groups and tolyl groups; aralkyl groups such as benzyl groups and phenethyl groups; and fluorine-substituted alkyl groups such as trifluoropropyl groups and heptadecafluorodecyl groups. From the viewpoint, a methyl group is preferable. R 5 is preferably hydrogen or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and specific examples thereof include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, and an acetyl group.
また、ｆは２〜１２の整数、好ましくは２〜６の整数、より好ましくは３であり、ｇは２〜４の整数、好ましくは２，３、より好ましくは２で、２と３を併用してもよい。ｈは１〜２００の整数、好ましくは１〜１００の整数、より好ましくは１〜５０の整数である。ｐ及びｑはそれぞれ０≦ｐ＜３．０、０＜ｑ＜３．０、かつ０＜ｐ＋ｑ≦３．０を満たす正数である。 F is an integer of 2 to 12, preferably an integer of 2 to 6, more preferably 3, and g is an integer of 2 to 4, preferably 2, 3, more preferably 2, and 2 and 3 are used in combination. May be. h is an integer of 1 to 200, preferably an integer of 1 to 100, more preferably an integer of 1 to 50. p and q are positive numbers satisfying 0 ≦ p <3.0, 0 <q <3.0, and 0 <p + q ≦ 3.0, respectively.
更に、ポリオキシアルキレン変性シリコーン中のポリオキシエチレンの含有量は３０〜８０質量％が好ましく、更に好ましくは４０〜６０質量％である。ポリオキシエチレンの含有量が３０質量％未満では水への溶解性に乏しいものとなり、組成物が濁ったり、分離する場合があり、８０質量％を超えると表面張力低下能が弱くなる場合がある。 Furthermore, the content of polyoxyethylene in the polyoxyalkylene-modified silicone is preferably 30 to 80% by mass, and more preferably 40 to 60% by mass. If the content of polyoxyethylene is less than 30% by mass, the solubility in water becomes poor, the composition may become cloudy or separate, and if it exceeds 80% by mass, the surface tension reducing ability may be weakened. .
また、ポリオキシアルキレン変性シリコーン中のケイ素原子数は、２〜２００個、特に２〜１０個と比較的低分子量のものが、水溶性や表面張力低下能に優れるためより好ましい。 In addition, the number of silicon atoms in the polyoxyalkylene-modified silicone is more preferably 2 to 200, particularly 2 to 10 in terms of relatively low molecular weight because of its excellent water solubility and ability to reduce surface tension.
このようなポリオキシアルキレン変性シリコーンとしては、下記式（４）〜（１３）で示されるものを例示することができるが、本発明はこれに限定されるものではない。 Examples of such polyoxyalkylene-modified silicones include those represented by the following formulas (4) to (13), but the present invention is not limited thereto.
これらシリコーン系界面活性剤〔成分（Ｂ）〕は、その１種を単独で又は２種以上を混合して使用することができる。 These silicone surfactants [component (B)] can be used alone or in combination of two or more.
本発明の界面活性剤組成物を調製する際に用いられる成分（Ｂ）の配合割合は組成物全体の５〜９５質量％であり、好ましくは２０〜８０質量％である。５質量％未満であると十分な濡れ、浸透性が得られず、インキの吸収性にバラツキが発生するし、９５質量％を超えると配合時の泡立ちが多くなり、顔料分散時に泡が発生し、ピンホールやムラなどの塗工不良が発生してしまう。 The compounding ratio of the component (B) used when preparing the surfactant composition of the present invention is 5 to 95% by mass, preferably 20 to 80% by mass, based on the entire composition. If the amount is less than 5% by mass, sufficient wettability and penetrability cannot be obtained, and the ink absorbability varies. If the amount exceeds 95% by mass, foaming occurs at the time of blending, and bubbles are generated when the pigment is dispersed. , Poor coating such as pinholes and unevenness will occur.
本発明においては、上記２成分の合計が１００質量％になるように用いるのが好ましい。第三成分〔成分（Ｃ）〕として、イオン交換水、あるいはエチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、グリセリンなどの水溶性有機溶剤は組成物全体の０質量％である。 In the present invention, used as the sum of the two components is 100 mass% is not preferable. As the third component [component (C)], ion-exchanged water or ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4- butanediol, water-soluble organic solvents such as glycerin Ru 0 mass% der of the entire set Narubutsu.
本発明の界面活性剤は、例えば、上記各成分をプロペラ式攪拌機などの公知の混合調製方法によって混合することにより得られる。また、常温にて固体の成分については、必要により加温して混合するものである。 The surfactant of the present invention can be obtained, for example, by mixing the above components by a known mixing preparation method such as a propeller type stirrer. Moreover, about a solid component at normal temperature, it heats and mixes as needed.
ここで、得られた界面活性剤組成物は、その０．１質量％水溶液の接触角が５０度以下、特に１〜４０度、とりわけ１〜２０度であることが好ましく、動的表面張力が５０ｍＮ／ｍ以下、特に１０〜５０ｍＮ／ｍ、とりわけ２０〜４０ｍＮ／ｍであることが好ましい。なお、接触角は接触角計ＣＡ−Ｄ型（協和界面科学社製）を用いて０．１質量％水溶液の滴下３０秒後の値を測定したものであり、動的表面張力はバブルプレッシャー型動的表面張力計クルスＢＰ−２（ＫＲＵＳＳ社製）を用いて０．１質量％水溶液の１Ｈｚ及び１０Ｈｚ時の値を測定したものである。 Here, the obtained surfactant composition preferably has a contact angle of its 0.1% by weight aqueous solution of 50 degrees or less, particularly 1 to 40 degrees, particularly 1 to 20 degrees, and has a dynamic surface tension. It is preferably 50 mN / m or less, particularly 10 to 50 mN / m, particularly 20 to 40 mN / m. The contact angle is a value measured 30 seconds after dropping 0.1% by weight aqueous solution using a contact angle meter CA-D type (manufactured by Kyowa Interface Science Co., Ltd.), and the dynamic surface tension is a bubble pressure type. The value at 1 Hz and 10 Hz of a 0.1% by mass aqueous solution is measured using a dynamic surface tension meter Cruz BP-2 (manufactured by KRUS).
０．１質量％界面活性剤組成物水溶液の滴下３０秒後の接触角が大きすぎると、インキに配合した際にハジキの発生や吸収性が悪くなるためインキの滲みが発生するおそれがある。同じく０．１質量％水溶液の１Ｈｚ及び１０Ｈｚ時の動的表面張力が大きすぎると、プリンターなどの印刷機で印刷などを行った際、ハジキや浸透力不足による滲みが発生する場合がある。 If the contact angle after 30 seconds of dropping of the 0.1% by mass aqueous surfactant composition solution is too large, the ink may bleed or absorb when mixed into the ink, and ink bleeding may occur. Similarly, if the dynamic surface tension of a 0.1% by weight aqueous solution at 1 Hz and 10 Hz is too large, bleeding due to repelling or insufficient penetrating power may occur when printing is performed with a printing machine such as a printer.
本発明の界面活性剤組成物を用いてインキを製造したり、紙コート剤の水性濡れ剤として使用したり、顔料分散液を製造したりする場合、インキ全量、紙コート剤全量又は顔料分散液全量に対して好ましくは０．０５〜１０質量％、より好ましくは０．０５〜５質量％の添加量で使用することが望ましい。 When producing an ink using the surfactant composition of the present invention, or as an aqueous wetting agent for a paper coating agent, or producing a pigment dispersion, the total amount of ink, the total amount of paper coating agent, or the pigment dispersion The total amount is preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。なお、例中の部及び％はそれぞれ質量部と質量％を示す。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the part and% in an example show a mass part and mass%, respectively.
［参考例１］
７０℃に加温した２，４，７，９−テトラメチル−５−デシン−４，７−ジオール（エアプロダクツ社製、商品名サーフィノール１０４）５５部をプロペラ式攪拌機付容器に投入後、攪拌しながら、下記式（４）
After charging 55 parts of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (trade name Surfinol 104, manufactured by Air Products) into a vessel equipped with a propeller type stirrer, While stirring, the following formula (4)
更に、組成物Ｍ−１の０．１部をイオン交換水１００部に加え、マグネチックスタラーにて０．１％水溶液とし、これを用いて下記の測定条件で水溶液の外観、接触角、動的表面張力、静的表面張力を測定した。その結果を表２に示す。 Further, 0.1 part of the composition M-1 was added to 100 parts of ion-exchanged water, and a 0.1% aqueous solution was made with a magnetic stirrer. Using this, the appearance, contact angle, dynamics of the aqueous solution were measured under the following measurement conditions. Surface tension and static surface tension were measured. The results are shown in Table 2.
また、この界面活性剤組成物を用いて下記の配合処方によりインキ、紙コート剤及び顔料分散液を作製し、インキ配合物の場合は、下記の測定条件で印字濃度、印字画像の解像度、インキ吸収性を測定し、その結果を表３に、紙コート剤の場合は、下記の測定条件でハジキ、起泡性を測定し、その結果を表４に示した。更に、顔料分散液の場合は、下記の測定条件で粘度安定性、消泡性、発色性を測定し、その結果を表５に示した。 In addition, using this surfactant composition, an ink, a paper coating agent and a pigment dispersion are prepared by the following formulation. In the case of an ink formulation, the print density, the resolution of the print image, the ink under the following measurement conditions: Absorbance was measured, and the results are shown in Table 3. In the case of a paper coating agent, repellency and foamability were measured under the following measurement conditions, and the results are shown in Table 4. Further, in the case of the pigment dispersion, the viscosity stability, antifoaming property, and coloring property were measured under the following measurement conditions, and the results are shown in Table 5.
（インキ配合）
染料（商品名Ｃｉｂａｆｉｘダイレクトブラック１９、日本チバガイギー社製）５部をイオン交換水７０部にプロペラ式攪拌機で攪拌しながら徐々に添加した後、界面活性剤組成物Ｍ−１を１部、ポリエチレングリコールを１０部、グリセリンを１５部添加し、１時間攪拌して、ブラック（Ｂ）インキ（以下、このインキをイ−１という）を得た。
更に、上記染料の代わりに、それぞれＣｉｂａｆｉｘダイレクトレッド９、Ｃｉｂａｆｉｘダイレクトブルー８６、Ｃｉｂａｆｉｘダイレクトイエロー２３（いずれも日本チバガイギー社製商品名）を用いて上記と同様の方法により、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキを作製した。
(Ink formulation)
After gradually adding 5 parts of a dye (trade name Cibafix Direct Black 19, manufactured by Ciba Geigy Japan Co., Ltd.) to 70 parts of ion-exchanged water while stirring with a propeller-type stirrer, 1 part of surfactant composition M-1 and polyethylene glycol 10 parts and glycerin 15 parts were added and stirred for 1 hour to obtain a black (B) ink (hereinafter, this ink is referred to as A-1).
Further, in place of the above dye, Cibafix Direct Red 9, Cibafix Direct Blue 86, Cibafix Direct Yellow 23 (all trade names manufactured by Ciba-Geigy Corporation of Japan) were used in the same manner as described above, and magenta (M), cyan ( C), yellow (Y) ink was prepared.
（紙コート剤配合）
紙コート剤用エマルジョン（日信化学社製、商品名ビニブラン２７５０）１００部に対して界面活性剤組成物Ｍ−１を１部添加し、プロペラ式攪拌機で３０分間攪拌した後、紙コート剤（以下、これをコ−１という）を得た。
(Contains paper coating agent)
One part of the surfactant composition M-1 is added to 100 parts of an emulsion for paper coating (manufactured by Nissin Chemical Co., Ltd., trade name Vinibrand 2750), and stirred for 30 minutes with a propeller-type stirrer. Hereinafter, this was referred to as co-1.
（顔料分散液配合）
イオン交換水３００部に界面活性剤組成物Ｍ−１を２０部加え、ディスパーにて１０００ｒｐｍで３０分間攪拌しながら溶解後、カーボンブラック（キャボット社製、パールズ４６０）１８０部を加えて回転数３０００ｒｐｍで１時間分散し、顔料分散液（以下、これをブ−１という）を得た。
(Contains pigment dispersion)
20 parts of surfactant composition M-1 was added to 300 parts of ion-exchanged water, dissolved with stirring at 1000 rpm for 30 minutes in a disper, 180 parts of carbon black (Pearls 460, manufactured by Cabot Corporation) was added, and the rotation speed was 3000 rpm. For 1 hour to obtain a pigment dispersion (hereinafter referred to as “bu-1”).
なお、各特性の測定は下記のようにして行った。
《界面活性剤組成物水溶液の評価》
（１）水溶液の外観
上記界面活性剤組成物の０．１％水溶液の外観、及び不溶解物の有無の確認を下記の基準により目視にて行った。
○ ：水溶液が透明で、不溶解物が認められない。
△ ：水溶液が白濁しているが、不溶解物は認められない。
× ：一部不溶解物が認められる。
××：ほとんど溶解せず。
Each characteristic was measured as follows.
<< Evaluation of Surfactant Composition Aqueous Solution >>
(1) Appearance of aqueous solution The appearance of a 0.1% aqueous solution of the surfactant composition and the presence / absence of insoluble matter were visually confirmed according to the following criteria.
○: The aqueous solution is transparent and no insoluble matter is observed.
(Triangle | delta): Although aqueous solution is cloudy, an insoluble matter is not recognized.
X: A partly insoluble matter is recognized.
XX: hardly dissolved.
（２）接触角
協和界面科学社製接触角計ＣＡ−Ｄ型を用いて、界面活性剤組成物の０．１％水溶液の滴下３０秒後の接触角を測定した。
(2) Contact angle Using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd., the contact angle after 30 seconds of dropping a 0.1% aqueous solution of the surfactant composition was measured.
（３）動的表面張力
ＫＲＵＳＳ社製バブルプレッシャー型動的表面張力計クルスＢＰ−２を用いて、界面活性剤組成物の０．１％水溶液の１Ｈｚ及び１０Ｈｚ時における動的表面張力を測定した。
(3) Dynamic surface tension Using a bubble pressure type dynamic surface tension meter Cruz BP-2 manufactured by KRUSS, dynamic surface tension was measured at 1 Hz and 10 Hz of a 0.1% aqueous solution of a surfactant composition. .
（４）静的表面張力
協和界面科学社製表面張力計ＥＳＢ−Ｖ型を用いて、界面活性剤組成物の０．１％水溶液の静的な表面張力を測定した。
(4) Static surface tension Static surface tension of a 0.1% aqueous solution of a surfactant composition was measured using a surface tension meter ESB-V manufactured by Kyowa Interface Science Co., Ltd.
《インキの評価》
（１）印字濃度
キヤノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）インキを用いて印字したドットについて、サクラマイクロデンシトメーターＰＤＭ−５型（サクラ製機社製）でドットの濃度を測定した。
<Evaluation of ink>
(1) Print density About the dot printed using the black (B) ink with Canon printer BJC455J, the dot density was measured with Sakura Microdensitometer PDM-5 (manufactured by Sakura Kikai Co., Ltd.).
（２）印字画像の解像度
キヤノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）インキをベタ印刷し、マクベス濃度計ＲＤ−９１８型（マクベス社製）で測定した。また、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキについても同様の方法により測定した。
(2) Resolution of printed image Black (B) ink was solid-printed with a Canon printer BJC455J and measured with a Macbeth densitometer RD-918 (manufactured by Macbeth). Further, magenta (M), cyan (C), and yellow (Y) inks were measured by the same method.
（３）インキ吸収性
キヤノンプリンターＢＪＣ４５５Ｊでブラック（Ｂ）、マゼンタ（Ｍ）、シアン（Ｃ）、イエロー（Ｙ）インキを同時に同一場所に噴射し、１秒後に紙押さえ板でこすり、インキによる汚れを下記の基準により測定した。
○ ：白色部分に汚れのないもの。
△ ：微かに汚れるもの。
× ：汚れがひどいもの。
(3) Ink absorbability Black (B), magenta (M), cyan (C), and yellow (Y) inks are simultaneously jetted to the same location with a Canon printer BJC455J, and rubbed with a paper presser plate after 1 second, and smudged with ink Was measured according to the following criteria.
○: The white part has no dirt.
Δ: Slightly dirty.
×: Severe dirt.
《紙コート剤の評価》
（１）ハジキ
日商グラビア社製印刷適正試験機（ＧＲＡＶＯ−ＰＲＯＯＦ）にて、紙コート剤を５０ｍ／分の塗工速度で塗工し、印刷面のハジキなどを目視にて下記の基準により確認した。
○ ：ハジキ及びピンホールが認められない。
△ ：一部ハジキ及びピンホールが認められる。
× ：ハジキ及びピンホールが多く認められる。
<Evaluation of paper coating agent>
(1) Hajiki Paper coating agent was applied at a coating speed of 50 m / min with Nissho Gravure's printing suitability tester (GRAVO-PROOF), and the repellency of the printed surface was visually observed according to the following criteria. confirmed.
○: No repelling or pinholes are observed.
Δ: Partial repelling and pinholes are observed.
X: Many repellencies and pinholes are observed.
（２）起泡性
紙コート剤をコート剤／水＝１／２の比率で希釈し、サンプルとした。このサンプル２０ｍｌを１００ｍｌメスシリンダーに入れ、１８０回往復／分のシェカーで１分間振盪し、振盪終了５分後のｍｌ数を測定した。
(2) Foaming property A paper coating agent was diluted at a ratio of coating agent / water = 1/2 to prepare a sample. 20 ml of this sample was placed in a 100 ml graduated cylinder, shaken for 1 minute with a shaker of 180 reciprocations / minute, and the number of ml 5 minutes after the end of shaking was measured.
《顔料分散液の評価》
（１）粘度安定性
上記方法で分散して得られた顔料分散液の分散直後及び室温にて２日間放置後の２５℃における粘度をＢ型粘度計にて測定した。
<< Evaluation of pigment dispersion >>
(1) Viscosity stability The viscosity at 25 ° C. was measured with a B-type viscometer immediately after dispersion of the pigment dispersion obtained by the above method and after standing at room temperature for 2 days.
（２）消泡性
顔料分散液サンプル／イオン交換水＝１／９の比率で希釈液を作製し、サンプルとした。作製したサンプルを１００ｍｌメスシリンダーに２０ｍｌ入れ、シェーカー（１８０回往復／分）にて振盪し、振盪停止直後、及び５分後の泡の量（ｍｌ数）を測定した。
(2) Antifoaming property A diluent was prepared at a ratio of pigment dispersion sample / ion-exchanged water = 1/9 and used as a sample. 20 ml of the prepared sample was put into a 100 ml graduated cylinder, shaken with a shaker (180 reciprocations / minute), and the amount of foam (number of ml) was measured immediately after stopping shaking and after 5 minutes.
（３）発色性
顔料分散液を６ＭＩＬのアプリケーターでガラス板に塗布し、デジタルマイクロスコープにて倍率５０倍で発色性（分散性）を確認し、下記の評価基準で評価した。
○ ：分散性、発色性良好。
△ ：一部、分散不良部分有り。
× ：分散性、発色性不良。
(3) Color developability The pigment dispersion was applied to a glass plate with a 6 MIL applicator, and the color developability (dispersibility) was confirmed at a magnification of 50 times with a digital microscope, and evaluated according to the following evaluation criteria.
○: Dispersibility and color developability are good.
Δ: There is a part of poor dispersion.
X: Dispersibility and color developability are poor.
［実施例１、参考例２〜４、比較例１〜６］
参考例１と同様にして表１に示される配合物の種類及び配合量（％）で攪拌混合し、界面活性剤組成物（Ｍ−２〜Ｍ−１１）を得た。なお、参考例１については、配合物の配合量を％で再記した。また、固体のものについては、７０℃に加温し、成分を混合した。
[Example 1, Reference Examples 2 to 4 , Comparative Examples 1 to 6]
The surfactant composition (M-2 to M-11) was obtained by stirring and mixing in the same manner as in Reference Example 1 with the type and amount (%) of the formulation shown in Table 1. For Reference Example 1, the blending amount of the blend was rewritten in%. Moreover, about the solid thing, it heated at 70 degreeC and mixed the component.
上記界面活性剤を用いて参考例１と同様にして０．１％水溶液を作り、同様にして水溶液の評価を行って、その結果を表２に示した。更に、参考例１と同様にしてインキ（イ−２〜イ−１１）及び紙コート剤（コ−２〜コ−１１）を作製し、同様にしてインキ及び紙コート剤の評価を行って、その結果を表３及び表４に示した。また、参考例１と同様にして顔料分散液（ブ−２〜ブ−１１）を作製し、これを用いて参考例１と同様の評価を行って、その結果を表５に示した。 Using the surfactant, a 0.1% aqueous solution was prepared in the same manner as in Reference Example 1, and the aqueous solution was evaluated in the same manner. The results are shown in Table 2. Further, ink (I-2 to I-11) and paper coating agent (co-2 to co-11) were prepared in the same manner as in Reference Example 1, and the ink and paper coating agent were evaluated in the same manner. The results are shown in Tables 3 and 4. Further, in the same manner as in Reference Example 1 to prepare a pigment dispersion liquid (Bed -2 Bed -11), and evaluated in the same manner as in Referential Example 1. As a result, the results are shown in Table 5.
［比較例７〜９］
市販品１：ダプロＷ−７７（エレメンティス・ジャパン社製商品名、サクシネート系界面活性剤）、市販品２：ノニポール１６０（三洋化成社製商品名、ポリオキシエチレンノニルフェニルエーテル）、市販品３：ＴａｍｏｌＮＮＡ４１０９（ＢＡＳＦジャパン社製商品名、β−ナフタレンスルホン酸ホルマリン縮合物）をそれぞれ用いて、参考例１と同様の評価を行い、その結果を表２〜５に示した。
[Comparative Examples 7 to 9]
Commercial product 1: Dapro W-77 (trade name, succinate surfactant, manufactured by Elementis Japan), commercial product 2: Nonipol 160 (trade name, polyoxyethylene nonylphenyl ether, manufactured by Sanyo Kasei Co., Ltd.), commercial product 3 : TamolNNA4109 (trade name, manufactured by BASF Japan Ltd., β-naphthalenesulfonic acid formalin condensate) was evaluated in the same manner as in Reference Example 1, and the results are shown in Tables 2-5.
＜成分Ａ＞
Ａ−１：２，４，７，９−テトラメチル−５−デシン−４，７−ジオール（サーフィノー
ル１０４：エアプロダクツ社製商品名）
Ａ−２：３，６−ジメチル−４−オクチン−３，６−ジオール（サーフィノール８２：エ
アプロダクツ社製商品名）
Ａ−３：２，５，８，１１−テトラメチル−６−ドデシン−５，８−ジオール（サーフィ
ノールＤＦ−１１０：エアプロダクツ社製商品名）
Ａ−４：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化
体（サーフィノール４６５：エアプロダクツ社製商品名、エチレンオキサイド付
加モル数：１０）
Ａ−５：２，４，７，９−テトラメチル−５−デシン−４，７−ジオールのエトキシル化
体（エチレンオキサイド付加モル数：５０）
<Component A>
A-1: 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfinol 104: trade name manufactured by Air Products)
A-2: 3,6-dimethyl-4-octyne-3,6-diol (Surfinol 82: trade name, manufactured by Air Products)
A-3: 2,5,8,11-tetramethyl-6-dodecin-5,8-diol (Surfinol DF-110: trade name manufactured by Air Products)
A-4: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfinol 465: trade name, manufactured by Air Products, with ethylene oxide, added moles: 10)
A-5: Ethoxylate of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (number of moles of ethylene oxide added: 50)
＜成分Ｂ＞
Ｂ−１：下記式（４）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：４７．３質量％）
B-1: Polyoxyalkylene-modified silicone represented by the following formula (4) (Polyoxyethylene content: 47.3 mass%)
Ｂ−２：下記式（５）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：５４．５質量％）
Ｂ−３：下記式（６）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：５５．７質量％）
Ｂ−４：下記式（７）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：４３．４質量％）
Ｂ−５：下記式（８）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：４８．４質量％）
Ｂ−６：下記式（９）で示されるポリオキシアルキレン変性シリコーン
（ポリオキシエチレンの含有量：５８．７質量％）
Claims (4)
で表されるアセチレングリコールのエトキシル化体から選ばれる１種又は２種以上
５〜９５質量％
（Ｂ）ポリオキシエチレンの含有量が４０〜６０質量％であるポリオキシアルキレン変性シリコーンからなるノニオン型シリコーン系界面活性剤 ５〜９５質量％
を含有し、イオン交換水及び水溶性有機溶剤が組成物全体の０質量％であることを特徴とする界面活性剤組成物。 (A) under following general formula (2)
1 type or 2 types or more chosen from the ethoxylated form of acetylene glycol represented by
5 to 95% by mass
(B) Nonionic silicone-based surfactant comprising polyoxyalkylene-modified silicone having a polyoxyethylene content of 40 to 60% by mass of 5 to 95% by mass
Containing, surfactant compositions deionized water and a water-soluble organic solvent and wherein 0% by mass Rukoto of the total composition.
Ｒ3 pＲ4 qＳｉＯ(4-p-q)/2 （３）
（Ｒ3は脂肪族不飽和結合を有しない置換又は非置換の炭素数１〜１０の１価炭化水素基、Ｒ4は一般式−ＣfＨ2fＯ（ＣgＨ2gＯ）hＲ5で示される有機基、Ｒ5は水素原子もしくは脂肪族不飽和基を有しない置換又は非置換１価炭化水素基、又はアセチル基である。ｆは２〜１２の整数、ｇは２〜４の整数、ｈは１〜２００の整数である。ｐ及びｑはそれぞれ０≦ｐ＜３．０、０＜ｑ＜３．０であり、０＜ｐ＋ｑ≦３．０を満たす正数であるが、ポリオキシアルキレン変性シリコーン中のポリオキシエチレンの含有量は、４０〜６０質量％である。） Polyoxyalkylene-modified silicone surfactant composition according to claim 1, characterized by being represented by the following average compositional formula (3).
R 3 p R 4 q SiO (4-pq) / 2 (3)
(R 3 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms having no aliphatic unsaturated bond, R 4 is a general formula —C f H 2f O (C g H 2g O) h R 5 R 5 is a substituted or unsubstituted monovalent hydrocarbon group having no hydrogen atom or aliphatic unsaturated group, or an acetyl group, f is an integer of 2 to 12, and g is 2 to 4. Integer, h is an integer of 1 to 200. p and q are 0 ≦ p <3.0 and 0 <q <3.0, respectively, and are positive numbers satisfying 0 <p + q ≦ 3.0 , The content of polyoxyethylene in the polyoxyalkylene-modified silicone is 40 to 60% by mass .)
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| US8216673B2 (en) * | 2005-08-03 | 2012-07-10 | Nissin Chemical Industry Co., Ltd. | Glass fiber-treating agent and glass fiber-treating composition |
| JP5817446B2 (en) * | 2011-11-08 | 2015-11-18 | セイコーエプソン株式会社 | Ink composition and inkjet recording method |
| WO2013131924A1 (en) * | 2012-03-06 | 2013-09-12 | Oce-Technologies B.V. | Ink composition |
| EP2925529B1 (en) * | 2012-11-28 | 2020-08-19 | Välinge Innovation AB | Method of producing a building panel using digital printing |
| JP6187300B2 (en) * | 2014-02-17 | 2017-08-30 | 日信化学工業株式会社 | Water-soluble surfactant composition and ink composition containing the same |
| JP6330727B2 (en) * | 2014-05-26 | 2018-05-30 | 日信化学工業株式会社 | Ink composition |
| KR20150136013A (en) * | 2014-05-26 | 2015-12-04 | 닛신 가가꾸 고교 가부시끼가이샤 | Ink composition |
| JP2016190981A (en) * | 2015-03-31 | 2016-11-10 | 日信化学工業株式会社 | Ink composition |
| JP6004065B2 (en) * | 2015-09-28 | 2016-10-05 | セイコーエプソン株式会社 | Ink composition and inkjet recording method |
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