JP7238806B2 - Water-soluble surfactant composition, paper coating agent and ink - Google Patents

Description

The present invention relates to a water-soluble surfactant composition, and in particular, when blended in a paper coating agent, ink, etc., it has excellent transparency and low static and dynamic surface tension, so it has excellent wettability. , A water-soluble surfactant composition that exhibits permeability and antifoaming properties, can be used for high-speed printing and high-speed coating, and is also compatible with recent environmental problems, and a paper coating agent containing the composition, and It relates to ink.

2. Description of the Related Art In recent years, printers for OA equipment such as personal computers have rapidly spread in offices and homes due to lower prices and improved print quality and reliability. Along with this, the demand for ink is expanding from general household use to industrial use, but on the other hand, in order to further improve print quality, color saturation, appearance, image, and storage stability, conventional dye inks are being replaced with pigment inks. Inks with more advanced properties are required, and the types of inks are increasing.

Also, in the printing industry and the paper manufacturing industry, the use of water-based ink is progressing due to environmental problems in recent years. However, when using water-based inks, the drying speed is slow, so the production speed is slower than that of solvent-based inks. There is a demand for improved performance of corresponding inks and paper coating agents.

Against this background, the ink and water-based paint industries require surfactants that impart excellent surface tension-lowering properties for imparting wetting, penetrating and dispersing properties to substrates. When selecting a surfactant, it is preferable that the static surface tension is excellent when the system is in a static state, and the dynamic surface tension is desirable when using at high speeds due to the need to increase printing speed due to the above-mentioned productivity improvement. The index of tension has become important.

Ethylene oxide adducts of nonylphenol and polyoxyalkylene alkyl ethers are conventionally known to be useful as inks, wetting agents for paints, dispersion aids, and the like. However, the ethylene oxide adduct of nonylphenol may be a substance containing endocrine disruptors, and its use is feared. In addition, polyoxyalkylene alkyl ether is highly safe, but has high foamability, which impairs pigment dispersibility and cannot be applied to high-speed printing.

Therefore, in JP-A-2002-348500, JP-A-2003-113397, JP-A-2003-253599 and JP-A-2003-080839 (Patent Documents 1 to 4), 2 , 4,7,9-tetramethyl-5-decyne-4,7-diol and its ethoxylated acetylene glycol surfactant compositions have been proposed. These water-soluble surfactant compositions have excellent surface tension lowering ability, contact angle lowering ability, and antifoaming ability. Surfactant compositions with defoaming properties are desired.

Further, Japanese Patent Application Laid-Open No. 2006-117664 (Patent Document 5) proposes a surfactant composition containing 2-hydroxy-3-alkoxypropyl sulfide, sulfone and sulfoxide. This surfactant composition is excellent in surface tension lowering ability, wettability, and antifoaming properties. , can not meet sufficient performance.

Japanese Patent Application Laid-Open No. 2002-348500 JP-A-2003-113397 JP-A-2003-253599 JP-A-2003-080839 JP 2006-117664 A

The present invention has been made to improve the above circumstances, and exhibits excellent transparency, excellent defoaming properties and dispersibility, and has a low dynamic surface tension, resulting in excellent wettability and penetration. A water-soluble surfactant composition that imparts properties and is compatible with high-speed printing and high-speed coating considering solubility in water and environmental problems, and paper coating agents and inks containing the composition. intended to provide

As a result of intensive studies to achieve the above object, the present inventors have found that (A) a specified thioether compound and (B) a polyoxyalkylene alkyl ether within a specified HLB range are contained in a specified ratio. The water-soluble surfactant composition, especially when blended with a paper coating agent or ink, exhibits excellent defoaming properties and dispersibility, and has a low dynamic surface tension, resulting in excellent wettability, The inventors have found that they impart permeability, have good solubility in water, can be applied to high-speed printing and high-speed coating, and are suitable for recent environmental problems, and have completed the present invention.

（式（Ｉ）において、Ｒ¹は炭素原子１～１２のアルキル基又は炭素原子１～１２の塩素原子で置換されたアルキル基を表す。）
で表されるチオエーテル化合物：３０～７０質量％、及び
（Ｂ）下記平均組成式（ＩＩ）
Ｒ²Ｏ（Ｃ₂Ｈ₄Ｏ）_a（Ｃ₃Ｈ₆Ｏ）_b（Ｃ₂Ｈ₄Ｏ）_c（Ｃ₃Ｈ₆Ｏ）_dＨ （ＩＩ）
（式（ＩＩ）において、Ｒ²は炭素数５～２０の直鎖状、分枝状又は環状のアルキル基であり、ａ，ｂ，ｃ，ｄは０又は０～２５の正数である。但しａ及びｂのいずれかは０ではなく、かつ０≦ａ＋ｃ≦５０、０≦ｂ＋ｄ≦３０である。）
で表されるＨＬＢ値が８～１７のポリオキシアルキレンアルキルエーテル：７０～３０質量％
を含有することを特徴とする水溶性界面活性剤組成物。
２．上記平均組成式（ＩＩ）のＲ²が、炭素数５～１５の直鎖状、分枝状又は環状のアルキル基である上記１記載の水溶性界面活性剤組成物。
３．０．１質量％水溶液の１Ｈｚ及び１０Ｈｚ時の動的表面張力がそれぞれ４６ｍＮ／ｍ以下である上記１又は２記載の水溶性界面活性剤組成物。
４．上記１～３のいずれかに記載の水溶性界面活性剤組成物を配合することを特徴とする紙コート剤。
５．上記１～３のいずれかに記載の水溶性界面活性剤組成物を配合することを特徴とするインキ。 Accordingly, the present invention provides the water-soluble surfactant composition, paper coating agent and ink shown below.
1. (A) the following average composition formula (I)

(In Formula (I), R ¹ represents an alkyl group of 1 to 12 carbon atoms or an alkyl group of 1 to 12 carbon atoms substituted with a chlorine atom.)
Thioether compound represented by: 30 to 70% by mass, and (B) the following average composition formula (II)
^R2O _{( C2H4O ) a} ( _C3H6O ) _b ( _C2H4O ) _c ( _C3H6O ) _{dH ( II} )
(In formula (II), R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, and d are 0 or positive numbers of 0 to 25. However, either a or b is not 0, and 0≤a+c≤50 and 0≤b+d≤30.)
Polyoxyalkylene alkyl ether having an HLB value of 8 to 17 represented by: 70 to 30% by mass
A water-soluble surfactant composition comprising:
2. 2. The water-soluble surfactant composition as described in 1 above, wherein R ² in the average composition formula (II) is a linear, branched or cyclic alkyl group having 5 to 15 carbon atoms.
3. The water-soluble surfactant composition according to 1 or 2 above, wherein the dynamic surface tension of the 0.1% by mass aqueous solution at 1 Hz and 10 Hz is 46 mN/m or less, respectively.
4. A paper coating agent comprising the water-soluble surfactant composition according to any one of 1 to 3 above.
5. 4. An ink comprising the water-soluble surfactant composition according to any one of 1 to 3 above.

The water-soluble surfactant composition of the present invention has a low dynamic surface tension. An excellent surfactant composition that exhibits wettability, penetration, and antifoaming properties to materials, exhibits printability and color development, is compatible with high-speed printing and high-speed coating, and is also compatible with environmental problems. is. Due to this property, the water-soluble surfactant composition of the present invention is extremely advantageous in practical use.

The water-soluble surfactant composition of the present invention contains (A) a specified thioether compound and (B) a polyoxyalkylene alkyl ether having a specified HLB range.

Here, the thioether compound of component (A) is represented by the following average compositional formula (I).

In the above formula (I), R ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms and substituted with a chlorine atom. Specific examples of R ¹ include methyl group, ethyl group, chloromethyl group, chloroethyl group, propyl group, chloropropyl group, butyl group, pentyl group, hexyl group, pentyl group and octyl group, with octyl group being preferred. .

Examples of the thioether compound represented by the above formula (I) include those described in JP-A-2006-117664 [0070] Example 3 to [0073] Example 6, and may be used alone or as a mixture. . For example, 2-hydroxyethyl-2′-hydroxy-3′-butoxypropyl sulfide, 2-hydroxyethyl-2′-hydroxy-3′-dodecyloxypropyl sulfide, 2-hydroxyethyl-2′-hydroxy-3′- Tetradecyloxypropyl sulfide, 2-hydroxyethyl-2'-hydroxy-3'-hexadecyloxypropyl sulfide, 2-hydroxyethyl-2'-hydroxy-3'-(2-ethylhexyloxy) propyl sulfide, 2-hydroxy ethyl-2'-hydroxy-3'-octyloxypropyl sulfide, 2-hydroxyethyl-2'-hydroxy-3'-decyloxypropyl sulfide and the like.

The thioether compound represented by the above formula (I) is a reaction product of epichlorohydrin, 2-mercaptoethanol and 1-octanol, 2-hydroxyethyl-2, from the viewpoint of low surface tension and low foaming properties. '-Hydroxy-3'-octyloxypropyl sulfide is preferred.

The blending ratio of component (A) used in preparing the water-soluble surfactant composition of the present invention is preferably 30 to 70% by mass, more preferably 40 to 60% by mass, based on 100% by mass of the composition. %.

The polyoxyalkylene alkyl ether which is the component (B) of the present invention is represented by the following average compositional formula (II).
^R2O _{( C2H4O ) a} ( _C3H6O ) _b ( _C2H4O ) _c ( _C3H6O ) _{dH ( II} )
(In the formula, R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, and d are 0 or positive numbers of 0 to 25, provided that a and Any of b is not 0, and 0≤a+c≤50, 0≤b+d≤30.)

In this case, R ² is preferably a linear, branched or cyclic alkyl group having 5 to 15 carbon atoms, more preferably 10 to 14 carbon atoms. R ² is the average number of carbon atoms and represents either a single alkyl group or a mixed alkyl group, specifically C ₁₀ H ₂₁ , C ₁₁ H ₂₃ , C ₁₂ H ₂₅ , _C13H27 , _C14H29 and other _alkyl groups _. Also, a, b, c, and d are 0 or positive numbers of 0-25, and a+b+c+d is preferably a positive number of 2-60, particularly a positive number of 5-50. Furthermore, neither a nor b is 0, and 0≤a+c≤50, preferably 3≤a+c≤45, 0≤b+d≤30, preferably 0≤b+d≤10.

The polyoxyalkylene alkyl ether of the component (B) may be any polyoxyalkylene alkyl ether represented by the formula (II). Specifically,
_{C12H25O ( C2H4O ) 6 ( C3H6O} ) ₂ ( _C2H4O ) ₆ ( _{C3H6O ) 8H ,
C13H27O ( C2H4O ) 6 ( C3H6O} ) ₂ ( _C2H4O ) ₆ ( _{C3H6O ) 8H ,
C12H25O ( C2H4O ) a} ( _{C3H6O ) b ( C2H4O ) c} ( _C3H6O ) _dH
(where a + c = 15, b + d = 4),
_{C13H27O ( C2H4O ) a ( C3H6O ) b ( C2H4O} ) _c ( _C3H6O ) _dH
(where a + c = 15, b + d = 4),
_{C12H25O ( C2H4O ) 8} ( _C3H6O ) _{2 ( C2H4O} ) _{6H ,
C13H27O ( C2H4O ) 8} ( _C3H6O ) _{2 (} C2H4O _{) 6H ,
C12H25O ( C2H4O ) 12} ( _{C3H6O ) 2} ( _C2H4O ) _{12H ,
C13H27O ( C2H4O ) 12} ( _{C3H6O ) 2} ( _C2H4O ) _{12H ,
CH3} ( _{CH2 ) 9} ( _CH3 ) _CHO ( _C2H4O ) ₇ ( _C3H6O ) _4.5H ,
_CH3 ( _{CH2 ) 11} ( _CH3 ) _CHO ( _C2H4O ) ₇ ( _C3H6O ) _4.5H ,
_CH3 ( _CH2 ) ₉ ( _CH3 ) _{CHO ( C2H4O} ) ₅ ( _C3H6O ) _3.5H ,
_CH3 ( _{CH2 ) 11} ( _CH3 )CHO( _C2H4O ) ₅ ( _{C3H6O ) 3.5H} ,
_C14H29O ( _C2H4O ) _{14 ( C3H6O ) 2H ,
C11H23O ( C2H4O} ) _{8H ,
C10H21O} ( _{C2H4O ) 11H ,}
RO( _C2H4O ) _{a ( C3H6O ) b} ( _C2H4O ) _{c ( C3H6O ) dH}
(where a + c = 15, b + d = 1, R: branched alkyl having 10 carbon atoms),
_RO ( _C2H4O ) _{a ( C3H6O ) b} ( _C2H4O ) _c ( _{C3H6O ) dH}
(where a + c = 4, b + d = 1, R: branched alkyl having 10 carbon atoms),
_RO ( _C2H4O ) _{a ( C3H6O ) b} ( _C2H4O ) _c ( _{C3H6O ) dH}
(where a + c = 44, b + d = 1, R: branched alkyl having 10 carbon atoms),
_RO ( _C2H4O ) _{a ( C3H6O ) b} ( _C2H4O ) _c ( _{C3H6O ) dH}
(where a + c = 19, b + d = 1, R: linear alkyl having 14 carbon atoms),
_RO ( _C2H4O ) _{a ( C3H6O ) b} ( _C2H4O ) _c ( _{C3H6O ) dH}
(where a + c = 19, b + d = 1, R: branched alkyl having 14 carbon atoms),
RO( _{C2H4O ) 11H}
(where R: linear alkyl having 10 carbon atoms)
etc., and one of them can be used alone or two or more of them can be used in combination.

The HLB value of the polyoxyalkylene alkyl ether as the component (B) is 8-17, preferably 9-15. If the HLB value of the component (B) is less than 8, the hydrophobicity increases, the solubility in water decreases, and sufficient water solubility cannot be obtained. On the other hand, when the HLB value of the component (B) exceeds 17, the dynamic surface tension is high and foaming is likely to occur, causing bleeding during printing.

The HLB value is defined as 20 for a hypothetical compound having an infinitely long hydrophilic group attached to the lipophilic group of the surfactant and having the highest hydrophilicity, and 0 for a lipophilic compound having no hydrophilic group. It is a value calculated for each surfactant as a relative value to , and can generally be calculated by Griffin's formula.
Griffin's formula used for calculating the HLB value is shown below.
HLB value = 20 x Mw/M
M: molecular weight of nonionic surfactant, Mw: molecular weight of hydrophilic portion

The amount of component (B) used in preparing the water-soluble surfactant composition of the present invention is 30 to 70% by mass, preferably 40 to 60% by mass, based on 100% by mass of the composition. . If the content of the component (B) is less than 30% by mass, the component (A) is not sufficiently solubilized, resulting in generation of aggregates and poor pigment dispersibility. On the other hand, if the content of component (B) exceeds 70% by mass, foaming increases during blending, pigment dispersibility is poor, and printing defects due to ejection failure or coating defects such as unevenness occur. Further, in the present invention, if other anionic or cationic surfactants are used, they may easily foam, which is not preferable.

The water-soluble surfactant composition of the present invention further contains ion-exchanged water, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, 1,3- A water-soluble organic solvent such as propanediol, 1,4-butanediol and glycerin may be used in combination. The amount of component (C) is 0 to 39% by mass, preferably 0 to 30% by mass, more preferably 0 to 30% by mass, based on 100% by mass of the composition, as long as the properties of the water-soluble surfactant composition are not impaired. It can be used in amounts of 0 to 25% by weight.

The water-soluble surfactant composition of the present invention can be obtained, for example, by mixing the components described above by a known mixing preparation method such as a propeller stirrer. In addition, components that are solid at room temperature are heated and mixed as necessary.

Here, the obtained water-soluble surfactant composition preferably has a dynamic surface tension of 46 mN/m or less, more preferably 45 mN/m or less, and still more preferably 44 mN/m or less at 1 Hz and 10 Hz. be. When the dynamic surface tension at 1 Hz and 10 Hz of a 0.1% by mass aqueous solution of the resulting water-soluble surfactant composition exceeds 46 mN/m, repelling is not observed during brush coating or bar coater coating. However, when printing with a printing machine or a coating machine, bleeding may occur due to repelling or insufficient penetrating power.

In addition, it is preferable that the water-soluble polymer compound has antifoaming properties. The post foam height is preferably 18 ml or less, more preferably 15 ml or less. If the height of the foam immediately after shaking exceeds 20 ml, bleeding may occur due to poor dispersibility of the ink.

Here, the above-mentioned water-soluble polymer compound is not particularly limited, and can be appropriately selected from known ones. For example, natural water-soluble polymer compounds include plant-derived polymer compounds such as gum arabic, tragan gum, guar gum, karaya gum, locust bean gum, arabinogalactone, pectin, and quince seed starch, and seaweeds such as alginic acid, carrageenan, and agar. animal-based high-molecular compounds such as gelatin, casein, albumin and collagen; and microbial-based high-molecular compounds such as xanthan gum and dextran. Water-soluble polymer compounds chemically modified from natural products include fibrous polymer compounds such as methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, and carboxymethyl cellulose, sodium starch glycolate, and sodium starch phosphate. and seaweed-based polymer compounds such as propylene glycol alginate. Examples of synthetic water-soluble polymer compounds include vinyl-based polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone and polyvinyl methyl ether; acrylic compounds such as polyacrylamide, polyacrylic acid or alkali metal salts thereof; system resin, water-soluble styrene maleic acid resin, water-soluble vinylnaphthalene acrylic resin, water-soluble vinylnaphthalene maleic acid resin, polyvinylpyrrolidone, polyvinyl alcohol, polyallylamine, polyethyleneimine, alkali metal salt of β-naphthalenesulfonic acid formalin condensate, Examples include polymer compounds having salts of cationic functional groups such as quaternary ammonium and amino groups in side chains.

The static surface tension is the value of a 0.1% by mass aqueous solution measured using a surface tensiometer DY-500 (manufactured by Kyowa Interface Science Co., Ltd.), and the dynamic surface tension is a bubble pressure type dynamic Values of 1 Hz and 10 Hz of a 0.1% by mass aqueous solution were measured using a surface tension meter Cruz BP-100 (manufactured by KRUSS).

When the water-soluble surfactant composition of the present invention is used as a water-based wetting agent for a paper coating agent or ink is produced, the water-soluble surfactant composition is It is desirable to use it in an amount of preferably 0.05 to 10% by mass, more preferably 0.05 to 5% by mass.

When the water-soluble surfactant composition of the present invention is used as a paper coating agent, it can contain fine particles, hydrophilic binders and other additives in addition to the water-soluble surfactant composition of the present invention.

Examples of fine particles include at least one fine particle selected from organic fine particles, silica fine particles, alumina fine particles, and pseudo-boehmite type aluminum hydroxide fine particles. Among these, silica fine particles, alumina fine particles, and pseudo-boehmite type aluminum hydroxide fine particles are preferable. The average primary particle size of the fine particles is preferably 50 nm or less, more preferably 30 nm or less, and particularly preferably 15 nm or less. In particular, when the average primary particle diameter of the fine particles is 15 nm or less, the ink absorbing property can be effectively improved, and at the same time, the glossiness of the ink receiving layer surface can be enhanced. Although the lower limit of the average primary particle size of the fine particles is not particularly limited, it is preferably 1 nm or more.

The amount of the fine particles used in preparing the paper coating agent is not particularly limited, but is preferably 1 to 50% by mass, more preferably 5 to 40% by mass in the paper coating agent.

Examples of hydrophilic binders include polyvinyl alcohol, oxidized starch, etherified starch, cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, casein, gelatin, soybean protein, silanol-modified polyvinyl alcohol, styrene-butadiene copolymer, and methyl methacrylate-butadiene. Conjugated diene latex such as copolymer, acrylic copolymer latex such as acrylate and methacrylate copolymer, vinyl polymer latex such as ethylene vinyl acetate copolymer, maleic anhydride resin, melamine resin , urea resin, polymethyl methacrylate, polyurethane resin, unsaturated polyester, polyvinyl butyral, alkyd resin, etc., and these can be used alone or in combination of two or more. Moreover, from the viewpoint of ink absorbability, it is preferable to contain at least one selected from polyvinyl alcohol-based resins, cellulose-based resins, ether bond-containing resins, carbamoyl group-containing resins, carboxyl group-containing resins, and gelatins. more preferred. When the polyvinyl alcohol is used, the degree of saponification is preferably 82 mol % or more, more preferably 86 to 99 mol %, from the viewpoint of color density. The degree of polymerization is preferably 300 to 4,500, more preferably 500 to 2,600, from the viewpoint of obtaining sufficient film strength.

The amount of the hydrophilic binder used in preparing the paper coating agent is not particularly limited, but it is preferably 45 to 95% by weight, more preferably 55 to 90% by weight, in terms of a 1 to 5% by weight aqueous solution in the paper coating agent.

Other additives include pigment dispersants, thickeners, fluidity improvers, defoamers, foam inhibitors, release agents, foaming agents, penetrants, coloring dyes, coloring pigments, fluorescent brighteners, ultraviolet rays, Absorbents, antioxidants, antiseptics, fungicides, water whitening agents, wet paper strength agents, dry paper strength agents, etc., may also be added as appropriate. These additives can be added to 100% by mass of the paper coating agent as the balance after removing the above materials.

By blending the water-soluble surfactant composition of the present invention, fine particles, hydrophilic binder, and other additives, a paper coating agent is obtained, and the surface to be coated for printing is dipped or coated with the coating agent of the present invention. A coated paper can be obtained by coating by a known method such as gravure coating, which is used for application, spraying, and the like. At this time, the coating amount is adjusted to 3 to 50 g/m ² , more preferably 5 to 20 g/m ² , and the coating speed is 20 to 2,000 m/min, more preferably 40 to 2,000 m/min. A coated paper can be obtained by controlling the speed at 000 m/min.

When the water-soluble surfactant composition of the present invention is used for ink, in addition to the water-soluble surfactant composition of the present invention, colorants, solvents such as water and solvents, resins, and other additives are optionally added. can be included in

A dye, an organic pigment, or an inorganic pigment can be preferably used as the colorant. For example, dyes are classified into acid dyes, direct dyes, reactive dyes, vat dyes, sulfur dyes, or food dyes in the Color Index, as well as oil-soluble dyes and basic dyes. can also be used. Further, as a pigment, for black ink, carbon black (C.I. Pigment Black 7) such as furnace black (color black), lamp black, acetylene black, channel black, etc. Specifically, for example, Rayvan ( Raven) 7000, Rayvan 5750, Rayvan 5250, Rayvan 5000, Rayvan 3500, Rayvan 2000, Rayvan 1500, Rayvan 1250, Rayvan 1200, Rayvan 1190ULTRA-II, Rayvan 1170, Rayvan 1255 (manufactured by Columbia), Black Pearls (Black) Pearls L, Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Vulcan (Valcan) XC-72R (manufactured by Cabot Corporation), Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Printex 140V, Special Black 6, Special Black 5, Special Black 4A, Special Black 4 (manufactured by Degussa), No. 25, No. 33, No. 40, No. 47, No. 52, No. 900, No. 2300, MCF-88, MA600, MA7, MA8, MA100 (manufactured by Mitsubishi Chemical Corporation), etc., or metals such as copper oxide, iron oxide (CI Pigment Black 11), titanium oxide, etc., aniline black (C.I. Pigment Black 1) and other organic pigments. Further, for color inks, C.I. I. Pigment Yellow 1 (Fast Yellow G), 3, 12 (Disazo Yellow AAA), 13, 14, 17, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55, 74, 81, 83 (Disazo Yellow HR), 93, 94, 95, 97, 98, 100, 101, 104, 108, 109, 110, 117, 120, 128, 138, 153, 180, C.I. I. Pigment Red 1, 2, 3, 5, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48:2 (Permanent Red 2B (Ba)), 48:2 (Permanent Red 2B (Ca)), 48 :3 (Permanent Red 2B (Sr)), 48:4 (Permanent Red 2B (Mn)), 49:1, 52:2, 53:1, 57:1 (Brilliant Carmine 6B), 60:1, 63: 1, 63:2, 64:1, 81 (rhodamine 6G lake), 83, 88, 101 (red red), 104, 105, 106, 108 (cadmium red), 112, 114, 122 (quinacridone magenta), 123, 146, 149, 166, 168, 170, 172, 177, 178, 179, 185, 190, 193, 202, 206, 209, 219, C.I. I. Pigment Violet 19, 23, C.I. I. Pigment Orange 36, C.I. I. Pigment Blue 1, 2, 15 (Phthalocyanine Blue R), 15:1, 15:2, 15:3 (Phthalocyanine Blue G), 15:4, 15:6 (Phthalocyanine Blue E), 16, 17:1, 56 , 60, 63, C.I. I. Pigment Green 1, 4, 7, 8, 10, 17, 18, 36, etc. can be used.

The amount of the colorant used in preparing the ink is not particularly limited, but is preferably 0.1 to 15% by mass, more preferably 2 to 10% by mass in the ink.

Solvents include water, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2,000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1 ,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycols such as glycerin, mesoerythritol, pentaerythritol, alkyl alcohols having 1 to 4 carbon atoms, glycols There are ethers, formamide, acetamide, dimethyl sulfoxide, sorbitol, sorbitan, acetin, diacetin, triacetin, sulfolane, etc., and one or more of these can be appropriately selected and used.

The amount of the solvent used in preparing the ink is not particularly limited, but it is preferably 50 to 99% by mass, more preferably 60 to 95% by mass in the ink.

As the resin, it is preferable that the hydrophobic group of the substance forming the polymer is at least one selected from an alkyl group, a cycloalkyl group and an aryl group. Moreover, it is preferable that the hydrophilic group is at least a carboxyl group, a sulfonic acid group, a hydroxyl group, an amino group, an amide group, or a base thereof. Specific examples of substances that form these dispersed polymers include monomers and oligomers having double bond-containing acryloyl groups, methacryloyl groups, vinyl groups, or aryl groups. For example, styrene, tetrahydrofurfuryl acrylate, butyl methacrylate, (α,2,3 or 4)-alkylstyrene, (α,2,3 or 4)-alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, Divinylbenzene, vinylnaphthalene, dimethylamino (meth)acrylate, dimethylaminoethyl (meth)acrylate, dimethylaminopropylacrylamide, N,N-dimethylaminoethyl acrylate, acryloylmorpholine, N,N-dimethylacrylamide, N-isopropylacrylamide , N,N-diethylacrylamide, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, ethylhexyl (meth)acrylate, other alkyl (meth)acrylates, methoxydiethylene glycol (meth)acrylate, ethoxy group, propoxy Diethylene glycol or polyethylene glycol (meth)acrylate with group, butoxy group, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, isobornyl (meth)acrylate, hydroxyalkyl (meth)acrylate, and other fluorine-containing , chlorine-containing, silicon-containing (meth)acrylate, (meth)acrylamide, maleic acid amide, (meth)acrylic acid, etc. When introducing a crosslinked structure in addition to monofunctional (mono, di, tri, tetra, poly) (meth)acrylates such as ethylene glycol di(meth)acrylate, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, tri Methylolpropane tri(meth)acrylate, glycerin (di, tri)(meth)acrylate, di(meth)acrylate of ethylene oxide adduct of bisphenol A or F, neopentyl glycol di(meth)acrylate, pentaerythritol tetra(meth)acrylate , dipentaerythritol hexa(meth)acrylate, and other compounds having an acrylic group or a methacrylic group can be used.

The amount of the resin used when preparing the ink is not particularly limited, but it is preferably 0 to 30% by mass, more preferably 0 to 20% by mass in the ink. In addition, when blending, it is preferable to make it 1 mass % or more.

As other additives, an ultraviolet absorber, an antioxidant, a pH adjuster, an antiseptic, a viscosity adjuster, and the like can be added as appropriate. These other additives can be blended as the balance in 100% by mass of the ink composition in addition to the above materials.

By dispersing, dissolving, mixing and stirring the water-soluble surfactant composition of the present invention, colorant, solvent, resin, other additives, etc., an ink having excellent properties can be obtained.
By adjusting the viscosity to 4 mPa·s or less (not including 0), the obtained ink has excellent printing characteristics.

EXAMPLES Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. In the following examples, parts and % indicate parts by mass and % by mass, respectively.

[Example 1]
After 50 parts of the thioether compound (A) shown in Table 1 below heated to 50 ° C. was charged into a propeller stirrer, and then heated to 50 ° C. with stirring, (B) B shown in Table 1 below was added. 50 parts of the -1 component was added, and after stirring for 2 hours, the mixture was cooled to room temperature. After cooling, the mixture was filtered through a 300-mesh filter cloth to obtain a surfactant composition of Example 1.

[Examples 2 to 10, Comparative Examples 1 to 9]
In the same manner as in Example 1, Examples 2 to 10 were obtained with the composition shown in Table 1. Further, in the same manner as in Example 1, Comparative Examples 1 to 9 were obtained with the composition shown in Table 2.

(A): 1-[(2-hydroxyethyl)thio]-3-(octyloxy)-2-propanol (B) Component B-1: RO(C ₂ H ₄ O)a(C ₃ H ₆ O) bH
R = alkyl having 12 and 14 carbon atoms, a = 7, b = 4.5, HLB value: 12
Component B-2: RO(C ₂ H ₄ O) a (C ₃ H ₆ O) b (C ₂ H ₄ O) c (C ₃ H ₆ O) dH
R = alkyl having 12 and 13 carbon atoms, a + c = 15, b + d = 4, HLB value: 15
Component B-3: RO(C ₂ H ₄ O)a(C ₃ H ₆ O)bH
R = alkyl having 12 and 14 carbon atoms, a = 5, b = 3.5, HLB value: 11
B-4 component: RO(C ₂ H ₄ O)aH
R = C11 alkyl, a = 8, HLB value: 13
Component B-5: RO(C ₂ H ₄ O)aH
R = alkyl having 10 carbon atoms, a = 11, HLB value: 14
B'-1 component: RO(C ₂ H ₄ O)aH
R = alkyl having 12 to 33 carbon atoms (average carbon number 23), a = 15, HLB value: 14
B'-2 component: RO(C ₂ H ₄ O)aH
R = C12 alkyl, a = 40, HLB value: 18
B'-3 components: RO(C ₂ H ₄ O)aH
R = C14 alkyl, a = 2, HLB value: 4

In addition, the measurement of each physical property was performed as follows. Table 2 shows the results.
<Water solubility>
The appearance of the aqueous solution and the presence or absence of insoluble matter were visually observed.
○: The aqueous solution is transparent and no insoluble matter is observed △: The aqueous solution is cloudy, but no insoluble matter is observed ×: Some insoluble matter is observed

<Static surface tension>
Using a surface tensiometer DY-500 manufactured by Kyowa Interface Science Co., Ltd., the static surface tension of a 0.1% aqueous solution of the surfactant composition was measured at room temperature.

<Dynamic surface tension>
Using a bubble pressure type dynamic surface tension meter Cruz BP-100 manufactured by KRUSS, the dynamic surface tension of a 0.1% aqueous solution of the surfactant composition at room temperature was measured at 1 Hz and 10 Hz.

<Application test>
Bar coater no. 7 was applied to a PET film, and cissing immediately after application was visually observed.
○: Repelling and pinholes are not observed △: Some repelling or pinholes are observed ×: Many repelling or pinholes are observed

[Containing paper coating agent]
[Example C-1]
As a paper coating agent, Example 1 1 part of the surfactant composition, 10 parts of vapor-phase silica fine particles (AEROSIL 300SF75, manufactured by Nippon Aerosil, average primary particle diameter 7 nm), and after stirring with a propeller stirrer for 30 minutes, the paper coating agent formulation ( Hereinafter, this is referred to as "Example Co-1").

[Examples C-2 to C-10, Comparative Examples C-1 to C-9]
In the same manner as in Example C-1, paper coating agent formulations (hereinafter referred to as "Examples C-2 to C-10") were obtained using Examples 2 to 10 with the formulations shown in Table 3.
Further, paper coating agent formulations using Comparative Examples 1 to 9 (hereinafter referred to as "Comparative Examples Co-1 to Co-9") were obtained according to the formulation shown in Table 4.

[Comparative Examples Co-10 and Co-11]
A paper coating agent “Comparative Example Co-10” using Comparative Example 1 and a paper coating agent “Comparative Example Co-11” using Comparative Example 3 were obtained with the formulations shown in Table 4, respectively.

[Comparative example C-12]
A paper coating agent "Comparative Example C-12" was obtained using Comparative Example 6 with the formulation shown in Table 4.

Each characteristic was measured as follows. The results are also shown in Table 2.
[Evaluation of paper coating agent]
1) Repelling Using a printing suitability tester (GRAVO-PROOF) manufactured by Nissho Gravure Co., Ltd., a paper coating agent is applied at a coating speed of 50 m / min to 8 g / m ² of non-sized paper, and repelling etc. on the coated surface The condition was confirmed visually.
○: Repelling and pinholes are not observed △: Some repelling or pinholes are observed ×: Many repelling or pinholes are observed

2) Foamability A sample was prepared by diluting a paper coating agent at a ratio of coating agent/water=1/2. 20 ml of this sample was placed in a 100 ml graduated cylinder and shaken for 1 minute with a shaker at 180 reciprocations/min. The foamability immediately after shaking is 20 ml or less, preferably 15 ml or less, and the foamability after 5 minutes is 15 ml or less, preferably 10 ml or less.

Claims (5)

(A) the following average composition formula (I)

(In formula (I), R ¹ represents an alkyl group of 1 to 12 carbon atoms or an alkyl group of 1 to 12 carbon atoms substituted with a chlorine atom.)
Thioether compound represented by: 30 to 70% by mass, and (B) the following average composition formula (II)
^R2O _{( C2H4O ) a} ( _C3H6O ) _b ( _C2H4O ) _c ( _C3H6O ) _{dH ( II} )
(In Formula (II), R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, and d are 0 or positive numbers of 0 to 25. However, either a or b is not 0, and 0≤a+c≤50 and 0≤b+d≤30.)
Polyoxyalkylene alkyl ether having an HLB value of 8 to 17 represented by: 70 to 30% by mass
A water-soluble surfactant composition comprising: 2. The water-soluble surfactant composition according to claim 1, wherein R ² in the average compositional formula (II) is a linear, branched or cyclic alkyl group having 5 to 15 carbon atoms. 3. The water-soluble surfactant composition according to claim 1, wherein the dynamic surface tension of a 0.1% by mass aqueous solution at 1 Hz and 10 Hz is 46 mN/m or less. A paper coating agent comprising the water-soluble surfactant composition according to any one of claims 1 to 3. An ink comprising the water-soluble surfactant composition according to any one of claims 1 to 3.