JP2021112701A - Water-soluble surfactant composition, paper coating agent and ink - Google Patents

Abstract

SOLUTION: A water-soluble surfactant composition contains (A) 70-30 mass% thioether compound exhibited as formula (I); (R1 is a 1-12C alkyl group or a 1-12C alkyl group substituted with chlorine atom) and (B) 30-70 mass% polyoxyalkylene alkyl ether which is exhibited as formula (II); R2O(C2H4O)a(C3H6O)b(C2H4O)c(C3H6O)dH(II) (R2 is a 5-20C linear, branched or cyclic alkyl group and a, b, c and d are each 0 or an integer of 0-25) and which has an HLB value of 8-17.EFFECT: A water-soluble surfactant composition improves the dispersibility of a fine particle used in an accepting layer when added to a paper coating agent and exhibits wettability to a base material, permeability, defoaming property, printing property and color development property when added to ink.SELECTED DRAWING: None

Description

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

In recent years, printers for office automation equipment such as personal computers have rapidly become widespread in offices and homes due to low prices, improved print quality, and improved reliability. Along with this, the demand for inks is expanding from general household use to industrial use, but on the other hand, in order to further improve print quality, saturation, appearance, image, and storage stability, conventional dye inks are replaced with pigments. Inks with more advanced characteristics such as ink are required, and the types of inks are increasing.

Also, in the printing industry and the paper industry, water-based inks are becoming more and more water-based due to recent environmental problems. However, when water-based inks are used, the drying speed is slower, and the production speed is slower than that of solvent-based inks. There is a demand for improved performance of compatible inks and paper coating agents.

Against this background, the ink and water-based paint industries require a surfactant that imparts excellent surface tension lowering ability in order to impart wettability, permeability and dispersibility to a substrate. 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 is used at high speed due to the necessity of speeding up printing due to the above-mentioned productivity improvement. The index of tension is important.

Conventionally, ethylene oxide adducts of nonylphenol and polyoxyalkylene alkyl ethers have been known to be useful as inks, paint wetting agents, dispersion aids and the like. However, the ethylene oxide adduct of nonylphenol may be an endocrine disrupter, and its use is feared. Further, although the polyoxyalkylene alkyl ether has high safety, it has high foaming property, which impairs pigment dispersibility and cannot cope with 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), polyoxyalkylene alkyl ether is used as 2 , 4,7,9-Tetramethyl-5-decyne-4,7-diol and an acetylene glycol-based surfactant such as an ethoxylated product thereof are blended in a water-soluble surfactant composition. These water-soluble surfactant compositions have excellent surface tension lowering ability, contact angle lowering ability, and defoaming property, but with the recent improvement in high-speed printing technology, pigment dispersion performance has become even more excellent. A surfactant composition having defoaming performance is 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 defoaming property, but due to its poor water solubility, it does not become a transparent coating agent and causes repelling during coating. , Sufficient performance cannot be met.

JP-A-2002-348500 Japanese Unexamined Patent Publication No. 2003-113397 Japanese Unexamined Patent Publication No. 2003-253599 Japanese Unexamined Patent Publication No. 2003-080839 Japanese Unexamined Patent Publication No. 2006-117664

The present invention has been made to improve the above circumstances, and has excellent transparency, excellent defoaming property and dispersibility, and further low dynamic surface tension, so that it has excellent wettability and penetration. A water-soluble surfactant composition that imparts properties and is compatible with high-speed printing and high-speed coating in consideration of water solubility and environmental issues, and paper coating agents and inks containing the composition. The purpose is to provide.

As a result of diligent studies to achieve the above object, the present inventors contained (A) a thioether compound to be specified and (B) a polyoxyalkylene alkyl ether in a specific HLB range in a specific ratio. When the water-soluble surfactant composition is blended with a paper coating agent or an ink, it exhibits excellent defoaming property and dispersibility, and has a lower dynamic surface tension, so that it has excellent wettability. We have found that it imparts permeability, has good solubility in water, can be used for high-speed printing and high-speed coating, and is also suitable for recent environmental problems, and has led to 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。 Therefore, the present invention provides the following water-soluble surfactant compositions, paper coating agents and inks.
1. 1. (A) The following average composition formula (I)

(In the formula (I), R ¹ represents an alkyl group having carbon atoms 1 to 12 or an alkyl group substituted with a chlorine atom having carbon atoms 1 to 12).
Thioether compound represented by: 30 to 70% by mass, and (B) the following average composition formula (II).
R ² O (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H (II)
(In formula (II), R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, d are positive numbers of 0 or 0 to 25. However, either a or b is not 0, and 0 ≦ a + c ≦ 50, 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 1 above, wherein R 2 of 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 containing the water-soluble surfactant composition according to any one of 1 to 3 above.
5. An ink comprising the water-soluble surfactant composition according to any one of 1 to 3 above.

Since the water-soluble surfactant composition of the present invention has a low dynamic surface tension, when it is added to a paper coating agent, the dispersibility of fine particles used in the receiving layer is improved, and when it is added to an ink, it is a base. An excellent surfactant composition that exhibits wettability, permeability and defoaming properties to materials, exhibits printability and color development properties, can be used for high-speed printing and high-speed coating, and is also suitable for 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 thioether compound to be specified and (B) a polyoxyalkylene alkyl ether in the range of the specified HLB.

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

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

Examples of the thioether compound represented by the above formula (I) include those described in JP-A-2006-117664 [0070] Examples 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 Examples thereof include ethyl-2'-hydroxy-3'-octyloxypropyl sulfide and 2-hydroxyethyl-2'-hydroxy-3'-decyloxypropyl sulfide.

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

The blending ratio of the 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 composition formula (II).
R ² O (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H (II)
(In the formula, R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, d are positive numbers of 0 or 0 to 25, where a and Any of b is not 0, and 0 ≦ a + c ≦ 50 and 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. Note that R ² is an average value of the 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 , and C ₁₂ H. Alkyl groups such as ₂₅ , C ₁₃ H ₂₇ and C ₁₄ H _{29 can be mentioned.} Further, it is preferable that a, b, c and d are positive numbers of 0 or 0 to 25, and a + b + c + d is a positive number of 2 to 60, particularly a positive number of 5 to 50. Further, any of a and b is not 0, and 0 ≦ a + c ≦ 50, preferably 3 ≦ a + c ≦ 45, 0 ≦ b + d ≦ 30, and preferably 0 ≦ b + d ≦ 10.

The polyoxyalkylene alkyl ether of the component (B) may be a polyoxyalkylene alkyl ether represented by the formula (II), but specifically, it may be a polyoxyalkylene alkyl ether represented by the formula (II).
C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₈ H,
C ₁₃ H ₂₇ O (C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₆ (C ₃ H ₆ O) ₈ H,
C ₁₂ H ₂₅ O (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 15, b + d = 4),
C ₁₃ H ₂₇ O (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 15, b + d = 4),
C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₈ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₆ H,
C ₁₃ H ₂₇ O (C ₂ H ₄ O) ₈ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₆ H,
C ₁₂ H ₂₅ O (C ₂ H ₄ O) ₁₂ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₁₂ H,
C ₁₃ H ₂₇ O (C ₂ H ₄ O) ₁₂ (C ₃ H ₆ O) ₂ (C ₂ H ₄ O) ₁₂ H,
CH ₃ (CH ₂ ) ₉ (CH ₃ ) CHO (C ₂ H ₄ O) ₇ (C ₃ H ₆ O) _4.5 H,
CH ₃ (CH ₂ ) ₁₁ (CH ₃ ) CHO (C ₂ H ₄ O) ₇ (C ₃ H ₆ O) _4.5 H,
CH ₃ (CH ₂ ) ₉ (CH ₃ ) CHO (C ₂ H ₄ O) ₅ (C ₃ H ₆ O) _3.5 H,
CH ₃ (CH ₂ ) ₁₁ (CH ₃ ) CHO (C ₂ H ₄ O) ₅ (C ₃ H ₆ O) _3.5 H,
C ₁₄ H ₂₉ O (C ₂ H ₄ O) ₁₄ (C ₃ H ₆ O) ₂ H,
C ₁₁ H ₂₃ O (C ₂ H ₄ O) ₈ H,
C ₁₀ H ₂₁ O (C ₂ H ₄ O) ₁₁ H,
RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 15, b + d = 1, R: branched alkyl having 10 carbon atoms),
RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 4, b + d = 1, R: branched alkyl having 10 carbon atoms),
RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 44, b + d = 1, R: branched alkyl having 10 carbon atoms),
RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 19, b + d = 1, R: linear alkyl having 14 carbon atoms),
RO (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H
(However, a + c = 19, b + d = 1, R: branched alkyl having 14 carbon atoms),
RO (C ₂ H ₄ O) ₁₁ H
(However, R: linear alkyl having 10 carbon atoms)
Etc., and one of them can be used alone or in combination of two or more.

The HLB value of the polyoxyalkylene alkyl ether which is the component (B) is 8 to 17, particularly preferably 9 to 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 large and foaming is likely to occur, which causes bleeding during printing.

The HLB value is defined as 20 for a virtual compound having an infinitely long hydrophilic group added to the lipophilic group of a 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 with respect to, and can be generally calculated by the formula of Griffin.
The Griffin formula used to calculate the HLB value is shown below.
HLB value = 20 x Mw / M
M: Molecular weight of nonionic surfactant, Mw: Molecular weight of hydrophilic part

The blending amount of the component (B) used when 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, aggregates are generated, and the pigment dispersibility deteriorates. On the other hand, if the content of the component (B) exceeds 70% by mass, foaming at the time of blending increases, pigment dispersibility is poor, and poor printing or uneven coating due to poor ejection occurs. Further, in the present invention, it is not preferable to use other surfactants such as anionic and cationic surfactants because they may easily foam.

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- as the third component (C). Water-soluble organic solvents such as propanediol, 1,4-butanediol, and glycerin may be used in combination. The blending amount of the 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 characteristics of the water-soluble surfactant composition are not impaired. It can be used in an amount of 0 to 25% by mass.

The water-soluble surfactant composition of the present invention can be obtained, for example, by mixing each of the above components by a known mixing preparation method such as a propeller type stirrer. Further, the components that are solid at room temperature are mixed by heating if necessary.

Here, the obtained water-soluble surfactant composition has a dynamic surface tension at 1 Hz and 10 Hz, preferably 46 mN / m or less, more preferably 45 mN / m or less, still more preferably 44 mN / m or less, respectively. be. When the dynamic surface tension of the obtained 0.1% by mass aqueous solution of the water-soluble surfactant composition at 1 Hz and 10 Hz exceeds 46 mN / m, no repellency is 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.

Further, it is preferable to have defoaming property with respect to the water-soluble polymer compound, and as an index thereof, the foaming property is such that the height of the foam immediately after shaking is preferably 20 ml or less, more preferably 19 ml or less, 5 minutes. The height of the subsequent foam is preferably 18 ml or less, more preferably 15 ml or less. If the height of the bubbles immediately after shaking exceeds 20 ml, bleeding may occur due to poor dispersibility of the ink or the like.

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 vegetable polymer compounds such as Arabic gum, tragan gum, guar gum, caraya gum, locust bean gum, arabinogalactone, pectin, and quince seed starch, and seaweeds such as alginic acid, carrageenan, and agar. Examples thereof include based polymer compounds, animal-based polymer compounds such as gelatin, casein, albumin and collagen, and microbial polymer compounds such as pectin gum and dextran. Examples of the water-soluble polymer compound 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 ester. Examples thereof include starch-based polymer compounds such as, and seaweed-based polymer compounds such as alginate propylene glycol ester. Examples of the synthetic water-soluble polymer compound include vinyl-based polymer compounds such as polyvinyl alcohol, polyvinylpyrrolidone, and polyvinylmethyl ether, polyacrylamide, polyacrylic acid or an alkali metal salt thereof, and acrylic such as water-soluble styrene acrylic resin. System resin, water-soluble styrene maleic acid resin, water-soluble vinyl naphthalene acrylic resin, water-soluble vinyl naphthalene maleic acid resin, polyvinyl pyrrolidone, polyvinyl alcohol, polyallylamine, polyethylene imine, alkali metal salt of β-naphthalene sulfonic acid formalin condensate, Examples thereof include polymer compounds having a salt of a cationic functional group such as quaternary ammonium or an amino group in the side chain.

The static surface tension was measured by measuring the value of a 0.1 mass% aqueous solution using a tensiometer DY-500 (manufactured by Kyowa Interface Science Co., Ltd.), and the dynamic surface tension was a bubble pressure type dynamic. The values of 1 Hz and 10 Hz of a 0.1 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 an aqueous wetting agent for a paper coating agent or an ink is produced, the water-soluble surfactant composition is used with respect to the total amount of the paper coating agent or the total amount of the ink. It is desirable to use it in an amount of 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 may contain fine particles, a hydrophilic binder, and other additives in addition to the water-soluble surfactant composition of the present invention.

Examples of the fine particles include at least one kind of fine particles 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 size of the fine particles is 15 nm or less, the ink absorption characteristics can be effectively improved, and at the same time, the glossiness of the surface of the ink receiving layer can be improved. The lower limit of the average primary particle size of the fine particles is not particularly limited, but 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 the hydrophilic binder 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. Conjugate diene latex such as copolymer, acrylic copolymer latex such as acrylic acid ester and methacrylic acid ester 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 and other synthetic resins, and one of these can be used alone or in combination of two or more. Further, from the viewpoint of ink absorbency, it may contain at least one selected from polyvinyl alcohol-based resin, cellulosic resin, resin having an ether bond, resin having a carbamoyl group, resin having a carboxy group, and gelatins. More preferable. When the above 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 development concentration. 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 is preferably 45 to 95% by mass, more preferably 55 to 90% by mass in a 1 to 5% by mass aqueous solution of the paper coating agent.

Other additives include pigment dispersants, thickeners, fluidity improvers, defoamers, defoamers, mold release agents, foaming agents, penetrants, color dyes, color pigments, optical brighteners, and ultraviolet rays. Absorbents, antioxidants, preservatives, antifoaming agents, water-whitening agents, wet paper strength enhancers, dry paper strength enhancers and the like can also be appropriately blended. These additives can be added as a balance excluding the above materials in 100% by mass of the paper coating agent.

By blending the above-mentioned water-soluble surfactant composition of the present invention, fine particles, hydrophilic binder, and other additives, a paper coating agent can be obtained, and the coating agent of the present invention is dipped or immersed in a surface to be coated for printing. A coated paper can be obtained by coating with a known method such as a gravure coat used for coating or spraying. 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, By controlling to 000 m / min, coated paper can be obtained.

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, a colorant, a solvent such as water or a solvent, a resin, or other additives are optional. Can be included in.

As the colorant, dyes, organic pigments or inorganic pigments can be preferably used. For example, as dyes, colorants classified into oil-soluble dyes and basic dyes in addition to those classified as acidic dyes, direct dyes, reactive dyes, virgin dyes, sulfur dyes or food dyes in the color index. Can also be used. Further, as a pigment, for black ink, carbon black (CI 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 1190 ULTRA-II, Rayvan 1170, Rayvan 1255 (above, made by Columbia), Black Pearls (Black) Pearls L, Legal 400R, Legal 330R, Legal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880, Monac 900, Monac 1000, Monac 1100, Monac 1300, Monac 1400, Vulcan (Valcan) XC-72R (above, manufactured by Cabot), 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 (all manufactured by Mitsubishi Chemical Corporation), etc., or metals such as copper oxide, iron oxide (CI pigment black 11), titanium oxide, aniline black Examples thereof include organic pigments such as (CI Pigment Black 1). 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) 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 (Bengara), 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 (Pphthalocyanine Blue R), 15: 1, 15: 2, 15: 3 (Pphthalocyanine Blue G), 15: 4, 15: 6 (Parthalocyanine Blue E), 16, 17: 1, 56 , 60, 63, C.I. I. Pigment Greens 1, 4, 7, 8, 10, 17, 18, 36 and the like 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.

As the solvent, 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, glycerin, mesoerythritol, pentaerythritol and other glycols, alkyl alcohols with 1 to 4 carbon atoms, glycol There are ethers, formamides, acetamides, dimethylsulfoxides, solvents, sorbitans, acetylines, diacetins, triacetins, sulfolanes and the like, 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 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 or an aryl group. The hydrophilic group is preferably at least a carboxyl group, a sulfonic acid group, a hydroxyl group, an amino group, an amide group, or a base thereof. As a specific example of the substance forming the dispersed polymer, a monomer or an oligomer having an acryloyl group, a methacryloyl group, a vinyl group or an aryl group having a double bond can be used. 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) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy group, propoxy Group, butoxy group diethylene glycol or polyethylene glycol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, isobonyl (meth) acrylate, hydroxyalkyl (meth) acrylate, and other fluorine-containing When introducing a crosslinked structure in addition to monofunctionals such as chlorine-containing, silicon-containing (meth) acrylate, (meth) acrylamide, maleic acid amide, and (meth) acrylic acid (mono, di, tri, tetra, poly) (Meta) 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. Methylolpropan 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 in preparing the ink is not particularly limited, but is preferably 0 to 30% by mass, more preferably 0 to 20% by mass in the ink. When blended, it is preferably 1% by mass or more.

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

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

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following example, parts and% indicate parts by mass and% by mass, respectively.

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

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

(A): 1-[(2-Hydroxyethyl) thio] -3- (octyloxy) -2-propanol (B) B-1 component: RO (C ₂ H ₄ O) a (C ₃ H ₆ O) bH
R = alkyl with 12 or 14 carbon atoms, a = 7, b = 4.5, HLB value: 12
B-2 component: 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 with 12 or 13 carbon atoms, a + c = 15, b + d = 4, HLB value: 15
B-3 component: RO (C ₂ H ₄ O) a (C ₃ H ₆ O) bH
R = alkyl with 12 or 14 carbon atoms, a = 5, b = 3.5, HLB value: 11
B-4 component: RO (C ₂ H ₄ O) aH
R = alkyl with 11 carbon atoms, a = 8, HLB value: 13
B-5 component: RO (C ₂ H ₄ O) aH
R = alkyl with 10 carbon atoms, a = 11, HLB value: 14
B'-1 component: RO (C ₂ H ₄ O) aH
R = alkyl with 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 = alkyl with 12 carbon atoms, a = 40, HLB value: 18
B'-3 component: RO (C ₂ H ₄ O) aH
R = 14 carbon alkyl, a = 2, HLB value: 4

The physical properties were measured as follows. The results are shown in Table 2.
<Water solubility>
The appearance of the aqueous solution and the presence or absence of insoluble matter were visually confirmed.
◯: The aqueous solution is transparent and no insoluble matter is observed. Δ: The aqueous solution is cloudy, but no insoluble matter is observed. ×: Some insoluble matter is observed.

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

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

<Application test>
A 0.1% aqueous solution of the surfactant composition was added to Barcoater No. It was applied to the PET film in No. 7, and the repellent immediately after the application was visually observed.
〇: No repellents or pinholes are seen Δ: Some repellents or pinholes are observed ×: Many repellents or pinholes are observed

[Paper coating agent combination]
[Example Ko-1]
Example 1 as a paper coating agent for 100 parts of a 2.5% aqueous solution of the trade name "Kuraray Poval 117" (degree of polymerization 1,700, degree of saponification 98-99 mol% polyvinyl alcohol) manufactured by Kuraray Co., Ltd. 1 part of the surfactant composition of No. 1 and 10 parts of vapor phase silica fine particles (AEROSIL300SF75, manufactured by Nippon Aerosil, average primary particle diameter 7 nm) were added, and the mixture was stirred with a propeller type stirrer for 30 minutes, and then the paper coating agent formulation (AEROSIL300SF75, manufactured by Nippon Aerosil, average primary particle diameter 7 nm) was added. Hereinafter, this is referred to as “Example Ko-1”).

[Examples Co-2 to Co-10, Comparative Examples Co-1 to Co-9]
In the same manner as in Example Ko-1, a paper coating agent formulation using Examples 2 to 10 with the formulations shown in Table 3 (hereinafter referred to as “Examples Ko-2 to Ko-10”) was obtained.
In addition, a paper coating agent formulation (hereinafter referred to as "Comparative Examples Co-1 to Co-9") using Comparative Examples 1 to 9 was obtained with the formulations shown in Table 4.

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

[Comparative Example Co-12]
A paper coating agent “Comparative Example Co 12” using Comparative Example 6 with the formulations shown in Table 4 was obtained.

Each characteristic was measured as follows. The results are also shown in Table 2.
[Evaluation of paper coating agent]
1) Hajiki Using a printing suitability tester (GRAVO-PROOF) manufactured by Nissho Gravure Co., Ltd., apply 8 g / m ^{2 of} paper coating agent to non-sized paper at a coating speed of 50 m / min to remove repellents on the coated surface. The condition was visually confirmed.
○: No repellents or pinholes △: Some repellents or pinholes are observed ×: Many repellents or pinholes are observed

2) Foamable paper coating agent was diluted with a coating agent / water = 1/2 ratio to prepare a sample. 20 ml of this sample was placed in a 100 ml graduated cylinder and shaken 180 times with a shaker for 1 minute, and the number of ml of foam was measured immediately after the shaking was completed and 5 minutes later. Immediately after the end of shaking, the foaming property is 20 ml or less, preferably 15 ml or less, and after 5 minutes, the foaming property is 15 ml or less, preferably 10 ml or less.

Claims (5)

(A) The following average composition formula (I)

(In the formula (I), R ¹ represents an alkyl group having carbon atoms 1 to 12 or an alkyl group substituted with a chlorine atom having carbon atoms 1 to 12).
Thioether compound represented by: 30 to 70% by mass, and (B) the following average composition formula (II).
R ² O (C ₂ H ₄ O) _a (C ₃ H ₆ O) _b (C ₂ H ₄ O) _c (C ₃ H ₆ O) _d H (II)
(In formula (II), R ² is a linear, branched or cyclic alkyl group having 5 to 20 carbon atoms, and a, b, c, d are positive numbers of 0 or 0 to 25. However, either a or b is not 0, and 0 ≦ a + c ≦ 50, 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. ^{The water-soluble surfactant composition according to claim 1, wherein R 2 of the} average composition formula (II) is a linear, branched or cyclic alkyl group having 5 to 15 carbon atoms. The water-soluble surfactant composition according to claim 1 or 2, wherein the dynamic surface tensions of the 0.1 mass% aqueous solution at 1 Hz and 10 Hz are 46 mN / m or less, respectively. A paper coating agent containing 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.