JP2002348500A - Water-soluble surfactant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a water-soluble surfactant composition which, because giving a low contact angle immediately after being dropped and besides a low dynamic surface tension, exhibits wetting property, permeability and antifoaming property for base materials when added in inks and can meet high speed printing and high speed coating, and which also complies with environmental issues. SOLUTION: The composition contains (A) 30-80 wt.% of one or more selected from acetylene glycol or its ethoxylated product and (B) 20-70 wt.% of one or more of polyoxyalkylene alkylethers having a HLB of 8-18 represented by formula (3) R<3> O(C2 H4 O)w (C3 H6 O)x (C2 H4 O)y (C3 H6 O)z H (3) [wherein R<3> is a 1-20C alkyl, w is an integer of 1-20, and x, y, and z are zero or an integer of 1-20]. Its 0.1 wt.% aqueous solution has a contact angle of <=40 deg. at 30 seconds after being dropped and a dynamic surface tension of each <=50 mN/m at 1 Hz and 10 Hz.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble surfactant composition, and in particular, when formulated into an ink or paper coating agent, has a low dynamic surface tension and therefore has excellent wettability and penetration. The present invention relates to a water-soluble surfactant composition which exhibits high water-repellency and defoaming properties, can cope with high-speed printing and high-speed coating, and is also suitable for recent environmental problems.

[0002]

2. Description of the Related Art In recent years,
The proportion of recording systems that use water-based inks in printers for OA equipment such as personal computers is increasing, and the demand for inks is also increasing with this. On the other hand, print quality, saturation, appearance, In order to improve the image, inks having higher characteristics have been required.

[0003] In the printing industry and the papermaking industry, it is inevitable to respond to higher speeds due to improved productivity.
There is a demand for improved performance of inks and paper coating agents corresponding to high-speed printing and high-speed coating.

[0004] Against this background, the ink and water-based paint industries require a surfactant that imparts an excellent surface tension lowering ability to wet and base the substrate. When selecting a surfactant, the static surface tension should be excellent when the system is in a static state, and the dynamic surface should be used at high speeds due to the need for speeding up printing due to the aforementioned productivity improvement. Tension indicators have become very important.

[0005] Acetylene glycol-based surfactants such as 2,4,7,9-tetramethyl-5-decyne-4,7-diol and ethoxylated products thereof have a low static surface tension and a high dynamic surface tension. It is well-balanced with its ability to lower, has almost no negative points of conventional nonionic and anionic surfactants, and has defoaming properties. It has been used as an auxiliary.

However, acetylene glycol-based surfactants have problems such as low solubility in water or solids at room temperature. Therefore, polyethylene glycol or polyoxyethylene nonyl phenyl ether is used in combination as a solubilizing agent. And self-emulsifying properties when added to aqueous inks and the like.

[0007] In Japanese Patent Application Laid-Open No. 2000-290549,
An example in which polyethylene glycol or the like is used in combination with an acetylene glycol-based surfactant for an aqueous ink is described, but unless a method such as pre-dissolving or dispersing both is used, the polyethylene glycol used as a solubilizing agent becomes water. Acetylene glycol-based surfactants.

[0008] In recent years, there has been a concern that the use of PRTR-controlling substances and environmental hormone-containing substances is feared due to environmental problems, and legal regulations are becoming stricter. As the demand for the agent increases, various companies offer alternatives to polyoxyethylene nonyl phenyl ether.

However, some of these substitutes have the same static surface tension, but have a large influence on the dynamic surface tension or have a high contact angle. When blended as a solubilizer, the same performance as the conventional product was not always obtained.

The present invention has been made in order to improve the above circumstances, and has a low dynamic surface tension, so that it exhibits excellent wettability, permeability and defoaming properties, and can be adapted to high-speed printing. It is another object of the present invention to provide a water-soluble surfactant composition that takes into account the solubility in water and environmental issues.

[0011]

Means for Solving the Problems and Embodiments of the Invention The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that an acetylene glycol-based surfactant and a specific HL
By using a blend of polyoxyalkylene alkyl ether in the range of B, when used as an additive such as ink or paper coating agent, excellent wettability, permeability and defoaming property due to low dynamic surface tension The present invention has been found to be able to solve the above-mentioned conventional problems because it has the following problems and is also suitable for environmental problems, and has accomplished the present invention.

That is, the present invention provides (A) the following formula (1)

Embedded image (Wherein, R ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms), and an acetylene glycol represented by the following formula (2):

[0013]

Embedded image (In the formula, R ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25, and m + n is 1 to 40.) One or more selected from ethoxylated forms of acetylene glycol 30 to 80% by weight

(B) The following formula (3): R ³ O (C ₂ H ₄ O) _w (C ₃ H ₆ O) _x (C ₂ H ₄ O) _y (C ₃ H ₆ O) _z H (3) (Wherein, R ³ is an alkyl group having 1 to 20 carbon atoms, w is a positive number of 1 to 20, x, y, and z are 0 or a positive number of 1 to 20). And 20 to 70% by weight of a polyoxyalkylene alkyl ether having a contact angle of 30 ° after 30 seconds of dropping of a 0.1% by weight aqueous solution thereof at 1 Hz and 10 Hz. A water-soluble surfactant composition having a dynamic surface tension of 50 mN / m or less.

Hereinafter, the present invention will be described in more detail.

As described above, the component (A) of the water-soluble surfactant composition of the present invention comprises an acetylene glycol represented by the following formula (1) and an ethoxylated acetylene glycol represented by the following formula (2): And at least one acetylene glycol selected from the group consisting of:

[0017]

Embedded image (Wherein R ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25,
+ N is 1 to 40. )

As the acetylene glycol of the above formula (1), for example, 2,5,8,11-tetramethyl-6-
Dodecine-5,8-diol, 5,8-dimethyl-6
Dodecine-5,8-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 4,7-dimethyl-5-decyne-4,7-diol, 8-hexadecine-7 , 10-diol, 7-tetradecine-6,9-
Diol, 2,3,6,7-tetramethyl-4-octyne-3,6-diol, 3,6-diethyl-4-octyne-3,6-diol, 3,6-dimethyl-4-octyne-3 , 6-diol, 2,5-dimethyl-3-hexyne-2,5-diol and the like;
Examples of the ethoxylated form of acetylene glycol include an ethylene oxide derivative of the above acetylene glycol. The number of moles of ethylene oxide unit added in the acetylene glycol is 0.5 to 25 mol, and the total number is 1 to 25. 40 moles. If the number of moles of added ethylene oxide exceeds 40 moles, the static and dynamic surface tensions increase and the effect as a wetting agent is lost.

These acetylene glycols (component (A)) can be used singly or as a mixture of two or more, and are used when preparing the surfactant composition of the present invention. The amount obtained is between 30 and 80% by weight, preferably between 40 and 70% by weight. If it is less than 30% by weight, the dynamic surface tension increases, causing repelling at the time of high-speed printing. If it exceeds 80% by weight, the solubility in water becomes poor, and an agglomerate is generated when blended. In addition, the effect of lowering the surface tension cannot be obtained, repelling occurs, and the low-temperature storage stability is remarkably reduced, making the compounding difficult.

The polyoxyalkylene alkyl ether of the component (B) mixed with the acetylene glycol of the component (A) is represented by the following formula (3): R ³ O (C ₂ H ₄ O) _w (C ₃ H ₆ O) _x (C ₂ H ₄ O) _y (C ₃ H ₆ O) _z H (3) (wherein, R ³ is an alkyl group having 1 to 20 carbon atoms, w is 1 to 2)
The positive number of 20, x, y, and z is 0 or a positive number of 1 to 20. ).

In this case, R ³ preferably has 5 to 1 carbon atoms.
5, more preferably 10 to 15 alkyl groups, and w + x + y + z is preferably 5 to 30, particularly preferably 5 to 25.

Examples of the polyoxyalkylene alkyl ether of formula (3), but may be a polyoxyalkylene alkyl ether enters in equation (3), specifically, 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) _w (C ₃ H ₆ O) _x (C ₂ H
₄ O) _y (C ₃ H ₆ O) _z H (where w + y = 15, x + z =
_{4), C 13 H 27 O} (C 2 H 4 O) w (C 3 H 6 O) x (C 2 H 4 O)
_y (C ₃ H ₆ O) _z H (where w + y = 15, x + z = 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 ) HO (C ₂ H ₄ O) ₇ (C ₃ H ₆ O) _4.5 H, C
H 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 and the like can be mentioned, and one kind thereof can be used alone or two or more kinds can be used in combination. The HLB of these components (B) is preferably from 8 to 18, particularly preferably from 10 to 16. If the HLB is less than 8, the hydrophobicity increases, the solubility in water decreases, and sufficient water solubility is obtained. Disappears,
If it exceeds 18, the dynamic surface tension is large, which causes bleeding during printing.

The amount of the component (B) used in preparing the surfactant composition of the present invention is 20 to 70% by weight,
Preferably it is 30 to 60% by weight. If the amount is less than 20% by weight, the acetylene glycols of the component (A) are not sufficiently solubilized, and agglomerates are generated. If the amount is more than 70% by weight, foaming at the time of compounding increases, resulting in poor printing due to poor discharge. Alternatively, coating defects such as pinholes and unevenness occur.

In the present invention, it is preferable to use the above two components so that the sum of the two components is 100% by weight. Further, as the third component [component (C)], pure water or ethylene glycol, diethylene glycol, triethylene glycol may be used. , Tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol,
1,3-propanediol, 1,4-butanediol,
A water-soluble organic solvent such as glycerin may be used in combination, and may be used in an amount of 0 to 25% by weight, preferably 5 to 20% by weight, as long as the properties of the present surfactant composition are not impaired.

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

Here, the obtained water-soluble surfactant composition has a contact angle of 0.1% by weight aqueous solution of 40 ° or less, preferably 10 to 40 °, more preferably 20 to 37 °.
And dynamic surface tension is 50 mN / m or less, preferably 10 to 50 mN / m, and more preferably 20 to 46 mN / m.
/ M. The contact angle was 0.1% by weight using a contact angle meter CA-D (manufactured by Kyowa Interface Science Co., Ltd.).
The dynamic surface tension was measured 30 seconds after the dropping of the aqueous solution, and the dynamic surface tension was measured using a bubble pressure type dynamic surface tensiometer Cruz BP-2 (manufactured by KRUSS) at 1 Hz and 10 Hz of a 0.1% by weight aqueous solution. Is measured.

If the contact angle of the 0.1% by weight aqueous solution of the surfactant composition after 30 seconds from the dropwise addition exceeds 40 degrees, bleeding of the ink occurs due to the occurrence of cissing and poor absorption after blending into the ink. And 1Hz of 0.1% by weight aqueous solution
If the dynamic surface tension at 10 Hz exceeds 50 mN / m, repelling or penetration occurs when printing is performed by a printing machine or a coating machine even if repelling is not recognized during brush coating or bar coater coating. Bleeding occurs due to insufficient force.

When an ink is produced using the surfactant composition of the present invention or used as an aqueous wetting agent for a paper coating agent, it is preferably 0.05 to 10% by weight based on the total amount of the ink or the total amount of the paper coating agent. %, More preferably 0.05-5
It is desirable to use in the amount of addition by weight.

[0029]

EXAMPLES The present invention will be described below in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the examples, parts and% indicate parts by weight and% by weight, respectively.

[Example 1] 2,4,7,
9-Tetramethyl-5-decyne-4,7-diol (trade name: Surfynol 104, manufactured by Air Products) 55
Part into a vessel equipped with a propeller-type stirrer, and then, while stirring, polyoxyalkylene alkyl ether (Neugen ET-
116B (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was gradually added and mixed. After continuous stirring for 2 hours, the mixture was cooled to room temperature. After cooling, the mixture was filtered with a 200-mesh filter cloth to obtain a surfactant composition (hereinafter referred to as M1).

Further, 0.1 part of the composition M1 was added to purified water 1
In addition to 00 parts, the mixture was stirred with a magnetic stirrer.
A 1% aqueous solution was used, and the appearance, contact angle,
Dynamic surface tension and static surface tension were measured. Table 2 shows the results.

Further, an ink and a paper coating agent were prepared using the surfactant composition according to the following formulation, and in the case of the ink composition, the print density, dot diameter, resolution of the printed image, and ink absorbency were measured. Table 3 shows the results, and in the case of the paper coating agent, repelling and foaming properties were measured. The results are also shown in Table 3.

<Ink formulation> 5 parts of a dye (Direct Black 19) was gradually added to 70 parts of pure water while stirring with a propeller stirrer, and then 1 part of surfactant composition M1 was added.
After adding 10 parts of polyethylene glycol and 15 parts of glycerin and stirring for 1 hour, an ink formulation (hereinafter referred to as "A-1") was obtained.

<Formulation of paper coating agent> Emulsion for paper coating agent (trade name: VINIBLAN 2750, manufactured by Nissin Chemical Co., Ltd.)
One part of surfactant composition M1 was added to 0 parts, and the mixture was stirred with a propeller stirrer for 30 minutes to obtain a paper coating composition (hereinafter referred to as Co-1). In addition, the measurement of each characteristic was performed as follows.

<< Evaluation of Aqueous Solution of Surfactant Composition >> 1) Appearance of Aqueous Solution The appearance of the aqueous solution and the presence or absence of insoluble matters were confirmed. ：: The aqueous solution is transparent and no insoluble matter is observed. Δ: The aqueous solution was cloudy, but no insolubles were observed. ×: Insolubles are partially observed. XX: Almost no dissolution. 2) Contact angle The contact angle of the 0.1% aqueous solution of the surfactant composition was measured 30 seconds after dropping using a contact angle meter CA-D manufactured by Kyowa Interface Science Co., Ltd. 3) Dynamic surface tension The dynamic surface tension at 1 Hz and 10 Hz of a 0.1% aqueous solution of the surfactant composition was measured using a bubble pressure type dynamic surface tensiometer Cruz BP-2 manufactured by KRUSS. 4) Static surface tension The 0.1% aqueous solution of the surfactant composition was measured for static surface tension using a surface tension meter ESB-V manufactured by Kyowa Interface Science Co., Ltd.

<< Evaluation of Ink Composition >> 1) Print Density Regarding dots printed with black ink using a Canon Printer BJC455J, the dot density was measured using a Sakura Micro Densitometer PDM-5 (manufactured by Sakura Seiki Co., Ltd.). . 2) Dot diameter Printing was performed using black ink with a Canon printer BJC455J, and the dot diameter was measured by enlarging it 100 times. 3) Resolution of print image Black (B) with Canon Printer BJC455J,
Magenta (M), cyan (C), and yellow (Y) were solid printed and measured with a Macbeth densitometer RD-918 (manufactured by Macbeth). 4) Ink Absorption Black, magenta, cyan, and yellow were simultaneously ejected to the same place by a Canon printer BJC455J, and rubbed with a paper press plate after one second, and the stain by the ink was measured. ：: No stain on white part △: Slight stain ×: Severe stain

<< Evaluation of Paper Coating Agent >> 1) Hajiki Nissho Gravure Co., Ltd. Printing Appropriation Tester (GRAVO-PRO)
OF), a paper coating agent was applied at a coating speed of 50 m / min, and cissing on the printed surface was visually checked. ：: No cissing or pinholes were observed. Δ: Repelling and pinholes were partially observed. ×: Many cissings and pinholes are observed. 2) Foaming property A paper coating agent was diluted at a coating agent / water ratio of 1/2 to obtain a sample. 20 ml of this sample was placed in a 100 ml graduated cylinder, shaken for 180 minutes with a shaker at 180 reciprocations / min, and the number of ml of foam was measured 5 minutes after the end of shaking.

[Examples 2 to 5, Comparative Examples 1 to 7] In the same manner as in Example 1, the composition and the amount (%) of the composition shown in Table 1 were mixed by stirring, and the surfactant composition (M2 ~ M1
1) was obtained. In addition, about Example 1, the compounding quantity of the compound was described in% again.

A 0.1% aqueous solution was prepared in the same manner as in Example 1, and the aqueous solution was evaluated in the same manner.
Further, an ink and a paper coating agent were prepared in the same manner as in Example 1, and the ink composition and the paper coating agent were evaluated in the same manner. The results are shown in Table 3. In the case of a solid, the mixture was heated to 50 ° C. and the components were mixed.

[0040]

[Table 1]

<Component A> S-82: Surfynol 82 (trade name, manufactured by Air Products, 3,6-dimethyl-4-octyne-3,6-diol) S-104: Surfynol 104 (manufactured by Air Products) Trade name, 2,4,7,9-tetramethyl-5-decyne-4,7-diol) S-440: Surfynol 440 (trade name, manufactured by Air Products, ethoxylated form of Surfinol 104, ethylene oxide added) S-465: Surfynol 465 (trade name, manufactured by Air Products, ethoxylated form of Surfynol 104, ethylene oxide added mole number: 10) DF-110: Surfynol DF-110 (manufactured by Air Products) Trade name, 2,5,8,11-tetramethyl-
6-dodecine-5,8-diol)

<Component B> NP-1: Neugen ET-116B (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, RO (C_TwoH_FourO)_w(C_ThreeH₆O)_xH, R: carbon
Alkyl of formulas 12 and 14, w = 7, x = 4.5, HLB
12.0) NP-2: Neugen DL-0415 (Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, RO (C_TwoH_FourO)_w(C_ThreeH₆O)_x(C_TwoH_FourO)
_y(C_ThreeH₆O)_zH, R: alkyl having 12 or 13 carbons,
w + y = 15, x + z = 4, HLB15.0) NP-3: Neugen ET-106A (Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, RO (C_TwoH_FourO)_w(C_ThreeH₆O)_xH, R: carbon
Alkyl of formulas 12 and 14, w = 5, x = 3.5, HLB
10.9) NP-4: Emulgen 1108 (trade name, manufactured by Kao Corporation, RO
(C_TwoH_FourO)_wH, R: alkyl having 11 carbon atoms, w =
8, HLB 13.4) NP-5: Lamigen ET-70 (Daiichi Kogyo Seiyaku Co., Ltd. product)
Name, RO (C_TwoH_FourO)_wH, R: C having 12 to 33 carbon atoms
NP-6: Neugen YX-400 (Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, RO (C_TwoH_FourO) _wH, R: Alkyl having 12 carbon atoms
NP-7: Neugen DH-0300 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, RO (C_TwoH_FourO)_wH, R: Al having 14 carbon atoms
Kill, w = 2, HLB4.0) NP-8: Neugen EA-160 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Product name, C₉H₁₉C₆H_FourO (C_TwoH_FourO)_wH, w = 16.
8, HLB 15.4)

[0043]

[Table 2]

[0044]

[Table 3]

[0045]

The water-soluble surfactant composition of the present invention has a low contact angle immediately after dropping and a low dynamic surface tension. It is an excellent surfactant composition that exhibits defoaming properties, can respond to high-speed printing and high-speed coating, and is also suitable for environmental issues. Due to this property, the water-soluble surfactant of the present invention is extremely advantageous in practical use.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) // B01F 17/42 B41J 3/04 101Y 4L055 F term (reference) 2C056 FC01 4D011 CB02 CB06 4D077 AA05 AA08 AB05 AC05 BA04 DC02 DC24Y DD32Y DE02Y DE08Y 4J038 EA011 JA20 JA27 KA09 MA08 MA10 NA06 4J039 AE07 BC09 BC13 BC14 BE02 BE16 BE22 BE28 CA03 EA48 4L055 AG34 AG88 AH29 AH35 AJ04 BE07 EA32 FA30 GA19

Claims (1)

[Claims] (A) The following formula (1): (Wherein, R ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms), and acetylene glycol represented by the following formula (2): (In the formula, R ¹ and R ² represent an alkyl group having 1 to 5 carbon atoms, m and n are each a positive number of 0.5 to 25, and m + n is 1 to 40.) One or more selected from the ethoxylated form of acetylene glycol 30 to 80% by weight (B) The following formula (3) R ³ O (C ₂ H ₄ O) _w (C ₃ H ₆ O) _x (C _{2 H 4 O) y (C} 3 H 6 O) z H (3) ( wherein, R ³ is an alkyl group having 1 to 20 carbon atoms, w is 1 to 20 positive, x, y, z are 0 Or one or more polyoxyalkylene alkyl ethers having an HLB of from 8 to 18 in an amount of 20 to 70% by weight, and a 0.1% by weight aqueous solution thereof. The contact angle after 30 seconds of dropping is 40 degrees or less, and the dynamic surface tension at 1 Hz and 10 Hz is 50 mN / m or less, respectively. Water-soluble surfactant composition.