JPS609850B2 - Co-low polymer type pigment dispersant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to an organic compound having a repeating unit consisting of a maleic acid derivative and an alkyl vinyl ether, which has an extremely low degree of polymerization, and is composed of heavy bodies with a narrow distribution width. This invention relates to pigment dispersants.

Traditionally, surfactants have been used as dispersants to disperse organic or inorganic differential materials in organic or aqueous media in fields such as the dye, pigment and paint industries, as well as civil engineering and agricultural materials. has been done.

Furthermore, surfactants are often used for the purpose of surface treatment and surface modification of such differential materials. Furthermore, the dispersion of fine powder materials into water-containing organic solvents is also an essential issue. For example, in recent years, when paints are made to be water-based, the development of suitable pigment dispersants has become an important issue. However, although many conventional surfactants are effective as dispersants, they generally have the property of easily foaming in water.
It has the disadvantage that the dispersion effect is lost due to changes in other coexisting additives, pH, and temperature.

The present inventors have conducted various studies to overcome these drawbacks found in conventional surfactant-based dispersants, and as a result, we have developed an alkyl vinyl ether-maleic acid derivative that does not have a long mirror lipophilic group. Although the low polymer is anionic, it exhibits excellent dispersion effects due to its surface active action, and when these homologs are used, it has excellent dispersibility for difficult-to-disperse organic pigments such as phthalocyanine pigments and carbon black. It has been found that a versatile dispersant can be obtained and that the object can be satisfied, and the present invention has been completed based on this knowledge.

That is, the present invention is based on the general formula (in which R is a saturated or unsaturated alkyl group having 2 to 4 carbon atoms, and X and Y are an alkali metal, an annium ion, an organic annium ion (this organic annium ion is , derived from organic amines.

) or an alkyl group, and the number n of repeating units is 3 to 10). It is something.

According to the present invention, organic or inorganic differential material is mixed with water,
Ampholytic or water-soluble oligomeric dispersants are provided for dispersion in water-containing organic solvents or organic solvents.

The oligosoap of the present invention has a surfactant effect and has excellent dispersion power and dispersion system stability for hydrophobic and difficult-to-disperse organic pigments, such as phthalocyanine pigments such as phthalocyanine full and phthalocyanine green, and carbon black. It has a softening effect. According to the present invention, individual dispersions can be selected from a large number of alternating copolymer renanide homologs of maleic acid promoters and alkyl vinyl ethers having different side chain alkyl group chain lengths and degrees of renanization. The advantage is that any dispersant can be effectively selected and used. Further, as a mixed dispersant, it is possible to provide versatility to mixed dispersoids. The alkyl vinyl ether-maleic acid derivative co-low polymer with a narrow polymerization degree distribution width used in the present invention is obtained by carrying out the polymerization reaction between the maleic acid derivative and the alkyl vinyl ether without using a chain transfer agent or a solvent. It can be prepared by rapid polymerization according to the bulk polymerization method. Generally, maleic acid converters are copolymerized with various pinyl monomers to give alternating copolymers. However, alternating copolymers of maleic acid derivatives and alkyl pinylethers obtained by conventional methods have a high degree of polymerization, and the average number of repeating units ranges from several tens to thousands. Since the distribution width is wide, ranging from 2 to several thousand, its uses have been limited.
Therefore, in order to obtain an oligomer with an extremely low degree of polymerization, it was necessary to perform a fractional precipitation treatment of the obtained copolymer. On the other hand, by rapidly advancing the polymerization reaction without using a chain transfer agent or solvent as described above, combined with the steric hindrance effect of bulky monomers such as maleic acid ester, polymerization with a repeating unit count of 2. However, an O-IJ gomer with a low degree of polymerization of 3 to 10 on average and a narrow distribution width can be obtained.

Furthermore, even when using monomers that are not expensive, such as maleic anhydride or n-butyl pinylether, n is much smaller with this method than with conventional telomerization reactions, resulting in a lower cage height. Although the low polymerization reaction is not as effective as with monomers, n is on average 11, including oligomers with a degree of polymerization of 10 or less.
More than several dozen oligomers can be obtained. Maleic acid and similar unsaturated acids, their anhydrides, salts, esters, amides, etc. can also be used as maleic acid derivatives used in the production of this alkyl vinyl ether-maleic acid derivative co-low polymer. can.

These are represented by the following general formula, and each R'' is selected from hydrogen, methyl and ethyl groups, and Z
is hydrogen, an alkyl group having 2 to 4 carbon atoms, such as a methyl group or an ethyl group.

. It is selected from pyru group, butyl group, and alkali metal. Examples include maleic acid, maleic anhydride, fumaric acid
acid, methyl maleic acid, dimethyl maleic acid, ethyl maleic acid, diethyl maleic acid, dimethyl maleate, diethyl dimethyl maleate, monomethyl-monomethyl maleate, dibutyl-diethyl fumarate, di-n
-propyl-monotylphumarate, methyl-ethyl-re-maleate, monomethyl maleic anhydride, diethyl maleic anhydride, methyl ethyl monohydric maleic acid, sodium dimethyl maleate, potassium diethyl fumarate, and the like. Mixtures of these substances may also be used. In addition, the alkyl group of the alkyl vinyl ether, which is the other component of the alternating copolymer, has 2 to 2 carbon atoms.
4 are used.

Examples include ethyl vinyl ether, chloroethyl vinyl ether, n-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, hexyl vinyl ether, and the like. The copolymer thus obtained is saponified or esterified with an alkali or alcohol, and then purified by a conventional method.

Examples of alkalis used at this time include ammonia,
Examples include lithium hydroxide, sodium hydroxide, potassium hydroxide, and organic monoamines such as aniline, toluidine, pyridine, ethylamine, and monoethanolamine. Note that when such an organic monoamine is used, the product forms an organic ammonium salt. Further, examples of alcohol include ethanol, ethanol, phthanol, diethylene glycol, and glycerin. These can be reacted alone or in combination of two or more. The dispersant of the present invention is used in the form of an aqueous solution, a water-containing organic solvent solution, or an organic solvent solution, and is dispersed in a powder such as an organic pigment.

The concentration usually used is 0.001-3.0%, preferably 0.01-1.5%. The characteristics of the dispersant of the present invention are as follows.

'1} Excellent temporary dispersion effect.

{2) Good long-lasting effects (lasts for several weeks to several tens of months).

{3' Since it has good compatibility with water, oil, and water-containing organic solvents, its range of use is extremely wide.

'4- Even if several types of dispersibility are mixed, the dispersion effect can be achieved. '5} It is economical because it is effective at low concentrations.

'61 Since it is colorless or pale yellow, objects are rarely colored. '7} It has low toxicity and can be used in a wide range of applications.

Next, the present invention will be explained in more detail based on Examples and Reference Examples. Reference example n-butyl vinyl ether 60.1 moles (0.60 mole), jetyl maleate 103.3 moles (0.60 mole)
When 3.3 moles (0.02 mol) of YamaBN and 3.3 moles of YamaBN were placed in a three-necked separable flask and heated to 7,000 at normal pressure while stirring in a nitrogen stream, a rapid temperature rise occurred even after the heating was stopped. After reaching 14500, the temperature drops.

The reaction time during this period is a short time of 60 minutes or less. The mixture was returned to room temperature and the evaporated components were evaporated under reduced pressure. The yield of the residue was 131 units (yield 80%), and the number of repeating units of the alternating copolymer measured by the boiling point increase method was 4 on average. Also,
Gel permeation chromatography (GPC) confirmed that it had a degree of polymerization of mostly 3, 4, and 5, which is consistent with the results obtained by the boiling point elevation method. A portion of the alternating copolymer thus obtained was dissolved in ethanol, and 1.1 times or 0.0 times the amount of ester base was taken. An aqueous solution containing an amount of sodium hydroxide dissolved in the minimum amount of water was added, and the mixture was heated under reflux for 2 hours. The former was purified by repeatedly separating the generated precipitate, dissolving it in warm water, and pouring it into ethanol for precipitation.The latter was obtained by separating the ethanol-soluble content from the dried product from which the solvent had been removed. In this way, the saponification degree is 100 depending on the amount of sodium hydroxide added.
% or 42% (calculated from the model structure of the molecule and Na analysis values, respectively). All of these were water-soluble. The latter partially saponified product also dissolved in organic solvents. Example 1 An alkyl vinyl ether-maleic acid derivative co-low polymer having a narrow polymerization degree distribution shown in Table 1 was prepared according to the method of Reference Example.

In Table 1, the partially saponified product with a degree of saponification of 42% has 58% ester groups remaining.

This product is soluble in water, alcohols such as ethanol, ethanol, and isopropanol, aromatic solvents such as acetone, benzene, and toluene, and cellosolve. Here, 0.25% and o. lo%
A solution was prepared, and the dispersion force and dispersion stabilizing effect on Phthalocyanine Flue Q type were measured by the method described below. Table 2 Example 2 1.0, 0.5, 0.1 and 0.01% aqueous solutions of this alkyl vinyl ether-maleic acid derivative co-low polymer were prepared and phthalocyanine fluoride was prepared as follows. - The dispersion force against was tested.

The results are shown in Table 3. [Dispersion test method] Place 9 of 50 fine powder pigments in a test tube with a scale of 30 mm, add 20 M of the sample solution to 30 mm, shake horizontally with an intruder (immediately in 400 times, amplitude 4 mm), and reduce to 3000 mm. Te4
h My eyes are still.

Next, insert the tip of the pipette from the liquid level of the test tube to the scale line marked 5, suck up 2 and 2 from that area, and transfer to another test tube. 25% of water was added to the liquid A. The dispersion force was determined using a photoelectric colorimeter using a wavelength of 445 nm, and the dispersion force was determined according to the following formula. Weak force = 3 move X・ooHere,
To: Transmittance of an aqueous solution obtained by adding water 25' to test solution 2 not containing pigment, Ts: Transmittance of A above.

We also conducted a dispersion stability test where the static time was longer than that. ship ship admiration Lotus Q Momofune Sho HHS Needle soup Sansan lotus Mine peak feeling report Mother Chinese Lotus S .

〇 vs. mother entering S doto feeling lower life Kuchiguchi the Gume qA Kawa Tsuchi /'ingredient ' Sewing paper three size - ship 0 Ikigo” too Sansan's Mii Yukigumo Shozo Go...Poison≧Kumi Go to Kikiyo Uka 6 Miyuki Kaiji The flowers on the car lid are also poisonous. 3S voice, MiC; Kiren Nada Heiji Heavy Electricity [N's Sumachi Nuino lost unemployment unemployed unemployment The following can be seen from the results in Table 3.

Although the dispersing powers of nonionic surfactants and SDS are greater, some oligosoap congeners exhibit superior dispersing powers that are close to equal.

In particular, the alkyl ether group of the oligosoap is C2-C4
It can be seen that long chain lengths such as C and 6 are not required. Additionally, partially saponified products have greater dispersion power than total renanodic products, so it is more effective to impart some degree of hydrophobicity to oligosoaps.Among oligosoap congeners, C40-Na42 has the highest dispersion power. "C2D-
The Na40 strength was also superior to this competition.

The dispersion power of the M series was generally small.

Next, an example of the dispersion stabilizing effect when phthalocyanine green is dispersed using C2D-Na40 as a dispersant is shown in terms of dispersion power (%).

It can be seen that the greater the initial dispersion force, the greater the stabilizing effect. Table 4 Example 3 The dispersion power of carbon black in water was tested in the same manner as in Example 2.

Table 5 shows the results.

Among oligosoap congeners, C4D-Na42, C40
-Na96 is good. Regarding the dispersibility of the mixed pigment of carbon black and titanium oxide or red iron, C4D-Na42 was better than NP-11. Table 5

Claims (1)

[Claims] 1. General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is a saturated or unsaturated alkyl group having 2 to 4 carbon atoms, and 1. A dispersant for organic pigments, characterized in that it consists of an alkyl vinyl ether-maleic acid derivative co-low polymer represented by an alkyl vinyl ether-maleic acid derivative (representing an alkyl ion, an organic ammonium ion, or an alkyl group, and the number n of repeating units is 3 to 10).