JPH02126929A - Dispersant - Google Patents

Abstract

PURPOSE:To prevent the aggregation of a pigment and to form a stable dispersion liq. by using polyether polyol prepd. by adding alkylene oxides to a hydroxy compd., etc., having active hydrogen in the molecule as starting material. CONSTITUTION:Polyether polyol represented by a formula A ((CxH2xO)b(CyH2yO)c(CxH2xO)dH)e or A((CxH2xO)b(CyH2yO)c(B)H)e (where A is a hydroxy compd., etc., having 4-100 (e) active hydrogen atoms, x is 2 or 3, y is an integer of 8-30, b is 0 or an integer of 1-50, c is 0 or an integer of 1-10, the average equiv. number of CyH2yO to one molecule is 0.6-10e, d is an integer of 1-50, e is an integer of 4-100 and B is an oxyalkylene chain obtd. by polymerizing ethylene oxide, etc.) is used as a dispersant for dispersing fine powder of an insoluble pigment in an org. liq. This dispersant has superior flowability and dispersion stability and hardly emits a bad odor.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to a dispersant, and particularly to a dispersant that has excellent fluidity and dispersion stability in a dispersion system in which a pigment as an insoluble fine powder is dispersed in an organic liquid.

[Conventional technology]

In various coating compositions such as printing inks and paints, practically useful pigments must consist of fine particles in order to exhibit vivid color tone and high coloring power. Therefore, dispersion of pigments into non-aqueous organic liquids is one of the important steps in the production of printing inks and paints. However, when pigments are dispersed in non-aqueous vehicles, it is difficult to obtain colorant compositions with excellent fluidity and storage stability, especially at high concentrations, and various problems occur that affect the manufacturing process and product quality. is known to cause problems. For example, dispersions containing pigments made of fine particles tend to have high viscosity, and during dispersion, stirring, mixing, transportation, storage, etc., the viscosity increases significantly, and even gels, making it difficult to use. It may happen. Separation of the vehicle and the pigment, sedimentation, aggregation, and color separation of the mixed pigment may also occur, as well as a decrease in coloring power, a decrease in gloss, and poor leveling due to these phenomena. Furthermore, color materials with good coating such as printing ink or paint,
It is made of finely dispersed pigments and has a high pigment C degree. In other words, in order to produce a dispersion liquid consisting of highly concentrated and fine pigments, a dispersant or the like is used to dissolve the aggregated particles.
Moreover, it holds stability for a good number of minutes! 1. It is a requirement to obtain armpits. Various pigment dispersants have been disclosed so far. For example, the pigment derivative disclosed in JP-A No. 59-227951 is colored, which limits the pigments that can be used and lacks versatility. Polyester which is a dehydrated condensation product of hydroxycarboxylic acid disclosed in No.
30057, the reaction product of the polyester and polyoctamethylene polyamine disclosed in JP-A No. 62-4433, the polyalkylene imine disclosed in JP-A-63-12335. Dispersants such as compounds made by reacting the reaction product of epoxide and epoxide with polyester are effective for weakly polar organic liquids such as aliphatic petroleum fractions and aromatic hydrocarbons, but they are not effective in terms of long-term storage stability. Furthermore, no dispersion effect is observed in highly polar liquids such as alcohols. As mentioned above, various dispersants have been disclosed in the past, but as pigment dispersants, the problems have not yet been fully satisfied, and there has been a demand for a dispersant that can solve these problems.

[Problem to be solved by the invention]

The present invention is extremely effective in preventing agglomeration of pigments in the dispersion and forming a stable dispersion when fine powders, solids, especially organic and inorganic pigments are dispersed in various organic liquids. The purpose of this invention is to provide a dispersant that has very little odor or virtually no odor, and which has no adverse effects due to coloration in practical use.

[Means and effects for solving the problems] This invention has the following features:
This was done by focusing on these conventional problems. That is, the following general formula (1) % formula %) (In the formula, A is a residue obtained by removing active hydrogen from a hydroxy compound or a phenolic hydroxyl group-containing compound that accommodates e active hydrogens, X is 2 or 3, y is an integer of 8 to 30, b is an integer of 0 or 1 to 50, C is a part of O or an integer of 1 to 1O, and the average number of C V H2V O (F) per molecule is 0.6e to 10e, d is an integer of 1 to 50, e is an integer of 4 to 100, and B is an oxyalkylene chain obtained by block polymerization or random polymerization of ethylene oxide and/or propylene oxide. It is a dispersant. The dispersant represented by the general formula (1) or 2) uses a hydroxy compound having 4 to 100 active hydrogens in the molecule or a compound containing a phenolic hydroxyl group as a starting material, and a specific fullkylene oxide in a specific order. The starting material used in the present invention is a hydroxy compound, such as diglyalin, which is a polyether polyol subjected to an addition reaction. Examples include polyglycerin such as triglycerin, pentaerythritol, sorbitol, sucrose, and reduced maltose. Furthermore, examples of compounds having a phenolic hydroxyl group include polyvinylphenol and aliphatic aldehyde condensates of aromatic compounds having a phenolic hydroxyl group; examples of aromatic compounds having a phenolic hydroxyl group include: 1) phenol, cresol; , xylenol. Phenols and substituted phenols such as butylphenol, nonylphenol, aminophenol, and hydroxybenzoic acid 2) Naphthols and substituted naphthols such as naphthol, methylnaphthol, butylnaphthol, and octylnaphthol 3) Polyhydric phenols such as catechol, resorcinol, and pyrogallol 4 ) Polyvalent naphthols such as naphresorcin and α-naphthohydroquinone; 5) mixtures of two or more aromatic compounds of the above (1) to (4). Examples of aliphatic aldehydes include formalin, acetaldehyde, and glyoxal. Formaldehyde is common. In this case, the degree of condensation by the aliphatic aldehyde is 4 to 20, and if it exceeds 20, there will be problems in handling. One or more of these starting materials can be used, and the alkylene oxide adduct can be easily produced by a conventional method. That is, the target product is obtained by subjecting a starting material to an addition reaction with fullkylene oxide at 100 to 180° C. and 1 to 10 atm under an alkali catalyst. The dispersant of the present invention contains a long-chain alkylene oxide having 8 to 30 carbon atoms as an essential component as shown in the general formula (1) or 2), and further contains ethylene oxide (hereinafter abbreviated as EO) and/or propylene oxide (hereinafter abbreviated as PO). It is a polyether polyol obtained by addition polymerization of (abbreviated as). Examples of long-chain alkylene oxides include α-olefin oxides, and those in which the alkyl group has 8 to 30 carbon atoms are effective.In this case, a mixture of two or more α-olefin oxides having different carbon numbers may be used. To obtain a good α-olefin oxide, it is necessary to add 1 part of active water to an average of 0.6 to 10 molar equivalents per unit, and outside this range, no excellent dispersion effect can be obtained. Furthermore, as the alkylene oxide, it is necessary to add-polymerize EO and/or PO, and the order of the addition reaction is important in order to obtain an effective dispersant. That is, the addition order of formula (1) can be specifically described as follows: ■ Starting material - α-olefin oxide - EO or PO ■ Starting material - EO or PO - α-olefin oxide - EO or PO. An average of 0.6 to 10 molar equivalents of α-olefin oxide is added per hydrogen, and 1 to 50 moles of EO or PO are added, and α-olefin oxide is produced after adding 1 to 50 moles of EO or PO. Examples include those to which 0.6 to 10 mole equivalents of EO or PO are added on average, and 1 to 50 moles of EO or PO are added. Furthermore, regarding the compound of formula (2), roughly EO is added to the compound to which α-olefin oxide shown in
and/or PO is added in a block or random manner in a total of 2 to 100 moles per active hydrogen. In this case, there may be a mixture of block-shaped parts and random parts, but it is preferable that the addition method is block-shaped and the degree of polymerization of one block is 5 or more, and the terminal of the compound is oxyethylene. It is effective regardless of the chain or oxypropylene chain. Furthermore, derivatives in which part or all of the terminal water-unfriendly groups of the polyether polyol compound are phosphoric acid esterified or sulfuric acid esterified are also effective. The pigments dispersed in organic liquids by the dispersants of the present invention are usually finely powdered solids with a particle size of 20 microns or less, such as titanium dioxide, red and yellow iron oxides, barium sulfate, aluminum hydroxide, calcium carbonate. , talc, clay, silica, lead chromate, zinc chromate, strontium chromate, carbon black, cadmium diro, cadmium red, Bengara, iron black, zinc white, deep blue, ultramarine, etc., azo pigments, lake, Toner, phthalocyanine pigment, perylene, perinone pigment. Examples include organic pigments such as isoindolinone pigments, quinacridone pigments, and dioxazine pigments. As used herein, "lake" means a water-insoluble salt or complex of an organic dye precipitated on a water-insoluble inorganic carrier such as alumina, and "toner" specifically refers to a water-insoluble salt or complex of an organic dye, such as an azo dye. Or extremely poorly soluble calcium, strontium,
Or barium salt or complex. Examples of organic liquids used in the dispersant of the present invention include aromatic hydrocarbon mineral spirits such as toluene and xylene, petroleum hydrocarbons such as mineral turpentine, chloroform, perchloroethylene, trichlorethylene, and chlorobenzene. halogenated hydrocarbons, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, amyl acetate, cellosolve acetate, alcohols such as methanol, ethanol, butanol, Among cellosolves such as ethyl cellosolve and butyl cellosolve, ketones, alcohols, cellosolves, and esters are particularly effective as organic liquids. Of course, a mixed solvent of two or more of these may be used, and known alkyd resins, epoxy resins, epoxy ester resins, melamine resins, acrylic resins, polyamide resins, polyurethane resins, polyester resins, salt-vinyl acetate resins, etc. There is no problem even if it is a mixed system with resin, phenol resin, nitrocellulose resin, etc. In addition, auxiliary agents for printing inks and paints include thickeners, anti-sagging agents, anti-color separation agents, viscoelastic modifiers, wetting agents, antifoaming agents, rust preventives, slip agents, dryers, and ultraviolet absorbers. Agents, antifouling agents, preservatives, flame retardants, etc. may be added, and these may be included. The dispersant of the present invention is used in an amount of 0.01 to 15% by weight, preferably 0.1 to 10% by weight, based on the entire dispersion. If the amount used is less than 0.01% by weight, the effect will be small;
Moreover, even if the amount exceeds 15% by weight, the improvement in the effect is not significant and it is economically disadvantageous. The pigment content in the dispersion is 5 to 80.
Although these values are expressed as weight %, these values should of course be selected from various combinations depending on the pigment and organic liquid used and the purpose of use. When using the dispersant of the present invention, any dispersing machine may be used, such as a ball mill, a sand mill, a visco mill, a roll mill, a kneader-attritor, a high-speed mixer, a homomixer, and the like. The dispersant of the present invention can be used by adding it alone to an organic liquid, by adding a mixed composition of a pigment and a dispersant, or by adding it to a dispersion of an organic liquid and a pigment. The effect of this can be obtained. The dispersant of the present invention may be used alone, and may be used in combination with other non-aqueous dispersants such as polyoxyethylene nonylphenyl ether, sorbitan oleate, lecithin, polyoxyethylene octyl ether phosphate, dodecylbenzenesulfonic acid calcium salt. 1. It may be used in combination with petroleum sulfonic acid calcium salt, fatty acid metal soap, etc.

【Example】

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the same extent by these examples. Here, the various dispersants used are shown in Table 1. In addition, parts in the examples mean parts by weight. (Left below) Example 1 Carbon black (C, 1, PigmentBlack)
7) 33 parts, n-butanol 60 parts, dispersant A7? B,
The 0 dispersion obtained by shaking and dispersing 180 parts of a steel pole with a diameter of 2 mm in a paint shaker for 2 hours dissolves the pigment well and has excellent fluidity, making it suitable for producing gravure printing ink and lasting for 45 days. Even after standing, no aggregation or sedimentation was observed, indicating good dispersion stability. Similar tests were conducted using each of Dispersants B-Q in place of Dispersant A, and similar dispersions were obtained. Example 2 Carbon black (C, 1, PigmentBlack
7) 30 parts, 30 parts of ethanol, 30 parts of toluene, 4 parts of vinyl chloride-vinyl acetate copolymer resin, 6 parts of dispersant D,
The 0 dispersion obtained by dispersing 180 parts of steel poles with a diameter of 2 mm in a paint shaker for 3 hours dissolves the pigment well and is suitable for producing gravure printing ink.
Even after standing for 45 days, no la accumulation or sedimentation was observed, indicating good dispersion stability. Similar tests were conducted using dispersants A-C and E-Q in place of the above-mentioned dispersant, and similar dispersions were obtained. Example 3 Brilliant carmine 6B (C, 1, Pigm-ent
Red57) 25 parts, methyl ethyl ketone 20 parts,
A dispersion of 40 parts of ethanol, 9 parts of butyl acetate, 86 parts of a dispersant, and 200 parts of a steel pole with a diameter of 2 mm was shaken and dispersed in a paint shaker for 2 hours, and the pigment was dissolved well and had excellent fluidity. It was suitable for producing gravure printing ink, and showed good dispersion stability with no aggregation or sedimentation observed even after 45 days of standing. The same test was conducted using each of Dispersants A-D and F-Q in place of Dispersant E, and similar dispersions were obtained. Example 4 Butalocyanine blue (C,1, Pigme-nt
Blue15-4) 23 parts, ethanol 45 parts, methyl isobutyl ketone 22 parts, butyl acetate 5 parts 1 Dispersant A
The 0 dispersion obtained by shaking and dispersing 5 parts and 180 parts of a steel pole with a diameter of 2 mm in a paint shaker for 3 hours dissolves the pigment well and is suitable for producing gravure printing ink. No sedimentation was observed, indicating good dispersion stability. Similar tests were conducted using each of Dispersants B-Q in place of Dispersant A, and similar dispersions were obtained. Example 5 Di, Suasoe o-AAA (C, I, P i gm
23 parts of e-nt Yellow 2), 40 parts of n-butanol, 30 parts of methyl ethyl ketone, 37 parts of a dispersant, and 180 parts of a steel pole with a diameter of 2 mm were shaken and dispersed in a paint shaker for 3 hours. The pigment in the dispersion was well dissolved, making it suitable for producing gravure printing ink, and showed good dispersion stability with no aggregation or sedimentation observed even after 45 days of standing. The same dispersion was obtained using the following pigments instead of Disaso Yellow AAA. (1) Permanent Red 2B Barium (C. 1, Pigment Red48-1) (2) Lake Red C (// Red53-(3) Dioxazine Violet (//Violet23) Example 6 Titanium oxide (C, 1, Pigment Wh-ite
6) The 0 dispersion obtained by shaking and dispersing 65 parts of ethanol, 20 parts of ethanol, 12 parts of butyl acetate, 1 part of dispersant H, and 130 parts of a steel pole with a diameter of 2 mm in a paint shaker for 2 hours was excellent because the pigment was well dissolved. It has good fluidity and is suitable for the production of gravure printing ink, and it does not agglomerate even after being left for 30 days.
No sedimentation was observed, indicating good dispersion stability. Zinc white (C, 1, Pi-gmen) instead of titanium oxide
tWhite4), barium sulfate (C,1,Pig
ment White21) or navy blue, 9 (C, 1,
The same dispersion was obtained using Pigment Blue 27). Comparative Example 1 Carbon black (C, 1, PigmentBlack
7) The same test as in Example 1 was conducted using 28 parts of n-butanol, 62 parts of n-butanol, and 10 parts of dispersant R. As a result, a gel-like mixture formed immediately after shaking, and no dispersion liquid was obtained. When the same test was conducted using each of the dispersants SU in place of the dispersant R, a gel-like mixture was similarly obtained, and no dispersion liquid was obtained. [Effects of the Invention] The pigment dispersant according to the present invention has particularly excellent coloring properties, film gloss and fluidity, and storage stability when used in the production of surface coating materials, such as non-aqueous paints and printing inks. This shows that it is possible to improve quality. In other words, it can prevent flocculation, flooding, floating, and improve leveling by stabilizing the pigment dispersion state. In particular, it is useful when preparing a pigment dispersion for producing gravure printing ink. The pigment dispersion mentioned here is a system consisting of a pigment, an organic solvent, and a dispersant,
Since printing inks can be easily prepared by blending with a desired vehicle depending on the purpose of use, the number of ink bases can be greatly reduced. Further application advantages include that compared to regular printing inks, it can be milled in a much higher pigment concentration and in a shorter time, reducing labor, electricity, and running costs for milling, and reducing dispersion. Since good fluidity can be maintained even if the pigment concentration in the liquid is increased, storage and transportation costs can be reduced. Patent applicant Daiichi Kogyo Seiyaku Co., Ltd.

Claims (1)

[Claims] 1. The following general formula (1) or (2) A[(CxH_2xO)b(CyH_2yO)c(Cx
H_2xO)dH)e...(1) A[(CxH_2xO)b(CyH_2yO)c(B)
H]e...(2) (wherein A is a residue obtained by removing active hydrogen from a hydroxy compound having e active hydrogens or a phenolic hydroxyl group-containing compound, x is 2 or 3, and y is 8 to 30 b is an integer of 0 or 1 to 50, c is a partial integer of 0 or 1 to 10, and the average number of equivalents of CyH_2yO per molecule is 0
．． 6e to 10e, d is an integer from 1 to 50, e is 4 to 100
, B is an oxyalkylene chain obtained by block polymerization or random polymerization of ethylene oxide and/or propylene oxide. 2. The dispersion medium is alcohols, ketones, cellosolves,
The dispersant according to claim 1, characterized in that it is one or more organic liquids selected from esters.