JP4679971B2 - Dispersant for inorganic powder - Google Patents

Description

  The present invention relates to a dispersant for inorganic powder and an inorganic powder dispersion composition containing the dispersant.

  Dispersants for inorganic powders are applied in various industrial fields, and paints and inks in which pigments and fillers are dispersed in resin solutions, and fillers such as calcium carbonate and titanium oxide are dispersed in plasticizers together with polyvinyl chloride resins. The resin composition for a flooring material, wallpaper, and sealing material, a resin composition in which an inorganic filler typified by filled PP is dispersed, or a spray cleaning agent containing an inorganic abrasive is used. Thus, when dispersing inorganic powder in water, an organic solvent, a plasticizer, resin, etc., a dispersing agent is generally used.

  The required performance of such a dispersant is easily dispersed even if inorganic powder is dispersed in a dispersion medium in a short time, and is stably dispersed without precipitating the inorganic powder for a long time, or even if the inorganic powder is precipitated. Can be redispersed. In addition, when the viscosity of the dispersion becomes high due to the blending of the inorganic powder and it becomes difficult to use for the intended purpose, an effect of exhibiting good dispersion characteristics and reducing the viscosity is expected.

  For the above required performance, polyoxyethylene alkyl ether, polyoxyethylene alkyl ether sulfate (see Patent Document 1) and the like have been proposed as dispersants for inorganic powders. However, these conventional techniques show a certain degree of dispersion performance and dispersion stability, but cannot sufficiently satisfy the required performance.

Japanese Patent Publication No. 3-13267

  An object of the present invention is to disperse an inorganic powder in a dispersion medium and to stably disperse the inorganic powder without settling for a long time, or to easily redisperse even if the inorganic powder settles. And providing an inorganic powder dispersion composition containing the same.

  The present invention relates to a dispersant for inorganic powder containing at least one selected from compounds represented by formula (I) (hereinafter referred to as compound (I)), and an inorganic powder dispersion composition containing the same.

RO- (AO) _a (EO) _b -SO ₃ M (I)

(In the formula, R represents a linear or branched alkyl group or alkenyl group having 1 to 22 carbon atoms, AO represents an oxyalkylene group having 3 to 18 carbon atoms, EO represents an oxyethylene group, and a represents an average added mole of AO. The number of 1 to 20 indicating the number, b is the number of 1 to 100 indicating the average number of moles of EO added, and a number of AOs may be the same or different. EO may be a block bond or a random bond, and M represents a cation.)

  The dispersant of the present invention can stably disperse the inorganic powder in the dispersion medium without settling for a long time, and can be easily redispersed even if the inorganic powder settles.

[Dispersant for inorganic powder]
The dispersant for inorganic powder of the present invention contains at least one selected from compound (I).
In the compound (I), R is an alkyl group or alkenyl group having 1 to 22 carbon atoms, which may be linear or branched, and preferably has 3 to 12 carbon atoms. Specific examples of R include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl; allyl, methallyl, 3-butenyl, 4-pentenyl, 3-methyl-3 Alkenyl groups such as -butenyl, 5-hexenyl, 8-nonenyl, 9-decenyl, 11-dodecenyl, etc., and alkyl groups such as propyl, butyl, hexyl, octyl, decyl, dodecyl, etc., having 3 to 12 carbon atoms Alkenyl groups such as allyl, methallyl, 3-butenyl, 4-pentenyl, 3-methyl-3-butenyl, 5-hexenyl, 8-nonenyl, 9-decenyl and 11-dodecenyl are preferred.

  In compound (I), M represents a cation, and the cation includes alkali metal ions such as sodium and potassium, alkaline earth metal ions such as calcium and magnesium, ammonium ions, alkyl groups having 1 to 4 carbon atoms, and alkanol groups. Examples thereof include ammonium ions substituted with at least one selected group. From the viewpoint of solubility in various solvents and performance, ammonium ions or ammonium ions substituted with at least one group selected from an alkyl group having 1 to 4 carbon atoms and an alkanol group are preferable.

  In the compound (I), AO represents an oxyalkylene group having 3 to 18 carbon atoms, and A in the AO part may be a straight chain or may have a branched chain. Examples of AO include oxyalkylene groups such as oxypropylene, oxybutylene, oxyisobutylene, oxybutylethylene, oxyoctylethylene, oxydecylethylene, oxidedecylethylene, oxytetradecylethylene, oxyhexadecylethylene, and the like. Is an oxyalkylene group having 3 to 4 carbon atoms such as oxypropylene, oxybutylene and oxyisobutylene.

A which shows the average added mole number of AO is 1-20, Preferably it is 1-15, More preferably, it is 3-13. The a AOs may be the same or different. Moreover, b which shows the average addition mole number of EO is 1-100, Preferably it is 1-50, More preferably, it is 5-30. The a pieces of AO and b pieces of EO may be block bonds or random bonds, but block bonds are preferable from the viewpoint of dispersibility. In the case of block coupling, the arrangement order of (AO) _a and (EO) _b may be any, but it is preferable that a AO and b EO are block-coupled in this order.

Specific examples of the compound (I) include POB (6) POE (15) 3-methyl-3-butenyl ether sulfate ammonium salt, POB (3) POE (10) 3-methyl-3-butenyl ether sulfate ammonium salt, POB (10) POE (20) 3-methyl-3-butenyl ether ammonium sulfate, POB (3) POE (15) octyl ether ammonium sulfate, and the like.
Here, POB (n) represents a polyoxybutylene chain having an average addition mole number n, and POE (m) represents a polyoxyethylene chain having an average addition mole number m.

  Although the manufacturing method of compound (I) is not specifically limited, For example, it can obtain by adding ethylene oxide to the compound represented by Formula (II), and also making it sulfuric ester.

RO- (AO) _a -H (II)
(In the formula, R, AO and a have the above-mentioned meanings.)

  The compound represented by the formula (II) is, for example, the formula (III)

ROH (III)
(In the formula, R has the above-mentioned meaning.)
It can obtain by making the alcohol represented by these, and a C3-C18 alkylene oxide react. Examples of the alkylene oxide having 3 to 18 carbon atoms include propylene oxide (1,2-epoxypropane), butylene oxide (1,2-epoxybutane), 2,3-epoxybutane, 1,2-epoxydodecane, 1,2 -Epoxyhexadecane, 1,2-epoxyoctadecane, etc. are mentioned, C3-C4 alkylene oxide is preferable.

  The catalyst used for the reaction of the alcohol represented by the formula (III) with the alkylene oxide having 3 to 18 carbon atoms is an alkali catalyst such as sodium hydroxide or potassium hydroxide, titanium chloride, ferric chloride, tin tetrachloride. Lewis acid catalysts such as boron bromide, boron trifluoride, boron trifluoride diethyl ether complex, boron trifluoride tetrahydrofuran complex and the like. When an unsaturated alcohol is used as the alcohol represented by the formula (III), a Lewis acid catalyst is preferable from the viewpoint of preventing isomerization of the terminal double bond of the unsaturated alcohol.

  To the compound represented by the formula (II) obtained as described above, ethylene oxide is added according to a conventional method, this is further sulfated with a sulfating agent, and further neutralized with a basic substance if necessary. Can give compound (I). Examples of the sulfating agent include sulfuric acid, amidosulfuric acid, sulfur trioxide, chlorosulfonic acid and the like. When an unsaturated alcohol is used as the alcohol represented by the formula (III), amidosulfuric acid is used from the viewpoint of reducing side reactions such as addition reaction of sulfuric acid group to double bond group and isomerization of double bond group. preferable. In addition, urea or the like is preferably used for the purpose of preventing side reactions such as isomerization of terminal double bonds to internal double bond groups and addition of sulfate groups to the double bond groups during the sulfate esterification.

  The content of the compound (I) in the dispersant of the present invention is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, and particularly preferably 30 to 100% by weight. When R in the compound (I) is an alkenyl group, the dispersant of the present invention may be a polymer obtained by polymerizing the compound (I) with another monomer within the above content.

  Other monomers that can be copolymerized with compound (I) include (meth) methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. ) Acrylic acid esters, aromatic vinyls such as styrene, α-methylstyrene, chlorostyrene, unsaturated carboxylic acids such as (meth) acrylic acid, itaconic acid, maleic anhydride, and unsaturated carboxylic acids such as (meth) acrylamide And acid amides, unsaturated nitriles such as (meth) acrylonitrile, vinyl halides such as vinyl chloride and vinyl bromide, and conjugated dienes such as butadiene, chloroprene and isoprene. These monomers may be used alone or in combination of two or more.

[Inorganic powder dispersion composition]
The inorganic powder dispersion composition of the present invention contains the dispersant of the present invention, an inorganic powder, and a dispersion medium.

  Examples of the inorganic powder used in the present invention include fillers, pigments, abrasives, and the like. Specifically, carbonates such as calcium carbonate, magnesium carbonate, barium carbonate, kaolin, aluminum silicate, calcium silicate, Silicates such as clay, talc, mica, sericite, bentonite, sulfates such as calcium sulfate and barium sulfate, metal oxides such as silica, alumina, magnesium, antimony trioxide, titanium oxide, white carbon, iron oxide, Examples thereof include metal hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide, bengara, carbon black and graphite. Among these, inorganic fillers are preferable, and calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, kaolin, talc, silica, bengara, titanium oxide, etc. are more preferable, and calcium carbonate, magnesium hydroxide, talc, clay, kaolin, etc. Titanium oxide is particularly preferable.

  In the present invention, the dispersion medium for dispersing the inorganic powder includes water, alcohols such as ethyl alcohol and isopropyl alcohol, di-2-ethylhexyl phthalate, dioctyl phthalate, ethyl acetate, soybean oil, linseed oil and other esters, methyl ethyl ketone, Ketones such as methyl isobutyl ketone, fuel oil such as kerosene, light oil and heavy oil, aliphatic hydrocarbons such as hexane, cyclohexane and isooctane, aromatic hydrocarbons such as benzene, toluene and xylene, 1,1,1- Examples thereof include halogenated hydrocarbons such as trichloroethane, trichloroethylene and chlorodifluoromethane, N-methylpyrrolidone, liquid paraffin, liquid resin for paint, and resin typified by polypropylene.

  The content of the dispersant of the present invention in the composition of the present invention is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the inorganic powder, from the viewpoint of dispersion effect and economy, and 0.1 to 5 parts by weight. Part by weight is more preferable, and 0.5 to 5 parts by weight is particularly preferable.

  The content of the dispersant of the present invention in the inorganic powder dispersion composition of the present invention is preferably 0.0001 to 10% by weight, more preferably 0.0003 to 7% by weight. The content of the inorganic powder in the inorganic powder dispersion composition of the present invention is preferably 0.5 to 70% by weight, and more preferably 1 to 60% by weight.

  The inorganic powder dispersion composition of the present invention includes other dispersants such as alkyl sulfosuccinate salts, fatty acid salts, polyhydric alcohol fatty acid esters such as sorbitan monooleate, rosin and the like within the range that does not impair the effects of the present invention. Resin acid salt such as sodium acid, and when dispersing resin with inorganic powder, alkyl ethers such as polyoxyethylene nonylphenyl ether, (poly) ethylene glycol, (poly) propylene glycol, etc. These ethers and their fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters and the like may be used in combination.

In order to obtain a dispersion of an inorganic powder using the dispersant of the present invention, it is only necessary to follow an ordinary dispersion manufacturing method. For example, the inorganic powder is blended in a dispersion medium in which the dispersant of the present invention is dissolved and stirred. A method of stirring and mixing with a machine or a method of stirring and mixing a treated inorganic powder obtained by previously mixing the dispersant of the present invention with an inorganic powder with a dispersion medium may be used.
The dispersant of the present invention is effective both in water and in oil, but exhibits a remarkable effect particularly when inorganic powder is dispersed in oil.

  The dispersant for inorganic powder of the present invention has a particularly remarkable effect that the inorganic powder is stably dispersed without being precipitated in the dispersion medium.

Synthesis Example 1: Synthesis Example of Dispersant (A-1) In a reaction vessel equipped with a stirrer, a thermometer, and a dropping funnel, 86.1 g of 3-methyl-3-buten-1-ol (Wako Pure Chemical Industries, Ltd.) (1. 0 mol) was cooled to −10 ° C. in a nitrogen gas atmosphere, and 5.68 g (0.04 mol) of boron trifluoride diethyl ether complex was added with stirring. While maintaining the reaction temperature at −8 to −12 ° C., 432.6 g (6.0 mol) of 1,2-epoxybutane (butylene oxide) was added dropwise over 7 hours, and then aged at the same temperature for 2 hours. After the temperature was raised to 0 ° C., the catalyst was neutralized with an aqueous NaOH solution, and the aqueous layer containing the decomposition component of the catalyst was removed. Dehydration under reduced pressure using an evaporator gave a 1,2-epoxybutane 6-mol adduct (intermediate) of 3-methyl-3-buten-1-ol. 518 g (1.0 mol) of this intermediate and 1.68 g (0.03 mol) of KOH were charged into an autoclave, dehydrated under reduced pressure at 100 ° C. and 0.65 kPa, and then at 120 ° C. and 0.3 MPa. 660 g (15 mol) of ethylene oxide was added. Next, 1178 g (1 mol) of the obtained reaction mixture, 101.9 g (1.05 mol) of amidosulfuric acid, and 6 g (0.1 mol) of urea were charged into a reaction vessel equipped with a stirrer and a thermometer, After reacting with stirring at 120 ° C. for 4 hours to perform sulfation, urea and unreacted amidosulfuric acid were removed by filtration to obtain a dispersant (A-1) represented by the following formula.

Synthesis Examples 2-3: Synthesis Examples of Dispersants (A-2) and (A-3) The reaction is performed under the same conditions as in Synthesis Example 1 except that the addition amounts of 1,2-epoxybutane and ethylene oxide are changed. Dispersants (A-2) and (A-3) represented by the following formulas were obtained.

Synthesis Example 4: Synthesis Example of Dispersant (A-4) 130 g (1 mol) of octyl alcohol and 1.68 g (0.03 mol) of KOH were charged into an autoclave, and 1,2- under conditions of 145 ° C. and 0.3 MPa. 216 g (3 mol) of epoxybutane was added, and then 660 g (15 mol) of ethylene oxide was added under conditions of 150 ° C. and 0.3 MPa. Next, 1006 g (1 mol) of the obtained reaction mixture and 101.9 g (1 mol) of amidosulfuric acid were charged into a reaction vessel equipped with a stirrer and a thermometer, and reacted with stirring at 120 ° C. for 90 minutes in a nitrogen atmosphere. Then, unreacted amidosulfuric acid was removed by filtration to obtain a dispersant (A-4) represented by the following formula.
CH ₃ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ O— (BO) ₃ (EO) ₁₅ —SO ₃ NH ₄

Synthesis Example 5: Synthesis Example of Dispersant (A-5) 32.5 g of Dispersant (A-1), 30.4 g of butyl acrylate, 23.8 g of methyl methacrylate, 130.1 g of toluene, 2.0 g of lauroyl peroxide Was charged into a four-necked flask equipped with a stirrer, a cooling tank and a thermometer, and after substitution with nitrogen, the mixture was reacted at 65 ° C. for 7 hours to obtain a copolymer (dispersant (A-5)).

Comparative Synthesis Example 1: Synthesis Example of Comparative Dispersant 1 Comparative Example 1 was obtained in the same manner as in Synthesis Example 1 except that sulfation was not performed.

Comparative Synthesis Example 2: Synthesis Example of Comparative Dispersant 2 An autoclave was charged with 186 g (1 mol) of lauryl alcohol and 1.68 g (0.03 mol) of KOH, and 132 g (3 mol) of ethylene oxide under conditions of 150 ° C. and 0.3 MPa. ) Was added. Next, 318 g (1 mol) of the obtained reaction mixture was charged into a reaction vessel equipped with a stirrer, a thermometer, and a blower, and 81.6 g (1.02 mol) of SO ₃ gas was blown at 50 ° C. for sulfation. Went. Next, 1242 g of ion-exchanged water and 40 g (1 mol) of NaOH were charged into a reaction vessel equipped with a stirrer and a thermometer, and after dissolution, 398 g of the obtained sulfur oxide was added, and a 25% aqueous solution of a compound represented by the following formula was added. (Comparative dispersant 2) was obtained.
C ₁₂ H ₂₅ O— (EO) ₃ —SO ₃ Na

Examples 1-5 and Comparative Examples 1-3
In a 50 ml screw tube, 0.3 g of titanium oxide (Typaque R670), 30 ml of toluene, 0.006 g of the dispersant obtained in the synthesis example or comparative synthesis example (in terms of solid content) are weighed and dispersed with ultrasound for 30 minutes, and evaluated. A sample was obtained. The evaluation sample was transferred to a sedimentation test tube having a diameter of about 1.1 cm and a height of about 38 cm (the liquid level of the evaluation sample in the sedimentation test tube was about 33 cm from the bottom surface of the test tube), and allowed to stand after shaking dispersion. The sedimentation rate of titanium oxide was measured (temperature condition: 25 ° C.) and evaluated according to the following criteria. Moreover, it evaluated similarly about the case where a dispersing agent is not added (comparative example 1). These results are shown in Table 1. The sedimentation surface is a boundary surface between the suspended layer (layer in which the inorganic powder is dispersed in the dispersion medium) and the transparent layer (the supernatant layer in which the inorganic powder is settled and is in a transparent state) Visual evaluation was made.

◎: After one day, the sedimentation surface is 20 cm or more from the bottom of the test tube ○: After one day, the sedimentation surface is 20 cm or less from the bottom of the test tube ×: After 5 hours, the sedimentation surface is 20 cm or less from the bottom of the test tube XX: Almost after 5 minutes Precipitation

Claims (4)

An inorganic powder, a dispersant for inorganic powder containing at least one selected from the compounds represented by formula (I) , and a dispersion medium, wherein the dispersion medium is an ester, a ketone, an aliphatic hydrocarbon, an aromatic An inorganic powder dispersion composition which is a hydrocarbon or a halogenated hydrocarbon .
RO- (AO) _a (EO) _b -SO ₃ M (I)
(In the formula, R represents a linear or branched alkyl group or alkenyl group having 3 to 12 carbon atoms, AO represents an oxyalkylene group having 4 carbon atoms, EO represents an oxyethylene group, and a represents the average added mole number of AO. The number of 1 to 20 shown, b is the number of 5 to 30 showing the average added mole number of EO, a aO may be the same or different, and a AO and b EO are a block coupling .M represents a cation.) The inorganic powder dispersion composition according to claim 1, wherein M in formula (I) is an ammonium ion or an ammonium ion substituted with at least one group selected from an alkyl group having 1 to 4 carbon atoms and an alkanol group . . The inorganic powder dispersion composition according to claim 1 or 2, wherein the dispersant for inorganic powder is contained in an amount of 0.05 to 10 parts by weight with respect to 100 parts by weight of the inorganic powder. The inorganic powder dispersion composition according to any one of claims 1 to 3, wherein the inorganic powder is selected from calcium carbonate, aluminum hydroxide, magnesium hydroxide, clay, kaolin, talc, silica, bengara, and titanium oxide.