JP6876329B2 - Dispersion aid - Google Patents

Description

The present invention relates to a dispersion aid.

Dispersants composed of acrylic acid-maleic acid copolymer salts are known as dispersants used when various powders are dispersed in water to form a slurry (Patent Documents 1 and 2).

JP-A-48-79230 Japanese Unexamined Patent Publication No. 53-129200

Dispersants such as those described in Patent Documents 1 and 2 have a problem that the dispersibility is not sufficient and sufficient dispersibility cannot be obtained even if the addition amount is increased.
An object of the present invention is to provide a dispersion aid capable of maximizing the dispersibility of the aqueous powder dispersant when used in combination with the aqueous dispersant for powder.

The feature of the dispersion aid of the present invention is that it contains the polyoxyalkylene compound (X) represented by the general formula (1) and the polyoxyalkylene compound (Y) represented by the general formula (2). It is a summary.

R ^1- O- (EO) _m · (PO) _n- H (1)
R ² {-(EO) _o / (PO) _p −H} _q (2)

R ¹ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, R ² is a residue obtained by removing a hydrogen atom from the hydroxyl group of a 2 to 8 valent polyhydric alcohol, H is a hydrogen atom, EO is an oxyethylene group, and PO. Is an oxypropylene group, m is an integer of 5 to 25, n is an integer of 2 to 20, o is an integer of 1 to 10, p is an integer of 10 to 30, q is an integer of 2 to 8, and is a block. Represents a random shape.

The feature of the powder slurry of the present invention is that it consists of water, powder, an aqueous dispersant for powder and the above-mentioned dispersion aid, and contains 0.01 to 10% by weight of this dispersion aid based on the weight of the powder. The point to be done is the gist.

When the dispersion aid of the present invention is used in combination with the aqueous dispersant for powder, the dispersibility of the aqueous dispersant for powder can be maximized.

Since the powder slurry of the present invention contains the above-mentioned dispersion aid, the dispersibility of the aqueous dispersant for powder can be maximized, and the viscosity becomes extremely low.

^{Examples of the alkyl group or alkenyl group (R 1} ) having 8 to 22 carbon atoms (preferably 10 to 20 and more preferably 12 to 18) include n-octyl, 2-ethylhexyl, n-nonyl, n-decyl and isodecyl. Examples thereof include n-undecylic, n-dodecyl, n-tridecylic, isotridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, isooctadecyl and octadecenyl.

^{Examples of the polyhydric alcohol constituting the residue (R 2} ) obtained by removing the hydrogen atom from the hydroxyl group of the 2-8 valent polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerin, and diglycerin. Examples thereof include triglycerin, tetraglycerin, pentaglycerin, hexaglycerin and trimethylolpropane.

Of these polyhydric alcohols, trihydric alcohols are preferable, and glycerin and trimethylolpropane are more preferable, from the viewpoint of dispersibility.

The ratio (m / n) of m to n in the general formula (1) is preferably 1.0 to 12.0, more preferably 1.5 to 11.5, and particularly preferably 1. It is 7 to 11.3, then preferably 1.9 to 11.1 and most preferably 2.0 to 11.0.

The ratio (o / p) of o to p in the general formula (2) ^{is preferably 3.0 × 10 -2 to} 1.0, more preferably 5.0 × 10 ^{-2 to} 9. 5 × 10 ^-1 , particularly preferably 7.0 × 10 ^{-2 to} 9.3 × 10 ^-1 , then preferably 9.0 × 10 ^{-2 to} 9.1 × 10 ^-1 , most preferably 10. It is 0 × 10 ^{-2 to} 9.0 × 10 ^-1 .

The sum (m + n) of m and n in the general formula (1) is preferably 7 to 45, more preferably 10 to 40, particularly preferably 15 to 35, and most preferably 20 to 30.

The sum (o + p) of o and p in the general formula (2) is preferably 11 to 40, more preferably 15 to 35, and particularly preferably 20 to 30.

The polyoxyalkylene compound (X) represented by the general formula (1) has a structure produced by a chemical reaction between an alkanol or alkanol (a1) having 8 to 22 carbon atoms and ethylene oxide and propylene oxide (a2). The amount of {(a1) 1 mol containing the polyoxyalkylene compound is preferably (a2) 7 to 45 mol. }.

Examples of the alkanol or alkenol (a1) having 8 to 22 carbon atoms include n-octyl alcohol, 2-ethylhexyl alcohol, n-nonyl alcohol, n-decyl alcohol, isodecyl alcohol, n-undecyl alcohol, and n-dodecyl alcohol. n-tridecyl alcohol, isotridecyl alcohol, n-tetradecyl alcohol, n-pentadecyl alcohol, n-hexadecyl alcohol, n-heptadecyl alcohol, n-octadecyl alcohol, isooctadecyl alcohol, octadecenyl alcohol, etc. Can be mentioned.

The polyoxyalkylene compound (Y) represented by the general formula (2) is a poly having a structure produced by a chemical reaction between a 2 to 8 valent polyvalent alcohol (a3) and ethylene oxide and propylene oxide (a2). The amount of {(a3) 1 mol containing the oxyalkylene compound is preferably (a2) 6 to 100 mol. }.

The 2 to 8 valent polyhydric alcohol (a3) is the same as "the polyhydric alcohol constituting ^{the residue (R 2} ) obtained by removing the hydrogen atom from the hydroxyl group of the 2 to 8 valent polyhydric alcohol".

The content (% by weight) of the polyoxyalkylene compound (X) is preferably 60 to 95, more preferably 65 to 90, based on the total weight of the polyoxyalkylene compound (X) and the polyoxyalkylene compound (Y). , Particularly preferably 70-85. Within this range, the dispersibility is further improved.

The content (% by weight) of the polyoxyalkylene compound (Y) is preferably 5 to 40, more preferably 10 to 35, based on the total weight of the polyoxyalkylene compound (X) and the polyoxyalkylene compound (Y). , Especially preferably 15 to 30. Within this range, the dispersibility is further improved.

The dispersion aid of the present invention may contain known additives (antifoaming agent, viscosity modifier, wetting agent, etc.), if necessary.

Examples of the defoaming agent include SN Deformer 180 and 184 (manufactured by San Nopco Ltd.), examples of the viscosity modifier include SN Sixner 601 and 612 (manufactured by San Nopco Ltd.), and examples of the wetting agent are SN Wet. 125 and 126 (manufactured by San Nopco Ltd.) and the like can be mentioned. When known additives are contained, the content thereof is preferably about 0.01 to 10% by weight based on the weight of the dispersion aid.

The method for producing the dispersion aid of the present invention is not particularly limited, and a known method can be applied. A polyoxyalkylene compound (X) and a polyoxyalkylene compound (Y) are prepared by a known alkylene oxide addition reaction or the like. , These can be obtained by uniformly mixing them. The uniform mixing temperature is not limited, but is preferably about 10 to 70 ° C. from the viewpoint of mixing efficiency.

When the dispersion aid of the present invention is used in combination with the aqueous dispersant for powder, the dispersibility of the aqueous dispersant for powder can be maximized.
Therefore, when the powder is dispersed using the dispersion aid of the present invention and the aqueous dispersant for powder, a low-viscosity powder slurry can be easily obtained.

Inorganic powders (silica, alumina, titanium oxide, magnesium hydroxide, silicon oxide, silicon carbide, silicon nitride, calcium hydroxide, calcium carbonate, magnesium carbonate, silver, gold, nickel, platinum, aluminum, tin , Copper, iron, zinc oxide, iron oxide, molybdenum oxide, ruthenium oxide, barium titanate, zirconium oxide, barium sulfate, trilead tetroxide, basic lead carbonate, lead chromate, zinc chromate, red phosphorus, phosphoric acid Aluminum, ammonium phosphate and carbon black, etc.), and organic powders (azo dyes, diazo dyes, phthalocyanine dyes, quinacridone dyes, isoindolinone dyes, dioxazine dyes, perylene dyes, perinone dyes, thioindigo dyes, anthraquinone dyes, quinophthalone dyes , Tris (2-ethylhexyl) phosphate, tris (2-butoxyethyl) phosphate, tris (hydroxymethyl) phosphine oxide, tris (hydroxypropyl) phosphine oxide, etc.) and the like.

As the aqueous powder dispersant, it can be used as any of anionic dispersants, cationic dispersions, and nonionic dispersants, and anionic dispersants are particularly preferable.

Anionic dispersants include organic compounds containing carboxy groups, sulfo groups and salts thereof (alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts, quaternary ammonium salts, etc.), and polyacrylic acids. Salt-type dispersant, acrylic acid-maleic acid copolymer salt-type dispersant, acrylic acid-styrene copolymer salt-type dispersant, acrylic acid-acrylic acid ester copolymer salt-type dispersant, maleic acid-styrene copolymer salt-type dispersion Agent, maleic acid-maleic acid ester-styrene copolymer salt type dispersant, naphthalene sulfonate type dispersant, acrylic acid-methacrylic acid copolymer salt type dispersant, methacryl-methacrylic acid ester copolymer salt type dispersant, etc. Can be mentioned. Of these, polyacrylate-type dispersants and acrylic acid-maleic acid copolymer salt-type dispersants are preferable.

Examples of the cationic dispersant include a quaternary ammonium salt type dispersant and a polyamine salt type dispersant.

Examples of the nonionic dispersant include sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyalkylene alkylamine.

The amount (% by weight) of the dispersion aid used is preferably 0.01 to 10 based on the weight of the powder, and more preferably 0.1 to 5.

The content (% by weight) of the dispersion aid contained in the powder slurry of the present invention is preferably 0.01 to 10 based on the weight of the powder, and more preferably 0.1 to 5.
The contents of water and the aqueous dispersant for powder contained in the powder slurry of the present invention are appropriately determined depending on the slurry concentration (powder concentration), the desired viscosity, and the like, respectively.

If necessary, the powder slurry of the present invention may contain known additives (antifoaming agent, viscosity modifier, wetting agent, etc.) and the like. These contents are preferably about 0.01 to 10% by weight based on the weight of the dispersion aid.

The powder slurry of the present invention can be easily obtained by dispersion treatment by a known method or the like. The dispersion aid may be mixed with the aqueous dispersant for powder or used separately, but when used separately, it should be mixed with the powder at the same timing as possible (for example, the dispersion aid). It is preferable to mix the agent and the aqueous dispersant for powder with water and, if necessary, known additives).

The powder slurry of the present invention can be used for various purposes, and is used for paints such as building paints or automobile paints, coating liquids for coating papers, paints for electronic materials such as electromagnetic and optical members, and structural materials using ceramics. It can be applied to coating compositions such as paints and paints for functional slurries to be applied to various molded bodies.

Hereinafter, unless otherwise specified, parts mean parts by weight and% means% by weight.

<Manufacturing example 1>
186 parts (1 mol part) of Calcol 2098 {n-dodecyl alcohol, Kao Co., Ltd.} and 0.07 part of potassium hydroxide were put into a pressure-resistant reaction vessel equipped with a stirrer, a heating / cooling device and a dropping cylinder, and nitrogen gas was added. The operation of pressurizing the gauge pressure to 0.2 MPa and discharging the gas to 0.1 MPa was repeated three times (hereinafter, this operation using nitrogen gas is abbreviated as "nitrogen gas replacement"). After that, the contents were sealed and the temperature of the contents was raised to 130 ° C. under reduced pressure (−0.097 MPa) with stirring. While stirring the contents, 616 parts (14 mol parts) of ethylene oxide (EO) was added dropwise over 2 hours, and stirring was continued for 1 hour at the same temperature, and then 392 parts (7 mol parts) of propylene oxide (PO) was added. The mixture was added dropwise over 2 hours, and stirring was continued at the same temperature for 2 hours. Polyoxyalkylene compound (X1: n-dodecyl alcohol-EO (14 mol) / PO (7 mol) block adduct: ratio (m / n) ) 2.0, sum (m + n) 21) was obtained.

<Manufacturing example 2>
The polyoxyalkylene compound (X2:) is the same as in Example 1 except that "392 parts (7 mol parts) of propylene oxide (PO)" is changed to "336 parts (6 mol parts) of propylene oxide (PO)". n-Dodecyl alcohol-EO (14 mol) · PO (6 mol) block adduct: ratio (m / n) 2.3, sum (m + n) 20) was obtained.

<Manufacturing example 3>
Changed "Calcol 2098 {n-dodecyl alcohol, Kao Co., Ltd.} 186 parts (1 mol part)" to "Calcol 8098 {n-octadecyl alcohol, Kao Co., Ltd.} 270 parts (1 mol part)", "Ethylene oxide 616 parts (14 mol parts) of (EO) was changed to 1188 parts (27 mol parts) of ethylene oxide (EO), and 392 parts (7 mol parts) of propylene oxide (PO) was changed to "propylene oxide (7 mol parts)". Addition of polyoxyalkylene compound (X3: n-octadecyl alcohol-EO (27 mol) / PO (3 mol) block) in the same manner as in Example 1 except that it was changed to 168 parts (3 mol) of PO). Body: ratio (m / n) 9, sum (m + n) 30) was obtained.

<Manufacturing example 4>
Changed "Calcol 2098 {n-dodecyl alcohol, Kao Co., Ltd.} 186 parts (1 mol part)" to "Calcol 8098 {n-octadecyl alcohol, Kao Co., Ltd.} 270 parts (1 mol part)", "Ethylene oxide "(EO) 616 parts (14 mol parts)" was changed to "ethylene oxide (EO) 968 parts (22 mol parts)", and "propylene oxide (PO) 392 parts (7 mol parts)" was changed to "propylene oxide (7 mol parts)". Polyoxyalkylene compound (X4: n-octadecyl alcohol-EO (22 mol), PO (2 mol) block adduct, in the same manner as in Example 1 except that it was changed to 112 parts (2 mol) of PO). : Ratio (m / n) 11, sum (m + n) 24) was obtained.

<Manufacturing example 5>
In the same reaction vessel as in Example 1, 92 parts (1 mol part) of purified glycerin {glycerin, Sakamoto Yakuhin Kogyo Co., Ltd.} and 0.07 part of potassium hydroxide were charged and then replaced with nitrogen gas. Then, the temperature is raised to 130 ° C. with stirring, and then at the same temperature, a mixture of 264 parts (6 mol parts) of ethylene oxide (EO) and 3360 parts (60 mol parts) of propylene oxide (PO) is applied over 3 hours. And the mixture was further added dropwise at the same temperature for 4 hours, and the polyoxyalkylene compound (Y1: glycerin-EO (6 mol) / PO (60 mol) random adduct: ratio (o / p) 0.1, sum. (O + p) 22) was obtained.

<Manufacturing example 6>
"264 parts (6 mol parts) of ethylene oxide (EO)" was changed to "396 parts (9 mol parts) of ethylene oxide (EO)", and "3360 parts (60 mol parts) of propylene oxide (PO)" was changed to "propylene oxide". Polyoxyalkylene compound (Y2: glycerin-EO (9 mol) / PO (51 mol) random adduct: in the same manner as in Example 5 except that it was changed to "2856 parts (51 mol) of ethylene oxide (PO)". A ratio (o / p) of 0.18 and a sum (o + p) of 20) were obtained.

<Manufacturing example 7>
"Purified glycerin {glycerin, Sakamoto Yakuhin Kogyo Co., Ltd.} 92 parts (1 mol part)" was changed to "TMP (flakes) {trimethylol propane, Mitsubishi Chemical Co., Ltd.} 134 parts (1 mol part)". 264 parts (6 mol parts) of ethylene oxide (EO) was changed to "1848 parts (42 mol parts) of ethylene oxide (EO)", and "3360 parts (60 mol parts) of propylene oxide (PO)" was changed to "propylene oxide". (PO) 2688 parts (48 mol) ", in the same manner as in Example 5, polyoxyalkylene compound (Y3: trimethylolpropane-EO (42 mol) / PO (48 mol) random adduct" : Ratio (o / p) 0.88, sum (o + p) 30) was obtained.

<Manufacturing example 8>
"Purified glycerin {glycerin, Sakamoto Yakuhin Kogyo Co., Ltd.} 92 parts (1 mol part)" was changed to "TMP (flakes) {trimethylol propane, Mitsubishi Chemical Co., Ltd.} 134 parts (1 mol part)". 264 parts (6 mol parts) of ethylene oxide (EO) was changed to "1716 parts (39 mol parts) of ethylene oxide (EO)", and "3360 parts (60 mol parts) of propylene oxide (PO)" was changed to "propylene oxide". (PO) 2520 parts (45 mol) ", in the same manner as in Example 5, polyoxyalkylene compound (Y4: trimethylolpropane-EO (39 mol) / PO (45 mol) random adduct" : Ratio (o / p) 0.87, sum (o + p) 28) was obtained.

<Example 1>
85 parts of the polyoxyalkylene compound (X1) obtained in Production Example 1 and 15 parts of the polyoxyalkylene compound (Y1) obtained in Production Example 5 were uniformly mixed to obtain the dispersion aid (1) of the present invention.

<Example 2>
70 parts of the polyoxyalkylene compound (X2) obtained in Production Example 2 and 30 parts of the polyoxyalkylene compound (Y2) obtained in Production Example 6 were uniformly mixed to obtain the dispersion aid (1) of the present invention.

<Example 3>
60 parts of the polyoxyalkylene compound (X3) obtained in Production Example 3 and 40 parts of the polyoxyalkylene compound (Y3) obtained in Production Example 7 were uniformly mixed to obtain the dispersion aid (3) of the present invention.

<Example 4>
95 parts of the polyoxyalkylene compound (X4) obtained in Production Example 4 and 5 parts of the polyoxyalkylene compound (Y4) obtained in Production Example 8 were uniformly mixed to obtain the dispersion aid (4) of the present invention.

<Evaluation of dispersibility of aluminum phosphate>
40 parts of water, SN Dispersant 5040 (40% aqueous solution of polyacrylate type dispersant, Sannopco Co., Ltd.) 2 parts, antifoaming agent (SN deformer 399: Sannopco Co., Ltd.) 0.3 parts and evaluation sample {dispersion aid After uniformly mixing 1 part of each of the agents (1) to (4) with a homogenizer, _{100 parts of aluminum phosphate (tertialuminum phosphate "AlPO 4} ", Kanto Chemical Co., Ltd.) is added while stirring. , Stirred at 3,000 rpm for 10 minutes to prepare an aluminum phosphate slurry. The temperature of the obtained slurry was adjusted to 25 ° C., and the viscosity of the slurry was measured using a B-type viscometer (TVB-20L, Tokimec Co., Ltd., the same applies hereinafter) at a rotation speed of 60 rpm. Further, as a blank, an aluminum phosphate slurry was prepared in the same manner as above except that the evaluation sample (dispersion aid) was changed to water. These viscosities are shown in the table below.

<Evaluation of dispersibility of calcium carbonate>
20 parts of water, SN Dispersant 5040 (40% aqueous solution of polyacrylate type dispersant, San Nopco Ltd.) 0.8 parts, antifoaming agent (SN deformer 399: San Nopco Ltd.) 0.3 parts, evaluation sample { After uniformly mixing 0.1 part of any of the dispersion aids (1) to (4) with a homogenizer, heavy calcium carbonate (Sunlight SL-300, volume average particle size 5 μm,: Takehara Chemical Co., Ltd.) Kogyo Co., Ltd. and "Sunlight" are registered trademarks of Kyoei Sangyo Co., Ltd.) 100 parts were added and stirred at 3,000 rpm for 10 minutes to prepare a calcium carbonate slurry. The temperature of the obtained slurry was adjusted to 25 ° C., and the viscosity of the slurry was measured at a rotation speed of 60 rpm using a B-type viscometer. Further, as a blank, a calcium carbonate slurry was prepared in the same manner as above except that the evaluation sample (dispersion aid) was changed to water. These viscosities are shown in the table below.

<Evaluation of dispersibility of titanium oxide>
30 parts of water, 40% aqueous solution of sodium salt of acrylic acid / maleic acid (molar ratio 100/25) copolymer (acrylic acid-maleic acid copolymer salt type dispersant, weight average molecular weight 4000, described in Patent Document 2 1.2 parts of sample (equivalent to No. 7), 0.3 parts of defoamer (SN deformer 399: Sannopco Co., Ltd.), evaluation sample {any of dispersion aids (1) to (4)} 0. After uniformly mixing 1 part with a homogenizer, while stirring, 100 parts of titanium oxide (Typake R-820, volume average particle size 0.3 μm: Ishihara Sangyo Co., Ltd., “Typake” is a registered trademark of the company). The mixture was added and stirred at 3,000 rpm for 10 minutes to prepare a titanium oxide slurry. The temperature of the obtained slurry was adjusted to 25 ° C., and the viscosity of the slurry was measured at a rotation speed of 60 rpm using a B-type viscometer. Further, as a blank, a titanium oxide slurry was prepared in the same manner as above except that the evaluation sample (dispersion aid) was changed to water. These viscosities are shown in the table below.

<Evaluation of dispersibility of hydrophilic silica>
60 parts of water, SN Dispersant 7347-C (20% aqueous solution of quaternary ammonium salt type dispersant, Sannopco Co., Ltd.) 10 parts, defoamer (SN deformer 399: Sannopco Co., Ltd.) 0.3 parts, evaluation sample {Any of dispersion aids (1) to (4)} After uniformly stirring 5 parts with a homogenizer, hydrophilic silica (nip seal NA, volume average particle diameter 9 μm: Toso Silica Co., Ltd., “Nip seal” Is a registered trademark of the same company.) 100 parts were added and stirred at 3,000 rpm for 10 minutes to prepare a hydrophilic silica slurry. The temperature of the obtained slurry was adjusted to 25 ° C., and the viscosity of the slurry was measured at a rotation speed of 60 rpm using a B-type viscometer. Further, as a blank, a titanium oxide slurry was prepared in the same manner as above except that the evaluation sample (dispersion aid) was changed to water. These viscosities are shown in the table below.

By using the dispersion aids (1) to (4) of the present invention in combination with the aqueous dispersant for powder, the slurry viscosity could be further reduced. That is, when the dispersion aid of the present invention was used in combination with the aqueous dispersant for powder, the dispersibility of the aqueous dispersant for powder could be maximized.

Claims (5)

A dispersion aid used together with an aqueous dispersant for powders.
A dispersion aid comprising a polyoxyalkylene compound (X) represented by the general formula (1) and a polyoxyalkylene compound (Y) represented by the general formula (2).
R ^1- O- (EO) _m · (PO) _n- H (1)
R ² {-(EO) _o / (PO) _p −H} _q (2)
( R ¹ is an alkyl group or alkenyl group having 8 to 22 carbon atoms, R ² is a residue obtained by removing a hydrogen atom from the hydroxyl group of a 2 to 8 valent polyhydric alcohol, H is a hydrogen atom, and EO is an oxyethylene group. PO is an oxypropylene group, m is an integer of 5 to 25, n is an integer of 2 to 20, o is an integer of 1 to 10, p is an integer of 10 to 30, q is an integer of 2 to 8, and · is a block. / Represents a random shape. ) The ratio of m to n in the general formula (1) (m / n) is from 1.0 to 12.0, the ratio p of o in the general formula (2) (o / p) is 5.0 × ^{10 -2} ~ The dispersion aid according to claim 1, which is 1.0. The dispersion aid according to claim 1 or 2, wherein the sum of m and n (m + n) in the general formula (1) is 7 to 45, and the sum of o and p (o + p) in the general formula (2) is 11 to 40. .. Based on the total weight of the polyoxyalkylene compound (X) and the polyoxyalkylene compound (Y), the content of the polyoxyalkylene compound (X) is 60 to 95% by weight, and the weight of the polyoxyalkylene compound (Y) is 5. The dispersion aid according to any one of claims 1 to 3, which is ~ 40% by weight. Consists of water, powder, water-based dispersant for powder and the dispersion aid according to any one of claims 1 to 4, and contains 0.01 to 10% by weight of this dispersion aid based on the weight of the powder. A powder slurry characterized by being made of.