JP5134351B2 - Dispersant composition in oil for electronic materials - Google Patents

Description

  The present invention relates to an oil-in-oil dispersant composition for electronic materials, and an oil-in-oil dispersion containing an electronic material-in-oil dispersant composition and an electronic material powder.

Conventionally, in order to obtain a dispersion in oil containing a powder for electronic materials, an aromatic solvent, particularly toluene, xylene, benzene, or a mixed solvent with these aromatic solvents is used as a solvent ( For example, Patent Document 1). However, in view of the influence on the environment, non-aromatic organic solvents having a high polarity are being used in recent years without blending aromatic solvents. However, when non-aromatic organic solvents are used, the conventional dispersants have poor dispersion performance, and a dispersion in oil having satisfactory dispersibility has not been obtained.
JP 2004-2164 A

  An object of the present invention is to provide an in-oil dispersant composition for an electronic material and a dispersion in oil which have sufficient dispersion performance even when a non-aromatic organic solvent having little influence on the environment is used.

The present invention is an amidation or esterification product of a copolymer of an olefin and an unsaturated dibasic acid, at least selected from those having an amidation rate or esterification rate of 10 to 60 mol% with respect to the unsaturated dibasic acid Dispersant composition in oil for electronic materials containing one type of dispersant and non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm ³ ) ^1/2 , and for this electronic material Provided is a dispersion in oil containing a dispersant composition in oil and a powder for electronic materials.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an in-oil dispersant composition for an electronic material and a dispersion in oil having good dispersion performance even when a non-aromatic organic solvent having little influence on the environment is contained.

[Dispersant composition in oil for electronic materials]
Dispersant composition in oil for electronic materials of the present invention is an amidated product or an esterified product of a copolymer of an olefin and an unsaturated dibasic acid, and has a specific amidation rate or esterification rate, And a non-aromatic organic solvent having the specific solubility parameter.

  The olefin constituting the dispersant of the present invention is preferably an olefin having 3 to 12 carbon atoms from the viewpoint of obtaining good dispersion performance, more preferably at least one selected from the group consisting of diisobutylene and isobutylene, and diisobutylene. Is more preferable.

  The unsaturated dibasic acid constituting the dispersant of the present invention is preferably an aliphatic unsaturated dibasic acid having 4 to 6 carbon atoms from the viewpoint of obtaining good dispersion performance, maleic anhydride, maleic acid and itaconic acid. More preferred is at least one selected from the group consisting of maleic anhydride and maleic acid.

  From the viewpoint of obtaining good dispersion performance, the ratio of olefin and unsaturated dibasic acid as constituent monomers of the dispersant of the present invention is olefin / unsaturated dibasic acid (molar ratio) = 80/20 to 20/80. Preferably, 70 / 30-30 / 70 is more preferable, and 65 / 35-35 / 65 is still more preferable.

  The amidation product of a copolymer of an olefin and an unsaturated dibasic acid used in the present invention is a copolymer of an olefin and an unsaturated dibasic acid, and an amine having an amidation rate with respect to the unsaturated dibasic acid. It can obtain by making it react so that it may become 10-60 mol%. The amine used here is preferably a primary amine having 4 to 22 carbon atoms, and specific examples include butylamine, octylamine, laurylamine, stearylamine, and oleylamine. These amines can be used alone or in combination of two or more.

  The amidation rate of the obtained amidated product (vs. unsaturated dibasic acid) is 10 to 60 mol% from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. -55 mol% is preferable and 40-55 mol% is more preferable.

  The esterified product of a copolymer of an olefin and an unsaturated dibasic acid used in the present invention has an esterification rate of the copolymer of an olefin and an unsaturated dibasic acid and an alcohol with respect to the unsaturated dibasic acid. It can obtain by making it react so that it may become 10-60 mol%. The alcohol used here is preferably an alcohol having 4 to 22 carbon atoms, and specifically includes butyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, stearyl alcohol, oleyl alcohol and the like. These alcohols can be used alone or in combination of two or more.

  The esterification rate (vs. unsaturated dibasic acid) of the obtained esterified product is 10 to 60 mol% from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. -55 mol% is preferable and 30-50 mol% is more preferable.

  The amidated or esterified product of the copolymer of olefin and unsaturated dibasic acid may be neutralized with an amine, betaine or the like, if necessary.

  The weight average molecular weight of the dispersant used in the present invention is preferably 700 to 500,000, more preferably 1,000 to 300,000 from the viewpoint of obtaining good dispersion performance and good solubility in a non-aromatic organic solvent. 3000 to 100,000 are more preferable.

  In addition, the weight average molecular weight of the dispersing agent in this specification is a value measured by GPC (gel permeation chromatography, converted to polystyrene) under the following conditions.

Column: α-M + α-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Detector: RI
Eluent: 60 mmol / L phosphoric acid, 50 mmol / L lithium bromide, DMF solvent Flow rate: 1.0 mL / min
Injection volume: 0.1 mL
Standard: polystyrene.

The organic solvent used in the present invention is a non-aromatic organic solvent in consideration of the environment, and the solubility parameter of the non-aromatic organic solvent is 8 from the viewpoint of improving the solubility of the dispersant of the present invention. .5~22 (cal / cm ^{3) 1/2,} preferably ^{8.5~18cal / cm 3) 1/2, 8.5~15cal} / cm 3) 1/2 is more preferred.

  The solubility parameter of the non-aromatic organic solvent is defined by the theoretical development of the regular solution, and is used as an index representing the solubility of the solvent. The solubility parameter (SP value) referred to in the present invention follows Hansen's formula, and details are obtained based on “SP value basics / applications and calculation methods” (Hideki Yamamoto, published by Information Technology Corporation).

  Specific examples of the non-aromatic organic solvent used in the present invention include methyl alcohol (SP value 14.49), ethyl alcohol (SP value 12.98), butyl alcohol (SP value 11.32), terpineol (SP value 11.09), butylcarbi Toll (SP value 9.61), acetone (SP value 9.75), ethyl acetate (SP value 8.74), ethylene glycol (SP value 16.07), diethylene glycol (SP value 14.56), propylene glycol (SP value 13.18), propylene glycol methyl ether ( SP value 9.07), propylene glycol methyl ether acetate (SP value 8.78), and the like. Among these, ethyl alcohol, acetone, diethylene glycol, and propylene glycol methyl ether acetate are preferable. These non-aromatic organic solvents can be used alone or in combination of two or more.

The content of the dispersant of the present invention in the dispersant for oil for electronic materials of the present invention is preferably 0.2 to 30% by weight, preferably 0.5 to 15% from the viewpoint of obtaining good dispersion performance. % Is more preferable. In addition, the content of the non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm ³ ) ^1/2 is preferably 60 to 100% by weight from the viewpoint of obtaining good dispersion performance, and 80 to 100 Weight percent is more preferred.

  The dispersant for an electronic material according to the present invention may contain an unreacted olefin, an unsaturated dibasic acid, or the like as long as the effects of the present invention are not impaired.

[Dispersion in oil]
The dispersion in oil of the present invention contains the in-oil dispersant composition for electronic materials of the present invention and the powder for electronic materials.

  Examples of the powder for electronic materials to be used in the present invention include calcium carbonate, calcium phosphate, zinc phosphate, clay, bentonite, satin white, zinc white, bengara, ferrite, titanium oxide, alumina, magnesium oxide, talc, white carbon, Examples thereof include cement, gypsum, carbon black, titanate, and silicate. Among these powders, powders used for electromagnetic / optical member fine ceramics are preferable, and titanates such as barium titanate and alumina are more preferable.

  Fine ceramics are basically composed of an inorganic compound, and are produced by a high-temperature reaction at 1000 ° C. or higher using a mineral as a raw material. Among them, the electromagnetic / optical member fine ceramics include, for example, IC packages, wiring boards, insulators, sensors, electrodes, magnetic bodies, semiconductors, capacitors, optical fibers, and the like.

  The content of the powder for electronic material in the dispersion in oil of the present invention is not particularly limited, but is preferably 50% by weight or more and 50 to 85% by weight from the viewpoint of improving the drying efficiency and increasing the productivity. Is more preferable, and 65-85 weight% is still more preferable. In addition, the content of the dispersant of the present invention in the dispersion in oil of the present invention is preferably 0.2 parts by weight or more with respect to 100 parts by weight of the electronic material powder from the viewpoint of obtaining good dispersibility. 0.2-30 weight part is more preferable, and 0.5-15 weight part is still more preferable.

Further, in the dispersion in oil of the present invention, the value of the B viscosity (25 ° C.) of the slurry having a powder content of 50% by weight or more is preferably 200 mPa · s or less, and more preferably 80 to 170 mPa · s.
In addition, B viscosity is measured by the method described in the Example.

  As a method for obtaining the dispersion in oil of the present invention, a usual slurrying method is used. For example, a method of adding the powder for electronic material to the dispersant composition in oil of the present invention and stirring and mixing, a method of adding the dispersant composition in oil of the present invention to the powder for electronic material and stirring and mixing, etc. Is mentioned. As a method of stirring and mixing, for example, a generally used stirring device such as a high-speed disper, a homomixer, or a ball mill can be used.

  In addition, when the ore or coarse particles of the powder for electronic materials is slurried simultaneously with the pulverization, the dispersant in oil of the present invention is added to the ore or coarse particles of the powder for electronic materials, A method of slurrying at the same time can be mentioned. A generally used wet pulverizer such as a bead mill can be used as a method of slurrying simultaneously with pulverization.

The dispersion in oil of the present invention can contain a binder, a plasticizer, and the like. Examples of the binder include ethyl cellulose, acrylic, polyvinyl butyral, polyvinyl acetal, polyvinyl alcohol, polyolefin, polyurethane, polystyrene, or a mixture thereof.
Examples of the plasticizer include dioctyl phthalate, adipic acid, phosphate ester, glycol and the like.

Although the dispersion stabilization mechanism of the dispersion in oil of the present invention is not clear, the group derived from the unsaturated dibasic acid constituting the dispersant of the present invention is adsorbed on the powder for electronic materials, and the present invention. It is presumed that the dispersion stabilization is improved by the group derived from the olefin constituting the dispersant of the solvent being dissolved and diffused in the non-aromatic organic solvent.

  Hereinafter, the present invention will be described in more detail with reference to production examples of dispersants, and examples and comparative examples of dispersions in oil, but the present invention is not limited to these examples.

Production Example 1
A reaction vessel equipped with a stirrer, a thermometer, a reflux condenser, a nitrogen inlet tube, and a dropping funnel was charged with 66.0 g of maleic anhydride and 60.7 g of propylene glycol methyl ether acetate (hereinafter abbreviated as PGMEA). After heating to 0 ° C., while maintaining this temperature, 87.9 g of 85 wt% diisobutylene PGMEA solution and 130.5 g of 4 wt% lauroyl peroxide PGMEA solution were added dropwise from another dropping funnel over 4 hours to carry out the polymerization reaction. went. After completion of the dropping, the mixture was aged at 100 ° C. for 10 hours to complete the polymerization reaction. After completion of the reaction, the mixture was cooled and 90 g of oleylamine was dropped from the dropping funnel over 1 hour while maintaining the temperature at 55 ° C. to carry out an amidation reaction. After completion of the dropwise addition, the mixture was aged at 55 ° C. for 1 hour to complete the reaction, whereby a maleic anhydride / diisobutylene copolymer amidated product was obtained. Table 1 shows the amidation rate and weight average molecular weight (values measured by the above method, the same applies hereinafter) of the copolymer amidated product.

Production Example 2
In the same manner as in Production Example 1 except that 18.9 g of 4 wt% lauroyl peroxide PGMEA solution was used for polymerization, and 27.3 g of stearyl alcohol was used instead of oleylamine for esterification and aging, A maleic anhydride / diisobutylene copolymer esterified product was obtained. Table 1 shows the esterification rate and the weight average molecular weight of the copolymerized product.

Production Example 3
In the same manner as in Production Example 1 except that 92.3 g of 4 wt% lauroyl peroxide PGMEA solution was used, 87.5 g of itaconic acid was used instead of maleic anhydride, and 37.4 g of isobutylene was used instead of diisobutylene. The polymerization reaction and aging were carried out to complete the polymerization reaction. After completion of the reaction, 48.4 g of laurylamine was used instead of oleylamine, and the amidation reaction and aging were performed in the same manner as in Production Example 1 to obtain an itaconic acid / isobutylene copolymer amidated product. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Production Example 4
At the time of polymerization, 21.2 g of 4 wt% lauroyl peroxide PGMEA solution was used, and 78.1 g of maleic acid was used instead of maleic anhydride, and the polymerization reaction and aging were performed in the same manner as in Production Example 1, The polymerization reaction was completed. After completion of the reaction, a maleic acid / diisobutylene copolymer esterified product was obtained in the same manner as in Production Example 1 except that 17.6 g of octyl alcohol was used instead of oleylamine for the esterification reaction and aging. Table 1 shows the esterification rate and the weight average molecular weight of the copolymerized product.

Production Example 5
In the same manner as in Production Example 1 except that 68.2 g of 4 wt% lauroyl peroxide PGMEA solution was used during polymerization and 72 g of oleylamine was used for aging, maleic anhydride / diisobutylene copolymer A polymer amidation product was obtained. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Production Example 6
In the same manner as in Production Example 1, except that 23.3 g of 4 wt% lauroyl peroxide PGMEA solution was used and 54 g of oleylamine was used for aging, and maleic anhydride / diisobutylene copolymer A polymer amidation product was obtained. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Production Example 7
In the same manner as in Production Example 1, except that 46.3 g of 4 wt% lauroyl peroxide PGMEA solution was used and 81 g of oleylamine was used for the amidation reaction and aging, both maleic anhydride / diisobutylene A polymer amidation product was obtained. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Production Example 8
In the same manner as in Production Example 1, except that 27.6 g of 4% by weight lauroyl peroxide PGMEA solution was used for polymerization, and 47.8 g of 2-ethylhexylamine was used in place of oleylamine for aging. Thus, an amidated product of maleic anhydride / diisobutylene copolymer was obtained. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Production Example 9
In the same manner as in Production Example 1 except that 28.4 g of 4 wt% lauroyl peroxide PGMEA solution was used during polymerization and 147.6 g of oleylamine was used for aging, maleic anhydride / di-acid An isobutylene copolymer amidated product was obtained. Table 1 shows the amidation rate and the weight average molecular weight of the copolymer amidated product.

Example 1
In a 500 mL disposable beaker, 100 g of alumina having an average particle size of 0.38 μm, 40 g of PGMEA (solubility parameter 8.78 (cal / cm ³ ) ^1/2 ), and the dispersant obtained in Production Example 1 (diluted with PGMEA) 2 g), which was adjusted to a solid content of 30% by weight, was stirred with a homodisper manufactured by Tokushu Kika Kogyo Co., Ltd. (2500 r / min × 2 minutes) to prepare a slurry. The obtained slurry was measured for B viscosity at 25 ° C. using a B-type viscometer manufactured by Tokyo Keiki Co., Ltd. after 1 minute at a rotational speed of the rotor of 60 r / min. The results are shown in Table 2.
In addition, as for a slurry, the thing whose B viscosity is 200 mPa * s or less is favorable.

Examples 2-4
Instead of the dispersant obtained in Production Example 1, 2 g of the dispersant obtained in Production Examples 2 to 4 (those diluted with PGMEA and adjusted to a solid content of 30% by weight) was used in the same manner as in Example 1. A slurry was prepared and B viscosity was measured in the same manner. These results are shown in Table 2.

Example 5
Instead of PGMEA, 40 g of ethanol (solubility parameter 12.98 (cal / cm ³ ) ^1/2 ) was used, and the dispersant obtained in Production Example 5 (diluted with ethanol) was used instead of the dispersant obtained in Production Example 1. A slurry was prepared in the same manner as in Example 1 except that 2 g was used, and the B viscosity was measured in the same manner. The results are shown in Table 2.

Example 6
Instead of PGMEA, 40 g of acetone (solubility parameter 9.75 (cal / cm ³ ) ^1/2 ) was used, and the dispersant obtained in Production Example 6 (diluted with acetone) was used instead of the dispersant obtained in Production Example 1. A slurry was prepared in the same manner as in Example 1 except that 2 g was used, and the B viscosity was measured in the same manner. The results are shown in Table 2.

Example 7
Instead of PGMEA, 40 g of diethylene glycol (solubility parameter 14.56 (cal / cm ³ ) ^1/2 ) was used. Instead of the dispersant obtained in Production Example 1, the dispersant obtained in Production Example 7 (diluted with diethylene glycol) A slurry was prepared in the same manner as in Example 1 except that 2 g was used, and the B viscosity was measured in the same manner. The results are shown in Table 2.

Example 8
A slurry was obtained in the same manner as in Example 1 except that 2 g of the dispersant obtained in Production Example 8 (diluted with PGMEA and adjusted to a solid content of 30% by weight) was used instead of the dispersant obtained in Production Example 1. The B viscosity was measured in the same manner. The results are shown in Table 2.

Comparative Example 1
Instead of the dispersant obtained in Production Example 1, a commercially available α-olefin / maleic anhydride copolymer partial ester (trade name Floren G-700, manufactured by Kyoeisha Chemical Co., Ltd., esterification rate 95 mol%, PGMEA A slurry was prepared in the same manner as in Example 1 except that 2 g was used. The B viscosity was measured in the same manner. The results are shown in Table 2.

Comparative Examples 2-4
Instead of PGMEA, hexane (solubility parameter 7.24 (cal / cm ³ ) ^1/2 ), water (solubility parameter 23.43 (cal / cm ³ ) ^1/2 ) or methyl isobutyl ketone (solubility parameter 8.31 ( A slurry was prepared in the same manner as in Example 1 except that 40 g of cal / cm ³ ) ^1/2 ) was used, and the B viscosity was measured in the same manner. These results are shown in Table 2.

Comparative Example 5
A slurry was obtained in the same manner as in Example 1 except that 2 g of the dispersant obtained in Production Example 9 (diluted with PGMEA and adjusted to a solid content of 30% by weight) was used instead of the dispersant obtained in Production Example 1. The B viscosity was measured in the same manner. The results are shown in Table 2.

Claims (7)

At least one dispersion selected from amidated or esterified products of copolymers of olefins and unsaturated dibasic acids, wherein the amidation rate or esterification rate with respect to the unsaturated dibasic acid is 10 to 60 mol% And a non-aromatic organic solvent having a solubility parameter of 8.5 to 22 (cal / cm ³ ) ^1/2 , and a dispersant composition for oil for electronic materials ,
An oil for electronic materials, wherein the olefin is at least one selected from the group consisting of diisobutylene and isobutylene, and the unsaturated dibasic acid is at least one selected from the group consisting of maleic anhydride, maleic acid and itaconic acid. Medium dispersant composition . The in-oil dispersant composition for electronic materials according to claim 1, wherein the amine used for amidation is at least one selected from butylamine, octylamine, laurylamine, stearylamine, oleylamine, and 2-ethylhexylamine. The dispersant in oil for electronic materials according to claim 1 or 2, wherein the dispersant is an amidated product having an amidation rate of 40 to 55 mol%. The weight average molecular weight of a dispersing agent is 3000-61000, The dispersing agent composition in oil for electronic materials in any one of Claims 1-3. The in-oil dispersant composition for electronic materials according to claim 1, wherein the alcohol used for esterification is at least one selected from butyl alcohol, octyl alcohol, decyl alcohol, lauryl alcohol, stearyl alcohol, and oleyl alcohol. The dispersion in oil containing the dispersing agent composition for oils for electronic materials in any one of Claims 1-5 , and the powder for electronic materials. The dispersion in oil according to claim 6, wherein the content of the powder for electronic material is 50% by weight or more, and the content of the dispersant is 0.2 part by weight or more with respect to 100 parts by weight of the powder for electronic material. body.