JPS5981362A - Production of inorganic powder having lipophilic surface - Google Patents

Abstract

PURPOSE:To produce the titled inorg. powder having excellent dispersibility in org. solvents or polymers, by dry-mixing a dispersant having a lipophilic group with an inorg. powder. CONSTITUTION:100pts.wt. inorg. powder having a particle size of 0.1-10mu, such as gamma-alumina, alpha-alumina or silica, and a dispersant having a lipophilic group, such as sodium octadecanoate, aluminum dodecanoate or soybean oil lecithin are dry-mixed for one min to 10hr by using a ball mill or an oscillating mill under a condition of impact value of 1G or above.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a 4p. ll
Concerning base system. More specifically, the present invention relates to a method for producing an inorganic powder with excellent dispersibility in organic solvents or polymers.

Inorganic powders have long been used as fillers for polymers, abrasive powders,
It is widely used as a pigment, reinforcing agent, etc.

The surface of inorganic powders is inherently hydrophilic and therefore easily wetted by water, so the affinity between inorganic powders and polymers is inherently limited, so when filling inorganic powders into polymers, When an inorganic powder is added to a solution of a polymer in an organic solvent to form a film, the problem of poor dispersibility is often encountered.

Furthermore, there is a disadvantage that the dispersibility is poor when dispersing inorganic powder into the 8-limbed body.

In order to improve this disadvantage, inorganic powder is dissolved in water with a surfactant such as sodium alkylbenzene sulfonate71.
A method of producing a lipophilic inorganic powder by polymerizing with stirring and drying, or a method of producing a lipophilic inorganic powder by dissolving an organic powder in an organic ditanate. However, they have drawbacks such as not being able to provide sufficient dispersibility and requiring considerable energy for drying. The latter method, ti, can provide sufficient dispersibility, but has drawbacks such as the treating agent having an a value and the desolvation treatment not being flexible.

In view of this situation, the present inventors and () have made extensive studies to overcome these inconveniences, and have found that by arranging a timed treatment for inorganic powder, it is possible to improve the dispersibility of the inorganic powder, and to solve the problem by using a solvent. The present inventors have discovered that it is possible to produce lipophilic inorganic powders without the need for frequent steps such as recovery, etc., and have completed the present invention.

That is, the present invention is 11? Provided is a method for producing an inorganic powder having a lipophilic surface, characterized by dry mixing a J-quality powder and a dispersant having a lipophilic property under conditions whose impact value is equal to or greater than IG. It is.

The inorganic powder used in carrying out the method of the present invention is not limited to bamboo, but any ordinary powder can be used as long as it is a regular powder.

Examples of such powders include aluminum hydroxide, T-alumina, α-alumina, silica, and
Bar, calcium carbonate, silicic acid) J lucium, aluminum silicate, magnesium hydroxide, magnesilano 1 oxide, talc, titanium oxide, Fil & Ich fyk, chromium oxide, zinc oxide, zirconium oxide, Chrono 8 oxide, tin oxide, etc. can give. It can be used as a mixture of the two.

T-aluminum on φ, α-aluminum
Miss, Shi 1) So J/:l\force S is suitable.

The shape of the inorganic powder is not particularly limited (and the particle size is also limited to bamboo, so there is no limit), and powders with a diameter of 5, generally 50 μm or less, preferably 0.017zm to 10 μm are used.

Examples of dispersants for dispersing lipophilic groups used in carrying out the method of the present invention include higher fatty acids such as decanoic acid, dodecanoic acid, thi-labcanic acid, hexadecanoic acid, octadecanoic acid, and oleic acid. salts, potassium salts, magnesylano salts, calcilano salts, aluminum salts, ammonium salts, decino-I-no-sulfate, dodecyl-sulfate, tetradecyl→no-decyl-sulfate, octadecyl-sulfate, etc. sodium salts of sulfuric acid esters of commercial alcohols, potassium salt, magnesium salt, calcium salt, aluminum salt, ammonium salt, decylbenzenesulfonic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzene-1
-'Alkylaryl sulfates such as sulfonate i'i'2 σ) putoliuno salts, potassium salts, magnesilano salts, lucium salts, aluminum salts, ammonium salts, di-2-ethylhexyl sodium N-sulfuccinates , di-2-ethylhexylpotassium sulfosuccinate, di-2-ethyl sulfosuccinate, monostylmagnesium sulfosuccinate, di-2-ethyl sulfosuccinate 2 ---
1-cho-1 thylhexyl calcium, sulfosuccinic acid di-2
- Ezylhexylaluminum, sulfosuccinic acid di-2
- Dialkyl sulfosuccinates such as edylhexyl ammonium, polyoxyethylene dodecyl ether sulfate, polyoxyethylene dodecyl ether sulfate, polyoxyethylene tetradecyl ether sulfate, polyoxyethylene hexadecyl ether sulfate, polyoxyethylene octadecyl ether sulfate, etc. Sodium salt, potassium salt, ゛7gnesium salt, calcium salt, aluminum salt, ammonia A h N polyoxyethylene decyl ether,
Polyoxyethylene higher alcohol ethers such as polyoxyethylene dodecyl ether, polyoxyethylene tetradecyl ether, polyoxyethylene tetradecyl ether, boxoxyethylene octadecyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, polyoxy Polyoxyethylene nonyl phenol ether, polyoxyethylene dodecyl phenol ether, polyoxyethylene dodecyl phenol ether, polyoxyethylene phenol, labucyl phenol ether, polyoxyethylene hexadodecyl phenol ether, polyoxyethylene Polyoxyethylene alkylphenol ether such as octadodecylphenol ether, sorbitan decane-1, sorbitan dodecanate, sorbitan tetradecanate,
Sorbitan hexadecane-1, nrubitan octadecane-1, sorbitan oleate-1, etc., nrubitan fatty acid nisdel, polyoxyedicyl chloride/sorbitan deno 1
Ne-1・, Polyoxyethylene Luhitane Dodecanate, Polyoxyethylene Sorbitante I・Radecane-1・
, polyoxyethylene sorbitan hexadecane-1.
Polyoxyethylene rubitan fatty acid nysdel, polyethylene glycol canate, polyethylene glycol decanate, polyethylene glycol tetradecane, etc., polyoxyethylene rubitan oleate, etc. , polyethyl/glycol hexadecane-1-, polyethyl
/ glycol octadecanate, polyethylene glycol oleate, polyoxyethylene decanate, polyoxyethylene dodecanate, polyoxyethylene tetradecane-1, polyoxyethylene hexadecanate, poly Polyo-1-diethylene fatty acid esters such as oxyethylene octadecane-1, glycerin fatty acid esters such as dodecanoic acid glyceride, octadecanoic acid glycerate, oleic acid glyceride, decylamine acetate, dodecylamine acetate, tetradecyl Alkyl achlorides such as amine acetate-1, hexadecylamine acetate, octadecylamine acetate, hexadecyltrimethylammonium chloride, octadecyltrimedylammonium chloride,
11th class ammonium salts such as didodecyl dimedylammonium chloride and dioctadecyl dimedylammonium chloride, polyoxyethylene decylamine, polyoxyethylene dodecylamine, polyA xyylene tetradecylamine, polyoxyethylene hexadecylamine , polyoxyethylene alkyl phenol such as polyoxyethyl octadecylamine, phosphoric acid ester of higher fatty acid such as lecithin, etc. in liquid or solid form.
Examples include activators. Particularly preferably dodecanoic acid
・Liu,／・, Sodium octadecanoate, Aluminum dodecanoate, Sodium dodecyl sulfate, Sodium phtadecyl acid, Sodium dodecylbenzenesulfonate, Sodium octadecylbenzenesulfonate, Di-2-ethyl sulfosuccinate Sodium hexyl, polyoxyethylene dodecyl ether sulfate
-lium, polyoxyethylene dodecyl ether, sorbitan monododecane-1, dodecylamine acedate, and lecithin. These dispersants are one type or another)
It can be used as a mixture of the two.

In carrying out the method of the present invention, the dispersant having a lipophilic group is used in an amount of 0.01 to 1 part by weight, preferably 0.02 to 10 parts by weight, per 100 parts by weight of the inorganic powder. If the blending ratio of the dispersant is less than 0.01 parts by weight, the effect of improving dispersibility will be slight12, while if it is more than 20 parts by weight, the hygroscopicity may increase depending on the purpose of use, and it may be economically disadvantageous. This is an inconvenience.

To carry out the method of the present invention, the inorganic powder and the dispersant having a lipophilic group are dry mixed under conditions such that the impact value is 10 or more, preferably 3 to 15 G. By performing dry mixing under such mixing conditions, an inorganic powder with extremely excellent dispersibility in the melt 2 can be produced. Mixing condition is impact value 1
If it is less than 0, for example ■yS+J, when mixed using a mixer, etc., it is not possible to produce inorganic powder with sufficient dispersibility, probably because there is no pressure mixing of the geometric powder and the dispersant. .

When the mixing conditions are wet rather than dry, the dispersant used impacts the surface of the inorganic powder and causes pressure -i'? Perhaps because this is not the case, it is not possible to produce inorganic powder with excellent uniform dispersibility.

Moreover, in the case of wet mixing, it is economically problematic because after mixing, one culm separation and two drying steps are required, but in the case of the method of the present invention, it is a dry method. There are advantages such as no post-processing required.

As a means to achieve dry mixing conditions, for example, ball mills, vibration mills, etc. may be used, especially impact value 3~]
A 5 G vibratory mill is preferably used. The mixing time may generally be 1 to 10 hours.

When the easily dispersible inorganic powder produced by the method of the present invention is dispersed in a solvent, it has extremely poor dispersibility (f).Although the reason for this is not clear, the dispersant firmly adheres to the surface of the solid zeta powder. J: I think so.

Since the easily dispersible inorganic powder produced by the method of the present invention described in detail below-1 has very little separation of the inorganic powder and the dispersant, it is suitable for applications that require lipophilicity, for example, by dispersing it in an organic solvent. It has the effect that it can be applied effectively in applications such as applications where it is blended into synthetic resins and the like.

The easily dispersible inorganic powder produced by the inventive method is particularly suitable as a filler for plastics for electronics and parts that require good abrasion resistance and conductivity.

The method of the present invention will be explained in detail below with reference to Examples, but the present invention is not limited to the following Examples as long as they do not go beyond the gist of the invention.

Example 1 α-alumina powder 1002 having an average primary particle size of 0.6 μm and sodium dodecanoate 1y were placed in a vibrating mill (impact value -6) having an internal volume of 3/20
Grind and mix for minutes.

The obtained alumina powder 002F and medium (methyl edyl ketone)]0+++/ were charged into a test tube (drops with a height of 1 cm) and shaken for 5 minutes. Next, after performing ultrasonic dispersion treatment, it was left to stand for 24 hours. +'='6 curves were measured.

The higher the sedimentation quality, the better the dispersibility.

For comparison, no dispersant was used.
Measure the sedimentation height in the same manner as in Section 4.

The above results are shown in Table 1.

Table 1 *After 2 hours, the sedimentation height will be 2 cm and 1.) Buko.

Example 2 α---'f'lumina powder 801 with an average particle size of 0.6 μm and fine T-alumina powder 20 f and 1! with an average particle diameter of 0°Olttm. Aluminum decanoate 3y was charged into a vibrating mill (9'L<+-'L-6') having a 31-meter inner diameter (4°) and pulverized and mixed for 20 minutes.

The dispersibility of the obtained alumina powder was the same as in Example 1.
As a result of measurement, the sedimentation height was 9.7 cm.

For comparison, when the dispersant was not used in "-", the treatment was carried out in exactly the same manner, and the dispersibility was investigated.
Sedimentation + Nb depth was O05rs (sedimentation height was 3 cm after 2 hours).

Example 3 α-Alumina powder 1009 having an average primary particle size of 0.6 μm and the dispersant shown in Table 2 and the same were charged into a vibrating mill having an internal volume of 31 mm, and pulverized and mixed for 20 minutes.

The dispersibility of the obtained alumina powder was as shown in Table 2.

Example 4 Silica powder 1002 having an average primary particle size of 1 μm and sodium dodecanoate 12 were charged into a ball mill having an internal volume of 31 mm, and pulverized and mixed for 4 hours.

The dispersibility of the obtained alumina powder was as follows: sedimentation height 8, . 9c
It was a mosquito.

For comparison, the treatment was performed in the same manner as above except that sodium dodecanoate was not used, and the sedimentation height was 0°5 a.
There was. From the above, it is clear that inorganic powders with excellent dispersibility in organic solvents or in coagulation can be produced stably, with t1 productivity, and economically by the method of the present invention.

Dingzoku Supplement 11 (Ren 1 Shu) December 1981 % l-1 'I', '? :? '11i Director Kazuo Wakasugi Tono1'
Table of Ml] 1. 19191157 Special γI Application No. 192888 Bow 2
Invention υ〕Name) ゛Semi-IJ fabrication υ of inorganic caustic powder that supports a depositing surface 3
Relationship with ITr'l, the person who does oil 11, 1'1;
,.

Address: Kitaru, Higashi-ku, Osaka City = 5'I'N!
F'i-8:', tll1 name (20i)) Residentization'7. iUlgyo Co., Ltd.? 1 Representative Takeshi Hijikata 4th Generation: [IIj Address Kitahama Fi ”J'l]l, Higashi-ku, Osaka City
Boi 5, sleeve it- evening・] 犀明t(11γ1[;) Invention Q 彘, ゛1′ Thin/, C theory “l
)] no i) t16 Ura 11゛ no 1 > 14 γ (1) 'Ij month:l'l 'r::'Q'r 5
, 51112 lines 1-ri 1 com (there is (Seriu 1
, -1 and R3', iE-+Jru3, (2) Minggi)+
9 (Do゛'i', l :2j:J In the 14th line, it says 1 powder or 1. Correct it to 1) or l (1).

(3) On page 18, line 5 of the specification, amend it to read "Manufacturing conductivity -1 (!: There is 1 - thermal conductivity").

(1) On page 13, line 18 of the specification, "Shikome-1" is corrected to read "1 shikome-1."

(5) In the 6th line of page 17 of Specification Pi, ``Alumina-1'' is corrected to ``Silica''.

2 Procedural amendment (voluntary) ■, Indication of minor matters 1982 Patent application No. 19281, February 2, Title of invention Process for producing semen powder having a lipophilic surface 3, Oil stopper f
f-″4-rosha + (Relationship with case 1n people on license) Address 5-J-1 #15, Kitahama, Higashi-ku, Osaka City
(209) Sumitomo Chemical Co., Ltd. 1i I'I; Shikikai 71 Representative H Takeshi Hijikata 4, Representative Jl, 1 Address Sumitomo Chemical Co., Ltd. 5-15 Kitahama, Higashi-ku, Osaka Name Patent attorney (859) , 7) Mitsuru Moroishi) 15
, Nfi1iJF,'s subject light #lTl嘗's invention revision: #,! ti explanation (1'
the law of nature.

6. Contents of correction (1) Akira f, Fly11, page 17 tr'x, line 10, ``As a result, the sedimentation height was 05 cm,'' and line 11, ``
From the above, according to the method of the present invention, the following sentence r;7 is inserted between ...-1.

[Example 5 100y of chromium oxide (Cr20B) powder having an average particle size of 0,'Lz(+n) and 100y of chromium oxide (Cr20B) powder having an average particle diameter of 0,'Lz(+n) and 100y of door'can fermentation sodium A1f were mixed in a shaking 11ij mill having an internal volume of 3t (impact value -5G) The resulting chromium oxide powder was pulverized and mixed for 20 minutes with a settling height of 9.
6tm and IE.

Since the comparison was 11 times higher, the treatment was carried out in the same manner as described above except that sulfur and lithium dodecanoic acid were not used, and the sedimentation height was 1 piece. ``It'' 2 procedures 7 mountains i1 missi 1 + (self 1) Ill) July 1958 / Z11 'l'f;t'l office F beat young (sugi soinu 1 [1fi
1, Display of i:jj r'l:+I/Jfl+ 57 years holding i7'FWjll No. 192
8 fl 8θ2, masterpiece of invention r'l +11 mlh IE iii'l ':r:
Yes-r Loj, l:G +fit 'r'< 15)
1. : No bar making method 3]'Yama+l-'+:・Those who do it・I child'(tono([)J section 11'-shiyamadell:
ii'j person (1-place person IJ force) jj river Kitahama 5'
, li::I 15%, 1l11・71 (2
(19) Sumitomo Chemical Soil) τ (1 (ceremony?; - generation; Q1'7
Ten direction ll (4, Shirokawa 1
Person flIJr Person 1! ! j 717, i4. j I
: Guka 11'? 5 'l'' [i L 5 W6JIl
i5. Claims column and Detailed Description of the Invention column of the specification to be amended.

6. Contents of amendment 1) Amend the claims as shown in Attachment '1.

2) In the 5th line of page 4 of the Meisei-zuri, amend r 1; 'Jitko' to 'JIi'.

3) Pressure is applied as shown below in the 8th line of the 1000th line of the Book of Ill.

"Hinyltrichlorosilane, Vinyl I-ethoxysilane, Vinyltris(β-methoxyl-quin)silane, and-crisitoxyzorobyltrimethoxysilane, γ-methacryloxypropyl!-rimeth, palm silane, N-β
(aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ
-Aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, β-(8,4-dioxychlorhexyl)ethyltrimethoxysilane, γ-mercazotobrovir Silane coupling agents such as trimethoxysilane, isopropyl triisostearoyl titanate, isozolobil tridodecylbenzenesulfonyl titanine, -
, isobutyl c + virtris (dioctylba f-rophosphate-1) titanate, tetra isopropylbis (
Dioctyl phosphite) titanate, tetraoctyl (ditridecyl phosphite) rapeseed -1.
, tetoh(2,2-diallyl"xymethyl-1-butyl)his(di-1,lysosyl)phosphite titanate,
Bis(dioctyl pyrophosphate-1) oxyacetate theta: t--+-, titanium coupling agents such as tris(dioctylpyrophosphate-1~) ethylene lentitate, decanoic acid, dodecanoic acid, te 1 -radecanoic acid,
7Ty-like or solid compounds such as fatty acids such as hexaracanoic acid, octadecanoic acid, and oleic acid" 4) Akira 11
1 page 10 1A lines 18-19 “-lecithin” and “ga”
Insert the following sentence 1;v between.

1-/j-(3,4 eboxychlorohexyl)ethyltrimeth; 1″-disilane, r-glycidoxy-j lobiltrimethoxysilane, r-mercaptonoyl [1 pyltrimethoxysilane zolopyltrimethoxysilane, N -β (aminoethyl)
γ-aminopropyl l-rimethoxycycin, ?・-Methacryloxib ■Cobiltrime 1-Xinran, Teto(2,2-diallyl sub-1-dinoderu]-butyl)
bis(di-1,su]yl)phosphite titanium-1-,
Dodecane n:? , octadecanoic acid, etc.
) fil. ] Table 2 on page 16 of the Liaosho Box is corrected as shown in Attachment 2.

Above 2, Claim 1) Dry mixing of an inorganic powder and a fraction having a lipophilic group (1) under condition F where the impact value to r is greater than or equal to IG; of inorganic powder with !'''!i+j
+. lJe.

2) The usage ratio of the dispersant with M'', U oil is rootless 7'
(The method for producing a chair-free monolithic powder according to claim 1, characterized in that the amount of H'F is 0.01 to 20 parts by weight per 100 parts by weight of powder.

`` ) H. WI+ = Use of dispersant to settle A'i 1 ratio or no ''! '7' (0.02 to 10 parts by weight per 10 parts by weight of powder)'η?11
Claims No. “J”l Nl! Ql
A method for producing a rice-free monolithic powder of ρ.

4) Having 3,411 groups of f1 female R11 has a convex i. ! ＞
7 Jl/U-R M acid Ha, dofu'sylben-l-insulfonic acid tritum, occudecylbenzeni/
, alkylaryl such as sodium sulfonate? i'f
W acid Ji. ,j.

Dialkyl succinates such as di-2-ethylhexyl sodium sulfosuccinate, polyoxyethylene argyl sulfate salts such as sodium polyoxyethyl 17-dodecyl ether sulfate, polyoxyethyl 1-nonalkyl ethers such as 1JA xyethylene dodecyl ether, sorbitan Sorhitan fatty acid esters such as monododecanate, polyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monododecanate, alkyl amine salts such as dodecylamine acetate, and phosphoric acids of higher fatty acids such as 1/cytin. 1.2 and 1.1 of the inorganic powder described on page 3J! 'l! Ji“r 1.7C.

Claims (1)

[Claims] 1) A dispersant containing an inorganic powder (!: lipophilic culm) is dry-mixed under conditions with an impact value of 1 (min or more than 1-) to cover the lipophilic surface. 2) The ratio of dispersant having a lipophilic group used is 10% of the inorganic powder.
A method for producing an inorganic powder according to claim 1, characterized in that the If part is 0.01 to 20 M per 0 part by weight. 3) The proportion of the dispersant with lipophilic acid is 1% of the inorganic powder.
0.02 to 10 parts by weight per 00 parts by weight; +'f1e method; 4) The dispersant having a lipophilic group is sodium dodecanoate.
Commercial grade fatty acid salts such as sodium octadecanoate, aluminum dodecanoate, sulfates of +1ζJ-class alcohols such as sodium dodecyl sulfate, 1-lium octadecyl sulfate, sodium dodecylbenzene sulfonate, and octadecyl benzene sulfone. Alkyl aryl sulfates of acid I and lithium q, gel sulfur salts such as di-2-edylhexyl sodium sulfosuccinate, polyoxyethylene alkyl sulfate salts such as polyA xyethylene r decyl ether sulfate, and polysulfosuccinate. Polyoxyethylene alkyl ether such as oxyethylene dodecyl needle, nrubitan monododecane;・Proprietary sorbitan 1
17? I fatty acid esters, polyolamine salts such as polyt-t-thiethyl/nnrubitan monododecane-1, etc., polyol-4 ethyl/nnrubitan fatty acid esdel, F-decylamine acebu-1, etc., lecithin, etc. I'MI
The inorganic powder according to claim 1, 2 or 3, which is a liquid or solid surfactant such as a phosphoric acid ester of a class fatty acid! I; made/ノξ.