JP2768733B2 - Surface modification method of inorganic flame retardant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is intended to increase the usable temperature and improve the compatibility of inorganic flame retardants added to thermoplastic resins or elastomers. And a surface modification method that can be performed.

[Conventional technology and problems] In recent years, the demand for highly flame retardant thermoplastic resins and elastomers used in electric cables, home electric appliances containers, electric connectors, and the like has been significantly increased. A combination of halide and antimony oxide, which has been taken as an effective means, generates a large amount of halogen-based gas at the time of fire and is considered dangerous because it is harmful, aluminum hydroxide,
Investigations are under way to fill hydrated metal compounds such as magnesium hydroxide.

However, since aluminum hydroxide starts a dehydration reaction at around 160 ° C., when it is added to a polyolefin resin such as polyethylene or polypropylene, a foaming phenomenon occurs when an attempt is made to form a flame-retardant molded product, and high quality is obtained. A molded product could not be obtained, and thus, its use was limited to resins that can be molded at a relatively low temperature, such as a vinyl chloride resin, an epoxy resin, and a polyurethane resin.

On the other hand, magnesium hydroxide is not performed unless the dehydration reaction reaches a temperature higher than 200 ° C., so it is possible to add it to a polyolefin resin to form a non-foamed molded product. Is poor in miscibility. Therefore, in order to obtain sufficient flame retardancy, magnesium hydroxide is mixed with the polyolefin resin in an amount of 50% by weight or more. . Furthermore, as a disadvantage of magnesium hydroxide itself,
Acid resistance may be poor, and improvement thereof has been desired.

Currently, aluminum hydroxide is treated with stearic acid at the time of pulverization, or those obtained by treating the surfaces of various manufactured particles with a silane-based or titanate-based coupling agent are commercially available. It is intended to improve the dispersibility in the matrix resin even if it gets tired, and does not contribute at all to the improvement in the control of the dehydration reaction, which is the property of aluminum hydroxide itself.

Further, regarding magnesium hydroxide, it has been studied to change the shape of the particles (Japanese Patent Publication No. 60-57457) or to obtain a specific particle size in order to better mix with the matrix resin (Japanese Patent Application Laid-open No. Sho 62-57457). Further, to improve acid resistance, it has been proposed to treat the surface with a fatty acid having an unsaturated double bond (Japanese Patent Application Laid-Open No. 62-177040). Has a weak adsorption power, and its properties cannot be completely changed.

[Means for Solving the Problems] As a result of various studies on monomolecular films, the present inventors have found that a water-insoluble long-chain hydrocarbon-based compound that can form an oriented adsorption film on the water surface and a semipolar bond When a film of a boron compound having one or more of the above or a mixed film with a compound obtained by adding a chlorinated nitrogen compound thereto is adsorbed on the surface of a hydrated metal compound such as aluminum hydroxide, magnesium hydroxide, etc. intrinsic stability adsorption film and van der Waals forces between the hydrocarbon chains in the transverse direction of the film, and interfacial adsorption force in the longitudinal direction exhibited by the atomic group containing boron atoms to try to take SP ³ hybrid orbital are enhanced both And the resulting composite material has arrived at the invention of completely changing the properties of the original hydrated metal compound. For example, we confirmed the fact that the activation energy of the dehydration reaction of aluminum hydroxide was increased, magnesium hydroxide was completely hydrophobized, and not only the miscibility with the matrix resin was improved but also the acid resistance was significantly improved. Obtained.

That is, the present invention provides an oriented adsorptive water-insoluble hydrocarbon-based compound (hereinafter, referred to as a predetermined hydrocarbon compound) on the surface of a hydrated metal compound (hereinafter, referred to as a predetermined hydrated metal compound). And a semi-polar organic boron compound having an atomic group represented by the following structural formula I (hereinafter, referred to as a predetermined boron compound) and / or a nitrogen compound having a predetermined boron compound and at least one basic nitrogen (hereinafter, referred to as a nitrogen compound) And a reaction product (hereinafter, referred to as a predetermined boron-nitrogen bond) with a reaction product (hereinafter, referred to as a predetermined boron-nitrogen bond) as a mixed film.

[Specific Description of the Invention] First, various compounds that make up the present invention will be described.

[1] The predetermined hydrated metal compound used in the predetermined hydrated metal compound present invention, OH ^-
Aluminum hydroxide, magnesium hydroxide, etc., which are combined with a plurality of metal ions, and even if they are mixed with magnesium carbonate, carbon powder, etc. Absent.

[2] Predetermined Hydrocarbon Compound The predetermined hydrocarbon compound in the present invention is known as a substance that forms an insoluble monomolecular film on the surface of water or another substance.
Fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, 12-hydroxystearic acid, and behenic acid and heavy metal salts thereof (soaps such as Ca ^++. Zn ^++. Ba ^++. Al ⁺⁺⁺ ) Or lower alcohol esters represented by the above-mentioned fatty acid methyl ester, ethyl ester, vinyl ester, ethylene glycol ester, glycerin ester, etc .; or the above-mentioned fatty acid and ammonia, monomethylamine, dimethylamine, mono (hydroxy Various amides which are dehydration products with ethyl) amine and the like, higher alcohols such as dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol, octadecenyl alcohol, behenyl alcohol, and heavy metal compounds thereof (Ca.Al Alcoholates such as .Ti) or above Examples of the above-mentioned higher alcohols include ethers represented by methyl ether, ethyl ether, vinyl ether, hydroxyethyl ether and the like, and lower carboxylic acid esters represented by acetate, acetate and the like.

[3] Predetermined boron compound As the predetermined boron compound in the present invention, for example, di (glycerin) = borate (bisglyceryl) as shown in Oil Chemistry, Vol. 22, pages 426 to 433 (1973) Di (polyol) = bollards and their di (polyols) formed by a 2: 1 (molar ratio) reaction between a polyhydric alcohol consisting of adjacent hydroxyl groups such as borate) and boric acid triesters of boric acid or lower alcohols Various fatty acid esters and, for example, non-ionic polyols of di (glycerin) = borate polyol ethers and various fatty acid esters thereof as shown in Oil Chemistry, Vol. 28, pp. 285-290 (1979). Semipolar organoboron compounds,
For example, various alkyl succinic anhydrides or various alkenyls with di (glycerin) = borate as shown in the Abstracts of Lectures on Oil Chemistry and Presentations on Oil Chemistry 30th Anniversary, p. 67 (1982). 1: 1 ~ with succinic anhydride
Anionic semipolar organoboron compounds produced by ring-opening esterification reaction at 2 (molar ratio)
63-37130 are tetrahedral semipolar organoboron polymer compounds and the like obtained by the following three kinds of production methods disclosed in JP-A-63-37130. Examples of the predetermined boron compounds are representative examples shown in Table 1. Can be mentioned.

General formula II [Wherein, q is 0 or 1, and when q = 1, A is-(X)
_1- (Y) _m- (Z) _n- group. Where X and Z
Is an oxygen-containing hydrocarbon group having a total of 100 or less carbon atoms having one terminal ether residue, (Where R is a hydrocarbon group having 1 to 82 carbon atoms) or (Where R 'is a hydrocarbon group having 2 to 13 carbon atoms);
mn is 0 or 1. 1 mol of boric acid or a boric acid triester of a lower alcohol having 4 or less carbon atoms or 0.5 mol of boric anhydride is reacted with 1 mol of one or more kinds of the compounds represented by Then, a triesterization reaction is performed. Alternatively, a polyetherification reaction is performed on one or more of di (glycerin) = borate or a diol having a total of 206 or less carbon atoms including a di (glycerin) = borate residue in the middle. Or di (glycerin) = borate or di (glycerin) = a dicarboxylic acid having 3 to 84 carbon atoms per 1 mol of a total of one or more diols having a total of 206 or less carbon atoms containing a borate residue (Hereinafter, referred to as a predetermined dicarboxylic acid), an ester of a lower alcohol having 4 or less carbon atoms and a predetermined dicarboxylic acid, a halide of a predetermined dicarboxylic acid, or a diisocyanate having 4 to 15 carbon atoms (hereinafter, a predetermined dicarboxylic acid). ) Is reacted in a total of 1 mol.

Examples of the compound represented by the general formula II as a raw material of the above method include diglycerin, di (glycerin) = malonate, di (glycerin) = maleate, di (glycerin) = adipate, di (glycerin) = terephthalate, (Glycerin) = dodecanate, poly (9 mol)
Oxyethylene = di (glycerin ether), di (glycerin) = tolylene dicarbamate, di (glycerin)
= Methylenebis (4-phenylcarbamate) and the like.

Examples of the predetermined dicarboxylic acid in the above method include malonic acid, maleic acid, succinic acid, adipic acid, sebacic acid, phthalic acid, terephthalic acid, dodecanedicarboxylic acid, dimer acid derived from linoleic acid, dodecyl maleic acid, and dodecyl maleic acid. Examples include decenylmaleic acid, octadecylmaleic acid, octadecenylmaleic acid, and maleic acid in which polybutenyl groups having an average degree of polymerization of 20 are linked.

Examples of the predetermined diisocyanate include ethylene diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, and methylene bis (4-phenyl isocyanate).

[4] Predetermined nitrogen compound As the predetermined nitrogen compound in the present invention, for example,
From the smallest monoamines like ammonia, ethylenediamine, monoethanolamine, diethanolamine,
Monoamines or polyamines including primary or secondary amines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, alicyclic, aromatic, heterocyclic and polycyclic such as morpholine, cyclohexylamine, triethylenediamine, pyridine, picoline and aniline Amines, trimethylamine, triethylamine, tributylamine, triethanolamine, dimethyl = ethanolamine, monomethyl = diethanolamine, diethylethanolamine, N, N'-tetra (hydroxyethyl) ethylenediamine, dodecyl = dimethylamine, N, N- Short or long chains such as polyoxyethylene hexadecylamine, oleyl dipropanolamine, tri (stearyloxyethyl) amine, benzyl di (behenyl) amine Tertiary amines having a hydride group, and amines containing a non-basic nitrogen in the molecule at the same time, such as stearamidopropyl = dimethylamine, di (lauamidoethyl) amine, etc. Any compound having basic nitrogen and exhibiting the effect of exciting δ + H into H ^{+ in} the above-mentioned (3) predetermined boron compound can be used.

(5) Predetermined boron-nitrogen bond The boron-nitrogen bond of the present invention is obtained by combining one or more predetermined boron compounds and one or more predetermined nitrogen compounds with one boron atom. Charged in a closed or open-type reactor at a rate designed to be one to one basic nitrogen atom, at normal pressure, 20 to 200 ° C., preferably 50 to 150 ° C.
It is produced by reacting at a temperature of ° C. At this time, the reaction can be carried out more easily if polar solvents such as alcohols, ethers and ketones coexist.

Typical examples of the predetermined boron-nitrogen bond include the typical examples shown in Table 2, which also belong to the tetrahedral type organic boron compound.

Next, the surface modification method of the present invention will be described in detail. The surface of a predetermined hydrated metal compound serving as an inorganic flame retardant is entirely mixed with an adsorbed film of a predetermined hydrocarbon compound and a predetermined boron compound or a predetermined carbonized compound. As covered by a mixed adsorption film of a hydrogen compound and a predetermined boron / nitrogen bond, based on 100 parts by weight of a predetermined hydrated metal compound, usually, a predetermined hydrocarbon compound and a predetermined boron compound and And / or 0.01 to 10 parts of a mixture with a predetermined boron-nitrogen binder.
Parts by weight, preferably 0.05 to 3 parts by weight, while mixing and adsorbing onto the surface of a predetermined hydrated metal compound while forming a eutectic at a temperature condition not lower than the melting point of the various compounds used. After expanding the membrane or preparing a solution in which various compounds to be used are dissolved in the respective good solvents, adding, adding, heating, and heating each solution on the surface of the predetermined hydrated metal compound. , While removing the solvent, to form a mixed adsorption film. Here, when the charged amount of the mixture between the predetermined hydrocarbon compound and the predetermined boron compound and / or the predetermined boron-nitrogen bond is less than 0.01 part by weight, the surface modification of the entire predetermined hydrated metal compound is performed. In some cases, the quality is not obtained, and when the amount is more than 10 parts by weight, an appropriate mixed adsorption film may be difficult to be formed. As a device, a Brabender or Henschel mixer is suitable, and the material is not particularly limited. However, since it is necessary to successfully form an appropriate mixed adsorption film in a short time, if the rotation speed of the stirrer is 1000 rpm (one minute). It is desirable to have the ability to exceed 1000 rotation speed). Further, the device may be either a closed type or an open type, but a system using a solvent naturally requires an open type. In addition, as a good solvent for various compounds used in the present invention, for example, a low-boiling-point petroleum-based solvent such as n-hexane and n-heptane is suitable for a predetermined hydrocarbon-based compound,
On the other hand, for the predetermined boron compound and the predetermined boron-nitrogen bond, methyl alcohol, ethyl alcohol, n
Polar solvents such as lower alcohols such as propyl alcohol and isopropyl alcohol, ethers such as dioxane, methoxyethyl methyl ether and di (methoxyethyl) ether, and ketones such as acetone and methyl ethyl ketone are suitable.

Here, in the surface modification method of the present invention, the compounding ratio between various compounds for forming a more effective mixed adsorption film is described. The compound occupies 10 to 70% by weight, particularly preferably 20 to 60% by weight, and the predetermined boron compound and / or the predetermined boron-nitrogen bond occupy 10 to 90% by weight, particularly preferably 40 to 80% by weight. It is desirable that the mixed adsorption film formed on the surface of the predetermined hydrated metal compound based on the blending ratio exhibits strong cohesive force and adhesive force in both the vertical and horizontal directions, and more completely forms the predetermined hydrated metal compound. Changes the physical and chemical properties of the surface.

In particular, when the predetermined hydrated metal compound is aluminum hydroxide, an aluminum salt of a fatty acid or a higher alcohol as a predetermined hydrocarbon compound with respect to a predetermined boron compound and / or a predetermined boron-nitrogen bond. When a mixed adsorption film is formed on aluminum hydroxide using an alcoholate of the formula (1) in an appropriate mixing ratio, very good reforming is performed.

In addition, unlike the surface modification method of the present invention, an adsorption film of only a predetermined hydrocarbon compound or a predetermined boron compound or a predetermined boron-nitrogen bond is formed on the surface of a predetermined hydrated metal compound, Alternatively, as in the present invention,
A predetermined hydrocarbon-based compound, a predetermined boron compound and / or a predetermined boron / nitrogen compound are adsorbed in separate stages without forming an adsorbed film in the form of a mixed film, and the single film is overlapped. Even if it is formed on the surface of a predetermined hydrated metal compound, the effect as in the present invention does not appear. Also, unlike the present invention, the effect of the present invention is not similarly exhibited when a trigonal type organic boron compound is used.

[Examples and the like] Hereinafter, examples will be described in further detail. "Parts" described in those examples means parts by weight, and "%" means% by weight.

Of the prescribed boron compounds in Table 1 and the prescribed boron-nitrogen bonds in Table 2 used in the following examples,
By combining the production example of the predetermined boron compound (1) in the table and the production example of the predetermined boron-nitrogen bond (1) in Table 2,
This is shown as a representative example.

Production of predetermined boron compound (1) and predetermined boron / nitrogen bond (1) In a four-necked flask equipped with a stir bar, a thermometer, a nitrogen gas inlet tube and a test tube, 1 mol of di (glycerin) borate is added. 1 mol of ricinoleic acid dimer (dimer acid) is charged and reacted for 6 hours at 230 to 240 ° C. under a nitrogen gas flow until dehydration of 2 mol is obtained. (1) was produced.

Next, the internal temperature was cooled down to 70 ° C., and the same amount of methyl ethyl ketone as the obtained predetermined boron compound 1 was injected.
After preparing a homogeneous solution, 1 mol of poly (25 mol) oxyethylene-dihexadecylamine was added and the mixture was heated at 70 to 75 ° C for 1 hour.
Allowed to react for hours. After the reaction is completed, under a reduced pressure of 150 mmHg,
It took 2 hours at 130 ° C. to distill the solvent methyl ethyl ketone out of the system to obtain a predetermined red-brown viscous boron-nitrogen bond (1).

Example 1 A Henschel mixer was mixed with aluminum hydroxide (however,
1 kg of an average particle diameter of 1 μm) is weighed, and while rotating at 2,000 rpm, 40 g of a 25% n-hexane solution of tri (cetyl) = aluminum is injected from one inlet, and a predetermined amount is injected from the other inlet. 20 g of a 50% isopropyl alcohol solution of boron compound 1 was added, respectively. After taking 30 minutes, while mixing, the internal temperature was set to 80 ° C., and n-hexane and isopropyl alcohol were completely removed from the system.Then, the mixture was gradually cooled down to 50 ° C., and the stirring was stopped. Surface modification of aluminum oxide was performed.

Next, using the treated aluminum hydroxide as a sample,
Differential thermal analysis (hereinafter abbreviated as DTA analysis) was performed under the conditions of cal / s, 2 ° C / min., as shown in Fig. 1, which was different from aluminum hydroxide before surface modification treatment. The presence of heat of dehydration and decomposition from around 160 ° C. was not observed, indicating that the heat was stabilized. This was supported by the results of the simultaneous measurement of the heating-water evaporation curve up to 220 ° C. (hereinafter abbreviated as MEA curve) (FIG. 2).

Examples 2 to 20 In the same manner as in Example 1, the surface modification of aluminum hydroxide was performed based on the mixing ratio shown in Table 3, and as a result,
In each of the examples, it was confirmed that the thermal decomposition temperature of the aluminum hydroxide treated according to the present invention was all increased.

Comparative Examples 1 to 5 The following five methods were tried as comparative examples of the examples of the surface modification method of the aluminum hydroxide of the present invention described above.
As shown in FIG. 1, the presence of heat of dehydration and decomposition at around 160 ° C. was observed in the DTA analysis of the aluminum hydroxide treated by these methods, which contributed to the improvement of the thermal stability of aluminum hydroxide. It was impossible.

Comparative Example 1 Aluminum hydroxide (provided that the average particle diameter is 1 μm)
m) 100 parts by weight of tri (cetyl) = aluminum used alone in 2 parts by weight and contacted with aluminum hydroxide in the same manner as in Example 1.

Comparative Example 2 Aluminum hydroxide (provided that the average particle diameter is 1 μm)
m) 100 parts by weight of a given boron compound (1) used alone in 2 parts by weight and contacted with aluminum hydroxide in the same manner as in Example 1.

Comparative Example 3 Aluminum hydroxide (provided that the average particle diameter is 1 μm)
m) 100 parts by weight of a given boron / nitrogen binder (1) used alone in 2 parts by weight and contacted with aluminum hydroxide in the same manner as in Example 1.

Comparative Example 4 Aluminum hydroxide (provided that the average particle diameter is 1 μm)
m)), 100 parts by weight of stearic acid was first added to 1 part by weight, and the mixture was brought into contact with aluminum hydroxide at 80 ° C. for 30 minutes with stirring at 2000 rpm. (1) 1 part by weight, and further stirred and mixed for 30 minutes.

Comparative Example 5 Aluminum hydroxide (however, average particle diameter 1 μm)
m) 100 parts by weight, and 1 part by weight of stearic acid and 1 part by weight of tri (octadecyl) borate were simultaneously added, and the mixture was brought into contact with aluminum hydroxide in the same manner as in Example 1.

Example 21 To a Henschel mixer, magnesium hydroxide (provided that
Weigh 1kg with an average particle diameter of 0.6μm) and 2,000rpm
While rotating, 20 g of a 1: 1 (weight ratio) mixture of stearic acid and a predetermined boron compound 2 was added, and the internal temperature was brought to 80 ° C. Next, after stirring and mixing at 80 to 85 ° C. for 30 minutes, the mixture was cooled, the stirring was stopped, and the surface modification of magnesium hydroxide was performed.

Next, add 2g of treated magnesium hydroxide sample
After weighing into a 25 ml measuring cylinder, followed by pouring in 20 g of water, forcibly shaking it 30 times in the vertical direction, and allowing it to stand, all magnesium hydroxide particles exhibited the property of floating on the water surface. It was found that the surface was completely modified.

Examples 22 to 40 The surface modification of magnesium hydroxide was carried out in the same manner as in Example 21 based on the composition shown in Table 4, and as a result, the magnesium hydroxide treated according to the present invention was used in each of the examples. It was confirmed that all particles exhibited the property of floating on the water surface.

Comparative Examples 6 to 10 The following five types of methods were tried as comparative examples of the examples of the surface modification method of magnesium hydroxide of the present invention described above. Magnesium hydroxide treated by those methods was water However, it did not exhibit the property of dispersing or settling on the surface and floating on the water surface.

Comparative Example 6 magnesium hydroxide (however, average particle diameter 0.6
(m) 100 parts by weight of stearic acid used alone in 2 parts by weight, and contacted with magnesium hydroxide in the same manner as in Example 21.

Comparative row 7: magnesium hydroxide (however, average particle size 0.6
μm), 100 parts by weight of the given boron compound (2) was used alone in an amount of 2 parts by weight.
Those that have been brought into contact with magnesium hydroxide.

Comparative Example 8 magnesium hydroxide (however, average particle size 0.6
The same boron-nitrogen binder (1) was used alone in an amount of 2 parts by weight with respect to 100 parts by weight (μm) and contacted with magnesium hydroxide in the same manner as in Example 21.

Comparative Example 9 magnesium hydroxide (however, average particle size 0.6
First, 1 part by weight of stearic acid was added to 100 parts by weight of 100 μm, and the mixture was contacted with magnesium hydroxide at 80 ° C. for 30 minutes under stirring at 200 γpm.
1 part by weight of the prescribed boron compound (2) is added,
Stir and mix for minutes.

Comparative Example 10: magnesium hydroxide (however, average particle diameter 0.6
1 μm of stearic acid and 1 part by weight of tri (octadecyl) borate were added simultaneously to 100 parts by weight of μm) and contacted with magnesium hydroxide in the same manner as in Example 21.

Example 41 40 parts by weight of polyethylene (with an MFR of 1.5 g / 10 min. And a density of 0.9 g / cm ³ ) in comparison with aluminum hydroxide and magnesium hydroxide surface-modified by Examples 1 to 40 60 parts by weight of each of the aluminum hydroxide and magnesium hydroxide treated according to Examples 1 to 10 was added, and after kneading at 185 ° C. for 20 minutes using a blast mill,
A sheet having a thickness of 1 mm was prepared, and only a successfully finished sheet was subjected to a bending whitening test and an acid resistance test by the following method.

A sheet was prepared by the same method using untreated aluminum hydroxide and magnesium hydroxide, and the sheet that was successfully finished was subjected to the following test.

Bending whitening test: The prepared sheet was bent at an angle of 120 °, and the degree of whitening at that location was observed.

 The standard of the price is as follows.

◎: No whitening at all ○: Very little whitening △: Less whitening ×: Many whitening Acid resistance test: After immersing the prepared sheet in a 10% hydrochloric acid aqueous solution at 50 ° C for 72 hours Was measured.

The test results are shown in Table 5. As for all the samples using aluminum hydroxide and magnesium hydroxide treated by the surface modification method of the present invention, the sheet was successfully formed and the physical properties of the sheet were improved. Has also been greatly contributed to.

[Effects of the Invention] The present invention provides a mixture of an oriented adsorptive water-insoluble hydrocarbon-based compound and a tetrahedral organic boron compound in the form of a mixed film, which is adsorbed on the surface of a hydrated metal compound.
This is a surface modification method capable of changing the surface energy and improving the performance to a material that can sufficiently be used as an inorganic flame retardant. This greatly promotes the practical application that has been desired conventionally.

[Brief description of the drawings]

Figure 1 shows the D of aluminum hydroxide from 20 ° C to 300 ° C.
It is a TA curve, and the code | symbols 1-7 in a figure are each about the aluminum hydroxide sample shown next. 1 ... untreated aluminum hydroxide sample 2 ... aluminum hydroxide sample surface-modified in Example 1 3 ... aluminum hydroxide sample treated in Comparative Example 1 4 ... in Comparative Example 2 Treated aluminum hydroxide sample 5: treated aluminum hydroxide sample of Comparative Example 3 6: treated aluminum hydroxide sample of Comparative Example 4 7: treated Comparative Example 5 Fig. 2 shows the temperature of aluminum hydroxide from 0 ° C to 220 ° C.
The reference numerals 1 and 2 in the figure are for the following aluminum hydroxide samples, respectively. 1 ... untreated aluminum hydroxide sample 2 ... aluminum hydroxide sample surface-modified according to Example 1

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09K 21/02 C08K 9/04 C09C 3 / 08,3 / 10 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. A semi-polar organoboron compound having an atomic group represented by the following structural formula I and a semi-polar organoboron compound having an atomic group represented by the following structural formula I on a surface of a hydrated metal compound. And / or adsorbing a reaction product of a predetermined organic boron compound and a nitrogen compound having at least one basic nitrogen as a mixed film at the same time.