JPH0112797B2 - - Google Patents

Description

[Detailed description of the invention]

TECHNICAL FIELD The present invention relates to a skin composition particularly useful for thickening aromatic liquid dispersion media. Mountain bark is well dispersed in water and can thicken water, but it has poor affinity with organic liquid dispersion media, especially aromatic liquid dispersion media, and it is difficult to increase the viscosity of water. It has almost no viscosity or gelling ability. As a result of intensive research into the properties of mountain bark, the inventors found that the general formula for mountain bark is

[Formula] [In the formula, R ₁ , R ₂ , and R ₃ are the same or different and represent hydrogen or hydrocarbon residues] When the benzyl ammonium ion is included, it can be dispersed even in an aromatic liquid dispersion medium. The inventors have found that the aromatic liquid dispersion medium can be easily thickened and gelled, and the present invention has been completed based on this knowledge. That is, the present invention provides the general formula

[Formula] [In the formula, R ₁ , R ₂ , and R ₃ are the same or different and represent hydrogen or hydrocarbon residues] A mountain skin composition and an aromatic liquid dispersion containing a benzyl ammonium ion General formula in medium

[Formula] [In the formula, R ₁ , R ₂ , and R ₃ are the same or different and represent hydrogen or hydrocarbon residues] An aromatic system characterized by the coexistence of a benzylammonium ion and mountain bark This is a method of thickening a liquid dispersion medium. The mountain skin composition of the present invention has a general formula for mountain skin.

It contains a benzyl ammonium ion represented by the formula: [wherein R ₁ , R ₂ and R ₃ are the same or different and represent hydrogen or hydrocarbon residues]. Here, mountain bark is a clay mineral that has a large number of hydroxyl groups on its surface, and includes sepiolite, a hydrous magnesium silicate, and hydrous magnesium aluminium silicate.
Attapulgite (alternative name: palygorskite)
It is called palygorskite. It is a general term for minerals commonly known as mountain cork, mountain leather, and mountain wood, and magnesium trisilicate, an antacid, is also one of these minerals. In the above general formula, the hydrocarbon residues represented by R ₁ , R ₂ , and R ₃ include, for example, methyl, ethyl,
Alkyl groups with 1 to 20 carbon atoms such as propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, e.g. phenyl, tolyl , xylyl, biphenylyl, naphthyl, anthryl, phenanthryl, etc., and aralkyl groups such as benzyl, phenethyl, methylbenzyl, naphthylmethyl. The number of carbon atoms mentioned above is 1 to 20
The alkyl group may be substituted with one or two hydroxyl groups, thiol groups, etc., for example. In order to incorporate the benzylammonium ion represented by the above general formula into the mountain hide, benzylamines or quaternary ammonium salts such as those exemplified below may be applied to the mountain hide. Examples of benzylamines include benzylamine, benzylmethylamine, benzyldimethylamine, benzylethylamine, benzyldiethylamine, benzylphenylmethylamine, benzylaniline, benzylmethylaniline, benzylethylaniline, benzyldiphenylamine, and N-benzyltoluidine. , dibenzylmethylamine, dibenzylamine, tribenzylamine, etc. What is quaternary ammonium salt?General formula [In the formula, R ₁ , R ₂ , and R ₃ are the same or different and represent hydrogen or hydrocarbon residues, and M represents an acid group or a hydroxyl group], and the acid group is:
For example, Cl ^- , Br ^- , I ^- , NO ₂ ^- , PF ₆ ^- ,
Examples include CH ₃ COO ^- . Specific compound names include, for example, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltripropylammonium chloride, benzyltributylammonium chloride, benzyltrimethylammonium bromide, benzyltriethylammonium bromide, benzyltripropylammonium bromide, benzyltributylammonium Bromide, hexafluorophosphate Benzyltrimethylammonium, benzyltrimethylammonium hydroxide, benzyltrimethylammonium iodide, acetoxybenzyltrimethylammonium, octylbenzyldimethylammonium chloride, nonylbenzyldimethylammonium chloride, decylbenzyldimethylammonium chloride, undecylbenzyldimethylammonium Chloride, Dodecylbenzyldimethylammonium chloride, Tridecylbenzyldimethylammonium chloride, Tetradecylbenzyldimethylammonium chloride, Pentadecylbenzyldimethylammonium chloride, Hexadecylbenzyldimethylammonium chloride, Heptadecylbenzyldimethylammonium chloride, Octadecylbenzyldimethylammonium chloride, Nona Examples include decylbenzyldimethylammonium chloride, eicosylbenzyldimethylammonium chloride, and methyldihydroxyethylbenzylammonium chloride. Specific means for applying benzylamines or quaternary ammonium salts to mountain bark include (1) when the benzylamines or quaternary ammonium salt is liquid, adding it to mountain bark powder; 2) adding benzyl amines or quaternary ammonium salt powder to an aqueous dispersion or paste of mountain bark, mixing uniformly, and then drying; (3) adding benzyl to an aqueous dispersion or paste of mountain bark; (4) means for drying the aqueous solution or aqueous dispersion of amines or quaternary ammonium salts after mixing until homogeneous; Means for kneading benzylamines or quaternary ammonium salts into a liquid or paste dispersed in a solvent such as an aromatic hydrocarbon to make it homogeneous, and then volatilizing the solvent; (5) Preliminary dispersion in the solvent as described above. or a means for adding mountain bark powder to dissolved benzylamines or quaternary ammonium salts to make them homogeneous and then volatilizing the solvent; and (6) benzylamines or quaternary ammonium salts previously dispersed or dissolved in the above solvent. An example of this method is to mix salt and a liquid obtained by dispersing mountain bark in an organic solvent, and then volatilize the solvent. In particular, when an aromatic hydrocarbon is used as a solvent in the means (5) and (6), the means for volatilizing it may be omitted. In the above method, the aqueous dispersion or paste of mountain bark is usually one in which mountain bark is dispersed in water in an amount of about 1 to 60% by weight. The liquid or paste obtained by dispersing mountain bark in a solvent is usually one in which mountain bark is dispersed in a solvent in an amount of about 1 to 60% by weight. When benzylamines or quaternary ammonium salts are dispersed or dissolved in a solvent, the concentration is preferably about 0.1 to 60% by weight. The mountain bark may be subjected to the following pretreatments, for example. (1) Heat the mountain bark to about 100-500℃ in advance. (2) Wash the mountain bark with a mineral acid of 6N or less, such as sulfuric acid, hydrochloric acid, or acetic acid. (3) Mg ²⁺ contained in mountain bark, for example,
Co ²⁺ , Fe ³⁺ , Al ³⁺ , Fe ²⁺ , Ni ²⁺ , Mn ²⁺ , Zn ²⁺
Transition metal ions such as or transition metal OH ^-
Exchange ions with ions. The ratio of benzylamines or quaternary ammonium salts to mountain bark cannot be determined unconditionally depending on the molecular weight of the benzylamines or quaternary ammonium salts, but it is approximately 0.05 to 40 parts by weight per 100 parts by weight of mountain bark.
Parts by weight, preferably about 1 to 20 parts by weight. Benzylamines or quaternary ammonium salts may be used in combination with amines such as octadecylamine, dodecyldimethylamine, and quaternary ammonium salts such as octadecyltrimethylammonium chloride. The mountain bark composition thus obtained is particularly effective for thickening aromatic liquid dispersion media. Examples of the aromatic liquid dispersion medium include benzene, toluene, O-xylene, m-xylene, and p-xylene.
-xylene, diylene, hexamethylbenzene,
Hydrocarbons with one benzene ring such as ethylbenzene, propylbenzene, cumene, hydrocarbons with two benzene rings such as diphenylmethane, hydrocarbons with fused rings such as indene, tetralin, etc., such as benzyl alcohol,
Aromatic alcohols such as β-phenylethyl alcohol, methylphenyl carbinol, such as 1-methylbenzene-2,6-diisocyanate, 1-methylbenzene-2,4-diisocyanate, 1-methylbenzene- 3,5-diisocyanate, 1,3-dimethylbenzene-2,4-diisocyanate, 1-ethylbenzene-2,4-
Diisocyanate, 1-isopropylbenzene-
2,4-diisocyanate, 1-chlorobenzene-2,4-diisocyanate, biphenyl-4,
Aromatic diisocyanates such as 4'-diisocyanate, e.g. styrene, α-methylstyrene,
Aromatic monomers having one or more ethylenically unsaturated groups, such as vinyl groups, substituted vinyl groups, allyl groups, such as divinylbenzene, allylbenzene, vinyltoluene, etc., such as phthalic acid monoethyl ester , methyl ethyl phthalate, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, didecyl phthalate, delauryl phthalate, dinonyl phthalate, diallyl phthalate Any aromatic compound that is liquid at room temperature, such as phthalate esters such as Two or more kinds of the above-mentioned aromatic liquid dispersion media may be mixed. Alternatively, it may be a solution in which a solid substance is dissolved in the above-mentioned aromatic liquid dispersion medium. In addition to the above-mentioned dispersion media, non-aromatic liquid dispersion media that are compatible with these (e.g., ketones such as acetone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether,
Limestones such as caprylic acid, myristic acid, and lauric acid, unsaturated acids such as fumaric acid and oleic acid, linseed oil, turpentine oil, etc.) may coexist. Furthermore, hydrophilic or lipophilic pigments, finely powdered metal oxides, carbides, nitrides, and the like may be dispersed in the aromatic liquid dispersion medium. When thickening the above-mentioned aromatic liquid dispersion medium,
It is sufficient to simply mix the mountain skin composition of the present invention and a dispersion medium. The proportion of the mountain bark composition varies depending on the type of aromatic liquid dispersion medium, but is usually about 0.5 to 30% by weight.
That's about it. The aromatic liquid dispersion medium thickened in this way can be used for example with thermosetting resins such as liquid epoxy resins, unsaturated polyester resins, and phenol resins, and thermoplastic resins such as liquid styrene resins, vinyl chloride resins, and urethane resins. By mixing it with a resin, etc., a thickened resin solution can be obtained. In the above-mentioned operation, a mixture of the mountain skin composition of the present invention and an aromatic liquid dispersion medium was added to the resin in advance, but if the resin contains an aromatic liquid dispersion medium, Alternatively, the mountain skin composition of the present invention may be directly mixed into the resin. Next, the present invention will be specifically explained with reference to Examples. Example 1 2 gr of Spanish sepiolite was added to 100 gr of xylene and stirred, but it accumulated at the bottom and did not disperse, making it impossible to impart thixotropy to the xylene. Next, add 2g of mountain bark to the same amount of xylene as above, add 0.2g of octadecylbenzyldimethylammonium chloride (Sanisol S; manufactured by Kao Soap Co., Ltd.), and stir until it becomes uniform. It did not settle even after a month had passed since it was dispersed. Example 2 Add 20g of Spanish sepiolite to 80g of styrene and mix well with a household mixer. When this was placed in a 100ml glass container, the styrene liquid separated immediately at the top and did not become a thixatropic paste. Next, add the same amount of mountain bark as above to the same amount of styrene, add 2g of methyldihydroxyethylbenzylammonium chloride (MDA-4B; manufactured by Meisei Chemical Industry Co., Ltd.), and mix with a household mixer. A creamy paste (greasy) was obtained. Take 50gr of this paste and add 50gr new styrene.
When the mixture was stirred and mixed until it became homogeneous, it was evenly dispersed and no sedimentation occurred even after one week. Example 3 Crushed Spanish mountain bark rough stone in water to give 1% by weight
Make an aqueous dispersion of approximately Filter press this liquid to make a paste containing about 40% mountain bark by weight. Add 80g of a 50% by weight aqueous solution of benzyltrimethylammonium chloride to 1kg of this paste and mix with a pony mixer (manufactured by Inoue Seisakusho) for about 30 minutes until uniform. Once homogeneous, it is dried and then ground to obtain a very bulky powder. Add 2% by weight of this powder to the following liquid dispersion medium.
In addition, the mixture was mixed using a homomixer M type (manufactured by Tokushu Kika Kogyo Co., Ltd.) for about 5 minutes until the mixture became homogeneous, and after 2 weeks it was checked whether the mixture had settled or not and whether it had been uniformly dispersed.

[Table] Poor dispersibility Example 4: 25 gr of mountain skin containing benzyltrimethylammonium chloride obtained in Example 3 was placed in 225 gr of styrene and mixed with the homomixer used in Example 3. Stir for 10 minutes to ensure uniform dispersion to obtain a paste-like styrene. The thixotropic coefficient of the styrene paste can be obtained by measuring the rotation speed with a Bruckfield viscometer at 6 and 60 revolutions. The numbers were as follows.

[Table] Take 10% of the total volume and add 225g of unsaturated polyester resin (Polymer 6409 manufactured by Takeda Products) to this.
was added and stirred again using a homomixer until the mixture became homogeneous. It did not settle even after three months.
The viscosity after one month was measured according to styrene paste.

[Table] From this, it can be seen that the product has thixotropic properties even after one month. Example 5 Even if you put 25g of Spanish mountain bark into 225g of styrene and stir it, it would not be uniformly dispersed, and a transparent part of styrene would immediately form at the top.
Mountain skin settles. Mountain skin in styrene 225gr
When I added 25gr of benzyldimethylamine and 2.4gr of benzyldimethylamine and stirred and dispersed them well using a homomixer, the mountain bark was evenly dispersed in the styrene. It did not settle even after two weeks. The thixotropic coefficient in this system was almost the same as that in Example 4. Instead of benzyldimethylamine, add 1.5g of benzyltrimethylammonium chloride and 1 octadecylamine (Furmin 80; manufactured by Kao Soap Co., Ltd.)
Similar results were obtained by adding g.

Claims (1)

[Claims] 1 General formula [Formula] [In the formula, R ₁ , R ₂ and R ₃ are the same or different and represent hydrogen or a hydrocarbon residue. A mountain bark composition containing benzylammonium ions represented by the following. 2. In an aromatic liquid dispersion medium, a compound of the general formula [Formula] [wherein R ₁ , R ₂ and R ₃ are the same or different and represent hydrogen or a hydrocarbon residue. ] A method for thickening an aromatic liquid dispersion medium, characterized by coexisting benzylammonium ions and mountain bark.