JP2004059347A - Concatenated clay mineral complex and application - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new modified concatenated clay mineral effectively freed of zeolitic water in the concatenated clay mineral, provided with ionic conductivity, and retaining thixotropy peculiar to the concatenated clay mineral. <P>SOLUTION: The concatenated clay mineral complex is obtained by substantially substituting a non-aqueous solution of an inorganic and/or organic electrolyte for zeolitic water in the mineral. The inorganic and/or organic electrolyte is contained by 0.01-75 wt.% on the basis of the solid content of the concatenated clay mineral. <P>COPYRIGHT: (C)2004,JPO

Description

混練条件；３．５インチ　デファレンシャルロールミルにて１７０℃、６分間混練

【００５６】（１０）ウレタン組成物の導電率の測定
下記の配合、及び成形条件で本発明品あるいは比較例の無機質を含有するウレタンフィルムを作製して、ウレタン組成物の導電率［Ｓ］を測定した。

上記配合物を、ＴＯＫＵＳＨＵ　ＫＩＫＡ　ＫＯＵＧＹＯＵ　製ホモディスパーにて２５００ｒｐｍ、５分間混合分散し、ガラス板上に１５０μｍフィルムアプリケータにて製膜し、常温乾燥して硬化後、フィルムの導電率［Ｓ］を測定した。
【００５７】
（電解質溶液の調整）
電解質溶液Ａ；ジオクチルフタレート（和光純薬製試薬一級）５０重量部に、字捨てアリルジメチルアンモニウムクロライド（花王製コータミンＤ８６Ｐ）１０重量部を室温にて溶解したもの。
電解質溶液Ｂ；ジオクチルアジペート（和光純薬製試薬一級）５０重量部に、字ステアリルジメチルアンモニウムクロライド（花王製コータミンＤ８６Ｐ）１０重量部と過塩素酸リチウム一水塩（和光純薬製試薬特級）１重量部を室温にて溶解したもの。
電解質溶液Ｃ；ポリエチレングリコール２００（和光純薬製試薬特級）５０重量部に、過塩素酸リチウム一水塩（和光純薬製試薬特級）５重量部を室温にて溶解したもの。
【００５８】
（実施例１）
スペイン産鎖状粘土鉱物セピオライト１５０ｇを、１Ｌ気密容器に仕込み、弱い減圧下に攪拌しながら粉温２５０℃まで昇温後、０．０４６ＭＰａ以下の圧力下に３０分間脱水した。加熱を停止し、乾燥状態を維持しながら粉温が１５０℃に降下した時、電解質溶液（Ａ）５０ｇを、１Ｌの気密容器に注入し、減圧無酸素下に強く攪拌し、更に　乾燥状態を維持して室温まで冷却した。
生成物の物性値と応用特性を表２に示した。
【００５９】
（比較例１）
鎖状粘土鉱物セピオライトそのものの物性値と応用特性を表２に示した。
【００６０】
（比較例２）
鎖状粘土鉱物セピオライト粉末５ｇを坩堝に入れ、電気炉で２５０℃、３０分脱水直後、５０ｍｌの密封容器に入れ室温に戻し、室温下に実施例１と同様に測定し、その物性値と応用特性を表２に示した　。
【００６１】
（比較例３）
セピオライト粉末１０ｇに電解質溶液Ａを２ｇ加え、メノウ乳鉢中で緊密混合した粉体について、実施例１と同様に測定し、その物性値と応用特性を表２に示した　。
【００６２】
（実施例２）
米国産鎖状粘土鉱物アタパルジャイトを用いた以外は、実施例１と同様にこれを処理した後、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６３】
（比較例４）
鎖状粘土鉱物アタパルジャイトそのものの物性値と応用特性を表２に示した。
【００６４】
（比較例５）
米国産鎖状粘土鉱物アタパルジャイトを用いた以外は、比較例２と同様にこれを処理した後、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６５】
（比較例６）
米国産鎖状粘土鉱物アタパルジャイトを用いた以外は、比較例３と同様にこれを処理した後、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６６】
（比較例７）
日東粉化（株）製炭酸カルシウム（ＮＳ−２００）を用いた以外は、比較例３と同様にこれを処理した後、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６７】
（比較例８）
日本アエロジル（株）製ヒュームドシリカ（♯３００）５０ｇを用い、電解質（Ａ）を１７ｇ用いた以外は、実施例１と同様にこれを処理した後、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６８】
（実施例３）
電解質溶液（Ｂ）３０ｇを、同（Ａ）５０ｇの代わりに用いた以外は、実施例１と同様にして行い、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００６９】
（実施例４）
電解質溶液（Ｃ）２０ｇを同（Ａ）５０ｇの代わりに用いた以外は、実施例１と同様にして行い、同様の測定法にて生成物を測定し、その物性値と応用特性を表２に示した。
【００７０】
【表２】

【００７１】
【発明の効果】
本発明によれば、鎖状粘土鉱物中に含まれるフッ石水が種々電解質溶液で実質上置換されている新規鎖状粘土鉱物錯体が提供される。
本発明の錯体の基体となる鎖状粘土鉱物は繊維構造を有しており、重合体の有機マトリックス中で絡み合った３次元状のネットワークを形成し、これによりチクソトロピー性を発現する。
それと同時に、個々の繊維構造自体がイオン導電性を有するため、有機マトリックス中には３次元状のイオン伝導回路が形成され、適度な電気伝導性乃至除電性を重合体の成形物やコーティングに付与することが可能となるものである。
かくして、本発明の鎖状粘土鉱物錯体は、塗料や接着剤などの揺変剤であると同時に、それらの電気的障害を除去しうる配合剤として有用である。
【図面の簡単な説明】
【図１】鎖状粘土鉱物の構造モデルを示す図である。
【図２】未処理の鎖状粘土鉱物の沸石水の状態を示す赤外線吸収スペクトルを示す図である。
【図３】鎖状粘土鉱物の沸石水の脱離状態を示す赤外線吸収スペクトルを示す図である。（未処理の鎖状粘土鉱物（Ａ）と本発明品鎖状粘土鉱物錯体（Ｂ））
【図４】未処理の鎖状粘土鉱物セピオライト（Ａ）と本発明品鎖状粘土鉱物セピオライト錯体（Ｂ）のＸ線回折図である。
【図５】未処理の鎖状粘土鉱物アタパルジャイト（Ａ）と本発明品鎖状粘土鉱物アタパルジャイト錯体（Ｂ）のＸ線回折図である。
【図６】未処理の鎖状粘土鉱物と電解質溶液Ａとの混合物（Ａ）と電解質溶液Ａで処理した本発明品鎖状粘土鉱物錯体（Ｂ）の示差熱重量分析曲線である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a chain clay mineral complex useful as an ion-conductive filler, and more particularly to a novel complex in which an inorganic or organic electrolyte is incorporated in a chain clay mineral structure in a non-aqueous form.
[0002]
[Prior art]
The chain clay mineral has a three-dimensional chain structure in which talc (talc) bricks are alternately stacked. The pores formed in the chain-like gaps have a large surface area, which causes an adsorption action and an absorption action, and also causes high viscosity and thixotropic properties when the chain-like clay mineral is made into a slurry.
[0003]
Due to this feature, chain clay minerals are widely used in various applications such as absorbents, adsorbents, humectants, deodorizers or deodorizing aids, catalysts or catalyst carriers, agricultural chemical carriers, thixotropic agents, ceramic binders and the like. I have.
For example, Japanese Patent Application Laid-Open No. 62-72769 discloses a coating composition comprising a coating resin, a mountain skin treated with a cationic surfactant, and a solvent, wherein the content of the mountain skin is 100% by weight of the coating resin. The coating composition is described as being 0.5 to 30 parts by weight per part.
[0004]
[Problems to be solved by the invention]
In the crystals of the chain clay mineral, water called fluorite water exists in addition to so-called crystal water. That is, although fluorite water is different from mere attached water or absorbed water in that it is water incorporated in the crystal lattice, it can be relatively easily dehydrated by heating, but it is easy to leave in air. There is a problem of condensing water.
[0005]
In addition, according to the study of the present inventors, it has been found that even when the chain clay mineral is used as a thixotropic agent of a paint or an adhesive, the fluorite water causes various adverse effects.
For example, blending chain clay minerals with urethane-based paints and adhesives causes premature curing of the paints and adhesives, significantly shortening the shelf life of the paints and adhesives, and shortening the coating life. There is a tendency to decrease the physical properties and adhesiveness, which is presumably because the fluorite water in the chain clay mineral acts as a curing agent for the urethane resin.
In addition, in resins containing an ester bond in the resin skeleton, such as alkyd resins, polyester resins, polyester-type urethane resins, and polyester-type acrylic resins, the fluorite water contained in the chain clay mineral causes water to be added. It has also been found that degradation of the resin due to decomposition occurs.
[0006]
The present inventors have found that the fluorite water of the chain clay mineral can be replaced with a non-aqueous solution of an inorganic or organic electrolyte, and the chain clay mineral complex formed by this replacement maintains excellent thixotropic properties. It has been found that they exhibit excellent ionic conductivity and can also avoid the adverse effects of the contained fluorite water.
[0007]
Accordingly, an object of the present invention is to provide a chain clay mineral complex in which the fluorite water contained in the chain clay mineral is substantially replaced with a non-aqueous solution of an inorganic and / or organic electrolyte.
It is another object of the present invention to provide a novel modification in which fluorite water in a chain clay mineral is effectively removed, ion conductivity is imparted, and thixotropic properties unique to the chain clay mineral are maintained. To provide chain-like clay minerals.
Still another object of the present invention is to provide a chain clay mineral complex useful as an ionic conductive filler for polymers, especially paints and adhesives.
[0008]
[Means for Solving the Problems]
According to the present invention, there is provided a chain clay mineral complex, wherein the fluorite water of the chain clay mineral is substantially replaced by a non-aqueous solution of an inorganic and / or organic electrolyte.
In the chain clay mineral complex of the present invention,
1. 0.01 to 75% by weight, especially 0.5 to 20% by weight of inorganic and / or organic electrolyte based on the solid content of the chain clay mineral;
2. 0.1 to 150% by weight, especially 10 to 50% by weight of a non-aqueous solution based on the solid content of the chain clay mineral;
3. The inorganic electrolyte is an electrolyte salt of a Group 1 or Group 2 metal of the periodic table (long period type);
4. The organic electrolyte is a quaternary ammonium salt,
5. The non-aqueous solution is a solution of a polyhydric alcohol or a plasticizer,
6. The chain clay mineral is sepiolite,
7. The chain clay mineral is attapulgite,
8. When the chain clay mineral is sepiolite, the spacing d ₁ = Around 10.2 angstroms, d-spacing ₂ = Near 8.2 angstrom, spacing d ₃ = 5.1 angstrom area, d-spacing ₄ = 4.4 angstrom vicinity and surface distance d ₅ = Having an X-ray diffraction peak around 2.3 Angstroms;
9. When the chain clay mineral is attapulgite, the spacing d ₁ = Near 9.1 angstroms, spacing d ₂ = 6.2 Angstrom vicinity, surface spacing d ₃ = 5.1 angstrom area, d-spacing ₄ = 4.6 angstrom vicinity and surface distance d ₅ = Near 4.4 angstrom and spacing d ₆ = Having an X-ray diffraction peak near 2.9 angstroms;
10. 1 × 10 when pressed with powder ^-6 Having a conductivity of S or higher,
Is preferred.
According to the present invention, there is also provided an ion conductive filler comprising the chain clay mineral complex.
According to the present invention, there is further provided a polymer composition obtained by blending the chain clay mineral complex in a polymer.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
[Action]
The novel complex of the present invention comprises a chain clay mineral and an inorganic and / or organic electrolyte as constituents, but the fluorite water of the chain clay mineral is substantially replaced by a non-aqueous solution of an inorganic and / or organic electrolyte. The feature is that.
[0010]
The chain clay mineral which is a component of the complex of the present invention typically has the formula (1)
(OH ₂ ) ₄ (OH) ₄ Mg ₈ Si ₁₂ O ₃₀ ・ 6-8H ₂ O ‥ (1)
And according to the structural model of Brauner and Preisinger, it has the structure shown in FIG.
That is, although a two-dimensional crystal structure such as talc forms a chain-like crystal structure in which bricks are alternately stacked, this unit crystal structure has, as shown in FIG. There are four hydroxyl groups, four crystal waters bonded to Mg, and eight fluorite waters. As is apparent from FIG. 1, it can be understood that the eight waters are incorporated in the crystal lattice, and thus are fluorite water.
In FIG. 1, the unit structure has eight fluorite waters. However, in the structure shown in the formula (1), it is shown that there may be 6 to 8 fluorite water. I have.
[0011]
According to the study of the present inventors, water (including hydroxyl group) in each of the above states has a wave number of 4000 cm in the infrared absorption spectrum. ^-1 ~ 3000cm ^-1 It appears as a peak of the stretching vibration of the hydroxyl group, but appears as peaks separated from each other according to the binding energy state.
[0012]
FIG. 2 is an infrared absorption spectrum of an untreated chain clay mineral. ^-1 ~ 3000cm ^-1 The peak of the stretching vibration of the hydroxyl group of ₁ , P ₂ , P ₃ , P ₄ , P ₅ It can be seen that the peaks appear as five separate peaks. Peak P ₁ Corresponds to the fluorite water 1 having the lowest binding energy state in FIG. ₂ Corresponds to the fluorite water 2 having the next lowest energy state in FIG. ₃ Corresponds to the fluorite water 3 having a high binding energy state in FIG. ₄ Corresponds to the crystallization water 4 in FIG. ₅ Is understood to correspond to the hydroxyl group 5 in the talc brick in FIG.
[0013]
On the other hand, FIG. 3 (B) shows an infrared absorption spectrum of a chain clay mineral complex obtained by replacing the fluorite water of a chain clay mineral with a dioctyl phthalate solution of a quaternary ammonium salt. And the peak P corresponding to the fluorite water 1, 2, 3 ₁ , P ₂ , P ₃ Has a sharp decrease, and the peak P corresponding to the crystallization water 4 has been reduced. ₄ Also reveals a very interesting fact that the absorbance is low. That is, the chain clay mineral complex of the present invention is characterized in that the fluorite water in the chain clay mineral is substantially replaced by a non-aqueous solution of an electrolyte. (FIG. 3 (A) is a spectrum of the case where the fluorite water is not replaced.)
[0014]
FIG. 4A is an X-ray diffraction image of the chain clay mineral sepiolite, and FIG. 4B is a chain clay mineral obtained by replacing the fluorite water of sepiolite with a dioctyl phthalate solution of a quaternary ammonium salt. It is an X-ray diffraction image of a complex.
From the comparison of these X-ray diffraction images, in the sepiolite complex according to the present invention, the interplanar spacing d, which is not observed in the raw chain clay mineral, is obtained. ₁ = Around 10.2 angstroms, d-spacing ₂ = Near 8.2 angstrom, spacing d ₃ = 5.1 angstrom area, d-spacing ₄ = 4.4 angstrom vicinity and surface distance d ₅ = 2.3 angstroms has an X-ray diffraction peak.
Further, FIG. 5 (A) is an X-ray diffraction image of the chain clay mineral attapulgite, and FIG. 5 (B) is a chain clay mineral complex obtained by replacing the fluorite water of the attapulgite with a dioctyl adipate solution of a quaternary ammonium salt. 3 is an X-ray diffraction image of the sample.
From the comparison of these X-ray diffraction images, in the attapulgite complex according to the present invention, the plane spacing d which is not observed in the raw chain clay mineral is considered. ₁ = Near 9.1 angstroms, spacing d ₂ = 6.2 Angstrom vicinity, surface spacing d ₃ = 5.1 angstrom area, d-spacing ₄ = 4.6 angstrom area, d-spacing ₅ = Near 4.4 angstroms, and d ₆ = 2.9 has an X-ray diffraction peak.
The chain clay mineral from which the fluorite water was removed has a remarkable tendency to condensate, and returns to the crystal structure shown in FIGS. 4A and 5A during the X-ray diffraction measurement. X-ray diffraction images of the chain clay minerals obtained cannot be shown, but the X-ray diffraction images shown in FIGS. 4 (B) and 5 (B) show that the complex obtained by substituting the fluorite water with another substance is also used. It is commonly accepted.
Further, the X-ray diffraction image of a mere mixture of the chain clay mineral and the non-aqueous solution of the electrolyte did not show any X-ray diffraction peak specific to the present invention.
[0015]
As described above, in the complex of the present invention, the fluorite water, which causes deterioration in the quality of the polymer, especially the paint or the adhesive, is removed by replacing the inorganic and / or organic electrolyte with the non-aqueous solution, and Since the binding site of the fossil water is covered with the non-aqueous solution, there is an advantage that the tendency to condensate is suppressed, and that the ion conductivity of the non-aqueous solution of the electrolyte can be obtained.
[0016]
Explaining this point, the chain clay mineral serving as the base of the complex of the present invention has a fibrous structure, and forms a three-dimensional network intertwined in the organic matrix of the polymer, whereby the thixotropic property is improved. Express.
At the same time, since the individual fiber structure itself has ionic conductivity, a three-dimensional ionic conduction circuit is formed in the organic matrix, and appropriate electrical conductivity or static elimination is imparted to the polymer molded article or coating. It is possible to do.
[0017]
The chain clay mineral complex of the present invention may contain 0.01 to 75% by weight, especially 0.5 to 20% by weight of an inorganic or organic electrolyte based on the solid content of the chain clay mineral. preferable.
When the content of the electrolyte is lower than the above range, the electric conductivity tends to be insufficiently provided as compared with the case where the content is within the above range. On the other hand, when the content exceeds the above range, the electrolyte bleeds out. This is not preferable because the tendency tends to increase and the cost tends to increase.
Further, the non-aqueous solution of the electrolyte is preferably contained in an amount of 0.1 to 150% by weight, particularly 10 to 50% by weight based on the solid content of the chain clay mineral. If the content of the non-aqueous solution is below the above range, the suppression of the condensate tendency becomes insufficient compared to the case where the content is within the above range, while the bleed-out tendency of the non-aqueous solution is high when the content exceeds the above range. It is also not preferable because the cost tends to increase.
[0018]
The chain clay mineral complex of the present invention is 1 × 10 ^-6 S or higher electrical conductivity, more preferably 1 × 10 ^-4 ~ 1 × 10 ^-3 It has an electrical conductivity of S. The chain-like clay mineral complex exhibits the above-mentioned conductivity in a powder state, thereby exhibiting a desirable effect of preventing accumulation of static electricity or eliminating static electricity when incorporated in a polymer matrix.
The conductivity of the powder in a pressurized state will be described in detail in Examples below, but refers to the value of the conductivity of a specific disk-shaped compact obtained.
[0019]
In the chain clay mineral complex of the present invention, since the non-aqueous solution of the electrolyte is incorporated in the chain clay mineral in the form of a complex, the thermal stability is higher than a mere mixture of the chain clay mineral and the non-aqueous electrolyte. Is significantly improved.
[0020]
FIG. 6 shows a differential thermogravimetric analysis curve of the chain clay mineral complex (B) according to the present invention and a simple mixture of the chain clay mineral and a non-aqueous electrolyte solution (A).
According to this analysis curve, a peak of weight loss is observed at 224 ° C. for the mere mixture, whereas a weight loss peak is observed at 260 ° C. for the chain clay mineral complex of the present invention, and the heat resistance of 30 ° C. or higher is observed. Improvement is observed.
[0021]
Furthermore, the complex of the present invention has the following formula (2)
TI = η ₆ / Η ₆₀ ‥ (2)
Where η ₆ Is the viscosity of a 5% dispersion of the medium chain clay mineral complex of dioctyl phthalate measured at 6 rpm, and η ₆₀ Is the viscosity of the dispersion measured at a rotation speed of 60 rpm.
Is characterized in that the thixotropic coefficient (TI) defined by the formula is 3.0 or more.
That is, although the complex of the present invention exhibits a small thixotropic coefficient (TI) as compared with the untreated chain-like clay mineral, it still has thixotropic properties in a range that can be sufficiently used as a thixotropic agent. I have.
[0022]
[Chain clay minerals]
Chain clay minerals are hydrated silicates of magnesium and are commonly found in jadeite as secondary minerals.
In the present invention, the specific surface area is 100 to 350 m ² / G and a chain clay mineral having an oil absorption of 100 to 300 ml / 100 g is preferably used. If the specific surface area is smaller than this range, the sorption of the electrolyte non-aqueous solution is small, while if it is larger than this range, no further effect can be obtained.
[0023]
The fibrous chain clay mineral suitably used in the present invention generally has a fiber diameter of 0.1 to 3 μm, a fiber length of 5 to 20 μm, and an aspect ratio of 10 to 100. It is preferable in terms of handling.
[0024]
Table 1 below shows an example of a general chemical composition of a chain clay mineral (a dried product at 110 ° C. for 2 hours).
[Table 1]
General chemical composition of chain clay minerals
SiO ₂ 52.50 (% by weight)
MgO 22.8
Al ₂ O ₃ 1.7
Fe ₂ O ₃ 0.8
CaO 0.8
H ₂ O + 10.4
H ₂ O-11.0
[0025]
[Electrolytes]
On the other hand, as the electrolyte used in the present invention, inorganic and / or organic electrolytes which can be dissolved in a non-aqueous solvent are used alone or in combination of two or more.
[0026]
One type of suitable electrolyte is an electrolyte salt of a Group 1 or Group 2 metal of the Periodic Table (Long Period Type), such metals including lithium, sodium, potassium, cesium, magnesium, zinc, and the like. Of these, alkali metals, particularly lithium, are preferred.
Suitable examples of the electrolyte salt include, but are not limited to, halides such as chloride and bromide, halogen oxyacid salts such as perchlorate and perbromate, tetrafluoroborate, and hexafluorophosphate. Salts, hexafluoroarsenate, trifluoromethylsulfonate and the like.
[0027]
Another type of suitable electrolyte is a quaternary ammonium salt, specifically hexadecyltrimethylammonium chloride (hereinafter sometimes referred to as HDTMA), decyltrimethylammonium chloride, dodecyltrimethylammonium chloride (hereinafter DDTMA). Alkylpyridinium chloride such as tetradecyltrimethylammonium chloride, octadecyltrimethylammonium chloride (hereinafter sometimes referred to as ODTMA), hexadecyltrimethylammonium bromide, hexadecyldimethylbenzylammonium chloride, dodecylpyridinium chloride Is mentioned.
[0028]
Non-aqueous solvents (organic solvents) include polyethers such as polyethylene glycol (hereinafter sometimes referred to as PEG), polypropylene glycol, polybutylene glycol, polyoxyethylene / polyoxypropylene copolymer; or glycerin, trimethylol Ethylene oxide adducts to propane, pentaerythritol, dipentaerythritol, mannitol, sorbitol and the like are used.
[0029]
As the polyether, a nonionic surfactant containing a polyoxyethylene unit can be used. Examples thereof include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene alkylphenyl ether, and polyoxyethylene. Examples include fatty acid amide ethers, polyoxyethylene polyhydric alcohol fatty acid esters, and the like.
[0030]
In the present invention, among the above-mentioned polyethers, polyethylene glycol, in particular, the following formula (3)
HO (CH ₂ CH ₂ O) nH ‥‥ (3)
Where n is a number from 4 to 100;
It is desirable to use polyethylene glycol represented by
[0031]
Examples of the non-aqueous solvent include organic solvents other than polyethers, such as furan solvents (tetrahydrofuran, 2-methyltetrahydrofuran, etc.); ether solvents (methylal, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1-ethoxy-2-dimethoxyethane, alkoxypolyalkylene ether, etc .; amide solvents (N-methylformamide, N-ethylformamide, N, N-dimethylformamide, N-methylacetamide, N-ethylacetamide, N-methyl) Nitrile solvents (acetonitrile, benzonitrile, 3-methoxypropionitrile, etc.); sulfolane solvents (sulfolane, tetramethylenesulfolane, dimethylsulfoxysulfolane, etc.); chain carbonate solvents (dimethylcarbonate, etc.) , Diethyl carbonate, methyl ethyl carbonate, methyl isopropyl carbonate, etc.); cyclic carbonate solvents (ethylene carbonate, propylene carbonate, butylene carbonate, etc.); lactone solvents (γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3) Alcohol solvents (ethylene glycol, propylene glycol, glycerin, methyl cellosolve, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol) , Diglycerin, polyoxyalkylene glycol, cyclohexanediol, xylene glycol, etc.) Phosphoric acid and phosphate ester solvents (normal phosphoric acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, phosphorous acid, trimethyl phosphate) 2-imidazolidinone-based solvent (1,3-dimethyl-2-imidazolidinone, etc.); pyrrolidone-based solvent; 1,4-dioxane; dioxolane; dichloroethane may be used alone or in combination. .
[0032]
As the non-aqueous solvent, a plasticizer can also be used. As the plasticizer, ester plasticizers such as phthalate plasticizer, adipate plasticizer, succinate plasticizer, and polyester plasticizer , A phosphate plasticizer, a chlorine plasticizer, an epoxy lubricant and the like.
[0033]
[Production method]
The complex of the present invention is produced by heating and dehydrating a chain clay mineral under reduced pressure, and then keeping the dried state in contact with a non-aqueous solution of an electrolyte to lower the temperature. In this production method, the chain clay mineral is preferably dehydrated at a pressure of 0.074 to 0 MPa and heating at 150 to 410 ° C.
[0034]
In the present invention, in order to bond the non-aqueous solution of the electrolyte to the chain clay mineral substrate, it is important to heat and dehydrate the chain clay mineral under reduced pressure. In general, it is preferable to dehydrate the chain clay mineral until its water content is reduced to 50% by weight or less of the water content before dehydration. For this reason, at a temperature of 150 to 410 ° C. under a pressure of 0.074 to 0 MPa. It is desirable to perform dehydration.
[0035]
The chain clay mineral that has been dehydrated under reduced pressure is subsequently contacted with a non-aqueous solution of an electrolyte under anhydrous oxygen-free condition to form a complex.The resulting complex is cooled down to room temperature and then taken out under atmospheric pressure. Products.
[0036]
[Complex]
The chain clay mineral complexes of the present invention have the chemical structure and crystallographic properties already described.
In this complex, since the fluorite water in the lattice is replaced by a non-aqueous solution of an electrolyte, the complex generally shows a smaller BET specific surface area and a smaller oil absorption than the original chain clay mineral.
That is, the BET specific surface area of the complex usually shows a value of about 40 to 55% of the upper limit specific surface area of the original chain clay mineral, and specifically, 125 to 155 m ² / G.
Also, the oil absorption measured using dibutyl phthalate (DBP) as an oil agent generally shows a value of about 40 to 55% of the oil absorption of the original chain clay mineral, and specifically, 40 to 55 ml / 100 g. In range.
[0037]
The pore volume of the chain clay mineral complex of the present invention measured by the mercury intrusion method is 0.5 to 0.6 ml / g in the pore diameter range of 2000 to 100 nm, and the pore volume in the pore diameter range of 100 to 2 nm. Is 0.34 to 0.45 ml / g. The pore volume of the untreated chain clay mineral in the pore diameter range of 100 to 2 nm is 0.32 ml / g.
That is, in the complex of the present invention, the pore volume in the range of the pore diameter of 100 to 2 nm is slightly larger than that of the untreated chain-like clay mineral, which indicates an increase in the particle gap due to complex formation. It is considered that the aggregation of particles due to the capillary force of water is prevented.
[0038]
The chain-like clay mineral complex of the present invention is formed by hydrolysis of an untreated chain-like clay mineral when it is added to a compound containing an ester bond in the skeleton of a resin, paint or adhesive, for example, a polyester-based compound. Deterioration of resin, paint or adhesive can be prevented. This can be understood from the examples described later because the hydrolysis index (Wd) is zero and the ester group is not reduced by hydrolysis.
[0039]
[Use]
Like the chain clay mineral, the chain clay mineral complex of the present invention can be used for a resin compounding agent, a paint compounding agent, an adhesive compounding agent, a fibrous reinforcing agent, etc. having ion conductivity and thixotropic properties. it can.
[0040]
According to the present invention, a thermoplastic resin, an elastomer or a thermoplastic elastomer, is blended with a resin compounding agent comprising the complex, and the compounding agent is uniformly and finely dispersed in a polymer. The inherent performance of the compounding agent can be exhibited while solving the problem.
[0041]
Examples of the thermoplastic polymer include low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, poly 1-butene, poly 4-methyl-1-pentene or ethylene, propylene, 1-butene, 4-methyl- Polyolefins such as random or block copolymers of α-olefins such as 1-pentene; ethylene-vinyl compound copolymers such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-vinyl chloride copolymer; Polymer, polystyrene, acrylonitrile / styrene copolymer, ABS, styrene resins such as α-methylstyrene / styrene copolymer, polyvinyl chloride, polyvinylidene chloride, vinyl chloride / vinylidene chloride copolymer, polymethyl acrylate , Poly (vinyl methacrylate) Compounds, polyamides such as nylon 6, nylon 6-6, nylon 6-10, nylon 11 and nylon 12, thermoplastic polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, polyphenylene oxides and the like, and mixtures thereof. Such resin may be used.
[0042]
Examples of the elastomer polymer include nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), polybutadiene (BR), polyisoprene (IIB), butyl rubber, natural rubber, ethylene-propylene rubber ( EPR), ethylene-propylene-diene rubber (EPDM), polyurethane, silicone rubber, acrylic rubber, etc .; thermoplastic elastomers, for example, styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, hydrogenated styrene- Examples include a butadiene-styrene block copolymer, a hydrogenated styrene-isoprene-styrene block copolymer, and a partially crosslinked olefin-based thermoplastic elastomer. Among these, hydrocarbon elastomers, particularly EPR and EPDM, are preferred.
Of course, they can also be used in the form of a blend of two or more.
[0043]
Depending on the use of the compounding agent, the hydrophobic resin compounding agent comprising the complex may be used in an amount of 0.01 to 200 parts by weight, especially 0.1 to 50 parts by weight, per 100 parts by weight of the thermoplastic resin, the elastomer or the thermoplastic elastomer. Therefore, it is preferable to mix an appropriate amount.
[0044]
For blending the compounding agent into the polymer, a so-called dry blending or melt blending method can be adopted, and a method of blending a masterbatch containing a relatively high concentration of a resin compounding agent with an unblended polymer is adopted. You can also. In addition, in the case of melt molding, a masterbatch may be prepared, the masterbatch may be mixed with a resin, melt-kneaded, and molded into predetermined fibers.
[0045]
The resin compounding agent of the present invention can be compounded in a coating material or an adhesive known per se to obtain a coating composition or an adhesive composition.
As the paint, nitrocellulose paint, alkyd resin paint, amino alkyd paint, vinyl resin paint, acrylic resin paint, epoxy resin paint, polyester resin paint, chlorinated rubber paint, phenolic resin, modified Phenolic resin, alkyd resin, vinyl resin, petroleum resin, epoxy resin, polyester resin, styrene resin, silicone resin, chlorinated resin, urethane resin, polyamide resin, polyimide resin, fluorine resin Paints containing one or more resins, such as resins, may be mentioned.
The adhesive includes an epoxy resin adhesive, a polyurethane adhesive, a urea resin adhesive, a melamine resin adhesive, a phenol resin adhesive, an α-olefin adhesive, an aqueous polymer-isocyanate adhesive. Agent, vinyl acetate resin (solvent type) adhesive, vinyl acetate resin emulsion adhesive, acrylic emulsion adhesive, cyanoacrylate adhesive, hot melt adhesive, anaerobic adhesive, chloroprene rubber adhesive, nitrile rubber Adhesive, SBR adhesive, ethylene copolymer resin adhesive, resorcinol adhesive, natural rubber adhesive, cellulose adhesive, isobutene-maleic acid copolymer adhesive, alkyd resin adhesive, furan Resin adhesive, saturated or unsaturated polyester resin adhesive, silicone resin adhesive, polyvinyl alcohol Le-based adhesive, nylon resin-based adhesive, one or adhesives containing two or more such inorganic adhesive. In addition, an appropriate curing agent or the like, for example, triethylamine, triethylenetetramine, diaminediamide or the like can be appropriately added to the epoxy resin to change the adhesive strength to the adherend.
The organopolysiloxane / chain clay mineral complex of the present invention can be used in an amount of 0.5 to 30 parts by weight based on 100 parts by weight of the adhesive resin.
[0046]
Further, the paint to be used may be an arbitrary one such as a solvent-based paint, a water-based paint, an ultraviolet-curable paint, a powder paint, or the like, depending on how the paint is used. Examples of the organic solvent for the solvent type paint include toluene, xylene n-heptane, n-hexane, cyclohexane, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone ethanol, propanol, butanol, diacetone alcohol tetrahydrofuran, dioxane ethyl cellosolve, and butyl cellosolve acetate. Dimethylsulfoxide solvent, or one or more kinds thereof. As the water-based paint, a self-emulsifying type or a surfactant emulsifying type paint is used in addition to an aqueous solution type paint. As the resin of the water-based paint, an alkyd resin, a polyester resin, an acrylic resin, an epoxy resin, or a combination of two or more of these, which are made water-soluble or self-emulsified in an aqueous medium, can be used. The resin concentration is generally in the range from 10 to 70% by weight, in particular from 20 to 60% by weight.
[0047]
【Example】
In the following examples, measurement of raw materials and products was performed by the following method.
(1) Infrared absorption spectrum
The absorbance of transmitted light was measured using a TGS sensor of FTIR610 manufactured by JASCO Corporation.
A sample was formed into a wafer using KBr powder, and a KBr wafer containing no sample was used as a reference, and the sample chamber was measured in a vacuum with no relative humidity. Further, the water content of the product of the present invention and the raw material powder were compared and measured using the peak area ratio mode of the data processing software of FTIR610.
Total number of times Auto
Disassembly 4 Kaiser
Zero filling ON
Apodization Cosine
Gain 8
Aperture 7.1mm
Scan speed 2mm / sec
[0048]
(2) Differential thermogravimetric analysis
Using an EXSTAR6000TG-DTA6300 system manufactured by Seiko Denshi Kogyo Co., Ltd., using α-alumina as a standard substance, the temperature was raised to 1150 ° C. at a rate of 10 ° C./min under a nitrogen flow atmosphere of 200 ml / min. The temperature at the maximum desorption rate of the component was measured by DTG.
[0049]
(3) X-ray diffraction
Using a Geigerflex RAD-1B system manufactured by Rigaku Corporation, the plane spacing (Å) and diffraction intensity (%) of the product were measured with Cu-Kα under the following conditions.
Target Cu
Filter Curved crystal graphite monochromator
Detector Scintillation counter
Voltage 40KV
Current 30mA
Count full scale 700c / s
Smoothing point 25
Scanning speed 2 degrees / min
Step sampling 0.02 degrees
Slit DS 1 RS 0.15 SS 1 mm
Irradiation angle 6 degrees
[0050]
(4) Condensate moisture absorption rate
The sample treated according to the present invention was placed immediately after the treatment, and the untreated sample such as a comparative sample was placed in a desiccator with a humidity control of 25 ° C. and 75% RH immediately after drying at 180 ° C. for 30 minutes, and weighed after 24 hours. The condensate rate (% by weight) was measured.
[0051]
(5) Hydrolysis index (Wd)
In the infrared absorption spectrum, the following formula (4)
Wd = (E ₀ -E _s ) / E ₀ ‥ (4)
Where E ₀ Is the wave number of the plasticizer dioctyl phthalate 1720-1750 cm ^-1 Peak area e ₀ (Derived from C = O stretching vibration of ester group) and wave number 2890-2980 cm ^-1 Peak area m up to ₀ (Derived from stretching vibration of methyl and methylene groups) ₀ / M ₀ And Es is a wave number of 1720 to 1750 cm for a liquid phase after heating a 5% by weight dioctyl phthalate suspension of a hydrous inorganic substance such as a chain clay mineral at 60 ° C. for 7 days. ^-1 Peak area e _s 2890-2980cm wave number of the same liquid phase ^-1 Ratio to peak area ms up to e _s / M _s Is,
Indicates the tendency to hydrolyze various hydrous inorganic esters such as chain clay minerals by the absorbance ratio (Wd) defined by
When no hydrolysis occurs, E ₀ = E _s And when Wd = 0 and all the esters are in a hydrolyzed state, _s = 0 and Wd = 1.
[0052]
(6) Measurement of conductivity (conductivity)
The conductivity [S] of the sample was measured with a resistivity meter Loresta IP MCP-T250 manufactured by Mitsubishi Yuka.
Note that the conductivity is 1 × 10 ^-7 S and below are represented as OR.
[0053]
(7) Measurement of thixotropic coefficient (TI)
The following equation (2)
TI = η ₆ / Η ₆₀ ‥ (2)
Where η ₆ Is the viscosity of a 5% dispersion of dioctyl phthalate medium chain clay mineral complex measured at 25 ° C. with a B-type viscometer at a rotation speed of 6 rpm, and η ₆₀ Is the viscosity measured at a rotation speed of 60 rpm for the dispersion.
Was used to calculate the TI value. The conductivity [S] of the dispersion (DOP 5% suspension) was also measured.
[0054]
(8) Measurement of conductivity of powder under pressure (conductivity of inorganic molded body)
Into a stainless steel container having an inner diameter of 7 cm and a depth of 2 cm, 20 g of the inorganic substance of the example or the comparative example was weighed smoothly on the bottom of the container, a stainless disk having a diameter of 7 cm and a thickness of 2 mm was placed on the powder, and the hydraulic pressure was 50 kg / cm. ² For 15 minutes to obtain a disc-shaped inorganic molded body, and its conductivity [S] was measured.
[0055]
(9) Measurement of conductivity of PVC composition
A 1-mm-thick hard PVC sheet containing the product of the present invention or the inorganic substance of the comparative example was prepared under the following composition and molding conditions, and the conductivity [S] of the PVC composition was measured.

Kneading conditions: Kneading at 170 ° C for 6 minutes in a 3.5 inch differential roll mill

(10) Measurement of conductivity of urethane composition
A urethane film containing an inorganic material of the present invention or a comparative example was prepared under the following composition and molding conditions, and the conductivity [S] of the urethane composition was measured.

The above composition was mixed and dispersed at 2500 rpm for 5 minutes with a homodisper manufactured by TOKUSHU KIKA KOUGYOU, formed into a film on a glass plate with a 150 μm film applicator, dried at room temperature and cured, and then the conductivity [S] of the film was measured. It was measured.
[0057]
(Preparation of electrolyte solution)
Electrolyte solution A: A solution prepared by dissolving 10 parts by weight of discarded allyldimethylammonium chloride (Kotamin D86P manufactured by Kao) at room temperature in 50 parts by weight of dioctyl phthalate (first grade reagent manufactured by Wako Pure Chemical Industries).
Electrolyte solution B: dioctyl adipate (Wako Pure Chemicals first grade reagent) 50 parts by weight, stearyl dimethyl ammonium chloride (Kao Cotamine D86P) 10 parts by weight and lithium perchlorate monohydrate (Wako Pure Chemicals first grade reagent) 1 What dissolved parts by weight at room temperature.
Electrolyte solution C: A solution prepared by dissolving 5 parts by weight of lithium perchlorate monohydrate (special grade of reagent manufactured by Wako Pure Chemical Industries) at 50 ° C. in 50 parts by weight of polyethylene glycol 200 (special grade manufactured by Wako Pure Chemical Industries, Ltd.).
[0058]
(Example 1)
150 g of sepiolite, a chain clay mineral produced in Spain, was charged into a 1 L airtight container, heated to a powder temperature of 250 ° C. while stirring under a weak reduced pressure, and then dehydrated under a pressure of 0.046 MPa or less for 30 minutes. When heating was stopped and the powder temperature dropped to 150 ° C. while maintaining the dry state, 50 g of the electrolyte solution (A) was poured into a 1 L airtight container, and the mixture was vigorously stirred under reduced pressure and oxygen-free atmosphere. Maintained and cooled to room temperature.
Table 2 shows the physical properties and application characteristics of the product.
[0059]
(Comparative Example 1)
Table 2 shows the physical property values and applied characteristics of the chain clay mineral sepiolite itself.
[0060]
(Comparative Example 2)
5 g of chain clay mineral sepiolite powder was put into a crucible, immediately after dehydration at 250 ° C. for 30 minutes in an electric furnace, put in a 50 ml sealed container, returned to room temperature, measured at room temperature in the same manner as in Example 1, and measured for physical properties and application. The characteristics are shown in Table 2.
[0061]
(Comparative Example 3)
2 g of the electrolyte solution A was added to 10 g of the sepiolite powder, and the powder mixed intimately in an agate mortar was measured in the same manner as in Example 1. The physical properties and application characteristics are shown in Table 2.
[0062]
(Example 2)
After treating this in the same manner as in Example 1 except that the U.S. chain clay mineral attapulgite was used, the product was measured by the same measuring method. The physical properties and applied characteristics are shown in Table 2.
[0063]
(Comparative Example 4)
Table 2 shows the physical properties and applied properties of the chain clay mineral attapulgite itself.
[0064]
(Comparative Example 5)
After treating this in the same manner as in Comparative Example 2 except that the U.S. chain-chain clay mineral attapulgite was used, the product was measured by the same measuring method. The physical properties and applied characteristics are shown in Table 2.
[0065]
(Comparative Example 6)
After treating this in the same manner as in Comparative Example 3 except that the U.S. chain-like clay mineral attapulgite was used, the product was measured by the same measurement method, and the physical properties and applied characteristics are shown in Table 2.
[0066]
(Comparative Example 7)
After treating this in the same manner as in Comparative Example 3 except that calcium carbonate (NS-200) manufactured by Nitto Powder Chemical Co., Ltd. was used, the product was measured by the same measurement method, and the physical properties and applied characteristics of the product were measured. Are shown in Table 2.
[0067]
(Comparative Example 8)
After treating this in the same manner as in Example 1 except that 50 g of fumed silica (# 300) manufactured by Nippon Aerosil Co., Ltd. and 17 g of the electrolyte (A) were used, the product was measured by the same measuring method. Table 2 shows the physical properties and application characteristics.
[0068]
(Example 3)
The product was measured in the same manner as in Example 1 except that 30 g of the electrolyte solution (B) was used instead of 50 g of the electrolyte solution (A), and the product was measured by the same measurement method. 2 is shown.
[0069]
(Example 4)
The same procedure was followed as in Example 1 except that 20 g of the electrolyte solution (C) was used in place of 50 g of the electrolyte solution (A), and the product was measured by the same measurement method. It was shown to.
[0070]
[Table 2]

[0071]
【The invention's effect】
According to the present invention, there is provided a novel chain clay mineral complex in which the fluorite water contained in the chain clay mineral is substantially replaced with various electrolyte solutions.
The chain clay mineral serving as the base of the complex of the present invention has a fibrous structure and forms a three-dimensional network intertwined in a polymer organic matrix, thereby exhibiting thixotropic properties.
At the same time, since the individual fiber structure itself has ionic conductivity, a three-dimensional ionic conduction circuit is formed in the organic matrix, and appropriate electrical conductivity or static elimination is imparted to the polymer molded article or coating. It is possible to do.
Thus, the chain-like clay mineral complex of the present invention is useful as a thixotropic agent such as a paint or an adhesive, and at the same time, as a compounding agent capable of removing the electrical obstacle.
[Brief description of the drawings]
FIG. 1 is a diagram showing a structural model of a chain clay mineral.
FIG. 2 is a view showing an infrared absorption spectrum showing a state of zeolite water of an untreated chain clay mineral.
FIG. 3 is a view showing an infrared absorption spectrum showing a desorbed state of zeolite water of a chain clay mineral. (Untreated chain clay mineral (A) and chain clay mineral complex of the present invention (B))
FIG. 4 is an X-ray diffraction diagram of an untreated chain clay mineral sepiolite (A) and a chain clay mineral sepiolite complex of the present invention (B).
FIG. 5 is an X-ray diffraction diagram of an untreated chain clay mineral attapulgite (A) and a chain clay mineral attapulgite complex of the present invention (B).
FIG. 6 is a differential thermogravimetric analysis curve of a mixture (A) of an untreated chain clay mineral and an electrolyte solution A and the chain clay mineral complex of the present invention (B) treated with the electrolyte solution A.

Claims (13)

A chain clay mineral complex, wherein the fluorite water of the chain clay mineral is substantially replaced by a non-aqueous solution of an inorganic and / or organic electrolyte. 2. The chain clay mineral complex according to claim 1, wherein the chain clay mineral contains 0.01 to 75% by weight of an inorganic and / or organic electrolyte based on the solid content of the chain clay mineral. 3. The chain clay mineral complex according to claim 1, wherein a non-aqueous solution of 0.1 to 150% by weight based on the solid content of the chain clay mineral is contained. The chain clay mineral complex according to any one of claims 1 to 3, wherein the inorganic electrolyte is an electrolyte salt of a Group 1 or Group 2 metal of the periodic table. The chain clay mineral complex according to any one of claims 1 to 3, wherein the organic electrolyte is a quaternary ammonium salt. The chain clay mineral complex according to any one of claims 1 to 5, wherein the non-aqueous solvent is a polyhydric alcohol or a plasticizer. The chain clay mineral complex according to any one of claims 1 to 6, wherein the chain clay mineral is sepiolite. The chain clay mineral complex according to any one of claims 1 to 6, wherein the chain clay mineral is attapulgite. Surface spacing d ₁ = 10.2 angstrom, surface spacing d ₂ = 8.2 angstrom, surface spacing d ₃ = 5.1 angstrom, surface spacing d ₄ = 4.4 angstrom, and surface spacing d ₅ = 2 The chain clay mineral complex according to claim 7, which has an X-ray diffraction peak around 0.3 Å. Surface spacing d ₁ = around 9.1 angstroms, surface spacing d ₂ = around 6.2 angstroms, surface spacing d ₃ = around 5.1 angstroms, surface spacing d ₄ = around 4.6 angstroms, and surface spacing d ₅ = 4 The chain clay mineral complex according to claim 8, wherein the complex has an X-ray diffraction peak around 0.4 Å and a plane spacing d ₆ = 2.9 Å. The chain clay mineral complex according to any one of claims 1 to 10, wherein the chain clay mineral has a conductivity of 1 × 10 ⁻⁶ S or more when pressed with a powder. An ion-conductive filler comprising the chain-like clay mineral complex according to claim 1. A polymer composition comprising the chain clay mineral complex according to any one of claims 1 to 11 blended in a polymer.

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