JPH0987096A - Lipophilic inorganic filler and composite resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a lipophilic inorg. filler well swollen with a small amt. of org. cations and improving the heat resistance and rigidity of a composite resin compsn. having a high aspect ratio. SOLUTION: Org. cations are intercalated into a swellable silicate represented by the formula [Aa (Xb Yc )(Si4-d Ald )O12 (OHe F2-e )] and having >=2μm average grain diameter of single crystal grains, 70-250Å<2> /charge charge density and a smectite structure to obtain the objective lipophilic inorg. filler. In the formula, 0.2<=a<=0.7, 0<=b<=3, 0<=c<=2, 0<=d<=4, 0<=e<=2, A is at least one cation selected from among alkali metal ions and alkaline earth metal ions, X and Y are cations entering into each octahedron in the smectite structure, X is at least one among Mg, Fe, Mn, Ni, Zn and Li, and Y is at least one among Al, Fe, Mn and Cr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a molding material obtained by intercalating an organic cation between layers of a swelling silicate and subjected to a lipophilic treatment, which is a lipophilic inorganic used as a filler for a synthetic resin. It relates to the filler.

[0002]

2. Description of the Related Art Clay minerals are dispersed as a means for improving the heat resistance and rigidity of resin compositions. Smectite-based swelling silicate, one of the clay minerals,
It is hydrophilic and has an ion-exchange effect, has a lower charge density than layered silicates such as vermiculite and mica, and has a weak interlayer attraction, so that it is easily swelled in a solvent such as water. However, even if the smectite-based swelling silicate is compounded as it is with the synthetic resin, its hydrophilicity lowers the dispersibility in the synthetic resin, and therefore the reinforcing effect due to the compounding is not sufficiently exerted. Therefore, an organic substance is intercalated between the layers in advance to make it lipophilic to improve the affinity with the synthetic resin. However, ordinary smectite swelling silicates have low crystallinity and a small crystal particle size of about 0.05 μm, so even if they are lipophilicized and dispersed in a synthetic resin, the aspect ratio of the dispersed particles is small. However, the heat resistance and rigidity of the resin composition could not be sufficiently improved.

[0003]

[Problems to be Solved by the Invention] The definition of clay in soil science is defined as the smallest inorganic particle in soil, and according to the International Soil Society Law, it is defined as a particle of 2.0 μm or less as a polycrystal ( Reference: “Clay Handbook”, 2nd edition, edited by The Japan Clay Society, Sections 1-6, Gihodo Publishing). That is, even if the smectite-based clay mineral, which is an aggregate of such fine crystal grains, is subjected to lipophilic treatment to improve its dispersion in the synthetic resin, a sufficiently complex-reinforced composite resin composition can be obtained. could not. In order to improve this drawback, highly crystalline layered compounds have been studied, but most of them have a strong electric attraction force (high charge density), and in order to sufficiently swell the layers, There is no choice but to increase the amount of organic cation required for ion exchange. However, a large amount of organic cation may cause a wax-like action in the resin composition, resulting in a decrease in heat resistance of the resin composition.

That is, when a layered silicate having a structure similar to smectite is used as an inorganic filler to form a composite,
Its functions include (1) high crystallinity and high strength as a filler, (2) keeping the aspect ratio high, (3)
The requirement is that the layers are easily opened with a small amount of organic cations. However, there is almost no research on highly crystalline swelling silicate having such a smectite structure, and at present, no research on organic intercalation has been carried out.

The present invention has been made to solve the above-mentioned problems, and is a composite in which heat resistance and rigidity are improved by a lipophilic inorganic filler which is sufficiently swelled with a small amount of organic cation and has a high aspect ratio. This is what makes resin materials possible.

[0006]

The lipophilic inorganic filler of the present invention has a general formula represented by the following formula, the average particle size of single crystal particles is 2 μm or more, and the charge density is 70 to 250Å ² / charge. It is characterized in that an organic cation is intercalated into a swelling silicate having a smectite structure. [A _a (X _b Y _c ) (Si _4-d Al _d ) O ₁₀ (OH
_e F _2-e )] where 0.2 ≤ a ≤ 0.7, 0 ≤ b ≤ 3, 0 ≤ c ≤ 2, 0
≦ d ≦ 4, 0 ≦ e ≦ 2, A is an interlayer exchangeable metal ion, and is at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, and X Y is a cation that enters the octahedron formed in the smectite structure, and X is Mg, Fe,
At least one of Mn, Ni, Zn, Li, Y
Is at least one of Al, Fe, Mn, and Cr.

According to the invention of claim 2, the organic cation is
A primary to tertiary amine salt, a quaternary ammonium salt, or an amino acid salt, wherein the swelling silicate is hydrophobized by intercalation of an organic cation between the layers. It is the lipophilic inorganic filler described.

According to the third aspect of the present invention, the metal cations between the layers of the swelling silicate are ion-exchanged with the organic cations, the ion exchange ratio is 0.3 to 1.0, and the amount of the organic cations is 25 to. The lipophilic inorganic filler according to claim 1 or 2, wherein the content is 195 meq / 100 g.

The composite resin composition of the present invention is characterized in that the lipophilic inorganic filler of the present invention is dispersed in a synthetic resin composition.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The swelling silicate applied in the present invention has a so-called smectite structure, and includes, for example, montmorillonite, beidellite, nontronite, volkonskoite, saponite, iron saponite, hectorite, sauconite, Examples include compositions such as stevensite. The swelling silicate need not have a smectite structure in a strict sense, and a swelling silicate having a similar structure having a smectite structure as a basic structure and having a similar action is also considered as the swelling silicate of the present invention. Of course, it will be done.

Further, the swelling silicate used in the present invention is one which satisfies the following formula. [A _a (X _b Y _c ) (Si _4-d Al _d ) O ₁₀ (OH
_e F _2-e )] where 0.2 ≤ a ≤ 0.7, 0 ≤ b ≤ 3, 0 ≤ c ≤ 2, 0
≦ d ≦ 4 and 0 ≦ e ≦ 2. A is an interlayer exchangeable metal ion, and is at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions. For example, Li, Na, K, Be, Mg, Ca
And the like. X and Y are cations that enter the octahedron formed in the smectite structure, and X is Mg,
At least one of Fe, Mn, Ni, Zn, Li
And Y is at least one of Al, Fe, Mn, and Cr.

Further, the charge density is 70 to 250Å ² / cha
The one of rge is applied. Furthermore, 70-200Å ² /
More preferable is charge. Charge density is 70Å ² / cha
When it is less than rge, CEC becomes large (charge becomes large) and the smectite structure is not taken, and 250 Å
^When it is larger than ² / charge, CEC becomes small and the smectite composition approaches the pyrophyllite composition, so that the swelling property is lost, which is not preferable. The charge density of the swellable smectite crystal is, for example, the column permeation method (see: “Clay Handbook”, Second Edition, The Clay Society of Japan, pp. 576-577, Gihodo Publishing Co., Ltd.), the methylene blue adsorption method (Japan Bentonite Industry Association standard test method, The cation exchange capacity (CEC) of the layered compound is measured by a method such as JBAS-107-91), and further the structure is analyzed by electron beam diffraction from the observation with a transmission electron microscope or the structure by the Libert method of powder X-ray analysis. The lattice constant is determined from the result of the analysis, and based on these results, it is calculated as the charge of the interlayer ion per unit lattice.

Further, as the swelling silicate in the present invention, a single crystal particle having an average particle diameter of 2 μm or more is applied. The particle size of conventional smectite crystals is about 0.0
The particle size of the swellable silicate of the present invention is very large, which is 5 μm, and the upper limit of what is called “clay” is 2 μm as described above. It does not exist. As described above, in the present invention, since the particle size is extremely large, the aspect ratio becomes large, and it becomes possible to dramatically improve the heat resistance and rigidity of the composite resin composition using the same. When measuring the particle size of smectite crystals, this is very small, the particle size is less than or equal to the wavelength of light, and since it has the property that the interlayer is easily cleaved by a solvent such as water, The sedimentation type particle size measuring method and the light scattering method are not suitable because an accurate particle size cannot be measured. Therefore, a method of directly observing the a- and b-axis directions of the crystal with a transmission electron microscope and a scanning electron microscope and obtaining the ratio from the major axis to the minor axis is adopted. Such a swelling silicate is produced by using a belt type high pressure press or a synthesizing device such as a piston cylinder at a special high temperature and high pressure of 1000 ° C. or higher and 3 GPa or higher. "FORM
ATION OF SMECTITECRYSTALS AT HIGH PRESSURES AND TE
MPERATURES (H.Yamada et al., Clays & Clay Minerals,
42, 674-678 (1994)).

The lipophilic inorganic filler of the present invention is obtained by intercalating an organic cation with such a peculiar swelling silicate. The kind of the organic cation used in the present invention is not particularly limited, but it is an aliphatic primary amine, an aliphatic secondary amine, an aliphatic tertiary amine and their chlorides, an aliphatic quaternary ammonium salt, an amine. A compound, an amino acid derivative, or a positively charged organic compound such as a phosphonium salt is preferable, and a quaternary ammonium salt having at least one chain having 4 or more carbon atoms is more preferable. Specifically, tetrabutylammonium ion, tetrehexylammonium ion, dihexyldimethylammonium ion, dioctyldimethylammonium ion, hexatrimethylammonium ion, octatrimethylammonium ion, dodecyltrimethylammonium ion, hexadecyltrimethylammonium ion, octadecyltrimethylammonium ion , Docosenyltrimethylammonium ion, hexadecylammonium ion, tetradecyldimethylbenzylammonium ion, octadecyldimethylbenzylammonium ion, dioleyldimethylammonium ion, polyoxyethylenedodecylmonomethylammonium ion, alkylaminopropyl quaternary compound and the like. .

The ion exchange reaction in which the organic cation is intercalated between the layers of the swelling silicate is performed by sufficiently swelling the powder of the swelling silicate with water, alcohol or the like, adding the organic cation, and stirring the mixture. It is made by substituting the exchangeable metal ions between the layers of the swelling smectite crystal with organic ions to make them hydrophobic (lipophilic). The lipophilic inorganic filler can be obtained by subsequently repeating washing and filtration to sufficiently remove the unsubstituted organic cation and drying.

The amount of organic cation added at this time is the amount of exchangeable metal ions (C) per unit weight of the layered silicate.
It is preferable to add such that the ion exchange ratio of the number (equivalent) of organic cations to EC) is 0.3 to 1.0, and the ion exchange ratio is 0.4 to 0.8. Is more preferable. If the ion exchange ratio is less than 0.3, a lipophilic inorganic filler in which organic cations are uniformly intercalated between layers cannot be obtained because the amount of organic cations is small, and thus the physical properties of the composite resin composition are stabilized. No
If it is higher than 1.0, the amount of organic cations will increase, so that it will cause a wax-like action in the composite resin composition, thus lowering the heat resistance. The ion exchange ratio of the lipophilically treated inorganic filler can be determined by the following method. The cation exchange capacity (CEC) per 100 g of the layered silicate is obtained in advance by the above method, and the equivalent weight of the organic molecule adsorbed per 100 g of the layered silicate is suggested. Obtained from the weight loss due to the decomposition of organic matter in the measuring device. The ion exchange ratio at that time is shown by the following equation.

[Equation 1]

The amount of organic cation in the obtained lipophilic inorganic filler is determined by the amount of the inorganic component (swelling silicate) 10
Expressed as an organic cation equivalent relative to 0 g, it is 25 to 19
It is preferably 5 meq / 100 g, 50 to 150
It is more preferable if it is milliequivalent / 100 g. 25 meq /
If it is less than 100 g, it does not exhibit good dispersibility when dispersed in a synthetic resin, so that the mechanical strength and heat resistance of the composite resin composition are insufficiently improved, and 195 meq / 100
When it is larger than g, the organic cation causes a wax-like action in the composite resin composition and reduces heat resistance, which is not preferable.

The lipophilic inorganic filler of the present invention is used as a composite resin composition dispersed in a synthetic resin composition. A thermoplastic polymer and a thermosetting polymer are applied as the resin composition in which the lipophilic inorganic filler is dispersed. For example, as the thermoplastic polymer, high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene copolymer, ethylene vinyl acetate copolymer Polymers, ethylene-methacrylate copolymers, polyolefin resins such as ionomer resins, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide resins such as amorphous polyamide and polymethacrylimide, and / or copolymers thereof, Polyester resins such as aliphatic polyester, aromatic polyester, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polystyrene, styrene-acrylonitrile copolymer, styrene-acrylonitrile Butadiene copolymer, styrene such as polyacrylonitrile, acrylonitrile resin, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-hexene-copolymer, styrene-ethylenebutene terpolymer, ethylene-vinyl acetate copolymer Examples thereof include polymers, ethylene-methacrylate copolymer polycarbonates, polyphenylene ethers, polyacetals, polysulfone resins, polyvinylidene chloride, polyvinylidene fluoride, and other halogen-containing resins. These may be a polymer alloy alone or in a combination of plural kinds. Examples of the thermosetting polymer include epoxy resin, phenol resin, unsaturated polyester resin, melamine resin, urethane resin and urea resin.

[0019]

EXAMPLES Examples of the present invention will be shown below, but the present invention is not limited to these examples.

First, the following fillers 1 to 7 were prepared. The fillers 1 to 4 correspond to the lipophilic inorganic filler of the present invention, and the fillers 1 to 3 are particularly preferable.

[Filler 1] As a raw material, Na ₂ CO ₃ , A
l ₂ O ₃ , MgO, and SiO ₂ were used, and after blending with a smectite composition, a belt high pressure press was pressed at 1000 ° C. and 3 GPa.
Pressurized, held for 20 minutes and quenched, the structural formula is [Na _0.4 (Al _1.61
Mg _0.33 ) Si ₄ O ₁₀ (OH) ₂ ] high pressure synthetic montmorillonite crystals were obtained. According to a transmission electron microscope observation, the particle size of the present single crystal particles has a particle size distribution of 9.5 to 80.3 μm,
The average particle size was 18 μm. The CEC was 100 meq / 100 g, and the charge density was 140Å ² / charge. 50 g of this high-pressure synthetic montmorillonite crystal was dipped in a beaker containing distilled water and stirred at about 60 ° C. while being quaternary ammonium salt octadecyltrimethylammonium chloride (Nippon Oil & Fat Co., Ltd. “Nissan cation”).
Aqueous solution was added and stirred well to prepare a homogeneous suspension. The mixing ratio of both was adjusted so that the ratio of the number of organic cations / the number of sodium ions between the high-pressure synthetic montmorillonite crystal layers was 1.0.

This suspension was washed, centrifuged, freeze-dried and then pulverized to be used as an intercalation compound. X-ray analyzer (Science, RINT200) for confirmation of intercalation
0) was used to measure the bottom spacing d (001) of the swelling silicate by the powder X-ray diffraction method.
In order to confirm the ion exchange ratio of the quaternary ammonium salt, thermogravimetric measurement was performed using a suggestive heat / thermobalance measurement (Rigaku, TAS200). In the powder X-ray diffraction measurement, the bottom spacing of the swelling silicate was 10Å to 3 due to the intercalation of octadecyltrimethylammonium chloride.
It was confirmed to increase to 7Å. Further, thermogravimetric measurement was performed to confirm the ion exchange ratio between the metal cation and the organic cation between the layers. As a result, the ion exchange ratio was 0.7 and the amount of octadecyltrimethylammonium was
It was 70 meq / 100 g with respect to the inorganic component of the swelling silicate. The above results are summarized in Table 1.

[Filler 2] In Filler 1, tetrabutylammonium chloride as an organic cation was intercalated between layers.

[Filler 3] In the filler 1, the amount of organic cation added is 2 in the aqueous solution in which the swelling silicate is dispersed.
A lipophilic inorganic filler was prepared with a volume of 00 meq / 100 g.

[Filler 4] The amount of organic cation is 10 milliequivalent in the aqueous solution in which the swelling silicate is dispersed in the filler 1.
/ 100 g was added to prepare a lipophilic inorganic filler.

[Filler 5] In Filler 1, the layered silicate has a crystal grain size of less than 0.2 μm and a CEC of about 90.
Using natural montmorillonite (Kunimine industry (Kunipia F)) with meq / 100g, charge density of 140Å ² / charge and structural formula of [Na _0.33 (Al _1.67 Mg _0.33 ) (Si ₄ O ₁₀ ) OH ₂ ]. The same treatment as that for the filler 1 was performed.

[Filler 6] In the filler 1, the swelling silicate has an average crystal particle diameter of about 12 μm, a CEC of about 234 meq / 100 g, and a charge density of 49Å ² / charge.
A treatment similar to that of the filler 1 was performed using a fluorine-type tetrasilicon mica (Topy Industry “DP-DM”) having a structural formula of [NaMg _2.5 (Si ₄ O ₁₀ ) F ₂ ].

[Filler 7] The swelling silicate used as the filler 6 was pulverized to have an average particle diameter of 1.3 μm, and the same treatment as that of the filler 1 was performed.

[0029]

[Table 1]

Each composite resin composition shown below was prepared using each of the above-mentioned fillers, and AS was prepared from the composite resin composition thus obtained.
According to the TM standard, a test piece was prepared by press molding with a bending elastic modulus and thermal deformation test die. Flexural modulus (kg / cm ² ) of the obtained composite material, Izod impact test (kg · cm
/ Cm ² : 23 ° C) and the heat distortion temperature (° C) were measured. The measurement results are shown in Table 2. The flexural modulus is ASTM D7
90 (dry state, 23 ° C., 2.5 mm / min). Izod impact test ASTM D256 (dry state, 2
(3 ° C). The heat distortion temperature is AST
According to MD648, 0.0464kg / m
As the fiber stress of m ² (66 psi) acts,
A load is applied to the center of the test piece for 5 minutes, 2 ± 0.2 ° C / min
The temperature was raised at the rate of.

Example 1 The lipophilic inorganic filler of the filler 1 prepared above and a synthetic resin were kneaded. The synthetic resin is a thermoplastic resin and has a melt viscosity (temperature: 250 ° C.,
A polyamide 6 (“Novamid” manufactured by Mitsubishi Engineering Plastics Co., Ltd.) having a shear rate of 100 sec ⁻¹ (measured by a flow tester) of 10,000 poise was used. To 95% by weight of this polyamide 6, 6.1% by weight (inclusive, swelling silicate component: 5.0% by weight) of the above lipophilic inorganic filler was added, dry blended beforehand with a Henschel mixer, and twin screw extrusion. The mixture was heated and kneaded at 260 ° C. with a machine (“Laboplast Mill” manufactured by Toyo Seiki Co., Ltd.) to obtain a composite resin composition.

Example 2 6.1 wt% of the filler 2 and 95 wt% of polyamide 6 were mixed and kneaded, and the same treatment and evaluation as in Example 1 were performed. [Example 3] Filler 1 and melt flow rate (MFR,
According to JIS K6758, load 2.16 kg, temperature 230 ° C) 38 g / 10 min, C _{E / M} 15% polypropylene block copolymer (Showa Denko Mfg. "Show Allomer M
K810 ") was used to perform the same treatment and evaluation as in Example 1.

Example 4 The same treatment and evaluation as in Example 1 were carried out except that the filler 3 was used. [Example 5] The same treatment and evaluation as in Example 1 were carried out except that the filler 4 was used.

Comparative Example 1 The same treatment and evaluation as in Example 1 were carried out except that the filler 5 was used. [Comparative Example 2] The same treatment and evaluation were performed using the lipophilic inorganic filler as the filler 5 and the polypropylene used in Example 3. [Comparative Example 3] The same treatment and evaluation as in Example 1 were carried out except that the filler 6 was used. [Comparative Example 4] The same treatment and evaluation as in Example 1 were carried out except that the filler 7 was used.

[0035]

[Table 2]

From Table 2, the lipophilic inorganic filler used in this example is a composite resin which is superior in flexural modulus, Izod impact strength and heat distortion temperature to the lipophilic inorganic filler of the comparative example. It can be seen that the composition makes possible.

[0037]

The lipophilic inorganic filler of the present invention, when dispersed in a synthetic resin composition, has good dispersibility even with a small amount of organic cations and can increase the aspect ratio. Further, a composite resin composition having heat resistance and excellent impact resistance can be realized.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kenshi Tamura 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Inside the Kawasaki Resin Research Laboratory, Showa Denko KK (72) Teruo Hosokawa 3 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa -2 Showa Denko KK Kawasaki Resin Research Laboratory (72) Inventor Hirofumi Inoue 3-2 Chidori-cho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Showa Denko Corporation Kawasaki Resin Research Laboratory (72) Inventor Yoshihiro Mogi Chidori, Kawasaki-shi, Kanagawa 3-2 Machi Showa Denko Co., Ltd. Kawasaki Resin Research Laboratory

Claims (4)

[Claims] 1. The general formula is represented by the following formula, the average particle size of single crystal particles is 2 μm or more, and the charge density is 70 to 250Å ² /
A lipophilic inorganic filler comprising an organic cation intercalated into a swelling silicate having a charge smectite structure. [A _a (X _b Y _c ) (Si _4-d Al _d ) O ₁₀ (OH
_e F _2-e )] where 0.2 ≤ a ≤ 0.7, 0 ≤ b ≤ 3, 0 ≤ c ≤ 2, 0
≦ d ≦ 4, 0 ≦ e ≦ 2, A is an interlayer exchangeable metal ion, and is at least one cation selected from the group consisting of alkali metal ions and alkaline earth metal ions, and X Y is a cation that enters the octahedron formed in the smectite structure, and X is Mg, Fe, Mn, N.
At least one of i, Zn, and Li, Y is Al,
It is at least one of Fe, Mn, and Cr. 2. The organic cation is a primary to tertiary amine salt, quaternary ammonium salt, or amino acid salt, and the swelling silicate is hydrophobized by intercalation of the organic cation between the layers. The lipophilic inorganic filler according to claim 1, wherein 3. The metal cations between the swelling silicate layers are ion-exchanged with organic cations, the ion exchange ratio is 0.3 to 1.0, and the amount of organic cations is 25 to 195 meq / 100 g. The lipophilic inorganic filler according to claim 1 or 2, characterized in that it is present. 4. A composite resin composition, wherein the lipophilic inorganic filler according to claim 1 is dispersed in a synthetic resin composition.