JPH09241918A - Fibrous composition containing composite metallic titanate fiber and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject composition, useful as a reinforcing material for a structural material, especially a dielectric continuous filament, etc., by dispersing a composite metallic titanate having toughness in a specific state in an organic polymer. SOLUTION: This organic fibrous composition comprises a composite metallic titanate fiber, oriented in the fiber axial direction and dispersed in an organic polymer. The fibrous composition is obtained by orienting and supporting the composite metallic titanate fiber in the organic polymer having spinnability in an organic polymer fiber by a method for adding and mixing the composite metallic titanate fiber in the organic polymer having the spinnability and forming the metallic titanate fiber into a continuous filament, etc., The resultant composition is useful as a part of electronic apparatuses such as a dielectric cloth for substrates, etc., from the viewpoint of reinforcing properties and dielectric characteristics thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous composition containing composite metal titanate fibers and a method for producing the same, which is a long fiber utilizing the toughness and electrical characteristics of metal titanate fibers. , Mainly to structural materials,
In particular, it aims to provide dielectric long fibers.

[0002]

2. Description of the Related Art In general, inorganic fibers in which fibers are oriented in the fiber axis direction are used as structural materials for reinforcing materials for improving toughness, and barium titanate and other ferroelectric oxides are It is applied to electronic devices such as capacitors, resonators, and substrates. The composite metal titanate fiber can be produced, for example, by the method described in JP-A-6-279025 developed by one of the applicants of the present invention.

As a method for molding an inorganic fiber, there is a method by melt spinning as found in glass fiber, alumina silica fiber and the like. A so-called sol-gel method is known as a method of obtaining inorganic fibers without requiring high temperatures as in melt spinning. In order to impart spinnability to a hydrated sol of an organoaluminum compound, a water-soluble polymer or water glass is added. And sintering the spun. Further, for dielectric long fibers such as barium titanate, various studies such as a production method by a sol-gel method have been added.For example, after soaking alginate fibers starting from sodium alginate in barium chloride and titanium trichloride solution, The method of heating and baking is also found in academic literature. However, in each case, the fiber length is short, the fiber orientation is low, and it is far from the filament (long fiber).

[0004]

If a filament having high toughness, excellent reinforcing property and dielectric properties can be produced, it can be applied as a new electronic material. As the form of the filament, the composite metal titanate fiber may be oriented and dispersed in the organic polymer, or may be oriented and dispersed in the carbon fiber in which the organic polymer is carbonized. Further, only the composite metal titanate fiber may be a sintered filament without disturbing the orientation of the fiber. However, it seems that filaments composed of such composite metal titanate fibers have not been obtained yet. The present invention has been made for the purpose of obtaining a filament of a composite metal titanate fiber or a staple having a relatively large fiber length obtained from the filament and establishing a manufacturing method thereof.

[0005]

A fibrous composition containing a composite metal titanate fiber obtained in the present invention (hereinafter, simply referred to as a fibrous composition) has a composite metal titanate fiber in the fiber axial direction. It is oriented and dispersed in an organic polymer.
This production method is characterized in that the composite metal salt of titanate is added to and mixed with an organic polymer having spinnability, and the fibers are made longer than the raw fibers by melt spinning or dry or wet spinning. The obtained fibrous composition is an organic fibrous composition that is oriented and supported in organic polymer fibers.

The present invention also provides an inorganic fibrous composition of composite metal titanate fibers. The content is that the composite metal titanate fiber is oriented in the fiber axis direction and sintered, and as a manufacturing means, the composite metal titanate fiber and the inorganic sintering aid are spinnable. It is characterized in that it is added and mixed into the organic polymer having the above-mentioned, and is made into long fibers by melting or dry or wet spinning, and is then fired at a temperature at which the orientation of the composite metal titanate fibers does not disappear.

The composite metal titanate fiber is an amorphous metal titanate crystal having a composition represented by the general formula MO.TiO ₂ (where M represents a divalent metal element). A fibrous material in which TiO ₂ is wrapped in a composite and integrated form, in which the molar ratio of the divalent metal M to Ti is in the range of 1: 1.05 to 1.5, and the fiber major axis ratio is 10 or more. So, for example, M is Ba, S
R, Ca, Mg, Co, Pb, Zn, Be, and Cd can be mentioned.

As the organic polymer, any one that can be melt-spun such as polyolefin, nylon and polyester, one that can be dry-spun such as a nitrocellulose polymer, and one that can be wet-spun such as polyvinyl alcohol can be used.

As the inorganic sintering aid, those generally referred to as inorganic glass materials are preferable, and in addition to SiO ₂ , Al ₂ O ₃ , TiO ₂ , B ₂ O ₃ , ZnO, CaO-Al ₂ O ₃ -Compound metal titanate with oxide such as P ₂ O ₅ type glass mixed with fiber and organic polymer and retain fiber morphology even after firing the filament obtained by spinning, and complex metal titanate It is essential for spinning under conditions in which the orientation of the fibers is not impaired. The addition amount of the inorganic sintering aid can be freely changed depending on the required performance of the fibrous composition, but it is set within a range that does not impair the spinnability and maintains the shape stability after firing. Usually, the mixing ratio of the composite metal titanate fiber and the inorganic sintering aid is 3:97 to 97: by weight.
It is advisable to add one or a mixture of two or more of the above-mentioned inorganic sintering aids in the range of 3, preferably 10:90 to 90:10. The firing temperature is usually in the range of 300 to 1,400 ° C., preferably 400 to 1,300 ° C., and set within the range in which the orientation of the composite metal titanate fiber is not impaired.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The fibrous composition of the present invention will be described in detail below with reference to specific examples. Examples 1 to 4 Composite barium titanate as composite metal titanate fiber was prepared by the following method. That is, fibrous titania hydrate (TiO ₂ 1 / 2H ₂ O, average fiber length 12 μm, average fiber diameter
0.3 μm) 2 parts was dispersed in 100 parts of deionized water, pH was adjusted to 9 by adding ammonia water while stirring, and then 26 parts of 20 wt% barium acetate aqueous solution and 15 wt% ammonium carbonate aqueous solution 17 Parts were dropped separately at the same time. The dropping was performed at room temperature with stirring for 60 minutes. At that time, every 10 minutes
The pH was confirmed, and the pH was adjusted to 8 to 10 with aqueous ammonia. After finishing the dropping, adjust the liquid temperature to 70 while continuing to stir.
The temperature was raised to 0 ° C., stirring was continued for 30 minutes, and then filtered, washed with water, and dried to obtain 6 parts of a white fibrous substance. From the results of X-ray diffraction, infrared absorption spectrum (IR) and scanning electron microscope (SEM) observation, this fibrous substance retains the fibrous shape of the fibrous titania compound as the raw material fiber and determines the average fiber length. The size was about 10 μm, the diameter was about 0.5 μm, and the average aspect ratio was about 20. Barium carbonate is deposited on the surface and Ba / T
It was found to have a composition of i = 0.9 / 1 (molar ratio). This fibrous substance was transferred to a magnetic crucible and heat-treated at 950 ° C. for 2 hours in the air atmosphere to obtain a composite barium titanate fiber made of a white fibrous substance.

As the organic polymer, a nitrocellulose polymer (321 manufactured by Cemedine Co., Ltd., the polymer content is 25%, and the solvent is alcohol is 75%) is used. Using these composite metal titanate fibers and organic polymers, four types of slurries were prepared in which the amount of composite metal titanate fibers was changed to 50, 60, 70, 80%. This slurry was continuously injected using an injection device (digital dispenser, Model 1500XL, manufactured by EFD, USA) with an injection pressure of 70 psi and a nozzle diameter of 0.6 mm.
The tensile strength and elongation of the prototype organic long fibrous composition were measured. The results are shown in Table 1. The equipment is Shimadzu's Autograph AG1000B, sample length 5 cm, pulling speed 5 m
It was measured under constant temperature and humidity of m / min, temperature of 25 ± 2 ° C. and humidity of 65 ± 3%. The dielectric constant was measured by a method according to JIS K-6911.

[0012]

[Table 1]

By using the slurry injecting device, the slurry can be continuously ejected and the long fibers can be produced. As for the appearance of the prepared fibrous compositions of Examples 1 to 3, the filamentous clean organic fibrous compositions were obtained as shown in FIGS. Table 1 shows the measurement results of the tensile strength, elongation, and relative dielectric constant of the fiber. A long fiber material having a tensile strength of about 230 gf and a relative dielectric constant of 10 to 60 was obtained.

Further, an SEM photograph of the organic fibrous composition comprising the long fibers, which was calcined at 1,000 ° C. for 6 hours to give an inorganic fibrous composition, is a composite metal titanate fiber content of Example 1 of 50. % Samples are shown in FIGS. 4 (a) and 4 (b). Although the orientation of the composite metal titanate fiber in the length direction of the fiber is recognized, the strength of the fiber itself is significantly reduced because it is not sintered, and the shape of the long fiber cannot be maintained due to brittleness when force is applied. It was a thing.

Comparative Examples 1 and 2 The physical properties of the spun fiber containing only nitrocellulose used in Example 1 in Comparative Example 1 are shown in the lower row of Table 1. As a matter of course,
The relative permittivity was as low as 3.1. The results are shown in the latter part of Table 1.

Examples 5 to 9 The same barium titanate fibers as in Examples 1 to 4 were used as the composite metal titanate fiber as the raw material. The organic polymer is also the nitrocellulose-based polymer (cemedine) having the mixing ratio of Example 3.
321, polymer content 25%, solvent is alcohol 7
5%) was used. Furthermore, as an inorganic sintering aid, SiO ₂ , B
_{A 2} O ₃ based glass composition was added. The composition is shown in Table 2. SiO
_A silica oligomer (HAS-6 manufactured by Colcoat) was used as the ₂ source, and phenylboric acid was used as the B ₂ O ₃ source in Examples 6 and 7.
The to 9 of B ₂ O ₃ source using boric acid. A slurry was prepared by using these composite barium titanate fibers, an organic polymer, an inorganic sintering aid, glycol and the like. This slurry was continuously injected using an injection device (digital dispenser, Model 1500XL, manufactured by EFD, USA) with an injection pressure of 70 psi and a nozzle diameter of 0.6 mm. The firing of long fibers is
It was carried out in an electric furnace at a predetermined temperature for 0.5 to 6 hours. After firing, the fiber was observed by SEM to determine the sinterability and the relative dielectric constant. Table 2 shows the relative dielectric constant of the fiber composition before and after firing.

[0017]

[Table 2]

Here, the long fibers of the sample of Example 8 and 10
SEM photographs after firing at 00 ° C. for 6 hours are shown in FIGS. Sintering of the composite barium titanate fiber was observed, the shape of the long fiber was maintained, and the relative dielectric constant was as shown in Table 2.
A sufficient relative dielectric constant of 28 was obtained. That is, the effect of the inorganic sintering aid was confirmed.

Examples 10 to 19 In addition to the composite barium titanate fibers of Examples 1 to 9, strontium of Examples 10 and 11, calcium of Examples 12 and 13 and Examples 14 and 15 were used as other metal fibers. Magnesium of Example 1 and lead of Examples 16 to 19 were changed by changing the organic polymer and the inorganic sintering aid. Table 3 summarizes the results.

[0020]

[Table 3]

In Table 3, the weight ratio of the metal titanate fiber and the inorganic sintering aid was 90:10, and the weight ratio of these inorganic substances and the organic polymer was adjusted to 70:30.

Melt spinning of polyethylene in Examples 14 and 15 was carried out under the following conditions. Magnesium titanate fiber 70
Part, high-density polyethylene 30 with a melting point of 130 ° C and a softening point of 126 ° C
Melted and mixed at 185 ° C., extruded, and stretched about 5 times to obtain a filament having a fineness of about 510 denier. The addition system of SiO ₂ —B ₂ O ₃ as the inorganic sintering aid in Example 15 is also a mixed system of 70 parts of inorganic material and 30 parts of polyethylene.

Wet spinning from the polyvinyl alcohol polymer mixed system in Examples 18 and 19 was carried out as follows. The composition ratio is 70:30 as the weight ratio of the inorganic substance to the organic polymer as in the above melt spinning. As the polyvinyl alcohol, a 15% aqueous solution of PVA117 manufactured by Kuraray Co., Ltd. was used, and a metal titanate metal salt fiber or a mixture thereof with an inorganic sintering aid in the above ratio was used as a spinning bath at an extrusion pressure of 1.7 Kg / cm ^2. An organic fibrous composition composed of filaments having a fineness of 500 denier was obtained by extruding into a 32% aqueous solution of Na ₂ SO _{4 at} 60 ° C., washing with water while stretching 3 times, and washing. The mixed inorganic sintering aid was further fired at 1,100 ° C. to obtain an inorganic fibrous composition.

As is clear from the data in Table 3, it was possible to make the fibers long, and the system in which the inorganic sintering aid was mixed maintained the fiber shape even after firing. In addition, from the SEM photograph, these long fibers had good orientation of the metal titanate fibers, and showed a good relative dielectric constant.

[0025]

INDUSTRIAL APPLICABILITY The fibrous composition of the present invention is a long fiber in which composite metal titanate fibers are oriented in the fiber direction, and in view of its reinforcing property and dielectric property, it can be used as a dielectric cloth or dielectric for a substrate or the like. It is very effective as a part of electronic equipment such as a transparent glass cloth.

[Brief description of drawings]

1 is a photograph of long fibers obtained in Example 1. FIG.

FIG. 2 is a photograph of the long fibers obtained in Example 2.

FIG. 3 is a photograph of the long fibers obtained in Example 3.

FIG. 4 is an SEM photograph showing the fine structure of the filaments after firing obtained in Example 1, (a) being 100 times and (b) being 5,000 times.

5 is an SEM photograph showing the fine structure of the filament after firing obtained in Example 8, (a) being 100 times and (b) being 5,000 times. FIG.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location D01F 6/92 301 D01F 6/92 301M 9/14 9/14 9/16 9/16 9/21 531 9/21 531 (72) Inventor Minoru Aki 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd., Tokushima Research Institute (72) Masayoshi Suzue 463 Kagasuno, Kawauchi Town, Tokushima City, Tokushima Prefecture Otsuka Chemical Co., Ltd. Company Tokushima Research Institute (72) Inventor Yoshiya Miura 3-1-1 Tsushimachu, Okayama City, Okayama Prefecture Okayama University

Claims (4)

[Claims] 1. An organic fibrous composition containing a composite metal titanate fiber in which the composite metal titanate fiber is oriented in the fiber axis direction and dispersed in an organic polymer. 2. An inorganic fibrous composition containing composite metal titanate fibers in which composite metal titanate fibers are oriented in the fiber axis direction and dispersed in a glassy matrix. 3. A composite metal titanate characterized in that the composite metal titanate fiber is added to and mixed with a spinnable organic polymer and spun to make a longer fiber than the raw material composite metal titanate fiber. A method for producing a fibrous composition containing fibers. 4. A composite metal titanate fiber and an inorganic sintering aid are added and mixed into a spinnable organic polymer, and after spinning to form a fiber, the raw material composite metal titanate fiber is oriented in the fiber axis direction. A method for producing a fibrous composition containing a composite metal titanate fiber, wherein the fibrous composition is fired at such a temperature that does not disappear.