JPH06340768A - Composite material and its production - Google Patents

Abstract

PURPOSE:To produce a light-weight composite material deformable in a certain extent at a normal temperature, having excellent gas barrier properties and water resistance. CONSTITUTION:P2O5-PbCl2-SnCl2-based or P2O5-PbO-SnCl2-based glass and an organic polymer compound both melt-mixable at 100-300 deg.C are melt-blended to produce a glass-organic polymer compound composite material.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composite material comprising glass and an organic polymer compound and a method for producing the same. More specifically, the present invention relates to a glass-organic polymer compound composite material which is excellent in properties of the composite material such as water resistance and is safe and practical in manufacturing the composite material, and a manufacturing method thereof.

[0002]

2. Description of the Related Art Glass and organic polymer compounds (for example, plastics) as materials have been widely used in various fields of daily society, but it is well known that these materials also have physical defects. Is.

For example, glass is chemically stable and has excellent properties such as transparency and gas barrier property, but on the other hand, it is fragile and easily broken, heavy, and difficult to deform (hard to bend). ) Etc. have been pointed out.

On the other hand, although plastic is generally lightweight and can be bent, it is generally easy to absorb odor and its gas barrier property is not always sufficient. The problem of poor gas barrier property is particularly noticeable in a molded product having a thin wall thickness. Further, it can be said that the chemical stability is generally significantly inferior to that of glass.

Glass and plastic have hitherto been used in various fields, for example, as containers for various liquid products. Liquid containers used to be made of glass in the past, but due to their weight and strength, some containers are gradually being replaced by plastic ones.

However, since plastic does not have sufficient gas barrier properties, the liquid filled in this container may have its components oxidized by external oxygen, or the carbonic acid of a carbonated beverage may escape to the outside. There were problems, and not all plastic containers were suitable for all liquids.

Therefore, various measures have been taken to improve the gas barrier property of plastics. For example, (a)
Development of plastics with improved gas barrier properties, (b) Method of inserting a gas barrier material (for example, plastic film or metal foil with good gas barrier properties) between plastics to form multiple layers, (c) Plastic On the surface, metal,
A method of forming a thin film of ceramic or the like by vapor deposition has been proposed.

However, these methods are not always satisfactory because the gas barrier property is still not at a satisfactory level, the moldability is insufficient, or the cost is low. In order to solve these problems, a composite material in which glass and an organic polymer compound are mixed has been prepared as a material having both excellent properties of glass and excellent properties of plastic.

As a method of obtaining a composite material obtained by mixing glass and an organic polymer compound, there is a method of mixing finely powdered glass and an organic polymer compound in a molten or fluid state. In order to obtain a composite material in which glass and an organic polymer compound are microscopically mixed by this method, it is considered to use finer glass. The commercially available fine glass has a minimum particle size of at most 10 to 20 microns, but obtaining finer glass than this is technically and economically difficult. Further, when the finely powdered glass and the organic polymer compound are physically mixed, there is a problem that it is not easy to mix the finely powdered glass and the organic polymer compound. This problem can be solved to some extent by modifying the surface of the fine powder glass with a treating agent such as a surfactant. However, the addition of such a treating agent tends to affect the physical properties of the composite material.

To solve this problem, it has been proposed to mix glass and an organic polymer compound in a molten state (see US Pat. No. 3,832,181 and JP-A-2-225343). However, in order to mix the glass and the organic polymer compound in a molten state, the melting point of the glass needs to be sufficiently lower than the oxidation or decomposition temperature of the organic polymer compound. However, when a glass having a high melting point is used, there is a limitation in the selection range of the organic polymer compound used in the production of the composite material, and as far as the present inventors are aware, it is possible to obtain a substantially uniform mixture. It was still insufficient from the viewpoint that it was difficult to obtain a composite material.

In order to solve these restrictions, the present inventors have developed a glass-organic polymer compound composite material using a glass having a low melting point (100 to 250 ° C.) (Japanese Patent Laid-Open No. 3-170558).
issue). The glass used for the composite material according to this prior invention is, for example, a SnF ₂ -P ₂ O ₅ -based or ZnCl ₂ -P ₂ O ₅ -based low-melting glass having a melting point of 100 to 250 ° C. Therefore, in the production of the composite material, the organic polymer compound is not damaged by oxidation or decomposition, and the produced composite material is substantially homogeneously mixed. However, since the low-melting-point glass used contains fluorine, harmful substances such as hydrogen fluoride are likely to be generated in the manufacturing process, and thus there is a problem that sufficient safety management is required in the manufacturing process. Further, when ZnCl ₂ —P ₂ O ₅ -based low melting point glass is selected as a raw material, there is a problem that the final composite material does not have sufficient water resistance. This problem of insufficient water resistance is even fatal when considering the use as a container for storing an aqueous solution. Therefore, under these circumstances, there is still room for improvement for mass production and practical application of the above-mentioned composite material using the low melting point glass.

[0012]

[Problems to be Solved by the Invention]

[0013]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> The glass-organic polymer compound material according to the present invention is a P ₂ O ₅ —PbCl ₂ —SnCl ₂ system or P ₂ O that can be melt-mixed together at a temperature of 100 to 300 ° C.
It is characterized by mixing a _5- PbO-SnCl ₂ based glass and an organic polymer compound in a molten state.

Further, according to the method for producing a glass-organic polymer compound composite material of the present invention, P ₂ O ₅ -PbCl ₂ -SnC which can be melt-mixed together at a temperature of 100 to 300 ° C.
l ₂ system or P ₂ O ₅ —PbO—SnCl ₂ system glass and an organic polymer compound are mixed in a molten state,
It is characterized by dispersing one into the other.

<Effect> The composite material according to the present invention comprises glass and an organic polymer compound dispersed substantially uniformly and finely.

Therefore, such a composite material also has properties peculiar to glass or an organic polymer compound. That is, the composite material according to the present invention is more metric than the glass material and can be deformed to some extent even at room temperature, so that it is hard to break and easy to process. Further, the composite material according to the present invention is chemically more stable than the organic polymer compound itself which is the component.

The manufacturing method of the composite material according to the present invention is 100-
It adopts a temperature range of 300 ° C. Since this temperature range is a temperature range sufficiently lower than the oxidation or decomposition temperature of a general organic polymer compound, it is possible to avoid the organic polymer compound from being deteriorated by heat. In addition, the production method according to the present invention can be carried out simply and in a short time due to the mixing. This can be said to be advantageous in terms of manufacturing cost.

The composite material of the present invention is remarkably excellent in water resistance, and further, in the production thereof, the treatment for safety management is reduced. It has various advantages (compared to the case of using the low melting point glass). Therefore, the composite material according to the present invention can be used for various applications by utilizing its excellent properties.

[Detailed Description of the Invention] <Low Melting Glass> The glass used in the present invention is
P ₂ O ₅ -PbCl ₂ -SnCl ₂ based glass or P ₂
O ₅ is -PbO-SnCl ₂ based glass. The preferred composition of these glasses is as follows. _{(B) P 2 O 5 -PbCl 2 -SnCl} 2 based glass 30 ≦ P ₂ O ₅ ≦ 60 mol% 1 ≦ PbCl ₂ ≦ 55 mol% 1 ≦ SnCl ₂ ≦ 70 mol% (b) P ₂ O ₅ -PbO glass used in -SnCl ₂ based glass 30 ≦ P ₂ O ₅ ≦ 60 mol% 1 ≦ PbO ≦ 30 mol% 1 ≦ SnCl ₂ ≦ 70 mol% present invention, without impairing the effect of the present invention, other than the above Ingredients may be included.

Here, P ₂ O ₅ -PbCl ₂ -SnCl
₂ and the expression P ₂ O ₅ —PbO—SnCl ₂ is in accordance with the convention used in the compositional representation of glass, and the components such as P ₂ O ₅ do not necessarily represent the state in the glass. Not shown, in both expressions P ₂ O
₅ has the meaning of showing the basic skeleton of glass rather than the raw material used for molten vitrification (for example, ammonium phosphate as a raw material to be charged), while PbCl ₂ , S
The input materials for nCl ₂ and PbO are usually these compounds.

The glass used in the present invention is 100
It can be melt-mixed in a temperature range of up to 300 ° C, preferably 150 to 250 ° C. Here, "melt-mixable" means that the viscosity of the glass (and the organic polymer compound) at the time of melting is 10 ⁴ pois or less.

The glass usable in the present invention is
Glass transition point is 70 ~ 200 ℃, preferably 100 ~ 150 ℃,
Glass deformation point 90 ~ 300 ℃, preferably 150 ~ 250 ℃,
Is within the range of.

The glass used in the present invention may be transparent or colored. Further, the glass may be a mixture of plural kinds.

<Organic Polymer Compound> The organic polymer compound used in the present invention can be melt-mixed in a temperature range of 100 to 300 ° C., and has a good dispersion state with the low melting point glass in the above temperature range. Any can be used as long as the above can be obtained. Here, "melt-mixable" means that the viscosity is 10 ⁴ pois or less, as described above.

One example of such an organic polymer compound that can be used in the present invention is plastic and elastomer. The “plastic” in this case also preferably has a certain degree of rubber-like elasticity. On the other hand, the elastomer is preferably one having a certain degree of plasticity such as a thermoplastic elastomer. Further, an ionomer obtained by introducing an ionic bond into a thermoplastic resin is also preferable. Particularly preferred among such organic polymer compounds are polyurethane, polyethylene, ethylene-propylene based elastic polymers such as poly (ethylene-propylene) (random or block copolymers and poly (ethylene-propylene-non-conjugated). Diene), polymethylmethacrylate, ionomers and other ethylene copolymers such as poly (ethylene-methyl acrylate).

<Composite Material> The composite material according to the present invention is 1
Glass that can be melt-mixed together at temperatures of 00 to 300 ° C 1
To 99% by volume and an organic polymer compound 99 to 1% by volume, wherein one of the above-mentioned glass or the above-mentioned organic polymer compound is dispersed as substantially uniformly dispersed particles in the other component. In addition, the glass and the organic polymer compound in the composite material are formed by being mixed in a molten state. In the present invention, the terms “volume” and “volume%” are the volume obtained from the weight and the true density, and the percentage based on that, and are not related to the voids between particles.

The ratio of glass to the organic polymer compound in the composite material can be appropriately determined depending on the intended composite material and the specific application. By changing the ratio of the glass and the organic polymer compound within an arbitrary range, glass is present as dispersed particles, organic polymer compound is present as dispersed particles, or a composite material in an intermediate stage between these. Can be obtained.

<Production of Composite Material> The production method of the composite material according to the present invention comprises 1 to 99% by volume of glass and 99 to 1% by volume of an organic polymer compound which can be melt-mixed together at a temperature of 100 to 300 ° C. It is characterized by mixing in a molten state and dispersing one into the other to produce. Here, "in the molten state, mixing and dispersing one into the other" means that the glass and the organic polymer compound both in the molten state have a dispersed phase of about 10 microns or less, particularly from submicron to several microns. , Is mixed intimately so that one of them is dispersed in the other.

In the present invention, glass and an organic polymer compound are "mixed in a molten state to disperse one into the other."
The glass and the organic polymer compound can be preliminarily mixed in the preceding step, and such premixing constitutes one preferred embodiment of the present invention. This preliminary mixing can be performed, for example, by mixing the glass and the organic polymer compound which are not in the molten state together, or by mixing the glass in the molten state with the organic polymer compound which is not in the molten state. During the preliminary mixing, the glass and / or the organic polymer compound (if they are not in the molten state) are in the form of fine powder (particle size 0.1
It is usually about ~ 3 mm).

In producing the composite material of the present invention, other components, such as PbO-B ₂ O ₃ -based low melting point glass, may be added, if necessary, as long as it does not violate the spirit of the present invention.
A silicon compound, chalcogen-based glass or the like can be used. Therefore, the composite material according to the present invention and the method for producing the same also include those comprising such a purposeful third component and its addition step.

[0031]

EXAMPLES Example 1 (a) As “glass”, P ₂ O ₅ —PbCl ₂ —Sn
Cl ₂ based glass, P ₂ O ₅ : 40 mol% PbCl ₂ : 20 mol% SnCl ₂ : 40 mol% chemical composition is selected, and NH ₄ H ₂ P is used as a raw material.
O ₄ , PbCl ₂ and SnCl ₂ were used.

After melting 50 g of this raw material at 450 ° C. for 30 minutes, it was poured out and rapidly cooled to obtain glass. This glass was crushed into a powder. The physical properties of the obtained glass were as follows. Glass transition point: 145 ℃ Glass deformation point: 163 ℃ Thermal expansion coefficient: 20 × 10 ^-6 Average particle size: Approximately 100 μm

(B) Polyurethane as "organic polymer compound" (trade name "E-2090R" manufactured by Toyobo Co., Ltd.)
It was used. It has a pellet shape with an average particle size of 3-4 mm.

(C) The above (a) and (b) are (1) 5: 9
5, (2) 20:80 and (3) 50:50 (volume ratio) were mixed in a ratio of 160 and each using a kneader (manufactured by Toyo Seiki Co., Ltd., trade name "Labo Plastomill 30C150 type"). , 190 and
The mixture was kneaded at 220 ° C. and a roller rotation speed of 50 rpm for 30 minutes.

Observation of a section of the kneaded material with an electron microscope (the same applies to the following examples) shows that the shape of the glass dispersed in a spherical shape and the shape of the glass dispersed in a fiber in the polyurethane depending on the mixing ratio and the kneading temperature. , And glass and polyurethane were three-dimensionally entangled. The obtained composite material satisfied the desired performance.

Example 2 The glass powder and / or polyurethane pellets obtained in Example 1 were surface-treated in advance with a silicon coupling agent to improve the wettability, and the particle size of the glass dispersed in polyurethane was found. Became smaller.

Example 3 In Example 1, when kneading was performed under reduced pressure, a large shearing force was applied to the glass and the dispersibility of the glass was improved.

Example 4 (a) As "glass", the same glass as in (a) of Example 1 was used. (B) As the “organic polymer compound”, high-density polyethylene (trade name “Mitsubishi Polyethylene” manufactured by Diapolymer Co., Ltd.) was used. It has a pellet shape with an average particle size of 3-4 mm. (C) The above (a) and (b) are (1) 5:95 (2) 20:80
(3) The mixture was mixed at a ratio of 50:50 (volume ratio) and kneaded using the kneader under the same conditions as in Example 1.

The kneaded product had a form in which glass was dispersed spherically in polyethylene and a form in which glass was dispersed in fiber form in polyethylene depending on the mixing ratio and kneading temperature. The obtained composite material satisfied the desired performance.

Example 5 (a) As "glass", the same glass as in (a) of Example 1 was used. (B) As the “organic polymer compound”, methyl methacrylate polymer (reagent from Wako Pure Chemical Industries, Ltd.) was used. It has a pellet shape with an average particle size of 3-4 mm. (C) The above (a) and (b) were mixed at a ratio of 20:80 (volume ratio), and kneaded using a kneader at 190 ° C. and a roller rotation speed of 50 rpm for 30 minutes. The kneaded product had a shape in which glass was spherically dispersed in methyl methacrylate. The obtained composite material satisfied the desired performance.

Example 6 (a) As "glass", the same one as in (a) of Example 1 was used. (B) As the “organic polymer compound”, poly (ethylene-
Methyl acrylate) (trade name “HRP” manufactured by Du Pont-Mitsui Chemicals, Inc.) was used. This has an average particle size of 3-4 m
It has a pellet shape of m. (C) The above (a) and (b) were mixed at a ratio of 20:80 (volume ratio), and kneaded using a kneader at 190 ° C. and a roller rotation speed of 50 rpm for 30 minutes. The kneaded product was poly (ethylene-methyl acrylate),
The glass had a spherically dispersed shape. The obtained composite material satisfied the desired performance.

Example 7 (a) As "glass", the same glass as in (a) of Example 1 was used. (B) As the “organic polymer compound”, an ionomer (purchased from Mitsui DuPont Chemical Co., Ltd., trade name “HIMIRAN”) was used. It has a pellet shape with an average particle size of 3-4 mm. (C) The above (a) and (b) were mixed at a ratio of 20:80 (volume ratio) and then divided, and each mixture was mixed with a kneader to obtain 130
Kneading was carried out for 30 minutes at a roller rotation speed of 50 rpm at 60 ° C, 160 ° C, 190 ° C or 220 ° C. The kneaded product at 130 ° C. was in the form of fibers dispersed in the ionomer. Further, when the kneading temperature was raised, the glass was not spherical but irregularly dispersed at 160 to 220 ° C. This dispersed state was significantly different from the case of using other organic polymer compounds. The obtained composite material satisfied the desired performance.

Example 8 (a) As "glass", P ₂ O ₅ -PbO-SnCl was used.
₂ type glass, P ₂ O ₅ : 40 mol% PbO: 30 mol% SnCl ₂ : 30 mol% chemical composition is selected, and NH ₄ H ₂ P is used as a raw material.
O ₄ , PbCl ₂ and SnCl ₂ were used. This stuff 5
After melting 0 g of the mixture at 450 ° C. for 30 minutes, it was poured out and rapidly cooled to obtain glass. This glass was crushed into a powder. The physical properties of the obtained glass were as follows. Glass transition point: 165 ℃ Glass deformation point: 185 ℃ Thermal expansion coefficient: 21 × 10 ^-6 Average particle size: Approx. 100 μm

(B) As the "organic polymer compound", an ionomer (manufactured by Mitsui DuPont Chemical Co., Ltd., trade name "HIMIRAN") was used. It has a pellet shape with an average particle size of 3-4 mm.

(C) The above (a) and (b) are replaced by 20:80.
The mixture was mixed at a ratio of (volume ratio) and kneaded at 190 ° C. for 30 minutes at a roller rotation speed of 50 rpm with a kneader.

The kneaded product had a form in which glass was dispersed in the ionomer in the form of fibers, or a form in which the glass was dispersed in an irregular shape instead of spherical shape. This dispersed state was significantly different from the case of using other organic polymer compounds. The obtained composite material satisfied the desired performance.

Example 9 Glass powder (about 100 μm) in which the composition of the glass was changed as shown in A to H of Table 1 and an organic polymer compound ionomer (3
~ 4 mm pellets) at a ratio of 20:80 (volume ratio) and a kneader at about 190 ° C and roller rotation speed 50 r.p.
A composite material was prepared by kneading at m. for 30 minutes. After smoothing the surface and immersing it in water for a certain period of time, the eroded state of the surface was observed. The results obtained are shown in Table 1.

The weight loss of each of the composite materials B, C, F and G when immersed in water was measured by the following method. The obtained results are also shown in Table 1. Composite material water resistance measurement method 10 × 10 × 3 (mm) plate-shaped composite material, 24
After the time immersion, the weight reduction rate (% by weight) is measured.

Table 1 Glass composition A B C D E F G H P ₂ O ₅ 30 40 40 30 30 40 40 40 ZnCl ₂ 60 40 SnCl ₂ 30 30 20 10 30 40 PbCl ₂ 10 20 30 40 50 50 PbO 30 20 Organic polymer compound Ionoma- ← ← ← ← ← ← ← ← Composite material water resistance × × ○ ○ ○ ○ ○ ○ Weight reduction rate − 3.0 0.3 − − 0.0 0.4 − In the table, ○ indicates no change, and × indicates that the glass portion was eluted and fine irregularities were observed on the surface.

[0050]

The composite material according to the present invention is lightweight, can be deformed to some extent even at room temperature, is excellent in gas barrier property and water resistance, and the method for producing the composite material according to the present invention is made of fluorine. The fact that no toxic substances such as compounds are generated and it is effective for mass production has been described in the section of [Summary of the Invention].

Claims (3)

[Claims] 1. A P ₂ O ₅ —PbCl ₂ —SnCl ₂ system or P, which can be melt-mixed together at a temperature of 100 to 300 ° C.
_A glass-organic polymer compound composite material comprising a ₂ O ₅ —PbO—SnCl ₂ -based glass and an organic polymer compound mixed in a molten state. 2. The organic polymer compound is polyurethane, polyethylene, poly (ethylene-propylene), poly (ethylene-propylene-nonconjugated diene), polymethyl methacrylate, poly (ethylene-methyl acrylate), or an ionomer. The organic polymer compound composite material according to claim 1. 3. A P ₂ O ₅ —PbCl ₂ —SnCl ₂ system or P, which can be melt-mixed together at a temperature of 100 to 300 ° C.
_A method for producing a glass-organic polymer compound composite material, which comprises mixing ₂ O ₅ -PbO-SnCl ₂ -based glass and an organic polymer compound in a molten state and dispersing one in the other.