JPH03170558A - Composite material and its production - Google Patents

Abstract

PURPOSE:To obtain a composite material which is composed of a uniform dispersion of two components, lighter than glass, difficultly breakable and easily processable by mixing glass and an organic polymer each of which is meltable in a specified range of a relatively low temperature in a molten state and thereby dispersing one in the other. CONSTITUTION:A composite material comprising 10-95wt.% glass (e.g. SnF2-P2O5 or ZnCl2-P2O5 glass) and 5-90wt.% organic polymeric compound (e.g. a thermoplastic elastomer prepared by the blending, polyaddition, polycondensation or graft-copolymerization of a rubber component such as polybutadiene with a resin component such as PS) each of which is meltable at 100-250 deg.C, composed of a dispersion formed by substantially dispersing one of the two components as dispersed particles in the other component, wherein the glass and the organic polymeric compound in the composite material are those formed after they have experienced a molten state. This composite material is lighter than glass and can deform to some extent even at room temperature, so that it can be difficultly breakable and can be easily processed. It is more stable than the organic polymeric compound as a component.

Description

DETAILED DESCRIPTION OF THE INVENTION [Background of the Invention] Technical Field The present invention relates to a composite material made of glass and an organic polymer compound and a method for producing the same.

According to the present invention, a mixture in which glass and an organic polymer compound are finely and substantially uniformly dispersed can be obtained.
The present invention can also be regarded as an invention relating to a method of mixing glass and an organic polymer compound, and a product thereof.

Prior art> Glass and organic polymer compounds as materials (e.g.
Although plastics have been widely used in various fields of everyday life, it is well known that these materials also have physical drawbacks.

For example, glass is chemically stable;
Although it has excellent properties such as transparency and gas barrier properties, on the other hand, it has been pointed out that it has problems such as being brittle, easy to break, heavy, and difficult to shape into a female shape (difficult to bend).

On the other hand, plastics are generally lightweight and bendable, but they generally have a unique odor and have not always been said to have sufficient gas barrier properties. The problem of poor gas barrier properties is particularly noticeable in hollow-shaped products with thin walls. Furthermore, it can be said that the chemical stability is generally significantly inferior to that of glass.

Traditionally, glass and plastics have been used in a number of fields. One such application field is, for example, each Fl! It is used as a container for liquid products. Glass containers used to be the mainstream for liquid products, but due to weight and strength concerns, plastic containers are gradually becoming more popular.

However, since plastic does not have sufficient gas barrier properties, the beverage filled in the container may be oxidized by external oxygen, or the carbon dioxide gas from the carbonated beverage may escape to the outside.

Therefore, a number of measures have been taken to improve the gas barrier properties of plastics. For example, (a) the development of plastics with improved gas barrier properties; (b) a method of inserting gas barrier materials (e.g., plastic films with good gas barrier properties, metallized) between plastic films to create a multilayer structure; (c) A method has been proposed in which a thin film of glass, ceramic, or the like is formed on the surface of plastic by vapor deposition.

However, with these methods, the gas barrier properties are still not at a satisfactory level, or the moldability is insufficient, or they are easily damaged by external shocks or changes in the thermal environment. However, it could not be said that it was necessarily satisfactory from the point of view of cost, etc.

As a method for preparing a composite material made by mixing glass and an organic polymer compound, there is a method of mixing finely powdered glass with an HA polymer compound in a melted or fluid state.

In this method, it is conceivable to use finer glass in order to obtain a composite material in which the glass and the 6-dimensional polymer compound are more microscopically mixed. Commercially available fine powder glass has a particle size of about 10 to 20 microns at most, but obtaining glass even finer than this poses many technical and economical difficulties.

For example, in dry powder frame methods using ball mills, jet mills, etc., the powder frame progresses due to the solidification of glass particles in the mill and the buffering effect of crushing energy due to increased adhesion and cohesiveness between particles due to atomization. In addition, the wet grinding method, which involves grinding in a suspended state, has the problem that the soluble components of the glass (
For example, there are problems in that alkalis, B2O3, P2O5, etc.) are easily eluted and the properties are easily deteriorated, and in any case, it is difficult to avoid increased costs and contamination with impurities.

Also, one of the problems with mixing powdered glass and organic polymer compounds is that it is not easy to mix the powdered glass and organic polymer compounds due to the influence of surface energy due to the increased surface area of the glass. There is. This problem is
A certain degree of resolution has been achieved by surface-modifying the surface of finely divided glass with a treatment agent such as a surfactant.

However, the addition of such treatment agents tends to affect the physical properties of the composite.

[Summary of the Invention] Summary of the Invention The present invention provides a method of finely mixing glass and an organic polymer compound, thereby compensating for the drawbacks of the glass or the organic polymer compound, which are qualitatively different from each other. H different functionality
By employing a specific low-melting point glass and specific mixing conditions, the present invention aims to provide a composite material with a specific low-melting point glass and specific mixing conditions.

Therefore, the composite material according to the invention has an
A composite compound consisting of 10 to 95% by weight of glass and 5 to 90% by weight of an organic polymer compound, both of which can be melted at a temperature of It is characterized in that it is substantially uniformly dispersed in other components as dispersed particles, and that the glass and white polymer compound in the composite material are each formed through a molten state. It is something to do.

Moreover, the manufacturing method of the composite material according to the present invention is 100 to 25
It is characterized in that it is produced by mixing 10 to 95% by weight of a glass that can be melted together at a temperature of 0°C and 5 to 90% by weight of an organic high resolution compound in a molten state and dispersing one in the other. It is something.

Such a composite material according to the present invention is obtained by mixing glass, an organic polymer compound, and potassium L in a molten state, and the glass and organic polymer compound are intimately and finely mixed and dispersed. That's what happens.

Therefore, conventional composite materials made by mixing glass fibers, glass beads, finely powdered glass, etc. with organic polymer compounds in a solid state differ depending on the size of the dispersed particles.
It is thought that the shape of the dispersed particles or their dispersion state are different.

Effect> The composite material according to the present invention has a structure in which the glass and the organic polymer compound are substantially uniform and fine (dispersed particles have a diameter of 0.1 to
(about 10 μm).

Therefore, such composite materials combine many of the properties found in glass and 6'-functional polymer compounds, and as a result, the properties that are generally considered to be disadvantageous in each of the above materials are improved. It is what was done. That is, the composite material according to the present invention is lighter than glass material, and can be shaped into a female shape to some extent even when bowing, so it is easy to process without being damaged. Further, the composite material according to the present invention is chemically stable compared to the organic polymer compound itself as a component thereof.

The method for manufacturing a composite material according to the present invention employs a temperature range of 100 to 250°C.

Since this temperature is sufficiently lower than the oxidation or decomposition temperature of general organic polymer compounds, deterioration of the organic commercial molecular compound can be avoided. By being able to adopt such relatively low temperature conditions, it has become possible to use organic polymer compounds that could not be used conventionally due to problems such as oxidation. Furthermore, the production method according to the present invention has a low possibility of contamination with impurities, and mixing can be carried out easily and in a short time. This can be said to be advantageous in terms of manufacturing costs.

Such a composite material according to the present invention can be used for various purposes by taking advantage of its various excellent properties.

[Specific description of the invention]

Glass> The glass used in the present invention has a temperature of 100 to 250°C.
As long as it is capable of melting in the temperature range of 150 to 200°C, preferably, and that a good dispersion state can be obtained with the polymeric compound (details will be described later) in the above temperature range, it is suitable. can be used. Here, "meltable" means that the viscosity is 104 pois or less. Such a glass that can be used in the present invention has a glass transition point of 50 to 150°C, preferably 70 to 120°C, and a glass sag. point is 90-170℃, preferably 100-150℃
, is within the range of .

In the present invention, preferred glasses include (a) SnF
2-P2O5-based glass (S n F 2 3 about 0 to 80% (% represents weight %. The same applies hereinafter), preferably 50 to 70%, P2
O52O to about 70%, preferably 25 to 50%) (This SnF2-P2O5 glass may contain other components (preferably pbo, PbCl2, PbF2
, AIF3, BaF2, especially PbO, PbC 1 2)
(can contain up to about 25%), and (mouth)
Z n C 1 2po type glass (znCl21
About 5 to 75% 25%, preferably 30 to 70%, about 25 to 85% P2O, preferably 30 to 70%) (this Z n C
The I 2 P 2 O 5-based glass may contain other components (preferably PbO, PbC12, AIF
3, B a F 2, especially pbo, PbC12) at 25
%).

The glass may be transparent or colored, but from the viewpoint of expanding the applications of the composite, it is preferably substantially transparent.

The glass may be a mixture of multiple types.

Organic polymer compound> The organic polymer compound used in the present invention is 100
Any material can be used as long as it can be melted in the temperature range of -250°C, preferably 150 - 200°C, and that a good dispersion state with the glass can be obtained in the above temperature range. Here, "meltable" means that the viscosity is 104 pois or less.

A specific example of such an organic polymer compound that can be used in the present invention is, for example, a plastic or an elastomer. The "plastic" in this case also preferably has a certain degree of rubber-like elasticity. On the other hand, it may be preferable for the elastomer to have some degree of plastic properties, such as a thermoplastic elastomer. Examples of such organic polymer compounds include thermoplastic elastomers (for example, (a) styrene-based, (b) olefin-based, (c) ester-based, (ii) urethane-based, (e)
Vinyl chloride type, (h)boryamide type, (t)fluorine type,
(f) Others).

The above thermoplastic elastomer contains a rubber component (e.g., polybutadiene, aliphatic polyester, aliphatic polyether, IIJ plasticized polyvinyl chloride, fluororubber, etc.) and a resin component (e.g., polystyrene, polyethylene, polypropylene, crystalline polyester, etc.). , crystalline polyamide, fluororesin, etc.) by blending, polyaddition, polycondensation or graft copolymerization.

Composite Material> The composite material according to the present invention is composed of 10 to 95% by weight of glass that can be melted together at a temperature of 100 to 250°C and 5 to 90% by weight of an organic polymer compound, in which one component is A composite material in which the glass or the organic polymer compound is substantially uniformly dispersed as dispersed particles in the other component, and the glass and the organic polymer compound in the composite material are each formed through a molten state. There is something
It is characterized by:

The ratio of glass and organic polymer compound in the composite material can be determined as appropriate depending on the physical properties of the intended composite material and the specific application, but preferably the glass is
80 ffl amount%, organic polymer compound 20 to 80% by weight
Particularly preferably, the glass content is 30 to 70% by weight, and the organic polymer compound is 30 to 70% by weight. By changing the ratio of glass and Hla polymer compound within the above range, it is possible to create composite materials in which glass exists as dispersed particles, organic polymer compounds exist as dispersed particles, or in an intermediate stage between these. Obtainable.

The particle diameter of the dispersed particles is 0.1 to 10μ, preferably 0.1μ to 10μ.
5 to 5μ.

In one preferred embodiment of the composite material according to the present invention, the "organic polymer compound" is a thermoplastic elastomer, and glass is dispersed in the dispersed phase of the thermoplastic elastomer.

<Manufacture of drawn material> The method for manufacturing a composite material according to the present invention involves combining 10 to 95% by weight of glass and 5 to 90% by weight of an organic polymer compound, which can be melted together at a temperature of 100 to 250°C, in a molten state. producing by mixing and dispersing one in the other;
It is characterized by: Here, "mixing in a molten state and dispersing one in the other" means to mix glass and an organic polymer compound, both in a molten state, so that the dispersed phase is on the order of several microns or less, especially submicrons. This refers to dispersing one into the other by intimately mixing the two.

In the present invention, the glass and the organic polymer compound can be preliminarily mixed in a step before "mixing the glass and the organic polymer compound in a molten state and dispersing one in the other", and such A preferred embodiment of the present invention is one in which a preliminary mixing is carried out. This preliminary mixing can be carried out, for example, by mixing non-molten glass and organic polymer compound a, mixing non-molten glass with molten organic polymer compound, or mixing glass in molten state with organic polymer compound in molten state. This can be carried out by mixing the glass and/or the polymer compound that is not in a molten state.In the preliminary mixing, the glass and/or the polymer compound (if they are not in a molten state) are mixed together. It is usually in the form of fine powder (particle size O, about 1 to 3 mm).

In producing the composite material of the present invention, other materials such as PbO-82O3 low melting glass, silicone compound, chalcogen glass, etc. may be used as necessary, as long as they do not go against the spirit of the present invention. Can be done. Therefore, the composite material according to the present invention and the method for producing the same include those comprising such a purposeful third component and its addition step.

Durability test example〉 Large example 1 ■ As the "glass", select a SnF2-P2O5 glass with a chemical composition of 67.2% SnF and 2°32.8% P2O5 (both by weight). , S n F 2 and NH4H2PO4 were used as raw materials. The physical properties of this glass are as follows. Glass transition point: 113°C, glass yield point: 129°C, coefficient of thermal expansion: 260×10 7 After melting this raw material (batch) at 450°C for 15 minutes,
After pouring it out and quenching it, it was crushed into powder.

■ As an "organic polymer compound", process oil (manufactured by Idemitsu Petrochemical Co., Ltd., product name: pw-90) was added to styrene-modified ethylene-propylene block copolymer (manufactured by Kuraray Co., Ltd., product name: KL-2O43). ) 1 : 1
(ffiffi ratio) was added to form an elastomer. The physical properties of the obtained elastomer are as follows. Styrene content = 13% by weight, ratio: 0.89, breaking strength = 122kg/cd, breaking strength:
1110%, hardness (JIS A): 36, thermal decomposition temperature: approximately 300°C.

Next, the above (1) and (2) were mixed at a ratio of 1:0.5 (tifc ratio). Note that this ■ uses particles coarsely ground to a particle size of about 1 mm, while ■ uses pellets (particle size of 1 to 1 mm).
2 mm) was used. This mixture was mixed with a kneader (manufactured by Toyo Seiki Co., Ltd., product name: Labo Blast Mill (30C 150
mold) at 180°C for 30 minutes using a roller rotor (100 r
pm. ) and then formed into a film. This film was bendable and satisfied the desired physical properties.

Length Example 2 ■ The same "glass" as in Length Example 1 (■) was used.

■ As an ``organic polymer compound,'' styrene-modified ethylene-propylene block'' (polymer (manufactured by Kuraray Co., Ltd.),
Product name: KL-2O02) and process oil (manufactured by Idemitsu Petrochemical Co., Ltd., product name: pw-90) at a ratio of 1:1.
(fflm ratio) was added to form an elastomer. The physical properties of the obtained elastomer are
It is as follows. Styrene content: 1:13% by weight, specific gravity: 0.89, breaking strength: 12Okg/cd, breaking elongation: 580%, hardness (JIS A): SO, thermal decomposition start temperature: about 300°C.

Next, the above (1) and (2) were mixed in a ratio of 3=1 (weight ratio), kneaded at 160° C. for 30 minutes in the method of Example 1, and then formed into a film. This film was bendable and satisfied the desired physical properties.

Example 3 ■ As the "glass", SnF2-P2O5pbo glass, SnF2:62. 3%, P
2O5: 37.7% (both weight%) of chemical silk was selected, and S n F 2, NH4H2P were used as raw materials.
O4 and pbo were used. The physical properties of this glass are as follows. Glass transition point: 139°C, glass yield point: 153°C, coefficient of thermal expansion: 275×10 7 After melting this raw material (batch) at 450°C for 15 minutes,
After pouring it out and quenching it, it was crushed into powder.

■ As the "organic molecular compound", the same one as in ■ of Example 1 was used.

Next, the above (1) and (2) were mixed at a ratio of 1:1 (weight ratio), mixed at 200°C for 30 minutes in the same manner as in Example 1, and then formed into a film. This film had M-ability in bending and satisfied the desired physical properties.

Example 4 ■ As the "glass", the same glass as in Example 3 (■) was used.

■ As the "organic polymer compound", the same compound as in Example 2 (■) was used.

Next, the above (1) and (2) were mixed in a ratio of 3=1 (weight ratio), kneaded at 200°C for 30 minutes in the same manner as in Example 1, and then formed into a film. Can this film be folded?
I1 ability, and satisfied the desired physical properties.

Example 5 ■ ZnCl2-P2O5PbO glass was used as the "glass". The composition and physical properties of this glass are as follows. ZnC12: 60%, P
2O5: 30%, PbO: To% (both weight%),
Glass transition point = 133°C, glass deformation point: 155°C, thermal expansion coefficient: 84 x 10 -7 ■ As the "organic polymer compound", the same one as in Example 1 (■) was used.

Next, the above (1) and (2) were mixed in a ratio of 1=5 (weight ratio), kneaded at 200°C for 30 minutes in the same manner as in Example 1, and then formed into a film. This film was bendable and satisfied the desired physical properties.

When this sample was observed with an electron microscope, it was found that 0.2 to 2μ
It was confirmed that the glass particles, which had been refined to a certain extent, were uniformly dispersed in the organic polymer compound (see Fig. 1).

Example 6 ■ ZnCl2-P2O5AIF3 as "glass"
glass was used. The composition and physical properties of this glass are as follows. Z n C 1 2 :6596, p
o 30%, AIF3: 5% (all percentages by weight), glass transition point: 125°C, glass deformation point = 145°C, coefficient of thermal expansion: 2O6X10' ■ As a "white organic polymer compound", The same material as in Example 2 (■) was used.

Next, the above ω and ■ were mixed at a ratio of 1:2 (weight ratio), kneaded at 200° C. for 30 minutes in the same manner as in Example 1, and then formed into a film. This film was bendable and met the desired physical properties.

When this sample was observed under an electron microscope, it was confirmed that glass particles down to a size of about 1 to 3 μm were uniformly dispersed in the organic polymer compound (see FIG. 2).

Example 7 ■ ZnC12-P2O5PbCl as “glass”
Type 2 glass was used. The composition and physical properties of this glass are
It is as follows. Z n C 1 2: 40%, P
2O5: 50%, PbCl2: 10% (both weight%
), glass transition point: 72°C, glass deformation point: 94°C, coefficient of thermal expansion: 106x10-7 ■ As the "organic polymer compound", thermoplastic fluororubber (manufactured by Daikin.1, product name: Daiel Thermoplastic T') -630) was used. The physical properties of this thermoplastic fluororubber are as follows.

Specific gravity: 1.89, breaking strength: 20. 4kg/cd
, breaking elongation: >1000%, hardness (JISA): 61,
Melting point: about 160°C, thermal decomposition onset temperature: about 400°C.

Next, the above (1) and (2) were mixed at a ratio of 1=1 (weight ratio), kneaded at 180° C. for 30 minutes in the same manner as in Example 1, and then formed into a film. This film was bendable and satisfied the desired physical properties.

When this sample was examined under an electron microscope, it was found that it was 0.5 to 2.
It was confirmed that glass particles as fine as μ were uniformly dispersed in the organic polymer compound (see Figure 3).
.

Example 8 A composite material was produced using the following sample and kneading conditions, and the hardness of the obtained composite material was measured.

1 Sample resin: Styrene-modified ethylene-propylene block copolymer (manufactured by Kuraray Co., Ltd., product name: KL-2O43) Plasticizer: Process oil (paraffin type) (manufactured by Idemitsu Petrochemical Co., Ltd., product name: PW- 90) Glass: Sn
F2P205 glass (SnF2
: 70%, P2O5: 30% (all % by weight) 2 Kneading conditions The above resin, i''II plasticizer and glass were kneaded in the proportions listed in Table 1 below.

The kneading conditions are as follows.

Mixer (manufactured by Toyo Seiki Co., Ltd., product name: Labo Blast Mill (3)
0C] at 150°C for 20 minutes with a roller rotor (50 rpm).

3 Measurement results Table 1 4.

[Brief explanation of the drawing]

Figures 1 to 3 are Granules of composite material according to the invention This is an electron micrograph showing child feeding.

Claims (1)

[Scope of Claims] 1. A composite material consisting of 10 to 95% by weight of glass and 5 to 90% by weight of an organic polymer compound that can be melted together at a temperature of 100 to 250°C, wherein one of the components is the above-mentioned Glass or the above-mentioned organic polymer compound is substantially uniformly dispersed in the other component as dispersed particles, and the glass and organic polymer compound in the composite material are each formed through a molten state. A composite material characterized by: 2. The composite material according to claim 1, wherein the dispersed particle size is 0.1 to 10μ. 3. The composite material according to claim 1 or 2, wherein the dispersed particles are glass. 4. Glass is SnF_2-P_2O_5 system or Zn
Claim 1, which is any one of the Cl_2-P_2O_5 system.
, 2 or 3. 5. The organic polymer compound is a thermoplastic elastomer.
Composite material according to claim 1, 2, 3 or 4. 6.Produced by mixing 10-95% by weight of glass and 5-90% by weight of organic polymer compound, both of which can be melted at a temperature of 100-250°C, in a molten state and dispersing one in the other. A manufacturing method for composite materials.