JPH07300539A - Glass/polymer composite and its production - Google Patents

Abstract

PURPOSE: To provide a phosphate-based glass/organic polymer composite material having improved durability.

CONSTITUTION: This material comprises a mixture comprising a matrix material comprising at least one organic thermoplastic or thermosetting polymer, at least one phosphate glass, and at least one water-soluble stabilizer component providing a supply source of metal cations having at least divalent positive charge.

COPYRIGHT: (C)1995,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to highly durable glass /
TECHNICAL FIELD The present invention relates to a polymer composite material and a method for improving durability of the composite material. Generally, in this method, a third component, a solid stabilizer, is added to the glass / polymer composite and this addition causes the glass phase to form an insoluble surface coating in the presence of moisture, ie hydration. A glass / polymer composite having improved durability to is obtained.

[0002]

2. Description of the Related Art Composite materials containing organic polymers are well known in the prior art. Generally speaking, polymer composites, in which the polymer is regarded as a multiphase material of two or more components consisting of continuous phases, are considered to contain fillers or reinforcing agents, the two functions of which often overlap. . Therefore, polymer composites conventionally consist of base polymers containing additives such as plasticizers, colorants, flame retardants, reinforcing fibers and / or whiskers, fillers and stabilizers against heat and / or sunlight. .

Such filled plastic products are commercially available and usually consist of organic polymers covering discrete organic or inorganic particles, flakes, fibers, whiskers, or other shapes of material. These filler materials are included primarily for the purpose of reducing the overall cost of the product without significantly compromising the properties of the polymer. For example, clay and talc are also added as inexpensive fillers. On the one hand, filler materials are included to improve certain physical properties exhibited by the polymer. For example, ceramic or glass fibers are included in the polymeric body to provide strength. The high strength exhibited in such products is primarily due to the strong bond between the inorganic fibers and the organic polymer.

Over the last two decades, research has been conducted into the possibility of forming a composite material composed of an inorganic glass exhibiting a low transition temperature and an organic polymer, preferably the body of which exhibits the combined properties of glass and plastic. Came. An example of that work is described in US Pat. No. 3,732,181 (Rey et al.). As seen therein, the decomposition temperatures of known thermoplastics and thermosets are so low that glass composites in which SiO ₂ is the predominant network or glass former are not used. Therefore, to be workable, the Tg of the glass is below 450 ° C., preferably 35
Lower than 0 ° C. (As is commonly defined, the Tg of a glass is the temperature at which the specific heat and coefficient of thermal expansion increase, accompanied by a sharp drop in viscosity. This temperature is near the annealing point of the glass. Often considered.)
Temperature limitations have led to the use of glasses in which P ₂ O ₅ and / or B ₂ O ₃ constitutes the major glass-forming component. Furthermore, although thermoplastics have been studied primarily for the use of glass-plastic composite products, it has been explained that thermosets obtained as thermosoftening precursors are also workable. Such resins can be blended with glass into composites and reformation and final heat curing can be completed in one operation.

US Pat. No. 3,732,181 discloses that glass in the form of fibers, films, flakes, powders or sheets is combined with a polymer, the composite material of which is compression molded, primary molded, drawn, extruded, hot pressed. ,injection molding,
And 7 general methods of forming the desired shape by various shaping means including spinning. In this patent, the ratio of polymer to glass is based on volume.
The range of 0.1: 99.9 to 99.9: 0.1 is described, but the concentration of glass in the polymer is typically around 5
It also states that it covers a range of -66% by volume.

Prior experience with glass compositions has shown that borate-based and phosphate-based glasses typically exhibit poorer chemical durability and resistance to moisture attack than silica-based compositions, And it has been shown that defects are exacerbated when such glasses are formulated to exhibit lower transition temperatures. For example, low T
Phosphate-based glasses exhibiting g usually degrade when exposed to humid environments and are often hygroscopic in practice. Such lack of resistance to attack by moisture, which is often encountered in phosphate-based glass compositions, is related to the dissolution rate described in US Pat. No. 3,732,181 with respect to the glass used in the working samples. Evidenced by data. Due to this poor chemical resistance and resistance to moisture attack demonstrated by phosphate-based and borate-based glasses with low Tg, both glass and polymers heat-deformable at similar temperatures. The glass-plastic composite products manufactured from are not commercially available to any extent. Therefore, although the glass-plastic composite products known in the prior art are not porous in physical terms, the polymers are permeable to water, which allows water to penetrate into the product. , Thereby coming into contact with the glass particles. Therefore, deterioration rapidly begins due to the high surface properties of the glass flakes, fibers, powders, etc. present in the composite product. This situation becomes more pronounced as the proportion of glass in the composite increases. However, in order to produce a product that exhibits high rigidity, high hardness, and good mechanical strength, the glass component should constitute a high volume fraction in the product.

US Pat. No. 4,079,022 (Ferrarini et al.) Contains 50-72 mol% P ₂ O ₅ and, on its surface, is selected from the group consisting of magnesium, calcium, barium, iron, aluminum, lead and zinc. Disclosed is a glass composition comprising a relatively hydrophilic phosphate glass in which is formed a water-insoluble phosphate of a metal. This patent describes a method of forming an insoluble surface coating by exposing the glass to an alkaline solution containing the metal ions listed above for a time sufficient to form a relatively water-insoluble component on the glass surface. Is also described.

The present invention differs in many respects from the Fellini reference. First of all, the Fellini reference claims a glass composition and a method of treating the glass composition, while the present invention provides a glass / polymer composite (as defined herein). And a method of improving the durability of the glass / polymer composite by providing a means of coating the glass phase with an insoluble layer in the presence of moisture. Second, glass compositions claimed in Fellini patent is comprised of P ₂ O ₅ of 50-72%, the glass phase of the glass / polymer composite is 28-40% of the P ₂ O ₅ It only contains. Finally, the stabilization method of the Fellini reference consists of exposing the glass to an alkaline solution containing metal ions, while the present invention adds the solid stabilizer component directly to the glass / polymer mixture. It consists of a distinguishable process. Rather than forming an insoluble layer as disclosed in the reference, the present invention describes a water soluble stabilizer component in the vicinity of the glass phase surface, which glass surface has the presence of moisture. Below, metal cations are released and then form an insoluble layer in situ.

[0009]

Accordingly, it is an object of the present invention to provide phosphate-based glass / organic polymer composites and methods of making composites that exhibit improved durability and thereby are less hydrated. Was to provide.

It is a further object of the present invention to provide a stabilizer added to glass / polymer composites which significantly slows the reaction of water with phosphate glass and a stabilization method using this stabilizer. there were.

Yet another object of the present invention is to form a protective coating on the phosphate glass phase that substantially limits the entrapment of water in the composite material, thereby making the glass less hydrated. Was to provide the means. Yet another object of the present invention was to provide a glass / polymer composite of the type described above which retains its physical performance properties for extended periods of time.

[0012]

SUMMARY OF THE INVENTION Accordingly, the present invention is a composite material having improved resistance to hydration, and a method of making such a composite material, comprising at least one phosphate glass and at least one phosphate glass. A method comprising admixing an organic thermoplastic or thermosetting polymer and a source of metal cations having a positive or greater positive valence of at least one water soluble stabilizer component. Is disclosed. The amount of stabilizer component is sufficient to improve the moisture resistance of the composite. Preferably, this mixture is composed of the three basic components in the indicated weight ratios: 1-99.5% matrix material; 0.1-95% phosphate glass; and 0.01-40% stabilizer component. The metal cations found in the stabilizer component are preferably Ba ²⁺ , Mg ²⁺ , Ca ²⁺ , A
selected from the group consisting of l ³⁺ , Zn ²⁺ , Sr ²⁺ and Fe ³⁺ .

The unique property of the composite material of the present invention lies in the action between the stabilizer and the phosphate glass. Therefore, as described immediately above, the stabilizer component is 2+ in the presence of moisture.
It is selected to produce metal ions with higher valence. Thus, when stabilizers are present near the surface of the glass phase, their released metal ions are either the insoluble metal phosphate surface layer or the hydrated metal phosphate surface layer that covers the glass surface. To form. This surface layer acts as a barrier that effectively stops or slows the reaction of water with the glass components. The end result is improved durability of the composite material while retaining performance characteristics.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on the embodiments shown in the drawings.

The term composite material as used herein is defined as being made up of separate parts, namely an organic polymer and glass fibers. In particular, in the present invention, the composite material is an engineering polymer filled with low temperature phosphate glass. In other words, there is no interaction between the separate glass and polymer parts in the glass / polymer composite.

The term composite material refers to US Pat. No. 5,043,
It should be distinguished from the term alloy used in 069 (Burn et al.). Alloys are defined therein as glass / polymer materials that exhibit a homogeneous, fine-grained microstructure resulting from the interaction between the phosphate glass phase and the organic polymer phase. In that respect, a homogeneous fine microstructure
It is more well defined.

The present invention discloses a composite material having increased moisture resistance consisting of a mixture of the following components: at least 1.
Matrix material consisting of one organic thermoplastic or thermosetting polymer; at least one phosphate glass; and a metal cation having a positive or positive valence of 2 or more sufficient to improve the moisture resistance of the composite. At least one water soluble stabilizer component that provides a source of ions. In other words, the amount of stabilizer component should be an amount effective to reduce the weight gain of the composite material over time. Preferably,
This mixture consists of the three basic components in the indicated weight ratios: 1-99.5% matrix material; 0.1-95% phosphate glass; and 0.01-40% stabilizer component.

As stated above, the composite material of the present invention preferably contains about 0.1-95% by weight of phosphate glass,
As used herein, the glass is a low temperature inorganic oxide glass having a composition within the following ranges, expressed in mole percent on an oxide basis: at least about total.
65%, 10-55% of ZnO, 28-40% of the P ₂ O _5, 10-
35% R ₂ O, where R ₂ O is 0-25% Li ₂ O,
0-25% of Na ₂ O, and consists of two alkali metal oxides in a ratio of displaying selected from the group consisting of 0-25% of K ₂ O. In addition, a total of 35% of optional ingredients may also be added to the base glass: this optional ingredient is 0-10.
% Al ₂ O ₃ , 0-15% B ₂ O ₃ , 0-15% Cu
₂ O, 0-25% Sb ₂ O ₃ , 0-35% PbO, 0-
35% SnO, 0-5% ZrO ₂ , 0-4% SiO
₂ , 0-20% MgO, 0-20% CaO, 0-20% SrO, 0-20% BaO, 0-10% MnO, 0-10
% Of WO _3, 0-10% of MoO _3, 0-5% of rare earth metal oxides, and is selected from the group consisting of 0-5% F, as where one fluoride analyzed in weight percent Exists. However, the above-mentioned glass compositions have the following further amount restrictions: Al ₂ O ₃ + B ₂
The amount of O ₃ does not exceed 15%, and the amount of WO ₃ + MoO ₃ is 15%
And the total amount of the combination of MgO + CaO + SrO + BaO + MnO does not exceed 20%.

Table I describes a group of preferred glass compositions, expressed in mole percent on an oxide basis, used to prepare the glass / plastic composites of the present invention. Each glass was compounded from oxide, carbonate, and phosphate batch materials. The batch materials were automatically tumble mixed or ball milled and allowed to melt in a silica crucible at temperatures near 1000 ° C for about 3 hours. Since the analytical values for P2O5 were generally a few tenths of a percent lower than the values calculated from the batch, only a small amount of P
It was found that ₂ O ₅ had volatilized.

[0020] Finely ground material is desirable to form the feedstock for mixing, so the melt was poured through a patterned metal roller to form a textured surface that could be easily milled into pieces of a given size. Or more preferably the melt was poured as a fine flow into a cold water bath. This work was called "dregaging". If desired, the glass particles / fragments may be pelletized for ease of handling.

The polymeric matox material, which preferably constitutes about 1-99.5% by weight of the inventive composite disclosed herein, comprises at least one organic thermoplastic or thermosetting polymer. The matrix material used in the examples disclosed later in this specification is a high temperature thermoplastic, especially polyether sulfone (PES). Although this specification does not describe only PES-containing composites, the improvement in durability due to the addition of the stabilizers disclosed herein can be applied to any composite containing phosphate glass and polymer. Considered to be effective. Specific polymers considered to be within the scope of the present invention include polypropylene, polyallyl ether ketone, polyolefin, ABS, polystyrene, polyphenylene sulfide, polyfluoro resin, polyether imide, liquid crystal polyester, polyether ether ketone, polyether ketone. Thermosetting plastics such as polyethyl terephthalate, polybutyl terephthalate, melamine, polyamides, polyphosphazines and polycarbonates. Thermoset plastics such as epoxy resins, silicone resins, polyimides, phenols, and diallyl phthalates are also included within the scope of the invention.

Preferably about 0.01 of the total composite material mixture
To 40% by weight of water-soluble stabilizer component, which provides a source of metal cations having a positive valence of 2 or more, ideally in sufficient amount, thereby forming a complex. The material has improved durability over that exhibited by the unstabilized composite material. In other words, a "stabilized composite" is an improved durability as indicated by a decrease in the percentage weight increase of the composite over time. The amount of water absorbed by the composite material, and ultimately the weight of the low-durability glass component, varies depending on the amount of glass in the mixture and the permeation rate of the polymer used in the composite material. Varies from polymer to polymer and from test temperature to test temperature, so stabilized composites, ie composites with effective amounts of stabilizers, cannot be defined by standard tests (eg, , Less than X% weight gain at 50 ° C. in X hours).
Therefore, the present invention measures the weight gain at 100 ° C. for polypropylene-based composites, but due to such changes no improvement can be defined for these conditions.

There is a requirement to determine which materials are effective, which potential stabilizers must meet. First, this material has a positive charge of two or more,
Preferably, Ba ²⁺ , Al ³⁺ , Mg ²⁺ , Ca ²⁺ , Z
It must constitute a source of metal cations selected from the group consisting of n ²⁺ , Sr ²⁺ and Fe ³⁺ . In addition, the material is partially soluble in water, thereby reacting with the surface layer of the glass to form ions or ionic complexes that form insoluble or durable metal phosphate layers or hydrated metal phosphate layers. discharge. For example, TiO ₂ , Al (O
H) ₃ and Al ₂ O ₃ are all sources of metal cations having a positive valence of 2 or more, but they form an insoluble glass layer because their solubility in water is too low. Cannot provide a sufficiently high concentration of ions or ionic complexes required for On the other hand, the additive must not have such a high solubility that it creates durability problems of its own:
The water should not be so soluble in water that it readily attacks the additive itself, producing a porous material. As an example, CaCl ₃ is an effective stabilizer component, although CaCl ₂ is too soluble to function as a stabilizer additive, but with very low but adequate solubility. Particularly for effective stabilizer components, the solubility of the components is in the range 0.00001 to 0.1 g / 100 cc in water at 25 ° C. Therefore, the actual component added to the glass / polymer mixture as a stabilizer component consists of a material, either oxide or other compound, which fulfills the above-mentioned requirements, and as an example the stabilizer component ZnO can be used.

As an alternative to, or as a complement to, the direct addition of stabilizers, the stabilizer component is added prior to the actual compounding of the composite material, ie, prior to glass and polymer composite material processing.
It is added by precoating the glass particles. Pre-coating of glass particles consists of adding the glass particles to an aqueous solution containing a stabilizer component; for example, if Ca ²⁺ is desired, 1% Ca (OH) ₂ or CaCl ₂
Aqueous solutions are suitable. After addition of the glass particles to the solution, the slurry mixture is filtered, washed to a pH of about 7 and dried. This precoated glass is then compounded with a polymer and additional stabilizer (if desired) to form a composite material of the present invention with improved durability.

The following outlines the specific mixing, stabilizing and molding parameters used in the examples described below:
In each example, glass fragments / pellets having an average particle size of about 10 microns were mixed with polymeric pellets having a similar average particle size and stabilizer components generally having a fine particle size of less than 1 micron. Prior to drying, it was dried overnight in a forced air oven operating at about 150 ° C. System 4
Trademark of N. J. The desired mixture of glass, stabilizer component and polymer was prepared using a torque rheometer mixing ball marketed by Hacke Buffler, Saddle Brook. This glass, stabilizers and polymers 18
Mix at a temperature of 0 ° C. and 100 RPM for 5-10 minutes; the temperature was sufficient to soften the polymer. Once thoroughly mixed, add 5 "x 0.5" x 0. to the glass / polymer mixture.
Hot pressed into a 125 "test bar.

Table II lists some representative composite compositions, both stabilized and unstabilized. These compositions were prepared from the glass compositions listed in Table I and extruded to 5 "x 0.5" x 0.125 "
Injection-molded into a test bar. These bars were then used in the durability test described below. Tables III and IV describe composite compositions prepared from the glasses listed in Table I, both stabilized and unstabilized. However, while all values listed in Tables III and IV are given in weight percent, each of the stabilized examples contained an equal volume percent of glass to the unstabilized example; It should be noted that the example consists of three components (addition of stabilizer), but the volume fraction of glass is constant.

[0027] In Table II, III and IV, with the abbreviation following meanings present therein: PP is commercially available as the current pro fax ^R 626, shown Wilmington Del, polypropylene obtained from Himont Corporation.

ZnO indicates the use of zinc oxide as a stabilizer.

CaCO ₃ refers to the use of calcium carbonate as a stabilizer component.

Mg (OH) ₂ indicates the use of magnesium hydroxide as a stabilizer component.

MgCa (CO ₃ ) ₂ indicates the use of dolomite as a stabilizer component.

The ratio of glass to polymer to stabilizer, eg,
40/50/10; Example 2 / PP / CaCO ₃ is glass weight%, polymer weight% and stabilizer weight%; in other words, 40
% Of Example 2 glass, 50% polypropylene and 10% calcium carbonate stabilizer.

Table II Composite Material Examples Weight Ratio Component A 40/60 /-Example 2 / PP /-B 40/50/10 Example 2 / PP / CaCO ₃ C 10/80/10 Example 2 / PP / CaCO ₃ D 20/60/20 Example 2 / PP / CaCO ₃ (calcite) E 20/80 /-Example 2 / PP /-F 20/60/20 Example 2 / PP / MgCa (CO ₃ ) ₂ G 20/60/20 Example 2 / PP / CaCO ₃ (aragonite) H 20/60/20 Example 2 / PP / Mg (OH) ₂ Table III Composite Material Examples Weight Ratio Component M ₁ 5.2 / 94.8 / - example ₂ / PP / - M 2 5/90/5 example 2 / PP / ZnO N ₁ 65/35 / - example _{2 / PP / - N 2 57.7} / 27.8 /14.5 example _{2 / PP / ZnO O 1 70/30} / - example _{2 / PP / - O 2 62.3} / 24 / 13.7 example _{2 / PP / ZnO P 1 20/80} / - example 2 / PP / --- Table IV Composite material example Weight ratio Component AA 20 / 79.9 / 0.1 Example 2 / PP / Z OBB 20 / 79.8 / 0.2 Example 2 / PP / ZnO CC 20 / 79.0 / 2.0 Example 2 / PP / ZnO DD 20 / 79.5 / 0.5 Example 2 / PP / ZnO FIGS. 1-6 show glass / polymer. It has been reported that the addition of a stabilizer component to the composite increases the durability of this composite; the Stabilization Examples are shown by the reduced weight gain exhibited by the stabilized composites. All have reduced water retention. Specifically, the accelerated durability test consists of placing the bar of each compositional example in deionized water maintained at a specified temperature, 70 ° C and / or 100 ° C. The test bar was then removed and weighed at regular intervals. Convert the weight gain data into percentage gains and see Figure 1-6.
Were plotted to produce the curve shown in Figure 1;
The durability (percentage weight gain) of the samples measured at 100 ° C is shown, while Figures 3-6 show the durability measured at both 70 ° C and 100 ° C. For example, the data shown in Tables V and VI are the actual weights, and the intervals were the intervals (hours) at which the samples of Examples N to P and AA to DD were weighed at 70 ° C and 100 ° C, respectively. . These data were converted to weight percentages that were plotted to generate the unique curves shown in Figures 3-6.

Table V Time M ₁ M ₂ N ₁ N ₂ O ₁ O ₂ P ₁ (100 ° C.) 0 1.9489 2.033 3.8115 4.3852 4.2750 4.9669 2.1173 41 1.9593 2.0352 4.0325 4.4081 4.5696 4.9912 2.1515 65 1.9657 2.0377 --4.4150 4.4767 4.9977 2.1664 93 1.9705 2.0394 --4.4207 --5.303 2.1799 112 1.9732 2.0404 --4.4233 --5.0 642.1870 166 1.9793 2.0419 --4.4301 --5.0140 2.1986 233 1.9853 2.0431 --4.4372 --5.0230 2.2060 Table VI Time M ₁ M ₂ N ₁ N ₂ O ₁ O ₂ P ₁ (70 ℃) 0 1.9266 1.9367 3.5174 4.2530 3.9042 4.5232 2.0821 41 1.9277 1.9374 3.5361 4.2622 3.9388 4.5367 2.0842 65 1.9283 1.9377 3.5580 4.2643 3.9762 4.5393 2.0854 93 1.9287 1.9379 3.5926 4.2656 4.0404 4.5413 2.0863 112 1.9286 1.9377 3.6163 4.2662 4.0662 166 1.9295 1.9382 3.6661 4.2680 4.2110 4.5440 2.0889 233 1.9302 1.9383 3.8332 4.2700 4.3414 4.5464 2.0916 Table VII time AA BB CC DD 0 2.2969 2.3807 2.3574 2.3118 50 2.3286 2.4108 2.3815 2.3350 72 2.3358 2.4172 2.3875 2.3411 96 2.34 32 2.4235 2.3930 2.3469 120 2.3517 2.4300 2.3985 2.3529 It can easily be seen from Figures 1 and 2 that each of the unstabilized Examples A and B showed a greater weight gain percentage than the Stabilized Example. Although the volume percentage of glass is reduced in the stabilized example, it is clear that it is stabilized by the large decrease in weight gain exhibited by the stabilized example. Comparison of unstabilized Example A with CaCO ₃ stabilized Example D of FIG. 1 shows that Example D was very durable; Example D showed a 0.5% weight gain after 16 days. However, Example A showed a weight gain of about 4.5% after 4 days. FIG. 2 shows that CaCO ₃ stabilization example K has about 25
It shows a weight gain of about 0.7% after day, while unstabilized Example I (identical glass weight percent) shows 4% after about 9 days.
It showed a greater weight gain.

Each of FIGS. 3-6 represents an unstabilized sample,
A comparison is made with a stabilized example having an equal volume percentage of a low durability water absorbing glass component. It becomes clearer that the improvement in durability, ie the humidity resistance, depends on the addition of the stabilizer component of the invention. Upon examining Figure 3-6, as compared to the weight increase of the unstabilized Example (M ₁ -O ₁ and P _1), all of the stabilizing embodiment (M ₂ -O ₂ and AA-
DD) Low weight gain over a period of time at either 70 ° C or 100 ° C; it is therefore very clear that the improvement in durability was achieved by the addition of the stabilizer component.

Since the coating is insoluble, it acts as a barrier to prevent water from attacking the glass structure and causing swelling, weight gain and poor performance of the glass / polymer composite. Specifically, this insoluble metal phosphate surface layer or hydrated metal phosphate surface layer is the result of the metal ion reaction of the phosphate groups found in the phosphate glass. Therefore, when external water penetrates the glass / polymer / stabilizer composite, the actual formation of the coating or protective layer takes place, which causes the stabilizer component near the surface of the glass phase to dissolve, It is believed to release cations. Either water, either as an aqueous solution or as phosphate sites on the glass surface, reacts with the metal ions to cover the surface of the glass element, as water hydrates the glass giving rise to phosphate ions. , An insoluble protective layer of either an insoluble metal phosphate surface layer or a hydrated metal phosphate surface layer is formed.

[Brief description of drawings]

1 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

FIG. 2 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

FIG. 3 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

FIG. 4 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

FIG. 5 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

FIG. 6 is a graph illustrating the effect of stabilizer components on the durability of glass / polymer composites.

 ─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Dana Craig Bookbinder New York, USA 14830 Corning Davis Road 2261 (72) Inventor James Edward Dickinson Jr. United States New York 14830 Corning Wall Street 202 (72) Inventor Brent Mar Wedding USA New York 14830 Corning East Third Street 3

Claims (22)

[Claims] 1. A composite material having increased moisture resistance, comprising: (a) a matrix material comprising at least one organic thermoplastic or thermosetting polymer; (b) at least one phosphate glass; and (c) ) A mixture of components of at least one water-soluble stabilizer component that provides a source of metal cations having a positive or higher divalent value in an amount sufficient to improve the moisture resistance of the composite material. A composite material characterized in that 2. The indicated weight ratio of the mixture of (a) 1-99.5% matrix material, (b) 0.1-95% phosphate glass, and (c) 0.01-40% stabilizer component. The composite material according to claim 1, wherein the composite material comprises: 3. The indicated weight ratio of said mixture to: (a) 5-95% matrix material, (b) 1-90% phosphate glass, and (c) 0.01-40% stabilizer component. The composite material according to claim 1, wherein the composite material comprises: 4. The metal cation is Ba ²⁺ , Mg ²⁺ ,
The composite material according to claim 1, characterized in that it is selected from the group consisting of Ca ²⁺ , Al ³⁺ , Zn ²⁺ , Sr ²⁺ and Fe ³⁺ . 5. The phosphate glass having a total content of at least 65%, expressed in mol percent on an oxide basis, of 10-.
55% ZnO, 28-40% P ₂ O ₅ , 10-35% R
₂ O, and 0-10% Al up to 35% total
₂ O ₃ , 0-15% B ₂ O ₃ , 0-15% Cu ₂ O, 0
-25% Sb ₂ O ₃ , 0-35% PbO, 0-35% S
nO, 0-5% ZrO ₂ , 0-4% SiO ₂ , 0-
20% MgO, 0-20% CaO, 0-20% SrO,
0-20% of BaO and 0-10% MnO, 0-10% WO _3, 0-10% of MoO _3, 0-5% of rare earth metal oxide, and 0-5% analyzed in weight percent Substantially consisting of any component in the indicated proportions selected from the group consisting of F, wherein R ₂ O is 0-25% Li.
_At least 2 in the indicated proportions selected from the group consisting of ₂ O, 0-25% Na ₂ O, and 0-25% K ₂ O.
Consists of two alkali metal oxides, where Al ₂ O ₃ +
B ₂ O ₃ does not exceed 15%, WO ₃ + MoO ₃ does not exceed 15%, and MgO + CaO + SrO + BaO + MnO 20%
The composite material according to claim 1, characterized in that 6. The matrix material is polyether sulfone, polypropylene, polyallyl ether ketone, polyolefin, ABS, polystyrene, polyphenylene sulfide, polyfluoro resin, polyether imide, liquid crystal polyester, polyether ether ketone, polyether ketone, Polyethyl terephthalate,
From high temperature thermoplastics selected from the group consisting of polybutyl terephthalate, melamine, polyamide, polyphosphazine and polycarbonate, or high temperature thermosetting plastics selected from the group consisting of epoxy resin, silicone resin, polyimide, phenol, and diallyl phthalate. The composite material according to claim 1, wherein 7. A portion of the glass component which comprises a stabilizer component which, in the presence of moisture, releases the metal cation to form either an insoluble metal phosphate or a hydrated metal phosphate surface layer. The composite material according to claim 1, which has a selective surface coating. 8. At least one providing at least one phosphate glass, at least one organic thermoplastic or thermosetting polymeric matrix material, and a source of metal cations having a positive or higher valence of 2. A method for producing a composite material having increased moisture resistance, which comprises two water-soluble stabilizer components, the method comprising: (a) a sufficient amount of the water-soluble stabilizer to improve the moisture resistance of the composite material. The polymer and the glass together with the agent component are heated to be thoroughly mixed, and (b) the mixture is formed into a product having a desired shape and dimension, and (c) the product is cooled to room temperature. And how to. 9. The composite material produced comprises: (a) 1-99.5% matrix material; (b) 0.1-95% phosphate glass; and (c) 0.01-40% stabilizer component. 9. The method of claim 8 consisting essentially of a mixture of components present in said weight ratio. 10. The composite material produced comprises: (a) 5-95% matrix material, (b) 1-90% phosphate glass, and (c) 0.01-40% stabilizer component. 9. The method of claim 8 consisting essentially of a mixture of components present in said weight ratio. 11. The glass component in the presence of moisture,
9. The method of claim 8 having a partial surface coating consisting of a stabilizer component that releases the metal cations and forms either an insoluble metal phosphate or a hydrated metal phosphate surface layer. . 12. The metal cation is Ba ²⁺ , M
^9. The method according to claim 8, characterized in that it is selected from the group consisting of g ²⁺ , Ca ²⁺ , Al ³⁺ , Zn ²⁺ , Sr ²⁺ and Fe ³⁺ . 13. The phosphate glass has a total of at least 65%, expressed in mole percent on an oxide basis, of 10%.
-55% of ZnO, 28-40% of the P ₂ O _5, 10-35% of R ₂
O, and up to 35% total, 0-10% Al ₂ O ₃ ,
0-15% of B ₂ O _3, 0-15% of Cu ₂ O, 0-25% of Sb ₂ O _3, 0-35% of PbO, 0-35% of SnO, 0
-5% of ZrO _2, 0-4% of SiO _2, 0-20% of the M
gO, 0-20% CaO, 0-20% SrO, 0-20%
BaO and 0-10% MnO, 0-10% WO ₃ ,
Consisting essentially of 0-10% MoO ₃ , 0-5% rare earth metal oxide, and 0-5% F analyzed by weight percent in any proportion in the indicated proportions. , Where R ₂ O is 0-25% Li ₂ O, 0-25
% Na ₂ O and at least two alkali metal oxides in the indicated proportions selected from the group consisting of 0-25% K ₂ O, wherein Al ₂ O ₃ + B ₂ O ₃ is 15
%, WO ₃ + MoO ₃ does not exceed 15%, MgO
The method according to claim 8, characterized in that + CaO + SrO + BaO + MnO does not exceed 20%. 14. The matrix material is polyether sulfone, polypropylene, polyallyl ether ketone, polyolefin, ABS, polystyrene, polyphenylene sulfide, polyfluoro resin, polyether imide, liquid crystal polyester, polyether ether ketone, polyether ketone, Polyethyl terephthalate,
From high temperature thermoplastics selected from the group consisting of polybutyl terephthalate, melamine, polyamide, polyphosphazine and polycarbonate, or high temperature thermosetting plastics selected from the group consisting of epoxy resin, silicone resin, polyimide, phenol, and diallyl phthalate. 9. The method of claim 8 wherein: 15. At least one phosphate glass, at least one organic thermoplastic or thermosetting polymer matrix material, and at least one providing a source of metal cations having a positive valence of two or more. A method of producing a composite material having increased moisture resistance, which comprises two water-soluble stabilizer components, the method comprising: (a) adding the phosphate glass sufficient to improve the moisture resistance of the composite material; (B) heating the treated phosphate glass and the matrix material to intimately mix, and (c) shaping the mixture into a product of the desired geometry. (D) A method comprising the steps of cooling the product to room temperature. 16. The at least one complete mixing step provides a source of metal cations having a positive or positive valence of two or more in an amount sufficient to improve the moisture resistance of the composite material.
16. The method of claim 15, comprising adding two water soluble stabilizer components. 17. A composition comprising: (a) 1-99.5% matrix material; (b) 0.1-95% phosphate glass; and (c) 0.01-40% stabilizer component. 17. The method of claim 16 consisting essentially of a mixture of components present in said weight ratio. 18. A display of said composite material comprising: (a) 5-95% matrix material, (b) 1-90% phosphate glass, and (c) 0.01-40% stabilizer component. 17. The method of claim 16 consisting essentially of a mixture of components present in said weight ratio. 19. The glass component in the presence of moisture,
17. The method of claim 16 having a partial surface coating consisting of a stabilizer component that releases the metal cations and forms either an insoluble metal phosphate or a hydrated metal phosphate surface layer. . 20. The metal cation is Ba ²⁺ , M
The method according to claim 16, characterized in that it is selected from the group consisting of g ²⁺ , Ca ²⁺ , Al ³⁺ , Zn ²⁺ , Sr ²⁺ and Fe ³⁺ . 21. The phosphate glass having a total of at least 65%, expressed in mole percent on an oxide basis, of 10.
-55% of ZnO, 28-40% of the P ₂ O _5, 10-35% of R ₂
O, and up to 35% total, 0-10% Al ₂ O ₃ ,
0-15% of B ₂ O _3, 0-15% of Cu ₂ O, 0-25% of Sb ₂ O _3, 0-35% of PbO, 0-35% of SnO, 0
-5% of ZrO _2, 0-4% of SiO _2, 0-20% of the M
gO, 0-20% CaO, 0-20% SrO, 0-20%
BaO and 0-10% MnO, 0-10% WO ₃ ,
Consisting essentially of 0-10% MoO ₃ , 0-5% rare earth metal oxide, and 0-5% F analyzed by weight percent in any proportion in the indicated proportions. , Where R ₂ O is 0-25% Li ₂ O, 0-25
% Na ₂ O and at least two alkali metal oxides in the indicated proportions selected from the group consisting of 0-25% K ₂ O, wherein Al ₂ O ₃ + B ₂ O ₃ is 15
%, WO ₃ + MoO ₃ does not exceed 15%, MgO
The method according to claim 16, characterized in that + CaO + SrO + BaO + MnO does not exceed 20%. 22. The matrix material is polyether sulfone, polypropylene, polyallyl ether ketone, polyolefin, ABS, polystyrene, polyphenylene sulfide, polyfluoro resin, polyether imide, liquid crystal polyester, polyether ether ketone, polyether ketone, Polyethyl terephthalate,
From high temperature thermoplastics selected from the group consisting of polybutyl terephthalate, melamine, polyamide, polyphosphazine and polycarbonate, or high temperature thermosetting plastics selected from the group consisting of epoxy resin, silicone resin, polyimide, phenol, and diallyl phthalate. 17. The method of claim 16, comprising: