JPH0492836A - Glass for filling resin - Google Patents

Abstract

PURPOSE:To provide glass capable of giving resin compositions having high transparency while maintaining desired heat resistance, chemical resistance and mechanical strength, by adopting SiO2-B2O3-K2O series or SiO2-K20-(ZnO+ PbO+SrO+BaO) series glass. CONSTITUTION:The glass comprises 40-75 of SiO2, 10-30 of B2O3, 0-15 of Al2O3, 3-25 of K2O, 0-10 of Na2O, 0-5 of Li20, 0-4 of (MgO+CaO+SrO+BaO+ ZnO) 0-10 of PbO, 0-10 of (TiO2+ ZrO2) O-3 of (As2O3+Sb2O3) and 0-15 (as fluorine) of the total amount of fluorides prepared by fluorinating the above-mentioned metal element oxides, and has a refractive index (Nd) of approximately 1.45-1.65. The glass can be dispersed in resins to provide highly transparent resin compositions.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a resin-filled glass composition suitable for producing a resin composition with excellent transparency.

[Prior Art] Conventionally, various resin compositions have been known in which glass powder is dispersed as a filler in a resin to improve heat resistance, chemical durability, mechanical strength, etc. of the resin. However, these resin compositions tend to become opaque during the filler dispersion process, etc., so they can be used in applications that require transparency, such as various window materials as main body materials or surface coating materials, sealing materials,
It is unsuitable for applications such as WA lamp covers, containers, kitchen utensils, washstands, and 8-tubs, and there is a need for the development of a glass composition that can be dispersed in resin and exhibit high transparency. . Therefore, various studies have been conducted on this type of glass composition, such as Japanese Patent Application Laid-Open No. 60-12733.
In Publication No. 4, S i 02-B203-R20-
(MO+Z no) system composition (M is alkaline earth metal)
glass is known. However, the glasses specifically shown in this publication are selected to have a refractive index that matches or is very close to the refractive index of the resin, which is considered good for improving the transparency of the final resin composition, or Even if the powder is surface-treated with a silane coupling agent or the like to strengthen the bond between glass and resin, it is not possible to obtain a resin composition with sufficiently excellent transparency. Na2O, which is contained in a large amount, is easily ionized and eluted during kneading with the liquid resin, which changes the PH value of the resin liquid, alters the resin, makes curing unstable, and also causes oxidation in the resin composition. generate bubbles, and
It is thought that even after curing, the resin and surface treatment agents such as cuffing agents deteriorate over time, resulting in deterioration of the transparency of the final resin composition.

Incidentally, a glass having the same composition as above is also known in JP-A-56-148538, and has the same drawbacks, but the specific explanation regarding the amounts of each component of R20 is unclear. , there are aspects that have not been fully disclosed.

[Problems to be Solved by the Invention] The purpose of the present invention is to eliminate the drawbacks found in the above-mentioned prior art, and to provide a final resin composition with desired heat resistance, chemical durability, and mechanical strength, while maintaining the desired heat resistance, chemical durability, and mechanical strength. An object of the present invention is to provide a resin-filled glass composition that can provide excellent transparency.

[Means for Solving the Problems] In order to achieve the above object, the present inventor has conducted various tests and studies, and as a result, two systems of glasses having specific composition ranges having SiO2 and 20 as common components, namely: S i 02
-B203- to 20 series glass or Si02- to 20
- By adopting (ZnO+PbO+SrO+BaO) glass, it prevents deterioration of the resin liquid and unstable curing, significantly reduces the generation of bubbles, and maintains the desired heat resistance, chemical durability, and mechanical strength. However, the present invention was made based on this knowledge.

The resin-filled glass according to the first invention of the present application is characterized by having SiO2 of 40 to 75% by weight.

B2O3 10-30%, Al2O30-15%, K2O
3-25%, Na200-10%, Li200-5%,
MgO+CaO+SrO+BaO+ZnO0～
4%, Pb00-10%, TiO2+ZrO20-10
%, A s203 +S b203 0 to 3%, and a total amount of 0 to 15% as F2 of the fluoride substituted with the oxide of each of the above metal elements, and the refractive index (Nd) value is about 1. It is in the range of 45 to 1.65.

The reason why the composition range of the glass of the present invention is limited as described above is as follows.

That is, if the amount of the SiO2 component is less than 40%, the chemical durability, heat resistance and mechanical strength of the glass will deteriorate, and if it exceeds 75%, it will be difficult to melt the glass.

The B2O3 component improves the melting properties of the glass and has the following properties:
0 component has the effect of improving the transparency of the resin composition, and in order to exhibit this effect, its amount is required to be 10% or more, but in order to maintain the chemical durability of the glass, 30%
up to %.

The Al2O3 component can be added as it is effective in improving the chemical durability, heat resistance and mechanical strength of the glass, but if its amount exceeds 15%, the meltability of the glass will deteriorate.

In the coexistence of the R20 component with the above B2O3 component,
It is an important component that has been found to suppress deterioration of the resin liquid and instability of curing, prevent the generation of bubbles, and provide high transparency to the resin composition. However, the amount of R20 component is 3
If it is less than 25%, the above effect will not be sufficient, and if it exceeds 25%, the chemical durability, heat resistance and mechanical strength of the glass will deteriorate.

Na2O and Li20 components can be added to improve the meltability of glass, but if their amounts exceed 10% and 5%, respectively, bubbles will be generated in the resin, resulting in a resin composition with high transparency. It becomes difficult.

MgO, CaO1SrO, BaO and ZnO components are
It can be added to improve the meltability and chemical durability of glass, but one or 21! If the total amount above exceeds 4%, the compatibility between the glass and the resin may be impaired, the pH value of the resin may change, and the transparency of the resin composition may be likely to be deteriorated.

Although the PbO component can be added to adjust the refractive index of the glass, it is limited to 10% or less in order not to deteriorate the chemical durability.

T i O2 and ZrO2 components may be added to improve the chemical durability, heat resistance and mechanical strength of the glass, but if the total amount of these components is 10% or
If it exceeds this, the meltability and stability of the glass will deteriorate.

As2O3 and 5b203 components may be added as fining agents during glass melting, but it is sufficient that the total amount of one of them or 2s is 3% or less.

The fluoride component substituted with one or more of the oxides of the above metal elements may be added to lower the refractive index of the glass or suppress the reactivity with the resin, but the total amount as F2 If the amount exceeds 15%, the glass tends to devitrify.

Next, the characteristics of the resin-filled glass according to the second invention of the present application are that, in weight percent, SiO2 40-75%, B2O30
~Less than 10%, A12030~20%, K2O3,5~
20%, Na2O0-15%, Li2O0-5%, except K20+N&20+Li20 3.5-25%.

ZnO+PbO+SrO+BaO10-30%, MgO
+CaO0~10%, TiO2+ZrO20~10%,
Contains A s203 + S b2o30-3% and a total amount of 0-15% as F2 of fluoride substituted with the oxide of each of the above metal elements, and has a refractive index (Nd) value of about 1.45-1 It's somewhere in the .65 range.

The reason why the composition range of the glass of the present invention is limited as described above is as follows.

That is, when the amount of the S i 02 component is less than 40%, the chemical durability, heat resistance, and mechanical strength of the glass deteriorate, and when it exceeds 75%, it becomes difficult to melt the glass.

The B2O3 component can be added to improve the meltability of the glass, but if its amount exceeds 10%, the chemical durability of the glass will deteriorate.

The Al2O3 component can be added to improve the chemical durability of the glass, but if its amount exceeds 20%, the meltability of the glass will deteriorate.

In the glass of the present invention, the K20 component is the following ZnO,
In the presence of one or more components of PbO, SrO, and Ba0 (F), the above-mentioned PH value of the glass is kept low, and the compatibility with the resin is improved, resulting in a significant improvement in the transparency of the resin composition. Although it is an important component, the appropriate amount of 20 is in the range of 3.5 to 20% in order to exhibit its effect. Further, Na2O and Li2O components may be optionally added to improve the meltability of the glass, but their amounts up to 15% and 5%, respectively, are sufficient.

However, the total amount of Ni2O, Na2O and Li2O components is limited to 25% in order to maintain the chemical durability of the glass. In addition, at this time, K20/(N a20+L i2
0)≧1.

ZnO, PbO, SrO, and BaO components have the effect of suppressing the above-mentioned pH value of the glass, improving compatibility with the resin, and further improving the transparency of the resin composition, but if they are contained in large amounts, the glass Therefore, the total amount of one or more of these components should be 10 to 30%.

MgO and CaO components can be added to improve the meltability of glass and adjust optical constants, but since they increase the pH value and deteriorate the light transmittance of the resin composition, one or two of these components may be added. The total amount of seeds should be up to 10%.

TiO2 and ZrO2 components improve the chemical durability of the glass and can be added;
If the total amount of 1 or 2 exceeds 10%, the stability and meltability of the glass will deteriorate.

As2O3 and S, b203m may be added as fining agents during glass melting, but it is sufficient that the total amount of one or two of these is 3% or less.

The fluoride component substituted with one or more of the oxides of the above metal elements can be added to adjust the refractive index of the glass and improve the light transmittance, but the total amount as F2 is 15
%, the glass tends to devitrify.

The above-mentioned components of the glass in the first and second inventions of the present application are preferably 90% or more in total, and in addition to the above-mentioned components, La2O3 may be added within a range that does not impair the desired properties. , Y2 03 , Gd2 03
, Ta20sN b205 , WO3, F205
, GeO2 and Bi2O3, or a total amount of two or more of each component may be added up to 10%. Also, 5
n02, MnO2, Ni01CoO, Fe203,
1 of colorants and opacifiers such as Cu2O, S and CdO
A species or two or more species can be added in a total amount of up to 5%, if necessary.

Both of the above glasses of the present invention are produced by blending glass raw materials whose component ratios are adjusted so that the refractive index matches the refractive index of the resin within an allowable range (refractive index difference: ±0.01), and then It can be obtained by melting it by a method. Thereafter, these glasses are used after being pulverized into spherical, flaky, and fiber shapes by hot working, or into amorphous crushed shapes by cold working. These powders may generally have an average particle size of about 100 μm or less, although depending on the type of resin or the intended use of the final resin composition, powders with smaller average particle sizes may be used.

Then, a desired resin composition can be obtained by filling and mixing 10 to 80 wt % of the resin into a resin liquid and then curing it by a conventional method.

In this case, the glass powder may be subjected to general techniques such as drying treatment or surface treatment such as silane coupling to improve the mechanical strength, chemical durability, or transparency of the resin composition. I can do it.

The resin to be filled with powder may have a refractive index that is approximately within the range of the refractive index of the glass.
Suitable examples include, but are not limited to, the use of epoxy shelves and acrylic resin.

[Example] Next, preferred composition examples (Nos. 1 to 6) of the resin-filled glass of the first invention of the present application are shown in Table-1. Further, preferred composition examples (Nos. 1 to 7) of the resin-filled glass of the second invention of the present application are shown in Table 2. Glass with these compositions has a refractive index difference (ΔNd) with the resin.
I hope that there will be a small amount! l! ! ! However, these
The compositions were melted at a temperature of about 1,300 to 1,450° C. depending on the difficulty of melting each composition using a conventional melting device and optical glass raw materials, stirred and homogenized, then formed into a block shape and slowly cooled. The refractive index (refractive index at the wavelength of the d-line of a helium lamp, hereinafter referred to as Nd) of the glass after slow cooling was measured, and the values are also listed in Tables 1 and 2.

Next, these glasses were ground in a pot mill and sieved to obtain a powder with an average particle size of 10 pm.

As a chemical durability test of these powders, the PH value of the glass component eluate in pure water at room temperature was measured, and the results are shown in Tables 1 and 2. This pH value is 420~
Glass crushed to a particle size range of 590 pm was taken in an amount 50 times the specific gravity Durum, placed in a quartz glass flask containing 200 mJL of pure water, and shaken in a shaker for 24 hours.

This is the value measured using a pH meter for the solution in the flask.

Next, each of the glass powders after being crushed in a pot mill was dried, and the glasses of Examples in Table 1 were placed in acrylic resin or epoxy resin, and the glasses of Examples in Table 2 were placed in epoxy resin. A transparent resin composition was obtained by filling a resin with a predetermined proportion of each, mixing uniformly, casting the mixture into a predetermined mold, and curing the mixture.

Regarding these resin compositions, the light transmittance (indicated by T350nm and T500nm, respectively) at wavelengths of 350nm and 500nm was measured on a face-to-face polished sample with a thickness of 1 shoe/rin, and the results are shown in the respective tables above. .

Table 3 shows comparative composition examples (No., A, and B) of the conventional glass for resin filling, together with test results conducted in the same manner as above. Here, the No. and A glass powders were filled with acrylic resin and resin, and the No. and H glass powders were filled with epoxy resin, respectively.

As is clear from Tables 1 and 2, the resin compositions using the glass of each practical composition example of the invention before the present application have a ΔNd
T 350nm and T
At 500 nm, both values are significantly higher, and the light transmission performance is significantly improved. The glasses of each of the above Examples had lower pH values and were less alkaline than the glasses of Comparative Examples, so that deterioration of the resin and instability of curing could be suppressed. Furthermore, microscopic observation also revealed that the generation of bubbles in the cured resin composition was significantly reduced, which is considered to be the main reason for the above-mentioned improvement in light transmission performance. Note that this reduction in bubbles is thought to be due to the good compatibility with the resin.

The resin compositions obtained using the glasses of the above-mentioned composition examples have excellent mechanical strength, heat resistance, and chemical durability in addition to the above-mentioned light transmittance.

[Effects of the Invention] As described above, the glass filler for resin filling according to both the present inventions has a 20-based composition for Soreso ttS i 02-B203- and a 20- (Z no + PbO + S) composition for S i 02-.
rO + BaO) system composition, there is no adverse effect such as deterioration on the resin, and therefore the resin composition has excellent light transmittance while maintaining the desired mechanical strength, heat resistance, and chemical durability. Therefore, it is useful as a glass for filling the above-mentioned applications that require these properties, as well as other resin compositions for dental applications, or resin compositions for applications that require flame retardancy.

Patent applicant Ohara Co., Ltd.

Claims (2)

[Claims] (1) In weight%, SiO_240-75%, B_2O_
310-30%, Al_2O_30-15%, K_2O
3-25%, Na_2O0-10%, Li_2O0-5
%, MgO+CaO+SrO+BaO+ZnO0~4%
, PbO 0-10%, TiO_2+ZrO_20-10%, As
It contains _2O_3+Sb_2O_30-3% and a total amount of 0-15% as F_2 of fluoride substituted with the oxide of each of the above metal elements, and has a refractive index (Nd) of about 1.
．． 45 to 1.65. (2) In weight%, SiO_240-75%, B_2O_
30 to less than 10%, Al_2O_30 to 20%, K_2
O3.5-20%, Na_2O0-15%, Li_2O
0 to 5%, however, K_2O+Na_2O+Li_2O
3.5-25%, ZnO+PbO+SrO+BaO10
~30%, MgO+CaO0~10%, TiO_2+Z
rO_20~10%, As_2O_3+Sb_2O_3
0 to 3% and a total amount of 0 to 15% as F_2 of fluoride substituted with the oxide of each of the above metal elements, and
A glass for resin filling, characterized in that the value of the refractive index (Nd) is in the range of about 1.45 to 1.65.