JP2004043242A - Organic-inorganic hybrid low melting glass and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a producible material which has a transition point of about 100°C or lower than 100°C, does not use an environmentally problematic substance such as lead, bismuth and the like as a glass composition factor, and has gastightness, long-term stability and strength and further has no problem such as attack by water and the like. <P>SOLUTION: The material is an organic-inorganic hybrid low melting glass represented by the formula: R<SB>3</SB>Si<SB>O.5</SB>-R<SB>2</SB>SiO-MO-P<SB>2</SB>O<SB>5</SB>(wherein R is methyl or ethyl; and M is a divalent metal) and is prepared by thermally reacting a trialkylchlorosilane and phosphoric acid, or a trialkylchlorosilane, phosphoric acid and a metal chloride, without using water. <P>COPYRIGHT: (C)2004,JPO

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel low-melting glass having a low softening point, for example, a low-melting glass useful as an optical functional material such as an optical waveguide, and a method for producing the same.
[0002]
[Prior art]
Low-melting glass is generally referred to as low-melting glass because it has a softening point of 600 ° C. or lower and has a lower softening start temperature, so-called “melting point”, than commercially available plate glass. . This low-melting glass has been widely used as a sealing / sealing material, passivation glass, glaze, and the like since ancient times. In addition, since firing can be performed at "low temperature" to the extent that organic molecules are not thermally decomposed, by dispersing functional organic molecules in transparent glass, it can be used as a basic optical functional material supporting photonics.
[0003]
Various composition systems have been proposed for the low-melting glass. For example, Sn-Pb-PFO-based glass developed by Tick et al. Has a glass transition point in a temperature range as low as about 100 ° C. and shows excellent water resistance. However, most of the glasses called low-melting glass contain lead as a main component, and therefore have a problem from the viewpoint of environmental protection. In recent years, lead-free glass systems have been proposed, but bismuth, cadmium and other compositional factors that have safety issues are included, and low-melting glass that is environmentally friendly has been proposed. I can't say it. Further, there is no known glass having a transition point of about 100 ° C. in a glass composition system containing no lead.
[0004]
As a low-temperature synthesis method of the glassy bulk material, there are a sol-gel method and a liquid phase reaction method. In the sol-gel method, a bulk body can be obtained by hydrolysis-dehydration condensation polymerization of a metal alkoxide. However, a completely dense bulk body cannot be obtained by heat treatment at 600 ° C. or lower. On the other hand, the liquid phase reaction method has a fatal problem of a low yield, and since hydrofluoric acid is used in the reaction system, extremely corrosive HF is generated. It is almost impossible to produce a glassy bulk material in practice.
[0005]
It has also been considered to use silicone as a polymer glassy amorphous bulk material. In the case of silicone, a bulk body can be obtained by entanglement of polymers having a siloxane skeleton or by crosslinking between polymers with a certain organic substance. The silicone-made bulk material thus obtained has a characteristic that it is more stable than plastics at higher temperatures, but has a fundamental problem that it is inferior to low-melting glass in airtightness and long-term stability.
[0006]
[Problems to be solved by the invention]
Conventional so-called low-melting glass contains lead, which is problematic in terms of environmental protection. Low-melting glass that does not contain lead contains bismuth, cadmium and other compositional factors having safety problems, and a glass having a transition point of around 100 ° C. is not known.
[0007]
For a glassy bulk material, a sol-gel method cannot provide a completely dense bulk material, and therefore, when viewed as a practical material, lack of strength of itself, oxidation of a substance to be introduced, and attack by water are serious problems. However, in the liquid phase reaction method, the yield was low and HF was generated during the reaction, so that it was almost impossible to synthesize a glassy bulk material in reality.
[0008]
That is, the transition point is around 100 ° C. or less than 100 ° C., and substances having environmental problems such as lead and bismuth are not regarded as glass composition factors, and the hermeticity, long-term stability and strength of the material, and the attack by water, etc. There was virtually no producible material without problems.
[0009]
[Means for Solving the Problems]
The present invention does not use low melting point glass having a transition point of less than 100 ° C., a material having environmental protection problems such as lead, bismuth, and cadmium as a composition factor, and hermeticity as a sealing material, long-term stability and strength, and It relates to the provision of materials that can be produced without problems such as water attack.
[0010]
The present invention is an organic-inorganic hybrid low-melting glass based on R ₃ SiO _0.5 —R ₂ SiO—MO—P ₂ O ₅ (where R is a methyl group or an ethyl group, and M is a divalent metal).
[0011]
Further, the present invention provides the above-mentioned organic-inorganic hybrid low-melting glass, wherein at least one of oxides of at least one of Nb, Zr, and Ti, at least one of V, Cr, Mn, Fe, Co, Cu, and Ni. Contains at least one rare earth metal ion of one transition metal ion, Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, and Tm, and at least one or more coloring components of an organic dye An organic-inorganic hybrid low-melting glass characterized in that:
[0012]
Further, the present invention is the above-mentioned method for producing an organic-inorganic hybrid low-melting glass, wherein the trialkylchlorosilane is reacted with phosphoric acid by heating.
[0013]
Further, the present invention is the above-mentioned method for producing an organic-inorganic hybrid low-melting glass, wherein the trialkylchlorosilane is reacted with phosphoric acid and a metal chloride by heating.
[0014]
In the present invention, as the metal chloride used in the coexistence during the reaction, a chloride of a divalent metal is preferable, and specifically, a chloride of Sn, Ge, Al, and Zn is preferably used.
[0015]
A feature of the production method of the present invention is that a trialkylchlorosilane R _x SiCl is used as a starting material. The organic-inorganic hybrid low-melting glass of the present invention is synthesized and produced based on a new concept completely different from silicone. You.
[0016]
That is, by terminating the siloxane skeleton with an organic functional group, the network dimension is reduced and the glass itself has a low melting point. Therefore, its physical properties are similar to those of a low-melting glass rather than a plastic.
[0017]
The organic-inorganic hybrid low melting point glass of the present invention has good airtightness when used as a sealant. Further, many applications are expected as a host of a functional organic material having optical functionality or the like.
[0018]
For this glass, Nb, Zr, Ti, In, or the like is introduced as an oxide to improve glass properties such as water resistance, or V, Cr, Mn, Fe, Co, Cu, Ni, or the like. Can be introduced. Further, rare earth ions (such as Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, and Tm) and organic dyes can also be contained. These should be contained within a range that does not impair the physical properties of the organic-inorganic hybrid low-melting glass. That is, when a large amount of Nb, Zr, Ti, In or the like is contained, a problem occurs that the softening point becomes too high. If a large amount of V, Cr, Mn, Fe, Co, Cu, Ni, etc. is contained, the coloring becomes too dark. Rare earth ions (Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm, etc.) are very expensive, and when contained in large amounts, concentration quenching tends to occur during light emission.
[0019]
The characteristics of the low melting point glass and the production method obtained by the present invention are listed as follows. -It is a uniform bulk body.
-Since the reaction system does not contain water, an anhydrous bulk body can be easily obtained.
-Because it can be synthesized at low temperature, it can contain organic dyes without decomposition and has high solubility.
-The obtained amorphous bulk body has the property of glass.
-The obtained bulk body has a high formability characteristic of glass, and is easily processed into a fiber or a thin film shape.
-Reaction products other than the target product are vaporized and released out of the system.
-Since it is formed by an oxide skeleton and an organic functional group bonded thereto, controllability of physical properties by composition is higher than that of a conventional organic-inorganic composite.
-Due to the presence of the organic functional groups, a large amount of functional organic substances can be introduced into the glass. Further, the type of the organic substance to be introduced by changing the type can be selected.
[0020]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to the following reaction when trialkylchlorosilane (R ₃ SiCl), dimethyldichlorosilane (Me ₂ SiCl ₂ ) and phosphoric acid (eg, H ₃ PO ₄ , H ₃ PO ₃ ) are used as starting materials. The organic-inorganic hybrid low-melting glass is formed based on the concept of (1).
P-OH + Si-Cl → Si-OP + HCl ↑
In this reaction, HCl as a reaction product is released out of the system as a gas, so that the reaction proceeds in one direction, so that a dense bulk body is formed. In addition, even if a metal chloride such as tin chloride is allowed to coexist with these systems and reacted, a dense and low-melting bulk material can be obtained. Even when chlorides of other metals are used, the basic reaction mechanism is the same. Ideally, all HCl is released out of the system as a gas, but in any case, the chlorine compound may remain as glass.
[0021]
The reaction of the organic-inorganic hybrid low-melting glass of the present invention can be synthesized at a low temperature of from room temperature to 300 ° C. or less, and the obtained glass has a low softening temperature and a high moldability (possible re-melting), and can be a fiber or thin film It can be easily processed into a shape and can be a host material that disperses functional organic molecules at a low temperature that does not cause thermal decomposition of the organic molecules.
[0022]
The preferred composition of the organic-inorganic hybrid low-melting glass obtained in the present invention is R ₃ SiO _0.5 —R ₂ SiO—MO—P ₂ O ₅ (where R is a methyl group or an ethyl group, and M is a divalent Organic-inorganic hybrid low-melting glass (where R is a methyl group or an ethyl group, M is a divalent metal), and is a trialkylchlorosilane and phosphoric acid, or a trialkylchlorosilane and phosphoric acid and metal chloride. Is produced by reacting with heat without using water. For example, in the case of Sn-based glass, the glass is mainly composed of R ₃ SiO _0.5 —R ₂ SiO—SnO—P ₂ O ₅ , but there are three R (eg, methyl groups) around Si. In many cases, the bonding property of the glass decreases, and as a result, a glass having a low transition point can be obtained.
[0023]
One of the features is that the reaction temperature is from room temperature to about 300 ° C. or lower, which is lower than the conventional one, and the energy required for bulk synthesis can be suppressed.
[0024]
【Example】
Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the following examples.
[0025]
(Example 1)
Phosphoric acid (H ₃ PO 4), dimethyldichlorosilane (Me ₂ SiCl ₂ ), and tin chloride (SnCl ₂ ) are used as starting materials. The composition of the prepared samples _{H 3 PO 4: Me 3 SiCl} : Me 2 SiCl 2: SnCl a mixing ratio of _{2 2:} 2x: 2.5x: 0.5 defined as, x is from 0, 0.5, 1 and 1 The study was conducted under four conditions of 0.5. Orthophosphoric acid was heated to 40 ° C. in a reactor under a nitrogen atmosphere to make it a liquid, and then trialkylchlorosilane was added, followed by heating and stirring for 3 hours. In this process, the temperature was gradually increased and heated to 100 ° C. At this stage, tin chloride was added. This was further heated for 1 hour at 250 ° C. in a nitrogen atmosphere to obtain an organic-inorganic hybrid low-melting glass as a final product as a total of six samples. The two-step heating reaction is performed to obtain a more dense bulk body, and the combination of the heating reaction temperature and time is arbitrary.
[0026]
FIG. 1 shows a production scheme of the organic-inorganic hybrid low-melting glass of the present invention. FIG. 2 is a graph showing the composition dependence of the glass transition temperature of an organic-inorganic hybrid low-melting glass using tin chloride. x was examined under four conditions of 0, 0.5, 1, and 1.5.
[0027]
As shown in the graph of FIG. 2, the obtained sample shows various glass transition points depending on the composition and the reaction time. The glass transition temperature varies according to the composition and time from −47 to 30 ° C., and the low glass transition temperature, which is a characteristic of low-melting glass, can be freely changed, and glass with an extremely low transition point can be obtained. did it.
[0028]
Unlike polymer glass, not only the network dimensions, but also the chemical bonding between the constituent elements of the bulk material affect the glass transition temperature, and by selecting the organic portion of alkylchlorosilane or the metal to be added at the same time, a very wide range can be achieved. Control of the physical properties (glass transition temperature) becomes possible.
[0029]
(Example 2)
A similar reaction was carried out in Example 1 except that germanium chloride was used instead of tin chloride. As a result, a pale yellow transparent plate-like final product similar to that of tin chloride was obtained. The composition of the prepared samples _{H 3 PO 4: Me 3 SiCl} : Me 2 SiCl 2: GeCl the mixing ratio of _{2 2:} 2x: 2.5x: 0.5 defined as, x is from 0, 0.5, 1 and 1 The study was conducted under four conditions of 0.5. The glass transition point (Tg) of this sample shows various tendencies depending on the composition. The results are shown in FIG. 3, which is a graph showing the composition dependence of the glass transition temperature of each organic-inorganic hybrid low melting point glass using germanium chloride, aluminum chloride, and zinc chloride.
[0030]
(Example 3)
The same reaction as in Example 1 was carried out except that aluminum chloride was used instead of tin chloride, and a pale yellow transparent plate-like final product similar to that of tin chloride was obtained. The composition of the manufactured sample was determined by setting the mixing ratio of H ₃ PO ₄ : Me ₃ SiCl: Me ₂ SiCl ₂ : AlCl ₃ to 2: 2x: 2.5x: 0.5, and x was 0, 0.5, 1, and 1. The study was conducted under four conditions of 0.5. The results are shown in FIG. It can be seen that the glass transition point (Tg) shows various tendencies depending on the composition.
[0031]
(Example 4)
The same reaction as in Example 1 was carried out except that zinc chloride was used instead of tin chloride, and a pale yellow transparent plate-like final product similar to the case of tin chloride was obtained. The composition of the manufactured sample was determined under the following conditions: a mixture ratio of H ₃ PO ₄ : Me ₂ SiCl ₂ : ZnCl ₂ was set to 2: x: 2, and x was 0, 0.5, 1, and 1.5. The results are shown in FIG. It can be seen that the glass transition point (Tg) shows various tendencies depending on the composition.
[0032]
【The invention's effect】
The organic-inorganic hybrid low melting glass of the present invention has properties that have not been achieved so far. That is, it can be synthesized from room temperature to a low temperature of 300 ° C. or less, has a low softening temperature and high moldability (remelting is also possible), is easy to process into a fiber or thin film shape, and has a low temperature that does not cause thermal decomposition of organic molecules. Can be a host material for dispersing the functional organic molecules.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram of an organic-inorganic hybrid low-melting glass reaction scheme of the present invention.
FIG. 2 is a graph showing the composition dependence of the glass transition temperature of an organic-inorganic hybrid low-melting glass using tin chloride.
FIG. 3 is a graph showing the composition dependence of the glass transition temperature of each organic-inorganic hybrid low-melting glass using germanium chloride, aluminum chloride, and zinc chloride.

Claims (7)

_{R 3 SiO 0.5 -R 2 SiO-} MO-P 2 O 5 based organic - inorganic hybrid low-melting glass (where, R represents a methyl group or an ethyl group, M is a divalent metal). The organic-inorganic hybrid low melting point glass according to claim 1, wherein the glass contains at least one oxide of Nb, Zr, and Ti. The organic-inorganic hybrid low-melting glass according to claim 1, wherein the organic-inorganic hybrid low-melting glass contains at least one transition metal ion among V, Cr, Mn, Fe, Co, Cu, and Ni. -An inorganic hybrid low melting glass. The organic-inorganic hybrid low-melting glass according to claim 1, wherein at least one of Ce, Pr, Nd, Sm, Eu, Tb, Dy, Ho, Er, and Tm is contained. An organic-inorganic hybrid low-melting glass characterized by the above-mentioned. The organic-inorganic hybrid low melting point glass according to claim 1, further comprising an organic dye. The method for producing an organic-inorganic hybrid low-melting glass according to claim 1, wherein the trialkylchlorosilane is reacted with phosphoric acid by heating. The method for producing an organic-inorganic hybrid low-melting glass according to claim 1, wherein the trialkylchlorosilane is reacted with phosphoric acid and a metal chloride by heating.

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