JP2005298796A - Organic metal polymer material and its preparation process - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic metal polymer material which has a high heat resistance and an excellent light-transparency, exhibiting a small optical transmission loss especially in 1,450-1,550nm wavelength region. <P>SOLUTION: This organic metal polymer material, which has an -M-O-M (wherein M is a metal atom) bond, contains a metal alkoxide having only one hydrolyzable group and/or its hydrolysate and preferably an anhydrous organic acid and/or an organic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention is an optical wiring substrate, various coating materials such as a surface protective film, an antireflection film, an optical transmission / reception module, an optical switch, an optical communication device such as an optical modulator, an optical waveguide, an optical waveguide, an optical propagation path such as a lens array, etc. The present invention relates to an organic metal polymer material that can be used for a structure, an optical device such as a light beam splitter, an optical component such as a lens, a microlens array, and a light guide plate, and a manufacturing method thereof.

  Inorganic materials such as metals and ceramics are excellent in heat resistance, mechanical strength, electrical characteristics, optical characteristics, chemical stability, etc., and are widely used industrially by taking advantage of their functions. However, in general, brittleness and hardness are high, and in order to process into a desired shape, molding at high temperature, mechanical processing, or the like is required, and its application may be limited.

  On the other hand, the organic polymer has excellent moldability and flexibility, and therefore has good workability. However, heat resistance and chemical stability are often inferior to those of inorganic materials. Therefore, in recent years, organic polymers using metal alkoxide as a starting material have been actively developed as organic-inorganic hybrid materials or organic-inorganic nanocomposites.

  In Patent Document 1 and Patent Document 2, attempts are made to apply such an organic-inorganic hybrid material to an optical waveguide.

However, in either case, the metal alkoxide as a starting material, if necessary as a material in a so-called sol-gel process a process called water was added, for carrying out the hydrolysis reaction, is in the material moisture (H ₂ Many O) and silanol groups (Si-OH) remain. In particular, the silanol group is difficult to remove by heating or the like, and thus becomes a major factor of light loss mainly in the infrared region, and has a great influence particularly in the vicinity of 1500 nm which is an optical communication wavelength band.
JP 2000-356722 A JP-T-2001-506372 JP-A-6-322136 JP 2003-195070 A JP 2000-336281 A JP 2000-34413 A

  An object of the present invention is to provide an organometallic polymer material having high heat resistance and excellent translucency, and a method for producing the same.

  The organometallic polymer material according to the first aspect of the present invention includes a metal alkoxide having only one hydrolyzable group in an organometallic polymer having a —M—O—M— bond (M is a metal atom), and And / or a hydrolyzate thereof.

  The metal alkoxide and / or the hydrolyzate thereof may be contained in a state where it is not bound to the organometallic polymer, or may be contained in a bound state.

  The hydrolyzate of metal alkoxide may be a polycondensate of the hydrolyzate.

  In the present invention, by containing a metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof, a metal alkoxide is added to the —OH group generated at the end of the molecule of the organometallic polymer. And / or its hydrolyzate can react to eliminate the —OH group. For this reason, the light propagation loss which arises in the wavelength range of 1450-1550 nm can be reduced.

  For example, when the metal atom M is Si, an alkoxy group represented by —Si—O—R may be present at the end of the organometallic polymer molecule. This alkoxy group absorbs moisture and hydrolyzes to generate a silanol group as follows.

_{-Si-O-R + H 2} O → -Si-OH + ROH ↑
ROH generated in the above reaction volatilizes. When the silanol group is present, the light propagation loss near 1500 nm increases as described above.

  According to the present invention, when a metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof is contained, the silanol group generated as described above can be eliminated. For example, an alkoxysilane having only one alkoxy group represented by the following formula absorbs moisture and hydrolyzes as follows.

R ′ ₃ Si—O—R ″ + H ₂ O → R ′ ₃ Si—OH + R ″ OH ↑
In the above reaction, R ″ OH is volatilized. The hydrolyzate produced as described above reacts with the silanol group at the end of the organometallic polymer as follows.

—Si—OH + R ′ ₃ Si—OH → —Si—O—SiR ′ ₃ + H ₂ O
By the above reaction, the silanol group at the end of the molecule of the organometallic polymer disappears. For this reason, according to the present invention, it is possible to reduce light propagation loss in the vicinity of a wavelength of 1500 nm.

  As described above, since the metal alkoxide is hydrolyzed and acts as a hydrolyzate, it may be included in the form of a metal alkoxide or may be included in the form of a hydrolyzate. In addition, when the organometallic alkoxide or a hydrolyzate thereof is contained in a state that does not bind to the organometallic polymer, when the organometallic polymer newly absorbs moisture and a silanol group or the like is generated at the terminal, A metal alkoxide in a non-bonded state or a hydrolyzate thereof acts on the silanol group and the like, and the silanol group and the like can be extinguished as described above.

  In the present invention, the metal alkoxide or the hydrolyzate thereof may contain a fluorine atom. That is, a metal alkoxide in which hydrogen in the hydrocarbon portion is substituted with a fluorine atom and a hydrolyzate thereof may be used. By containing a fluorine atom, it is possible to further reduce the optical loss in the long wavelength region.

  The organometallic polymer material according to the second aspect of the present invention contains an organic acid anhydride and / or an organic acid in an organometallic polymer having a —M—O—M— bond (M is a metal atom). It is characterized by that.

  Since the anhydrous organic acid absorbs and hydrolyzes moisture, the moisture in the organometallic polymer can be reduced by including the anhydrous organic acid. Accordingly, absorption due to moisture is reduced, and light propagation loss in the wavelength range of 1300 to 1350 nm and 1450 to 1550 nm can be reduced by adding only an organic acid anhydride. Moreover, the organic acid contained in the organometallic polymer promotes the reaction of silanol groups and the like. For this reason, it can promote that a silanol group etc. disappear. For example, the reaction between the silanol groups at the ends of the molecules of the organometallic polymer can be promoted.

  The anhydrous organic acid and / or organic acid is preferably also contained in the organometallic polymer in the first aspect of the present invention. That is, by containing an organic acid anhydride and / or an organic acid together with a metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof, in addition to removing moisture by the organic anhydride, The hydrolyzate of metal alkoxide having only one decomposable group reacts with the —OH group generated at the end of the molecule of the organometallic polymer, and the reaction of eliminating the —OH group is promoted. Light propagation loss can be reduced in the wavelength range.

  In Patent Document 3 and Patent Document 4, trifluoroacetic acid is used as a catalyst for the purpose of promoting the hydrolysis reaction of the hydrolyzable silane compound. This is added to make the reaction solution acidic during the sol-gel process in which water is added to advance the reaction, and is not trifluoroacetic anhydride. This is because trifluoroacetic anhydride reacts violently with water and immediately changes to trifluoroacetic acid. In addition, as in the present invention, there is no disclosure about the addition to the final product (cured product) or the effect of reducing light loss by the acid anhydride.

Moreover, when adding trifluoroacetic anhydride or trifluoroacetic acid, it is preferable that the addition amount is a level detectable by infrared absorption spectroscopy. Specifically, the ratio of the absorption peak height of trifluoroacetic acid (near 1780 cm ⁻¹ ) / the absorption peak height resulting from SiO (near 1100 cm ⁻¹ ) is preferably 0.05 or more.

  When the said metal alkoxide or its hydrolyzate is alkoxysilane or its hydrolyzate, what is represented by the following general formula is mentioned as an example.

(Here, R ₁ , R ₂ and R ₃ are organic groups having 1 to 15 carbon atoms, preferably alkyl groups. R ₄ is an alkyl group having 1 to 4 carbon atoms.)
Specific examples include trialkylalkoxysilanes such as trimethylalkoxysilane and triethylalkoxysilane. Examples of the alkoxy group include a methoxy group and an ethoxy group.

  Specific examples of the organic acid anhydride include trifluoroacetic anhydride, acetic anhydride, propionic anhydride, and the like. Particularly preferably, trifluoroacetic anhydride is used. Specific examples of the organic acid include trifluoroacetic acid, acetic acid, propionic acid and the like. Particularly preferably, trifluoroacetic acid is used.

  In the present invention, the organometallic polymer can be synthesized, for example, by hydrolysis and polycondensation reaction of an organometallic compound having at least two hydrolyzable groups. Examples of such an organometallic compound include trialkoxysilane or dialkoxysilane containing an organic group. Examples of the organic group include an alkyl group, an aryl group, and an aryl-containing group. As the aryl group, a phenyl group is preferable. More preferable examples include phenyltrialkoxysilane and diphenyl dialkoxysilane, and more preferable are phenyltriethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.

  The organometallic compound preferably contains an organometallic compound having a functional group that crosslinks by heating and / or energy ray irradiation. Examples of energy rays include ultraviolet rays and electron beams. Examples of such functional groups that crosslink include acryloxy groups, methacryloxy groups, styryl groups, epoxy groups, and vinyl groups. Therefore, trialkoxysilanes having these functional groups are preferably used.

  When a radical polymerizable functional group such as acryloxy group, methacryloxy group, styryl group, and vinyl group is contained, it is preferable that a radical polymerization initiator is included. Examples of the radical polymerization initiator include 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1, oxy-phenyl-acetic acid 2- [2-oxo-2-phenyl-acetoxy-ethoxy] -ethyl-ester, oxy-phenyl-acetic acid 2- [2- Mention may be made of hydroxy-ethoxy] -ethyl-esters and mixtures thereof.

  Moreover, when the organometallic compound which has an epoxy group is contained, it is preferable that the hardening | curing agent contains. Examples of such curing agents include amine curing agents, imidazole curing agents, phosphorus curing agents, and acid anhydride curing agents. Specific examples include methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, and tetraethylenepentamine.

  When an organometallic compound having a functional group and an organometallic compound not having a functional group are mixed and used, the mixing ratio is 5 by weight ratio (organometallic compound having a functional group: organometallic compound not having a functional group). It is preferable that it is -95: 95-5.

  The content of the metal alkoxide or the hydrolyzate thereof is preferably 0.1 to 15 parts by weight, more preferably 0.2 to 2.0 parts by weight with respect to 100 parts by weight of the organometallic polymer. .

  Moreover, it is preferable that it is 0.1-10 weight part with respect to 100 weight part of organometallic polymers, and, as for content of an organic acid anhydride or organic acid, More preferably, it is 1-5 weight part.

  In the present invention, the metal alkoxide, the hydrolyzate thereof, the organic acid anhydride and the organic acid may be added in the process of synthesizing the precursor (liquid) before curing the organometallic polymer. You may add just before hardening. Moreover, you may add by the method of moistening to the organometallic polymer after hardening.

  In the present invention, M in the —M—O—M— bond of the organometallic polymer is preferably Si, Ti, Nb or Zr or a combination of these metals, and particularly preferably Si. In the case of Si, the organometallic polymer can be formed from, for example, a silicone resin. Moreover, what was synthesize | combined by the hydrolysis and polycondensation reaction of at least 1 sort (s) of alkoxysilane may be used. In this case, at least one of the alkoxysilanes may be a trialkoxysilane having an acryloxy group, a methacryloxy group, a styryl group, a vinyl group or an epoxy group.

  In the present invention, the organometallic polymer may contain at least one kind of particles made of a material having a refractive index different from that of the organometallic polymer. By including such particles, the refractive index of the organometallic polymer material can be controlled. The size of the particles is preferably in the range of 5 nm to 1 μm, and particularly when used as an optical material, the size is preferably 10 nm to 20 nm in order to reduce light scattering.

  As the particles, particles made of an inorganic material and particles made of an organic material can be used, and metal oxide particles are particularly preferably used. Examples of the metal oxide particles include silicon oxide, niobium oxide, zirconium oxide, titanium oxide, aluminum oxide, yttrium oxide, cerium oxide, and lanthanum oxide. Among these, silicon oxide, niobium oxide, zirconium oxide, and titanium oxide are particularly preferably used.

The metal atom M in the organometallic polymer, when a Si, in an infrared absorption spectrum (the height of the absorption peaks of Si-OH bonds in the vicinity of 3400cm ^-1) / (C-H in the vicinity of 2900 cm ^-1 It is preferable that the amount of silanol groups (Si—OH) in the organometallic polymer is adjusted so that the ratio of the bond absorption peak height is 0.2 or less. By setting the peak ratio to 0.2 or less, it is possible to reduce the optical propagation loss at wavelengths of 500 to 1100 nm, 1300 to 1350 nm, and 1450 to 1550 nm to 1.5 dB / cm or less.

  In the present invention, the boiling point of the metal alkoxide or a hydrolyzate thereof is preferably not higher than the thermosetting temperature of the organometallic polymer. Thereby, the metal alkoxide or its hydrolyzate excessively contained in the organometallic polymer can be evaporated and removed by heating.

  Moreover, it is preferable that the boiling point of the said organic acid anhydride or organic acid is also below the thermosetting temperature of the said organometallic polymer. Thereby, excess organic acid anhydride or organic acid can be evaporated and removed by heating.

  The organometallic polymer material of the present invention preferably has a light propagation loss of 1.5 dB / cm or less in a wavelength range of 500 to 1100 nm, 1300 to 1350 nm, and 1450 to 1550 nm.

  The organometallic polymer material of the present invention may further contain an organic polymer as an additive. Examples of the organic polymer include acrylate resins, epoxy resins, urethane resins, urethane acrylate resins, polyester acrylate resins, and epoxy acrylate resins. The addition amount of the organic polymer is preferably in the range of 5 to 95% by weight, more preferably in the range of 20 to 60% by weight.

  The production method of the present invention is a method by which the organometallic polymer material of the present invention can be produced, and includes a first organometallic compound having at least two hydrolyzable groups, heating and / or energy rays. Hydrolyzing and polycondensing a mixture of a functional group that crosslinks upon irradiation and a second organometallic compound having at least two hydrolyzable groups, and hydrolyzable group 1 in the polycondensate A step of adding only one metal alkoxide and / or a hydrolyzate thereof, and a step of curing the polycondensate by causing a crosslinking reaction by a functional group by heating or irradiating the polycondensate after the addition. It is characterized by comprising.

  In a preferred aspect of the production method of the present invention, an organic anhydride and / or an organic acid is added to the polycondensate together with the metal alkoxide and / or a hydrolyzate thereof.

  The production method according to another aspect of the present invention includes a first organometallic compound having at least two hydrolyzable groups, a functional group that crosslinks by heating and / or irradiation with energy rays, and at least two hydrolyzable groups. A step of hydrolyzing and polycondensing a mixture of a second organometallic compound having a group, a step of adding an organic acid anhydride and / or an organic acid to the polycondensate, and heating the polycondensate after the addition Alternatively, the method includes a step of curing the polycondensate by causing a crosslinking reaction by a functional group by irradiation with energy rays.

  The optical component of the present invention is formed using the organometallic polymer material of the present invention or the organometallic polymer material produced by the method of the present invention.

  The adhesive composition of the present invention is characterized by comprising the organometallic polymer material of the present invention or the organometallic polymer material produced by the method of the present invention.

  An optical component can be produced by bonding a plurality of optical components using the adhesive composition of the present invention.

  The laminated structure of the present invention is a laminated structure formed on a substrate using the organometallic polymer material of the present invention or the organometallic polymer material produced by the method of the present invention, and bonded to the metal atom M. It is characterized in that the amount of OH groups is large on the substrate side and small on the surface side of the laminated structure.

  As described above, by increasing the amount of OH groups on the substrate side and decreasing the amount of OH groups on the surface side of the laminated structure, adhesion to the substrate can be improved. For example, when the metal atom M is Si, the amount of Si—OH groups is large on the substrate side and small on the surface side.

  By forming an inclined structure with respect to the amount of OH groups in the laminated structure, a structure having good adhesion to the substrate can be formed without impairing the physical properties of the surface of the laminated structure. For example, the smaller the amount of OH groups, the better the physical properties such as heat resistance. However, in the laminated structure of the present invention, the amount of OH groups on the surface side can be reduced, so that the physical properties such as heat resistance are improved. An excellent structure can be obtained. In addition, the light loss can be reduced when the amount of OH groups is small. However, in the laminated structure of the present invention, the amount of OH groups on the surface side can be reduced. A member can be formed.

  As methods for improving the adhesion between the organic polymer and the substrate, Patent Documents 5 and 6 disclose a method of changing the component ratio of the organic component and the inorganic component. However, in such a method, the physical properties are greatly different between the substrate side and the surface side, and for example, in a region where there are many organic components, there arises a problem that heat resistance is lowered.

  Since the organometallic polymer material of the present invention is composed of an organometallic polymer having a —M—O—M— bond, it has high heat resistance. Further, since it contains a metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof, it is possible to eliminate a silanol group or the like present at the end of the molecule of the organometallic polymer. Light propagation loss in the wavelength range of ˜1550 nm can be reduced. For this reason, it has the outstanding translucency.

  Since the organometallic polymer material of the present invention has high heat resistance, excellent translucency, and also has the characteristics of being flexible, it can be used for electrical wiring boards, mechanical component materials, antireflection. Various coating materials such as films and surface protective films, optical transmission / reception modules, optical switches, optical communication devices such as optical modulators, optical propagation path structures such as optical waveguides, optical fibers, lens arrays, and light beams such as optical beam splitters including them Devices, integrator lenses, microlens arrays, reflectors, light guide plates, projection screens and other display device (display or liquid crystal projectors) related optical elements, glasses, CCD optical systems, lenses, composite aspherical lenses, 2P ( Photoreplication Process) Lens, optical filter, diffraction grating, interferometer, optical coupler, optical multiplexer / demultiplexer, optical sensor Hologram optical element, other optical component materials, photovoltaic devices, contact lenses, medical artificial tissues, is a useful material in the molding material or the like of the light emitting diode (LED).

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by a following example.

(Examples 1-15 and Comparative Examples 1-2)
In each of the following examples and comparative examples, the synthesis of the material is performed by the following process P or process Q.

<Process P>
(1)
Organometallic compound A shown in Table 1: 5.5 ml (5.4 g in the case of Example 1)
Organometallic compound B shown in Table 1: 5.8 ml (in the case of Example 1, 6.2 g)
An aqueous solution containing hydrochloric acid as a reaction catalyst (hydrochloric acid having a concentration of 2N: 1.65 ml)
Ethanol: 20.5ml
After mixing, the organometallic compound A and the organometallic compound B were hydrolyzed and polycondensed by allowing to stand for 24 hours.

(2)
4 ml of the resulting polycondensate solution is taken in a petri dish, 10 mg of 1-hydroxy-cyclohexyl-phenyl-ketone is dissolved as a polymerization initiator, and then heated at 100 ° C. to evaporate and remove ethanol to give a viscosity of about 1 g. Liquid A was obtained.

In 1 g of viscous liquid A, metal alkoxide X shown in Table 1: 3 ml (in the case of Example 1, 2.3 g)
Organic acid Y shown in Table 1: 0.8 ml (in the case of Example 1, 1.2 g)
The mixture was allowed to stand for 24 hours, and then dried by heating to 100 ° C., whereby excess metal alkoxide X and organic acid Y were removed by evaporation to obtain viscous liquid B.

(3)
The viscous liquid B was irradiated with ultraviolet rays (wavelength 365 nm) and cured to be solidified.

<Process Q>
(1)
Organometallic compound A shown in Table 1: 5.5 ml (5.4 g in the case of Example 4)
Organometallic compound B shown in Table 1: 5.8 ml (in the case of Example 4, 6.2 g)
An aqueous solution containing hydrochloric acid as a reaction catalyst (hydrochloric acid having a concentration of 2N): 1.65 ml
Ethanol: 20.5ml
After mixing, the organic metal compound A and the organic metal compound B were hydrolyzed and polycondensed by allowing to stand for 24 hours.

(2)
4 ml of the resulting polycondensate solution was placed in a petri dish, 10 mg of 1-hydroxy-cyclohexyl-phenyl-ketone was dissolved as a polymerization initiator, and then heated at 100 ° C. to evaporate and remove ethanol. A viscous liquid A was obtained.

(3)
In 1 g of viscous liquid, metal alkoxide X shown in Table 1: 0.02 ml (in the case of Example 4, 15 mg)
Organic acid shown in Table 1: 0.01 ml (15 mg in the case of Example 4)
Were mixed and stirred to obtain a viscous liquid C.

(4)
The viscous liquid C was irradiated with ultraviolet rays (wavelength 365 nm) and cured to be solidified.

  Hereinafter, the raw material used in each Example and each comparative example is demonstrated.

(Example 1)
3-Methacryloxypropyltriethoxysilane was used as the organometallic compound A, phenyltrimethoxysilane was used as the organometallic compound B, trimethylethoxysilane was used as the metal alkoxide, and trifluoroacetic anhydride was used as the organic acid Y.

(Example 2)
Example 1 was repeated except that trifluoroacetic acid was used as the organic acid Y.

(Example 3)
Except not using the metal alkoxide X, the procedure was the same as in Example 1.

Example 4
It was produced in the same manner as in Example 1 except that it was synthesized by Step Q.

(Example 5)
A metal alkoxide X and an organic acid Y were produced in the same manner as in Example 4 except that the amount of metal alkoxide X and organic acid Y was reduced to one third of that in Example 4.

(Example 6)
Example 1 was repeated except that trifluoropropyltrimethoxysilane was used as the organometallic compound B.

(Example 7)
The procedure was the same as Example 1 except that the organic acid Y was not used.

(Example 8)
The same procedure as in Example 1 was carried out except that terminal silanol-type polydimethylsiloxane (OH [Si (CH ₃ ) ₂ O] nH) (n = average 2000), which is the raw material of the silicone resin, was used as the organometallic compound B.

Example 9
Example 1 was repeated except that 3-methacryloxypropyltrimethoxysilane was used as the organometallic compound A and zirconium isopropoxide was used as the organometallic compound B.

(Example 10)
Example 3 was repeated except that 3-acryloxypropyltrimethoxysilane was used as the organometallic compound A and titanium isopropoxide was used as the organometallic compound B.

(Comparative Example 1)
The procedure was the same as Example 1 except that the metal alkoxide X and the organic acid Y were not used.

(Comparative Example 2)
Comparative Example 1 was performed except that terminal silanol-type polydimethylsiloxane was used as organometallic compound B.

(Examples 11 to 15)
Viscous liquid B was synthesized using organometallic compounds A and B, metal alkoxide X, and organic acid Y shown in Table 2, and cured by irradiating it with ultraviolet rays.

[Evaluation of light propagation loss]
The viscous liquid B or C was dropped onto a quartz glass substrate having a thickness of 1 mm, irradiated with ultraviolet rays (wavelength 365 nm), and cured to prepare a sample. Two types of samples were prepared, and the thicknesses of the samples were 70 μm and 300 μm, respectively. Using these samples, the transmittance was obtained by a spectrophotometer, and the light propagation loss (dB / cm) in the wavelength range of 500 to 1100 nm, 1300 to 1350 nm, and 1450 to 1550 nm was measured from the transmittance. The results are shown in Tables 1 and 2.

  Moreover, the relationship between the wavelength and the light propagation loss in the sample of Example 1 is shown in FIG. FIG. 3 shows the comparative example 1.

[Infrared absorption spectroscopy]
Using each of the above samples, infrared absorption spectroscopy (IR) analysis was performed. 1A and 13A are those of Example 1, and FIGS. 1B and 13B are those of Comparative Example 1. FIG. FIGS. 13A and 13B are IR spectra with a wave number range of 800 to 4000 cm ⁻¹ . 14 (a) and 14 (b) show IR spectra of the precursor (liquid) before light irradiation in Example 1 and Comparative Example 1. FIG. As is clear from the comparison between FIG. 1 (a) and FIG. 13 (a) and FIG. 1 (b) and FIG. 13 (b), in the sample of Example 1 according to the present invention, silanol groups in the vicinity of 3400 cm ⁻¹ ( It can be seen that the peak of (SiOH group) has disappeared. This is considered to be because the silanol group in the organometallic polymer was reacted with the silanol group by containing the metal alkoxide X, thereby eliminating the silanol group.

Further, in the infrared absorption spectroscopic analysis, ratio values of absorption peak height of trifluoroacetic acid (near 1780 cm ⁻¹ ) / absorption peak height due to Si—O (near 1100 cm ⁻¹ ) are shown in Tables 1 and 2. It was shown to.

When the metal atom M is Si, the cured product of the organometallic polymer material of the present invention has a (high absorption peak height of Si—OH bond in the vicinity of 3400 cm ⁻¹ ) / (2900 cm) in the IR spectrum as described above. It is preferable that a silanol group (Si—OH) is included so that the ratio of the absorption peak height of the C—H bond in the vicinity of ⁻¹ is 0.2 or less. By setting the peak ratio to 0.2 or less, it is possible to reduce the optical propagation loss at wavelengths of 500 to 1100 nm, 1300 to 1350 nm, and 1450 to 1550 nm to 1.5 dB / cm or less. The peak ratios of the IR spectra in Examples 1, 5, and 7 and Comparative Example 1 are shown below.

Example 1: 0.08
Example 5: 0.2
Example 7: 0.12
Comparative Example 1: 0.42

[Measurement of residual amount of alkoxide hydrolyzate]
The amount of trimethylsilanol in the cured organometallic polymer was measured. Specifically, trimethylsilanol in the solid material was extracted with a solvent, and the extract was measured by gas chromatography. The measurement results are shown in Tables 1 and 2.

(Analysis of reaction products)
In the solid material prepared using trimethylethoxysilane and trifluoroacetic acid, the generated compound was analyzed in more detail. Specifically, the analysis was performed using a heat extraction gas chromatograph mass spectrometer. In this apparatus, a substance that is desorbed by heating a sample is introduced into mass separation gas chromatography for analysis. As a result of the analysis, an ester (CF ₃ COOC ₂ H ₅ ) derived from trifluoroacetic acid was detected from the sample using trifluoroacetic acid, and the hydrolysis polycondensate of trimethylethoxysilane from the sample using trimethylethoxysilane. Hexamethyldisiloxane (CH ₃ ) ₃ SiOSi (CH ₃ ) ₃ ) was detected, and both compounds were detected from the sample using both trifluoroacetic acid and trimethylethoxysilane. By detecting these substances, it can be confirmed that trifluoroacetic acid and trimethylethoxysilane are added in the material synthesis step or the like.

[Measurement of transmittance maintenance ratio]
Using the sample, the change with time in transmittance at 1550 nm was evaluated. Specifically, the transmittance before and after leaving at room temperature for 1000 hours is measured, and (transmittance after leaving) / (transmittance before leaving) × 100 is set as the maintenance factor of transmittance. The results are shown in Tables 1 and 2.

  As shown in Table 1 and Table 2, it can be seen that Examples 1 to 15 according to the present invention have reduced light propagation loss in the wavelength region of 1450 to 1550 nm compared to Comparative Examples 1 and 2. This is because silanol groups in the organometallic polymer are reduced by the addition of metal alkoxide X and / or organic acid Y.

  Further, it can be seen that those having a large residual amount of alkoxide tend to have a high transmittance maintenance factor. Therefore, the maintenance factor of the transmittance can be increased by the alkoxide remaining in the organometallic polymer. This is considered to be because the alkoxide annihilates the silanol group generated by the water absorbed by the organometallic polymer.

(Examples 15-1 to 15-7)
Viscous liquid B was synthesized using organometallic compounds A and B, metal alkoxide X, and organic acid Y shown in Table 3, and cured by irradiating it with ultraviolet rays. The cured samples were evaluated in the same manner as in Examples 11 to 15, and the results are shown in Table 3.

(Examples 15-8 to 15-11)
The organometallic polymer material was synthesized by the following step R.

<Process R>
A viscous liquid B was synthesized in the same manner as in Step P using the organometallic compounds A and B, the metal alkoxide X, and the organic acid Y shown in Table 4. Further, the particles Z shown in Table 4 were added to the solvent S so as to have a ratio of 10% by weight and mixed and dispersed to obtain a particle dispersion. 1 g of this particle dispersion was added to 1 g of viscous liquid B and stirred, and then heated and dried at 100 ° C. to evaporate and remove solvent S, whereby viscous solution D was obtained.

  The viscous solution D was cured by irradiating it with ultraviolet rays, and the cured sample was evaluated in the same manner as in the above Example. The results are shown in Table 4.

  The average particle size of the particles Z shown in Table 4 is as follows.

ZrO ₂ particles (Example 15-8): about 10 nm
Nb ₂ O ₅ particles (Example 15-9): about 10 nm
TiO ₂ particles (Example 15-10): about 20 nm
SiO ₂ particles (Example 15-11): about 10 nm
Table 4 also shows the evaluation results of Example 1.

As is clear from a comparison between Example 1 and Examples 15-8 to 15-11 shown in Table 4, the refractive index of the organometallic polymer material can be controlled by adding the particles Z. When ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles are added as the particles Z, the refractive index can be increased. Further, when SiO ₂ particles are added as the particles Z, the refractive index can be lowered.

(Examples 15-12 to 15-14)
The organometallic polymer material was synthesized by the following step S.

<Process S>
(1)
Organometallic compound A shown in Table 5: 10 ml
Organometallic compound B shown in Table 5: 4.1 ml
An aqueous solution containing hydrochloric acid as a reaction catalyst (hydrochloric acid having a concentration of 2N: 1.65 ml)
Ethanol: 20.5ml
After mixing, the organometallic compound A and the organometallic compound B were hydrolyzed and polycondensed by allowing to stand for 24 hours.

(2)
4 ml of the resulting polycondensate solution is taken in a petri dish, 10 mg of 1-hydroxy-cyclohexyl-phenyl-ketone is dissolved as a polymerization initiator, and then heated at 100 ° C. to evaporate and remove ethanol to give a viscosity of about 1 g. Liquid A was obtained.

In 1 g of viscous liquid, metal alkoxide X shown in Table 5: 3 ml
Organic acid Y shown in Table 5: 0.8 ml
The mixture was allowed to stand for 24 hours, and then dried by heating to 100 ° C., whereby excess metal alkoxide X and organic acid Y were removed by evaporation to obtain viscous liquid B.

(3)
0.45 g (45 wt%) of the organic polymer Z shown in Table 5 was added to 0.55 g of the viscous liquid B, followed by stirring to obtain a viscous solution E.
The viscous solution E was irradiated with ultraviolet rays and cured, and the cured sample was evaluated in the same manner as in the above Example. The results are shown in Table 5.
In addition, as the organic polymer Z, the following are used in each Example.
Example 15-12: Urethane acrylate photocurable resin Example 15-13: Polyester acrylate photocurable resin Example 15-14: Epoxy acrylate photocurable resin

  In the formulation of Examples 15-12, even when the amount of the urethane acrylate resin was changed in the range of 5 to 95% by weight, a transparent material was obtained, and the transmittance of the sample having a thickness of 3 mm was at a wavelength of 630 nm. It was 80% or more. In particular, when the amount of the urethane acrylate resin was 20 to 60% by weight, a high transmittance was obtained. Specifically, in a sample having a thickness of 3 mm, a transmittance of 90% or more was obtained at a wavelength of 630 nm.

  Further, when an acrylate resin, an epoxy resin, or a urethane resin was used as the organic polymer Z, the same result as above was obtained.

[Evaluation of various properties]
Various characteristics were evaluated using the sample prepared in Example 1.

(1) Glass transition temperature The glass transition temperature was evaluated using a dynamic viscoelasticity measuring apparatus. FIG. 15 shows the results. In FIG. 15, E ′ is a storage elastic modulus, E ″ is a loss elastic modulus, and TAN DELTA.
Indicates a loss tangent. E ′, E ″ and TAN DELTA do not change up to around 350 ° C. Therefore, it can be seen that the sample produced in Example 1 has a high glass transition temperature of 300 ° C. or higher.

(2) Thermal deformation temperature The thermal deformation temperature was measured using a thermomechanical analyzer (manufactured by Shimadzu Corporation, TMA-50). Using this apparatus, the material was heated in a state where the indenter was pressed against the material surface with a constant load, and the displacement and temperature at that time when the indenter entered the material by softening the material were measured. The measurement results are shown in FIG.

  As shown in FIG. 16, the amount of change in the position of the indenter is increased around 380 ° C., and it can be seen that the sample has a high heat distortion temperature of 350 ° C. or higher.

(3) Temperature dependence of refractive index The temperature dependence of the refractive index was measured at a measurement wavelength of 630 nm using a prism coupler device. The measurement results are shown in FIG. From the slope of the straight line shown in FIG. 17, it can be seen that the refractive index temperature dependency of the sample is about 2 × 10 ⁻⁴ / ° C.

(4) Measurement of birefringence characteristics Birefringence characteristics were measured at a measurement wavelength of 630 nm and 1300 nm using a prism coupler device. Here, the birefringence characteristics were evaluated by the absolute value of the difference (Δn) between the refractive index of the TE mode and the refractive index of the TM mode. As a result of measurement with 10 samples, Δn was 0.0005 or less at both wavelengths of 630 nm and 1300 nm.

(5) Measurement of density As a result of measuring the density of the sample according to the underwater substitution method (JIS K7112-1980), it was about 1.2 g / cm ³ at 23 ° C. The volume hardening shrinkage calculated using this density was about 3.5%.

(6) Measurement of refractive index control range In Example 1, a sample in which the mixing ratio of organometallic compound A (MPTES) and organometallic compound B (PhTMS) was changed was prepared, and the refractive index of each obtained sample was measured. Measurements were made. The refractive index was measured at a measurement wavelength of 630 nm using a prism coupler device.

  FIG. 18 is a diagram showing the relationship between the MPTES content (% by weight) in the sample and the refractive index of the sample. As shown in FIG. 18, it is understood that the refractive index can be controlled by changing the mixing ratio of the organometallic compounds A and B.

(7) Measurement of water absorption rate The water absorption rate was measured for each sample prepared in (6) above, in which the mixing ratio of the organometallic compound A (MPTES) and the organometallic compound B (PhTMS) was changed. The measured water absorption is the water absorption when left in water at 23 ° C. for 24 hours, and was measured according to JIS K7209-1984. As a result, the water absorption of all the samples was 1% by weight or less.

(8) Molecular weight of precursor (liquid before curing) The degree of polymerization of the precursor before ultraviolet irradiation in Example 1 was measured by gel permeation chromatography analysis. Chloroform was used as the eluent. As a result, the weight average molecular weight was about 2000.

(9) Change in birefringence characteristics due to difference in curing method The birefringence characteristics of the organometallic polymer material obtained when the viscous liquid B of Example 1 is cured by heating, and the viscous liquid B of Example 1 with ultraviolet light The birefringence characteristics of the organometallic polymer material obtained when cured were compared. Viscous liquid B is dropped on a glass substrate and cured by heating at temperatures of 100 ° C., 120 ° C., 140 ° C., 160 ° C., and 180 ° C. The birefringence characteristics were evaluated at a measurement wavelength of 630 nm using a coupler apparatus. The evaluation results are shown in FIG. The heating time was 1 hour.

Further, after the viscous liquid B was dropped onto the glass substrate in the same manner as described above, the viscous liquid B was cured by irradiation with ultraviolet rays (wavelength 365 nm) at room temperature so as to have an intensity of about 4 μmW / cm ² . The ultraviolet irradiation time was 10 minutes, 20 minutes, 40 minutes and 60 minutes. For the cured coating film (thickness 20 μm), the birefringence characteristics were evaluated in the same manner as described above, and the evaluation results are shown in FIG.

  As shown in FIG. 21, when the heating temperature was 100 ° C. and 120 ° C., it could not be cured. Moreover, as shown in FIG. 22, when the ultraviolet irradiation time was 10 minutes, it could not be cured. As is clear from FIG. 21, a tendency for the birefringence to increase as the heating temperature increases was observed. On the other hand, in the case of curing by ultraviolet irradiation, as shown in FIG. 22, even when the ultraviolet irradiation time was increased, almost no change in birefringence was observed. It is considered that the difference in thermal expansion coefficient between the glass serving as the substrate and the organometallic polymer material is considered to be a cause of the increase in birefringence as the heating temperature increases.

  FIG. 23 is a diagram showing an IR chart of an organometallic polymer material heat-cured at 180 ° C. for 1 hour. As shown in FIGS. 23 and 13 (a), it can be seen that substantially the same peak is obtained in the case of heat curing and in the case of ultraviolet curing, and almost the same cured product is obtained.

  From the above, it is understood that ultraviolet curing is preferable when it is desired to form an organometallic polymer material having low birefringence.

(10) Relationship between Refractive Index and Birefringence In Example 1, the mixing ratio of the organometallic compounds A and B was changed, thereby changing the refractive index, and the relationship between the refractive index and birefringence was examined.
FIG. 24 is a diagram showing the refractive index and birefringence when the mixing ratio of the organic metals A and B is changed. As can be seen from FIG. 24, even when the refractive index is changed, the birefringence hardly changes, and a low birefringence can be obtained.

(Example 16)
A cylindrical lens was produced using the viscous liquid B of Example 1. 4A, a silicone rubber mold 2 having a cylindrical recess 2a having a diameter of 5 mm and a depth of 10 mm is used. As shown in FIG. 4B, a viscous liquid is applied to the recess 2a of the mold 2. Solution 1 consisting of B was poured.

  Next, as shown in FIG. 4C, ultraviolet light 3 was irradiated to cure the solution 1 to produce a cylindrical lens 4.

(Example 17)
A hemispherical lens was manufactured using the viscous liquid B of Example 1. As shown in FIG. 5 (a), a silicone rubber mold 2 having a hemispherical recess 2a having a diameter of 5 mm is used, and as shown in FIG. As shown in FIG. 5C, ultraviolet light 3 was irradiated to cure the solution, and a hemispherical lens 5 was produced.

(Example 18)
As shown in FIG. 6A, the cylindrical lens 4 produced in Example 16, the hemispherical lens 5 produced in Example 17, and the solution 1 consisting of the viscous liquid B of Example 1 are used as an adhesive. Pasted together.

  In the state shown in FIG. 6B, the ultraviolet ray 3 was applied to cure the adhesive 6 to produce a bullet-type lens 7 as shown in FIG. 6C.

(Example 19)
As shown in FIG. 7A, a rectangular beam 10 (wavelength 1550 nm) having a beam size of 2 mm × 5 mm was incident on the cylindrical lens 4 manufactured in Example 16, and the emitted light was observed with the infrared camera 11. As a result, a beam having a spot size of 0.1 mm × 5 mm was obtained, and it was confirmed that the cylindrical lens 4 has a light collecting property.

  As shown in FIG. 7B, a light beam (wavelength 1550 nm) having a beam diameter of 2 mm was incident on the hemispherical lens 5 manufactured in Example 17, and the emitted light was observed with the infrared camera 11. As a result, a beam having a spot size with a diameter of 0.1 mm was obtained, and it was confirmed that the hemispherical lens 5 has a condensing characteristic.

  As shown in FIG. 7C, a light beam (wavelength 1550 nm) having a beam diameter of 2 mm was incident on the bullet-type lens 7 produced in Example 18, and the emitted light was observed with the infrared camera 11. As a result, a beam having a spot size with a diameter of 0.1 mm was obtained, and it was confirmed that the cannonball type lens 7 had a condensing characteristic.

(Comparative Example 3)
In Example 18, instead of using the viscous liquid B of Example 1 as an adhesive, a bullet-type lens was produced using an acrylic ultraviolet curable resin. When this bullet-type lens was subjected to a heat resistance test at 180 ° C. for 10 hours, peeling of the adhesive portion occurred in 8 out of 10 samples. On the other hand, in the bullet-type lens produced in Example 18, no peeling at the bonded portion was observed in all ten samples.

(Example 20)
10 parts by weight of a white fluorescent material is mixed with 100 parts by weight of the viscous solution B of Example 1, this mixed solution is molded around an ultraviolet LED chip, cured by irradiation with ultraviolet rays (365 nm), and a white LED element. Was made. FIG. 8 is a cross-sectional view showing this white LED element. As shown in FIG. 8, a mold 20 is formed around the ultraviolet LED chip 21, and the electrode REIT 22 is taken out from the mold 20 to the outside.

  The decrease rate of the light output after 1000 hours of continuous lighting was about 2%.

(Comparative Example 4)
In Example 20, it replaced with the viscous solution B and produced the white LED element molded using the epoxy resin. The decrease in light output after 1000 hours of continuous lighting was about 4%.

(Example 21)
Using the viscous liquid B of Example 1, an optical communication lens array was produced. A silicone rubber mold 12 shown in FIG. 9A was used. A rectangular recess 12a is formed in the mold 12, and a hemispherical recess 12b is further formed on the bottom surface of the recess 12a. As shown in FIG. 9B, the viscous solution 1 made of the viscous liquid B was poured into the recesses 12a and 12b, and the ultraviolet light 3 was irradiated to cure the solution 1. As a result, a lens array 13 having a hemispherical lens portion 13a as shown in FIG. 9C was obtained. The hemispherical lens portions 13a are formed at intervals of 250 μm.

  Next, as shown in FIG. 10, this lens array 13 is installed between the optical fiber 14 and the optical splitter 15, and the optical fiber 14 and the lens array 13, and between the lens array 13 and the optical splitter 15, are shown in Example 12. The liquid was fixed using a viscous liquid B and optically coupled. As a result, compared to the case where the lens array 13 is not used, the coupling loss can be reduced by 0.4 dB.

(Example 22)
The photocured product of the viscous liquid B of Example 1 is used as a core material, and the refractive index after photocuring is about 0.006 smaller than the photocured product of the viscous liquid B by changing the mixing ratio of the organometallic compounds A and B. A four-branch optical waveguide was manufactured using the set photocured product of the viscous liquid B ′ as a clad.

  FIG. 11 is a plan view showing a branch pattern of the core of the manufactured four-branch optical waveguide. As shown in FIG. 11, the core 24 branches into four branch cores 24 a to 24 d, and these are surrounded by the clad 22.

  FIG. 12 is a cross-sectional view showing a process of manufacturing the four-branch optical waveguide shown in FIG. As shown in FIG. 12A, a viscous liquid B ′, which is a clad solution, is applied on a glass substrate 31 to form a clad solution layer 22a. Next, as shown in FIG. 12B, a convex stamper 32 is pressed against the clad solution layer 22a, and in the state shown in FIG. 12C, the clad solution layer 22a is irradiated with ultraviolet light having a wavelength of 365 nm. A first cladding layer 22 was formed. The first cladding layer 22 has a recess 23a and a recess 23b.

After removing the convex stamper 32, as shown in FIG. 12D, the viscous liquid B, which is a core solution, is applied onto the first cladding layer 22, and the core solution is filled in the recesses 23a and 23b. Then, the silicone rubber flat plate 33 having a durometer hardness of A56 was pressed at a pressure of 200 gf / cm ² , and in this state, ultraviolet light having a wavelength of 365 nm was irradiated to cure the core solution layer 24a. Thereby, the core 24 (core diameter 7 μm) and the light absorber layer 28 were formed. The light absorber layer 28 is made of the same material as the core 24 and has an effect of absorbing light leaking from the core 24. The light absorber layer 28 is not shown in FIG.

  After the flat plate 33 is removed and brought into the state of FIG. 12 (f), a viscous liquid B ′, which is a clad solution, is applied on the core 24 and the light absorber layer 28 to form a clad solution layer, and then a glass substrate. 30 was placed thereon, and the clad solution layer was cured by irradiating with ultraviolet rays to form the second clad layer 26a.

  As a result of introducing light having a wavelength of 1300 nm and 1550 nm into a four-branch optical waveguide manufactured as described above using a single-mode optical fiber having a core diameter of about 7 μm, light branched into four from the output end after four branches is output. It was confirmed by an infrared camera.

  As described above, the organometallic polymer material of the present invention can be used as various optical components and adhesive compositions.

  The organometallic polymer material of the present invention is excellent in heat resistance and translucency, and heat resistance having a glass transition temperature of 300 ° C. or higher is obtained.

  Further, by using the organometallic polymer material of the present invention, processing at a high temperature, which has been difficult with conventional plastic substrate materials, becomes possible. For example, when a plastic substrate is used in a dye-sensitized solar cell using titanium oxide as a power generation layer, the conventional plastic substrate cannot be heated at a high temperature, so that the sintering of titanium oxide does not proceed and the conversion efficiency is about 5%. However, by using the organometallic polymer material of the present invention, heating at about 300 ° C. is possible, and the conversion efficiency can be increased to about 8%.

(Example 23)
As described above, the organometallic polymer material of the present invention is applied on a substrate to form a layer having good adhesion. As described above, the amount of OH groups such as silanol groups is increased on the substrate side, and on the surface side. A method of reducing it is mentioned. Examples of the laminated structure of the present invention according to this method will be described below.

  FIG. 19 is a cross-sectional view showing an example of a laminated structure according to the present invention. A first organometallic polymer layer 32 is formed on the glass substrate 31, and a second organometallic polymer layer 33 is formed thereon. The first and second organometallic polymer layers 32 and 33 are both organometallic polymers formed from metal alkoxide. The first organometallic polymer layer 32 contains relatively many silanol groups, which are OH groups, and the second organometallic polymer layer 33 has relatively few silanol groups.

  The first organometallic polymer layer 32 was formed using the precursor (viscous liquid) of Comparative Example 1. Specifically, the precursor of Comparative Example 1 was spin-coated on the glass substrate 31, and then heated at about 140 ° C. for 1 hour to form a first organometallic polymer layer 32 of about 2 μm. Next, after applying the precursor (viscous liquid) of Example 1 onto the first organometallic polymer layer 32, it was cured by irradiating with ultraviolet rays in the same manner as in Example 1, and the thickness was about 70 μm. A second organometallic polymer layer 33 was formed.

  As a comparison, as shown in FIG. 20, a second organic metal polymer layer 33 was directly formed on the glass substrate 31 without forming the first organic metal polymer layer 32.

  Ten samples were prepared, and each sample was left for 48 hours under high temperature and high humidity conditions of 85 ° C. and 80%, and then a peel test was performed. In the comparative sample shown in FIG. 20, 3 out of 10 samples were peeled off, but in the sample in which the first organometallic polymer layer 32 shown in FIG. 19 was formed, no peeling was observed in all the samples. .

  In the laminated structure shown in FIG. 19, the reason why the adhesion to the substrate is improved as described above is considered as follows. That is, many OH groups are present on the surface of a substrate mainly composed of an oxide such as glass, but the second organometallic polymer layer 33 reduces the optical loss. The group is reduced as much as possible, and the polycondensation reaction with the OH group on the substrate surface is difficult. By providing the first organometallic polymer layer 32 having a relatively large amount of OH groups between the second organometallic polymer layer 33 and the substrate 31, the OH groups on the substrate surface and the first OH groups on the first organometallic polymer layer 32 are provided. It is considered that the OH group of the organometallic polymer layer is bonded by polycondensation. In addition, it is considered that strong bonding occurs between the first organometallic polymer layer 32 and the second organometallic polymer layer 33 due to photopolymerization of the acrylic group. It has been confirmed that the material of the first organometallic polymer layer 32 has a glass transition temperature of 300 ° C. or higher, like the material of the second organometallic polymer layer 33.

(Example 24)
In Example 23, in forming the laminated structure shown in FIG. 19, the first organometallic polymer layer 32 was formed using only the organometallic compound A (MPTES) without using the organometallic compound B (PhTMS). A laminated structure was produced in the same manner as in Example 23 except that the precursor (viscous liquid) prepared in the same manner as in Example 1 was used. When 10 samples of the obtained laminated structure were subjected to a peel test in the same manner as in Example 23, no peel was observed for all 10 samples.

(Example 25)
In the production of the four-branch optical waveguide of Example 22 shown in FIG. 12, the first organometallic polymer layer having a relatively large amount of OH groups is formed on the glass substrate 31 with a thickness of 2 μm in the same manner as in Example 23. Then, a four-branch optical waveguide was produced in the same manner as in Example 22 except that the clad solution layer 22a was formed thereon. When the obtained optical waveguide was subjected to a peel test in the same manner as in Example 23, no peel was observed in all 10 samples. Therefore, it was confirmed that the adhesion with the substrate was good.

(Example 26)
A composite aspherical lens was produced using the viscous solution B of Example 1. A composite aspherical lens is an aspherical lens produced by using a spherical lens or flat plate made of glass or resin as a base material and forming an aspherical resin layer or the like on the optical surface of the base material. .

  As shown in FIG. 25 (a), a viscous solution 41 was dropped on a glass spherical lens 40 (base glass) having a diameter of 5 mm and a maximum thickness of 1 mm. The viscous solution 41 is the viscous solution B of Example 1. Next, as shown in FIG. 25B, a nickel mold 42 having an aspherical shape on the inner surface is pressed against the viscous solution 41 on the glass spherical lens 40, and then as shown in FIG. 25C. The ultraviolet ray 44 was irradiated from the glass spherical lens 40 side to cure the viscous solution 41 to form a resin layer 43 made of an organometallic polymer material.

  Next, as shown in FIG. 25 (d), the mold 42 was removed, and as shown in FIG. 25 (e), a composite aspherical lens 45 composed of a glass spherical lens 40 and a resin layer 43 was obtained.

  Next, spherical aberration was observed using the apparatus shown in FIG. 26 for the obtained composite aspheric lens and the spherical lens on which no resin layer was formed. A lens 47 is arranged between the screen 48 on which the mesh pattern is formed and the CCD camera 46, and the mesh pattern on the screen 48 is enlarged and observed by the CCD camera 46. The mesh pattern on the screen 48 is a mesh pattern 49 having an interval of 0.5 nm as shown in FIG.

  When the glass spherical lens 40 was used as the lens 47, a distorted mesh pattern image as shown in FIG. 27B was observed due to the spherical aberration unique to the spherical lens. On the other hand, when the composite aspherical lens 45 manufactured as described above was used as the lens 47, an image in which the mesh pattern was faithfully enlarged as shown in FIG. 27A was obtained. .

  When a composite aspherical lens was produced in the same manner as described above using the viscous solution obtained in Examples other than Examples 15-12, for example, Example 1, the same results as above were obtained. .

  As described above, the organometallic polymer material of the present invention has high heat resistance and excellent translucency. By adding an organic or inorganic functional material to the organometallic polymer material of the present invention, the functionality of the functional material can be imparted.

The figure which shows the infrared absorption analysis chart in the Example of this invention. The figure which shows the relationship between the wavelength and light propagation loss in the Example of this invention. The figure which shows the relationship between the wavelength and light propagation loss in a comparative example. The perspective view which shows the process of producing the cylindrical lens in the Example of this invention. The perspective view which shows the process of producing the hemispherical lens in the Example of this invention. The perspective view which shows the process of producing the bullet-type lens in the Example of this invention. The schematic diagram which shows the evaluation method of the cylindrical lens, hemispherical lens, and bullet-type lens which were produced in the Example of this invention. Sectional drawing which shows the white LED element produced in the Example of this invention. Sectional drawing which shows the manufacturing process of the lens array produced in the Example of this invention. The perspective view which shows the state which has arrange | positioned the lens array produced in the Example of this invention between the optical fiber and the optical splitter. The top view which shows the 4 branch optical waveguide produced in the Example of this invention. Sectional drawing which shows the process of manufacturing the 4 branch optical waveguide shown in FIG. The figure which shows the infrared absorption analysis chart of the hardened | cured material of the organometallic polymer material in Example 1 of this invention. The figure which shows the infrared absorption analysis chart of the viscous liquid before hardening of the organometallic polymer material in Example 1 of this invention. The figure which shows the measurement result of the glass transition temperature of the hardened | cured material of the organometallic polymer material in Example 1 of this invention. The figure which shows the measurement result of the heat deformation temperature of the hardened | cured material of the organometallic polymer material in Example 1 of this invention. The figure which shows the measurement result of the temperature dependence of the refractive index of the hardened | cured material of the organometallic polymer material in Example 1 of this invention. The figure which shows the change of a refractive index when the mixing ratio of the organometallic compounds A and B in Example 1 of this invention is changed. Sectional drawing which shows an example of the laminated structure of this invention. Sectional drawing which shows the structure produced as a comparison. The figure which shows the relationship between the heating temperature and birefringence in the case of forming the organometallic polymer layer of this invention by heat curing. The figure which shows the relationship between the ultraviolet irradiation time and birefringence in the case of forming the organometallic polymer layer of this invention by ultraviolet curing. The figure which shows IR chart of the organometallic polymer material in the case where the organometallic polymer layer of this invention is heat-cured, and when ultraviolet-cured. The figure which shows the relationship between the mixture ratio of organometallic compound A and B, refractive index, and birefringence. The typical sectional view showing an example of the process of manufacturing the compound type aspherical lens of the present invention. The schematic diagram which shows the apparatus for observing the spherical aberration of a composite aspherical lens. The figure which shows the mesh pattern image at the time of observing using a glass spherical lens and a composite type aspherical lens.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... viscous solution 2 ... type | mold 2a ... recessed part 3 ... ultraviolet-ray 4 ... cylindrical lens 5 ... hemispherical lens 6 ... adhesive 7 ... bullet-type lens 10 ... incident light 11 ... infrared camera 12 ... type | mold 12a ... rectangular-shaped recessed part 12b ... Hemispherical concave portion 13 ... lens array 13a ... lens portion 14 ... optical fiber 15 ... optical splitter 20 ... mold 21 ... UV LED chip 22 ... electrode lead 31 ... substrate 32 ... first organometallic polymer layer 33 ... second organometallic Polymer layer 40 ... spherical glass lens 41 ... viscous solution 42 ... mold 43 ... resin layer 44 ... ultraviolet ray 45 ... composite aspheric lens 46 ... CCD camera 47 ... lens 48 ... screen with mesh pattern 49 ... mesh pattern

Claims (31)

  A metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof is contained in an organometallic polymer having a —M—O—M— bond (M is a metal atom). Organometallic polymer material.   2. The organometallic polymer material according to claim 1, wherein the metal alkoxide or a hydrolyzate thereof is contained in a state where it is not bonded to the organometallic polymer.   2. The organometallic polymer material according to claim 1, wherein the metal alkoxide or a hydrolyzate thereof is contained in a state of being bonded to the organometallic polymer.   The organometallic polymer material according to any one of claims 1 to 3, wherein the hydrolyzate of the metal alkoxide is a polycondensate of the hydrolyzate.   The organometallic polymer material according to any one of claims 1 to 4, wherein the organometallic polymer further contains an organic acid anhydride and / or an organic acid.   An organometallic polymer material characterized by containing an organic acid anhydride and / or an organic acid in an organometallic polymer having a MOMOM bond (M is a metal atom).   The said organometallic polymer is synthesize | combined by the hydrolysis and polycondensation reaction of the organometallic compound which has at least 2 hydrolyzable group, The any one of Claims 1-6 characterized by the above-mentioned. Organometallic polymer material.   8. The organometallic polymer material according to claim 7, wherein at least one of the organometallic compounds has a functional group that is cross-linked by heating and / or irradiation with energy rays.   9. The boiling point of the metal alkoxide or its hydrolyzate and / or the boiling point of the organic anhydride or organic acid is not higher than the thermosetting temperature of the organometallic polymer, 2. The organometallic polymer material according to item 1.   The organometallic polymer material according to any one of claims 1 to 5 and 7 to 9, wherein at least one of the metal alkoxide or a hydrolyzate thereof contains a fluorine atom. . At least 1 sort (s) of the said metal alkoxide or its hydrolyzate is the alkoxysilane represented by the following general formula, or its hydrolyzate, The any one of Claims 1-5 and 7-10 characterized by the above-mentioned. 2. The organometallic polymer material according to item 1.

(Here, R ₁ , R ₂ , and R ₃ are organic groups having 1 to 15 carbon atoms, and R ₄ represents an alkyl group having 1 to ₄ carbon atoms.)   The organometallic polymer material according to any one of claims 5 to 11, wherein the organic acid anhydride is trifluoroacetic anhydride and the organic acid is trifluoroacetic acid.   The organometallic polymer material according to claim 8, wherein the organometallic compound having a functional group has an acryloxy group, a methacryloxy group, a styryl group, a vinyl group, or an epoxy group as a functional group.   14. The organometallic polymer material according to claim 1, wherein M in the —M—O—M— bond of the organometallic polymer is Si, Ti, Nb, or Zr.   14. The M according to claim 1, wherein M in the —M—O—M— bond of the organometallic polymer is at least two of Si, Ti, Nb, and Zr. Organometallic polymer material.   14. The organometallic polymer material according to claim 1, wherein M in the —M—O—M— bond of the organometallic polymer is Si. In the infrared absorption spectrum, the ratio is 0.2 or less (the height of the absorption peaks of Si-OH bonds in the vicinity of 3400 cm ^-1) / (height of the absorption peak of the C-H bond around 2900 cm ^-1) Thus, the amount of silanol groups (Si-OH) in the organometallic polymer is adjusted.   The organometallic polymer material according to claim 16 or 17, wherein the organometallic polymer is a silicone resin.   The organometallic polymer material according to claim 16 or 17, wherein the organometallic polymer is synthesized by hydrolysis and polycondensation reaction of at least one alkoxysilane.   The organometallic polymer material according to claim 19, wherein at least one of the alkoxysilanes is an alkoxysilane having an acryloxy group, a methacryloxy group, a styryl group, a vinyl group, or an epoxy group.   21. The organometallic polymer according to any one of claims 1 to 20, wherein the light propagation loss in the wavelength range of 500 to 1100 nm, 1300 to 1350 nm, and 1450 to 1550 nm is 1.5 dB / cm or less. material.   The organic metal according to any one of claims 1 to 21, wherein the organometallic polymer contains at least one kind of particles made of a material having a refractive index different from that of the organometallic polymer. Polymer material.   The organometallic polymer material according to claim 22, wherein the particles are at least one selected from silicon oxide, niobium oxide, zirconium oxide, and titanium oxide. A first organometallic compound having at least two hydrolyzable groups; a second organometallic compound having a functional group that crosslinks by heating and / or irradiation with energy rays; and at least two hydrolyzable groups Hydrolyzing and polycondensing the mixture of
Adding a metal alkoxide having only one hydrolyzable group and / or a hydrolyzate thereof to the polycondensate;
A step of curing the polycondensate by causing a crosslinking reaction by the functional group by heating or irradiating the polycondensate after the addition. .   25. The method for producing an organometallic polymer material according to claim 24, wherein an organic acid anhydride and / or an organic acid is added to the polycondensate together with the metal alkoxide and / or a hydrolyzate thereof. A first organometallic compound having at least two hydrolyzable groups; a second organometallic compound having a functional group that crosslinks by heating and / or irradiation with energy rays; and at least two hydrolyzable groups Hydrolyzing and polycondensing the mixture of
Adding an anhydrous organic acid and / or an organic acid to the polycondensate;
A step of curing the polycondensate by causing a crosslinking reaction by the functional group by heating or irradiating the polycondensate after the addition. .   It formed using the organometallic polymer material of any one of Claims 1-23, or the organometallic polymer material manufactured by the method of any one of Claims 24-26, It is characterized by the above-mentioned. Optical component.   28. The optical component according to claim 27, wherein the optical component is a composite aspheric lens.   An adhesive composition comprising the organometallic polymer material according to any one of claims 1 to 23 or the organometallic polymer material produced by the method according to any one of claims 24 to 26. Stuff.   30. An optical component obtained by bonding a plurality of optical components using the adhesive composition according to claim 29. A laminated structure formed on a substrate using the organometallic polymer material according to any one of claims 1 to 23 or the organometallic polymer material produced by the method according to any one of claims 24 to 26. A laminated structure characterized in that the amount of OH groups bonded to the metal atom M is large on the substrate side and small on the surface side of the laminated structure.

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