JP2002309094A - Polymer material and polymer film - Google Patents

Abstract

(57) [Problem] To provide a highly reliable polymer material and a polymer film. SOLUTION: A highly reliable polymer material and polymer film can be obtained by adding a predetermined amount of a silicone compound and a photoacid generator to a branched polysilane compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a polymer material and a polymer film.

[0002]

2. Description of the Related Art Recently, polymer materials having high light transmittance have been used for protecting surfaces of glass, ceramics, plastics, etc., for preventing light reflection, for filter films for optical communication, and the like. As the above materials, PMMA (polymethyl methacrylate), polystyrene, epoxy, polyimide, silicone, polysilane and the like have been studied. It is desired that these materials do not easily change in refractive index, coefficient of thermal expansion, and the like with a change in temperature. for that reason,
Among the above polymer materials, polyimide-based, epoxy-based, and polysilane-based materials have attracted attention and have been improved.

As these materials, for example, a linear polysilane material is used for optical purposes (Japanese Patent Laid-Open No. 6-22 / 1994).
No. 2234), an example using amorphous polysilane (JP-A-11-287916), and an example using a linear polysilane or a branched polysilane (JP-A-8-267).
728).

[0004]

However, the above-mentioned conventional materials have the following problems. (1) The refractive index changes significantly with temperature. As a result, the characteristics of an optical component made of a film formed of such a material are greatly changed, and desired performance cannot be obtained. (2) When an electronic component or an optical component is solder-mounted at around 200 ° C. near the polymer film, the value of the refractive index of the polymer film changes to a value shifted from the initial value, and the temperature is returned to the original value. Also, the refractive index value does not return to the original value. (3) Even if the refractive index of the polymer film is significantly changed with good reactivity by irradiating ultraviolet light, the change in the refractive index changes discontinuously with respect to the irradiation energy. It is difficult to obtain with high irradiation energy with high accuracy.

Accordingly, an object of the present invention is to solve the above problems and provide a highly reliable polymer material and polymer film.

[0006]

To achieve the above object, the polymer material of the present invention is obtained by adding a predetermined amount of a silicone compound and a photoacid generator to a branched polysilane compound.

In addition to the above structure, the polymer material of the present invention may use, as the polysilane compound, a compound bonded to a hydrocarbon group, an alkoxy group, or a hydrogen atom in addition to the Si atom.

In addition to the above constitution, the polymer material of the present invention is a branched polysilane compound having a degree of branching of 2% or more and 50% or more.
% Of the compound is preferably used.

[0009] In addition to the above constitution, the silicone compound of the polymer material of the present invention comprises a crosslinkable or alkoxy group, and is preferably added at a compounding ratio of 40 to 90 wt% with respect to the polysilane compound.

In addition to the above constitution, the polymer material of the present invention uses trichloromethyltriazine as a photoacid generator,
It is preferable that the trichloromethyltriazine-based compound is added to the polysilane compound at a mixing ratio of 1 wt% or more and 5.5 wt% or less.

In addition to the above constitution, the polymer material of the present invention may use a deuterated branched polysilane compound as the polysilane compound.

In addition to the above constitution, the polymer material of the present invention may use a partially or completely halogenated compound as the polysilane compound.

In addition to the above constitution, the polymer material of the present invention may use a deuterated compound as the silicone compound.

[0014] In addition to the above constitution, in the polymer material of the present invention, the silicone compound may be a compound partially or wholly halogenated.

In addition to the above constitution, the compound of the polymer material of the present invention may be dissolved in a compatible organic solvent.

The polymer film of the present invention is prepared by pouring the polymer material solution having the above-mentioned composition into a mold or applying it on a substrate in an environment not irradiated with ultraviolet light, and then performing a heat treatment at 100 ° C. or more and 280 ° C. or less. Cured.

In addition to the above structure, the polymer film of the present invention may have a refractive index changed by irradiating the polymer material with ultraviolet light.

In the polymer film of the present invention, in addition to the above structure, an ultraviolet light cut layer may be formed on the surface of the polymer material.

According to the present invention, by adding a predetermined amount of a silicone compound and a photoacid generator to a branched polysilane compound, the baking temperature is raised to about 250 ° C., or the ambient temperature during use is increased to 250 ° C. Even if it rises to the extent, there is almost no change in the refractive index, and the change in the refractive index can be generated with high sensitivity and high accuracy to the irradiation of the ultraviolet light. In particular, the above effect increases as the desired photoacid generator is added up to the soluble upper limit.

Further, the light transmittance can be improved as the amount of the silicone compound added to the branched polysilane compound is increased, and the above effects can be further exerted by adding the silicone compound at an optimum blending ratio. Can be.

In order to increase the sensitivity of the change in the refractive index of the polysilane compound due to the irradiation of ultraviolet light, it is effective to add a sensitizer. Generally, a photoreactive peroxide or a photoacid generator is used. Is used.

The photoacid generator is preferably a trichloromethyltriazine-based material. Even a trichloromethyltriazine-based material is a material having a high light transmittance in a long wavelength region, and has a maximum absorption wavelength substantially equal to that of polysilane in an ultraviolet wavelength region. A material having a close value or a material having a high melting point is preferable in terms of improving the light transmittance of the polymer material and the polymer film, the reactivity to the change in the refractive index by irradiation with ultraviolet light, the temperature stability of the refractive index, and the like.

The materials used will be described below. (Branched Polysilane) As the polysilane used in the present invention, a branched type, not a linear type, may be mentioned. The branched type and the linear type are distinguished by the bonding state of Si atoms contained in the polysilane. The branched polysilane is Si
This is a polysilane containing Si atoms in which the number of bonds between an atom and an adjacent Si atom is 3 or 4.

On the other hand, the linear polysilane is represented by S
The polysilane has two bonds between an i atom and an adjacent Si atom.

Since the valence of a Si atom is usually 4, the Si atom having a bond number of 3 or less among the Si atoms present in the polysilane is not limited to a Si atom, but may be a hydrocarbon group, an alkoxy group, or a hydrogen atom. Are combined. As such a hydrocarbon group, an aliphatic hydrocarbon group which may be substituted by a halogen having 1 to 10 carbon atoms and an aromatic hydrocarbon group having 6 to 14 carbon atoms are preferable.

Specific examples of the aliphatic hydrocarbon group include a methyl group, a propyl group, a butyl group, a hexyl group, an octyl group,
A chain type such as a decyl group, a trifluoropropyl group and a nonafluorohexyl group, and an alicyclic type such as a cyclohexyl group and a methylcyclohexyl group are exemplified.

As specific examples of the aromatic hydrocarbon group,
Examples include a phenyl group, a p-tolyl group, a biphenyl group and an anthracyl group.

Examples of the alkoxy group include those having 1 to 8 carbon atoms. Specific examples include a methoxy group, an ethoxy group, a phenoxy group, an octyloxy group and the like. Considering ease of synthesis, methyl and phenyl groups are particularly preferred among these groups.

In the case of a branched polysilane, the ratio of Si atoms having 3 or 4 bonds between Si atoms and adjacent Si atoms to the total number of Si atoms in the branched polysilane is 2% or more. Is preferred. Those having a ratio of less than 2% or linear polysilane have high crystallinity, and microcrystals are easily generated in the film, which causes scattering and lowers transparency.

The polysilane used in the present invention is obtained by a polycondensation reaction by heating a halogenated silane compound in an organic solvent such as n-decane or toluene in the presence of an alkali metal such as sodium at a temperature of 80 ° C. or higher. Can be manufactured. Further, it can also be synthesized by an electrolytic polymerization method or a method using metal magnesium and metal chloride.

The branched polysilane comprises an organotrihalosilane compound, a tetrahalosilane compound, and a diorganodihalosilane compound, and the organotrihalosilane compound and the tetrahalosilane compound account for at least 2 mol% of the total amount. By heating and subjecting the halosilane mixture to polycondensation, the desired branched polysilane is obtained.

Here, the organotrihalosilane compound serves as a Si atom source having 3 bonds with adjacent Si atoms, and one tetrahalosilane compound serves as an adjacent S atom.
It becomes a Si atom source having a bond number of 4 with an i atom. In addition,
Confirmation of the network structure can be confirmed by measuring an ultraviolet light absorption spectrum or a nuclear magnetic resonance spectrum of Si.

The halogen atom of each of the organotrihalosilane compound, the tetrahalosilane compound and the diorganodihalosilane compound used as a raw material of the polysilane is preferably a chlorine atom. Examples of the substituent other than the halogen atom included in the organotrihalosilane compound and the diorganodihalosilane compound include the above-described hydrocarbon group, alkoxy group, and hydrogen atom.

The branched polysilane is not particularly limited as long as it is soluble in an organic solvent and can form a transparent film by coating. Preferred as such organic solvents are hydrocarbons having 5 to 12 carbon atoms, halogenated hydrocarbons, and ethers.

Examples of the hydrocarbon system include pentane, hexane, heptane, cyclohexane, n-decane, n-dodecane, benzene, toluene, xylene, methoxybenzene and the like. Examples of halogenated hydrocarbons include carbon tetrachloride, chloroform, 1,2-dichloroethane, dichloromethane, chlorobenzene, and the like.
Examples of the ether type include diethyl ether, dibutyl ether, tetrahydrofuran and the like.

When a compound having a degree of branching of 2% or more is used as the branched polysilane compound, the higher the degree of branching, the more the light transmittance can be increased.
Alternatively, a part or all of a halogenated compound, particularly a fluorinated compound can be used, so that absorption at a specific wavelength is suppressed, and light transmittance is high over a wide wavelength range,
Further, the refractive index can be changed with high sensitivity and high precision to the irradiation of ultraviolet light, and the thermal stability of the refractive index can be improved. Note that the upper limit of the degree of branching is limited in preparing a soluble polymer solution by dissolving in an organic solvent, and the upper limit is 50%. (Silicone compound) The silicone compound used in the present invention is represented by the following formula:

[0037]

Embedded image

## EQU1 ##

Wherein R1 to R12 are an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen or a glycidyloxy group, or an aromatic hydrocarbon group having 6 to 12 carbon atoms. And a group selected from the group consisting of alkoxy groups having 1 to 8 carbon atoms, which may be the same or different (a, b, c, and d are integers including 0, and a + b
+ C + d ≧ 1).

Specific examples of the aliphatic hydrocarbon group contained in the silicone compound include a chain type such as a methyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, a trifluoropropyl group and a glycidyloxypropyl group. And an alicyclic type such as a cyclohexyl group and a methylcyclohexyl group.

As specific examples of the aromatic hydrocarbon group,
Examples include a phenyl group, a p-tolyl group and a biphenyl group.

Specific examples of the alkoxy group include methoxy, ethoxy, phenoxy, octyloxy, t
and an er-butoxy group.

The types of R1 to R12 and a, b,
The values of c and d are not particularly important, and are not particularly limited as long as they are compatible with the polysilane and the organic solvent and the film is transparent. In consideration of compatibility, the polysilane used preferably has the same hydrocarbon group as the polysilane used. For example, when using a phenylmethyl-based polysilane as the polysilane, it is preferable to use the same phenylmethyl-based or diphenyl-based silicone compound. Further, a silicone compound having two or more alkoxy groups in one molecule, in which at least two of R1 to R12 are alkoxy groups having 1 to 8 carbon atoms, can be used as a crosslinking agent. Examples of such a material include methylphenylmethoxysilicone and phenylmethoxysilicone containing 15 to 35% by weight of an alkoxy group.

The molecular weight of the silicone compound is 10
000 or less, particularly preferably 3000 or less.

The silicone compound can also be deuterated or partially or entirely halogenated, especially fluorinated, so that absorption at a specific wavelength can be suppressed and light transmittance over a wide wavelength range can be suppressed. In addition, the refractive index can be changed with high sensitivity and high precision to ultraviolet light irradiation, and the thermal stability of the refractive index can be improved. (Photoacid Generator) The photoacid generator is not particularly limited as long as it is a compound that generates an acid by light, but 2,4,6-tris (trihalomethyl) -1,3,5-triazine and its 2-position Or a compound in which the 2- and 4-positions are substituted. The substituents of these compounds are an aliphatic or aromatic hydrocarbon group which may have a substituent. Generally, a triazine having a trichloromethyl group is used.

The addition of the photo-acid generator causes the Si—Si bond to be
This is based on the fact that it is efficiently cleaved by a halogen radical and an acid generated therefrom.

The above-mentioned branched polysilane compound, silicone compound and photoacid generator can be dissolved in uniform ultrafine particles with good compatibility by using an organic solvent such as toluene. In an environment where ultraviolet light is not irradiated, after pouring into a mold or applying to a substrate surface, baking can be performed to uniformly form a desired structure or film.

If an ultraviolet light cut layer is formed on the surface of the polymer material or the polymer film, it is possible to suppress changes in the refractive index and the light transmittance due to exposure to unnecessary ultraviolet light.

[0049]

Embodiments of the present invention will be described below in detail with reference to the accompanying drawings.

A method for preparing a branched polysilane will be described.

First, a 100 ml flask equipped with a stirrer was charged with 40 ml of dry toluene and 1.33 g of sodium. The contents of this flask were heated to 111 ° C. and stirred at high speed to disperse sodium finely in toluene. 4.21 g of phenylmethyldichlorosilane and 0.41 g of tetrachlorosilane were added to the contents,
Polymerization was performed by stirring for 3 hours. Thereafter, excess sodium was quenched by adding 10 ml of ethanol to the resulting reaction mixture. After washing with water, the separated organic layer was poured into 200 ml of ethanol to precipitate polysilane. By precipitating the obtained crude polysilane three times from ethanol,
A branched polymethylphenylsilane having a weight average molecular weight of about 14,000 was obtained at a yield of 30%.

Next, the fact that the effect of the thermal stability of the refractive index differs depending on the type of the sensitizer to be added will be described.

FIG. 1 is a graph showing the relationship between the baking temperature of a polymer material and the refractive index when a peroxide is used as a photoacid generator. That is, FIG. 1 shows that a photoreactive peroxide was added as a sensitizer to a branched polysilane film to which 50% of a commercially available methoxy group-containing phenylmethylsilicone resin (GE Toshiba Silicone TSR-165) was added as a silicone compound. This shows how the refractive index changes depending on the baking temperature when a film in which no film is added and a film in which 5% is added are formed.

In the figure, the horizontal axis indicates the bake temperature axis,
The vertical axis indicates the refractive index axis. L1 shows a characteristic curve when the wavelength is 633 nm and the amount of peroxide added is 0%, L2 shows a characteristic curve when the wavelength is 633 nm and the amount of peroxide added is 5%, and hereafter, L3 shows the characteristic curve. 1550 nm, the amount of peroxide added is 0%, and L4 shows the characteristic curves when the wavelength is 1550 nm and the amount of peroxide added is 5%, respectively. However, the refractive index was measured in a state where the refractive index was lowered to room temperature.

From the figure, it can be seen that the film to which no peroxide is added has better thermal stability of the refractive index than the film to which 5% is added.
It can be seen that the refractive index hardly changes up to a temperature close to ° C. In addition, it can be seen that the film to which 5% peroxide was added had extremely poor thermal stability. That is, it can be said that peroxide is not preferable as a sensitizer.

Next, a polymer film to which trichloromethyltriazine as a photoacid generator is added as a sensitizer will be described.

FIG. 2 shows the measurement results of the thermal stability of the refractive index with respect to the baking temperature at a wavelength of 633 nm.
FIG. 3 is a diagram showing a refractive index characteristic with respect to a baking temperature at a wavelength of 1550 nm. 2 and 3, the horizontal axis indicates the bake temperature axis, and the vertical axis indicates the refractive index axis.

Further, paramethoxystyryltrichloromethyltriazine was used as the trichloromethyltriazine-based material. 2 and 3 show the results of measuring the baking temperature dependence of the refractive index by preparing a film in which the blending ratio of trichloromethyltriazine is 0.1, 5 wt% (L5 is the amount of the triazine-based sensitizer added). Is a characteristic curve when the addition amount of the triazine sensitizer is 1%, L6 is a characteristic curve when the addition amount is 5%, and L8 is an addition characteristic curve when the addition amount of the triazine sensitizer is 1%. A characteristic curve when the amount is 0%, a characteristic curve when L9 is 1%, and a characteristic curve when L10 is 5%
, Respectively. ).

FIGS. 2 and 3 show that the greater the amount of trichloromethyltriazine added, the better the thermal stability of the refractive index. Further, the amount of trichloromethyltriazine may be increased, but if the amount is further increased, the light transmittance deteriorates. Therefore, the blending ratio of trichloromethyltriazine is preferably 1 wt% or more and 5.5 wt% or less.

FIG. 4 is a table showing the relationship between the structure of the sensitizer and the sensitivity.

Assuming that the exposure amount at which the UV absorption of the polysilane with no relative sensitivity reduced by half is 1, the chemical structures, maximum absorption wavelengths, transmittances and toluene solubility of the sensitizers were compared. The transmittance was measured in a 10 mm cell by heating a sample added to the silicone resin at 250 ° C. for 30 minutes.

It can be seen from the figure that a material having a light transmittance of approximately 100% at a wavelength of 830 nm and having high solubility in toluene is more preferable. That is, a wavelength of 800 nm
When used as a polymer material and a polymer film for optical communication in the 1,300 nm band and the 1550 nm band, the above-mentioned trichloromethyltriazine material having a high light transmittance is preferable.

Next, an embodiment in which a desired refractive index value is realized by irradiating one polymer material and a polymer film with ultraviolet light to cause a change in the refractive index will be described.

FIG. 5 shows that trichloromethyltriazine was added to the 50% silicone-added branched polysilane film shown in FIG.
FIG. 6 is a diagram showing the relationship between the irradiation time of ultraviolet light and the refractive index of the film in the case of%.
It is a figure which shows the relationship between the irradiation time of ultraviolet light, and a refractive index with respect to the film | membrane at the time of adding 5% of trichloromethyl triazine to the 0% addition branched polysilane film. 5 and 6, the horizontal axis indicates the UV light irradiation time axis, and the vertical axis indicates the refractive index axis. In both figures, L11 indicates a characteristic curve when the addition amount of triazine is 0% and the wavelength is 633 nm.
12, the addition amount of triazine is 0%, and the wavelength is 1550 nm.
And L13 indicates that the additive amount is 5
%, A characteristic curve when the wavelength is 633 nm, and L14 shows a characteristic curve when the addition amount is 5% and the wavelength is 1550 nm, respectively.

Here, the ultraviolet light is obtained by irradiating the film surface with ultraviolet light from a 150 w mercury xenon lamp using a fiber bundle scope, and measuring the refractive index of the film with respect to the irradiation time. However, the output of the fiber bundle scope was 1200 mJ / cm ² .

As shown in FIG. 5, when trichloromethyltriazine is 0%, the refractive index changes discontinuously with respect to the irradiation time of ultraviolet light. That is, it can be said that it is difficult to obtain a desired refractive index by adjusting the irradiation time. On the other hand, it can be seen that the refractive index of the film in which 5 wt% of trichloromethyltriazine is added in FIG. 6 can be continuously changed with respect to the irradiation time of the ultraviolet light. Also, it can be seen that the reactivity of the refractive index to ultraviolet light is high and the sensitivity is good. This is clearly due to the effect of adding trichloromethyltriazine.

Here, trichloromethyltriazine is
Among these systems, it is preferable to add a material which has good light transmittance in a long wavelength band, has a maximum absorption wavelength close to the ultraviolet light absorption wavelength of the polysilane compound, and has a melting point as high as possible.

According to the present invention, (1) a polymer structure and a polymer film using the polymer material of the present invention can be manufactured at a temperature (bake temperature) of about 250 ° C. even if the ambient temperature during use is within the above range. There is almost no change in the refractive index even when the temperature rises to about the temperature. (2) When irradiating the structure and the film with ultraviolet light to achieve a desired refractive index, with respect to ultraviolet light irradiation energy,
The refractive index can be changed with high sensitivity and high precision. (3) As the photoacid generator, trichloromethyltriazine is preferable, and its compounding ratio is 1 wt% or more and 5.5 wt%.
% Is preferable from the viewpoint of realizing thermal stability of the refractive index and high light transmittance in a long wavelength band. The added amount can be uniformly dissolved with good compatibility with the branched polysilane compound and the silicone compound in toluene. Also, among the triazine-based materials, it is preferable to add a material that has good light transmittance in a long wavelength band, has a maximum absorption wavelength close to the ultraviolet light absorption wavelength of the polysilane compound, and has a melting point as high as possible. By adding this triazine, the refractive index can be made substantially constant up to a higher temperature. Further, a change in the refractive index due to irradiation with ultraviolet light can be realized with high accuracy and high sensitivity. (4) The polymer material of the present invention and a polymer film using the same,
The above effects can be obtained only by combining a branched polysilane compound having a desired branching degree, a silicone compound having a desired addition amount, and a trichloromethyltriazine-based acid generator having a desired addition amount.

[0069]

In summary, according to the present invention, the following excellent effects are exhibited.

It is possible to provide a highly reliable polymer material and polymer film.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between a baking temperature and a refractive index of a polymer material when a peroxide is used as a photoacid generator.

FIG. 2 is a diagram showing a measurement result of thermal stability of a refractive index with respect to a baking temperature at a wavelength of 633 nm.

FIG. 3 is a diagram showing a refractive index characteristic with respect to a baking temperature at a wavelength of 1550 nm.

FIG. 4 is a table showing the relationship between the structure of a sensitizer, sensitivity, and the like.

FIG. 5 is a diagram showing the relationship between the irradiation time of ultraviolet light and the refractive index when the trichloromethyltriazine is 0% in the 50% silicone-added branched polysilane film shown in FIG.

FIG. 6 is a diagram showing the relationship between the irradiation time of ultraviolet light and the refractive index of the film when 5% of trichloromethyltriazine is added to the 50% silicone-added branched polysilane film shown in FIG.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 83/04 C08L 83/04 C09D 5/00 C09D 5/00 Z 183/04 183/04 183/16 183 / 16 // B29K 83:00 B29K 83:00 B29L 7:00 B29L 7:00 (72) Inventor Hiroshi Tsushima 19-17 Ikedanakamachi, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Hidemi Watanabe 19-17 Ikedanakamachi, Neyagawa-shi, Osaka F-term (reference) in Nippon Paint Co., Ltd. FD20 GP00 4J035 JA01 JB03 JB05 LA05 LB20 4J038 AA011 AA012 DL011 DL012 DL031 DL032 DL071 DL072 GA12 HA431 HA432 JB36 NA17 PA17 PA19

Claims (13)

[Claims] 1. A polymer material, wherein a predetermined amount of a silicone compound and a photoacid generator are added to a branched polysilane compound. 2. The polymer material according to claim 1, wherein the polysilane compound is a compound bonded to a hydrocarbon group, an alkoxy group, or a hydrogen atom in addition to a Si atom. 3. A compound having a degree of branching of 2% or more and 50% or less as the branched polysilane compound.
Or the polymer material according to 2. 4. The silicone compound is cross-linkable or comprises an alkoxy group, and
The polymer material according to any one of claims 1 to 3, which is added at a compounding ratio of 40 to 90 wt%. 5. A photo-acid generator comprising a trichloromethyltriazine compound, wherein the trichloromethyltriazine compound is at least 1 wt% based on the polysilane compound.
5. The composition according to claim 1, wherein said compound is added at a mixing ratio of 5 wt% or less.
The polymer material according to any one of the above. 6. The polymer material according to claim 1, wherein a deuterated branched polysilane compound is used as the polysilane compound. 7. The polymer material according to claim 1, wherein a partially or completely halogenated compound is used as the polysilane compound. 8. The polymer material according to claim 1, wherein a deuterated compound is used as the silicone compound. 9. The polymer material according to claim 1, wherein the silicone compound is a compound partially or wholly halogenated. 10. The polymer material according to claim 1, wherein the compound is dissolved in a compatible organic solvent. 11. The polymer material solution according to claim 10, which is poured into a mold under an environment not irradiated with ultraviolet light.
Alternatively, apply it on a substrate and then
A polymer film cured by heat treatment at 0 ° C or lower. 12. A polymer film whose refractive index is changed by irradiating the polymer material according to claim 8 with ultraviolet light. 13. A polymer film, wherein an ultraviolet light cut layer is formed on the surface of the polymer material according to claim 8.