JP2008280453A - Pigment functional material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment functional material improved in an optical amplification function and excellent in stability and durability. <P>SOLUTION: This pigment functional material is obtained by intercalating the organic pigment with a deoxyribonucleic acid and/or deoxyribonucleic acid salt, and dispersing the intercalated pigment material in a polymer matrix. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a dye functional material. More specifically, the present invention relates to a dye functional material that is excellent in stability and durability and is useful for optical devices, optical waveguides, optical amplifiers, and the like.

Conventionally, a complex in which a functional substance is introduced into deoxyribonucleic acid (hereinafter referred to as DNA) has been developed. For example, in Patent Document 1, a functional material is obtained by introducing (intercalating) an ultraviolet absorbing substance, a fluorescent or phosphorescent emitting substance into DNA or a salt of DNA (a quaternary ammonium salt having a long chain alkyl group). ing.
Since the functional substance introduced into DNA is intercalated between nucleobases, it can be made into a material with very little bleed out.
However, these materials have poor water resistance due to the use of DNA as a matrix and lack stability and durability. Therefore, a material that does not have such drawbacks has been desired.
On the other hand, an optical amplifier capable of amplifying signal light by including a fluorescent organic dye typified by a rhodamine dye in a plastic optical fiber (see Non-Patent Document 1) has a higher amplification effect. An optical amplifier was desired.

JP 2001-294597 A Akihiro Takatani, Yasuhiro Koike, Keisuke Sasaki, “Plastic Fiber Optical Amplifier”, Applied Physics: Japan Society of Applied Physics, Vol. 64, No. 1, pp. 32-35 (1995)

As a result of intensive studies in view of the above, the present inventors have found that the above-mentioned drawbacks can be solved by dispersing the dye intercalating material in the polymer matrix, and such a dye intercalating material has been dramatically improved. The present invention has been found to have an optical amplification function.
Therefore, an object of the present invention is to provide a dye functional material having excellent stability and durability. A further object of the present invention is to obtain an optical device such as an optical waveguide or an optical amplifier using this, having a strong fluorescence emission intensity and an excellent optical amplification function.

The present inventors have reached the present invention as a result of intensive studies in view of the above.
That is, the present invention is a dye functional material in which an organic dye is intercalated with deoxyribonucleic acid and / or deoxyribonucleic acid salt, and a dye intercalating material is dispersed in a polymer matrix.

  The present invention also provides the dye functional material, wherein the polymer matrix is obtained by curing a curable substance.

  The present invention also provides the dye functional material, wherein the polymer matrix is obtained by curing a curable substance having a silicon atom.

  The present invention also provides the above-described dye functional material, wherein the polymer matrix is obtained by curing a photocurable resin having a polysiloxane structure and / or a thermosetting resin having a polysiloxane structure.

  The present invention also provides the dye functional material, wherein the salt of deoxyribonucleic acid is a quaternary ammonium having a hydrophobic group.

  The present invention also provides the dye functional material, wherein the hydrophobic group is an alkyl group having 6 or more carbon atoms.

The present invention also provides an optical device using the dye functional material.
The present invention also provides an optical waveguide using the dye functional material.
The present invention also provides an optical amplifier using the dye functional material.

  The effect of the present invention resides in providing a dye functional material that is excellent in stability and durability. Furthermore, the present invention provides an optical device such as an optical waveguide and an optical amplifier that uses this and has a strong fluorescence emission intensity and an excellent optical amplification function.

  Although the DNA used in the present invention is not particularly limited, for example, salmon, trout, herring, mackerel, cod and other fish white larvae (testis), scallop sea urchin, cow mammary gland, etc. are extracted as raw materials, and further purified as desired Thus, the obtained DNA or the like can be used.

Examples of the purification method include a solvent extraction method and an enzyme method.
In the solvent extraction method, for example, a filtrate obtained after homogenizing cells is added to a DNA extract composed of sodium chloride and sodium dodecyl sulfate (SDS), heated and extracted at 60 to 100 ° C., and centrifuged. In this method, ethanol is added to the supernatant to precipitate DNA.
The enzyme method is a method obtained by, for example, adding a proteolytic enzyme such as a protease to a filtrate containing DNA and protein to decompose the protein, and then adding ethanol to precipitate the DNA.
As a method for obtaining high purity DNA, the solvent extraction method is advantageous in terms of cost, but an enzyme method is suitable for mass production.

  The DNA itself is an acid and can usually be obtained as a Na salt as described above, and these DNAs (salts) are hydrophilic. When it is intended to be used as a hydrophilic material, it can be used as it is (in this case, a hydrophilic polymer is selected as the polymer matrix). On the other hand, when a low hydrophilic polymer matrix is used as a low hydrophilic material or a hydrophobic polymer matrix is used as a hydrophobic material, a DNA-Na salt is used. Is exchanged with a quaternary ammonium having a hydrophobic group to convert the DNA to a salt with a quaternary ammonium having a hydrophobic group, thereby improving compatibility with a polymer matrix having low hydrophilicity or a hydrophobic polymer matrix. Can be improved.

The quaternary ammonium is not particularly limited as long as it has at least one hydrophobic group. The at least one hydrophobic group includes an alkyl group having 6 or more carbon atoms (preferably carbon An alkyl group having 8 to 20 atoms) and a benzyl group having one or more alkyl groups having 1 to 20 carbon atoms as a substituent. The other group of quaternary ammonium should just be a C1-C4 alkyl group, and three groups may comprise a pyridinium ring with a nitrogen atom.
At least one hydrophobic group is preferably one or two.

Preferable specific examples of such at least one hydrophobic group include octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, palmityl group (also referred to as cetyl group), stearyl group and the like. Can be mentioned.
Specific examples of the quaternary ammonium include cetyltrimethylammonium, cetyldimethylethylammonium, dodecyltrimethylammonium, cetylpyridinium, and the like.
The molecular weight of such a DNA (salt) is appropriately selected depending on the type of organic dye to be intercalated and the product to which the dye functional material of the present invention is applied, and is not particularly limited.

  The organic dye that can be used in the present invention is not particularly limited because any organic dye that can intercalate with DNA can be used and may be selected depending on the purpose. Examples of organic dyes suitable for applications such as light amplification include 9-methylanthracene, BBO, BBQ, Bis-MSB, BMP, BPBD, COT cyclooctatetraene, DASBI, DASPI, DBASMPI, DBO, DCI- 2, DCM, DCMII, DDC-4, DDCI-4, DDI, DDTTC, DMETCI, DMQ, DMT, DNTPC, DNTCI, DOCI, DODCI, DOTC, DPS, DQOCI, DQTCI, DTCI, DTDC, DTTC, HDTC, HIDC, HITC, IR125, IR132, IR140, IR144, IR25, IR26, IR5, LD390, LD423, LD425, LD466, LD473, LD688, LD690, LD700, LDS698, LDS722 LDS730, LDS750, LDS751, LDS765, LDS798, LDS821, LDS867, LDS925, NCI, PBBO, PBD, PC-propylene carbonate, POPOP, PPF, PPO, PQP, p-terphenyl, QUI, TBS, TMP, α-NPO, Amonix, Uranine, Exalite 376, Exalite 389, Exalite 398, Oxazine 720, Oxazine 725, Oxazine 750, Carbostyril 3, Carbostyril 7, Quinolone 390, Coumarin 102, Coumarin 120, Coumarin 2, Coumarin 4, Coumarin 440 , Coumarin 445, Coumarin 450, Coumarin 460, Coumarin 478, Coumarin 480, Coumarin 481, Coumarin 485, Coumarin 490, Coumarin 500, Marine 503, Coumarin 504, Coumarin 510, Coumarin 515, Coumarin 519, Coumarin 521, Coumarin 522, Coumarin 523, Coumarin 535, Coumarin 540, Coumarin 540A, Coumarin 6, Coumarin 7, Cresyl Violet, Sulfurorhodamine 640, Cyptocyanine, Styryl 15, styryl 9, stilbene 1, stilbene 420, nile blue 690, phenoxazone 660, furan 1, brilliate sulfaflavin, fluorescene 548, fluorol 555, hexacyanine 3, hexacyanine 2, polyphenyl 1, polyphenyl 2, malachite green, Examples include methyl-DOTC, rhodamine B, rhodamine 110, rhodamine 575, rhodamine 610, rhodamine 6G, and rhodamine 800. .

  Among these, preferable examples include DBASMPI, xanthene rhodamine B, rhodamine 6G, rhodamine 110, and the like, as well as coumarin-based coumarin 2, coumarin 6, coumarin 7, coumarin 102, and the like. Further preferred is DBASMPI. DBASMPI is also referred to as trans-4- [4- (dibutylamino) style] -1-methylpyridinium iodide.

The method of intercalating the organic dye into the DNA (salt) is not particularly limited because it can be easily intercalated if mixed in an environment where both can behave freely. For example, a method of adding an organic dye desired to intercalate to an aqueous solution of DNA or DNA-Na and polishing with a mortar or the like (the aqueous solution becomes the dye color, and the aqueous solution of the intercalated DNA (salt) of the dye A method in which a polar solvent solution (for example, methanol solution) of an organic dye desired to intercalate is mixed with an aqueous solution of DNA or DNA-Na, and the solvent is removed; An aqueous solution of a quaternary ammonium salt having one hydrophobic group (the counter anion is preferably a chloride ion) is mixed, and the resulting precipitate is obtained (if desired, dissolved in a non-aqueous or hydrophobic organic solvent, And a method of intercalating by dissolving the precipitate in a non-polar solvent that dissolves the precipitate and mixing it with a dye dissolved in the solvent. That.
Further, when a curable substance described later acts as a solvent, the curable substance described later can be used as the solvent, and can be efficiently mixed and dispersed.

  The use ratio of DNA and organic dye is not particularly limited, but is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of DNA (salt) to be used for efficient expression of dye function (particularly light amplification effect). More preferably, 1 to 25 parts by mass of an organic dye can be used.

  The dye intercalating material in which the organic dye as described above is intercalated with the DNA (salt) as described above can be used as long as the DNA itself maintains a high molecular weight. Although it can be formed into a film as a structural material, such a material has extremely high water absorption and is inferior in stability and durability. Therefore, in the present invention, such a dye intercalating material is dispersed in a polymer matrix. It is something to be made.

  Such a polymer matrix used in the present invention is not particularly limited. When the dye intercalating material is a material obtained by intercalating DNA or DNA-Na with an organic dye, that is, a highly hydrophilic dye intercalating material, a highly hydrophilic polymer is used as a matrix. On the other hand, a dye intercalating material in which an organic dye is intercalated in a low-hydrophilic or hydrophobic DNA salt that has been salt-exchanged with a quaternary ammonium salt having at least one hydrophobic group has a hydrophobic property. A polymer is used as the matrix. In this way, a polymer having such a property that the dye intercalating material is well dispersed may be selected according to the property of the dye intercalating material, and the polymer and the dye intercalating material may be mixed. (When a curable substance is used as a solvent as described above, it is already dispersed in the curable substance at the time of production of the dye intercalating material)

Examples of the mixing method include a method in which the dye intercalate material and the polymer are dissolved in a co-soluble solvent, and then, if necessary, removed by molding or casting.
However, in order to more effectively express the function of the organic dye, the polymer matrix is preferably a cured curable substance. For example, the dye intercalate material and the monomer or macromonomer corresponding to the polymer are dissolved in a co-soluble solvent (especially when the monomer or macromonomer itself is liquid and can dissolve the dye intercalate material, a co-soluble solvent is used. If necessary, a polymerization initiator (or curing agent) may be further mixed and cured. Upon curing, it can be molded or cast as desired.
The use ratio of the dye intercalating material and the curable substance is not particularly limited, but from the viewpoint of efficiency as a dye functional material, preferably 0.1 mg to 1 g as an organic dye, more preferably 100 g of the curable substance. Can be a ratio of 1 mg to 500 mg.

  Although the said curable substance is not specifically limited, For example, the curable substance hardened | cured by a sol-gel method, a radically polymerizable substance, a cationically polymerizable substance etc. can be illustrated. Each of these curable materials is preferably a curable material having a silicon atom.

In the sol-gel method, a metal alkoxide that is a liquid, for example, a so-called sol such as tetraethoxysilane or tetraethoxytitanium is hydrolyzed with water or a polyhydric alcohol or an alkoxy group exchange reaction is performed between the metals via oxygen. This is a method of forming a glassy solid as a so-called gel insolubilized by three-dimensional crosslinking. For example, it is a technique that is used to make high-performance ceramics such as superconductors, which are metal ceramics that become non-uniform by the mixing method. That is, the curable substance cured by the sol-gel method is a curable substance typified by an aqueous solution of such a metal alkoxide (preferably tetraethoxysilane).
The curable substance to be cured by the sol-gel method is prepared by dissolving the dye intercalate material in a metal alkoxide that is a liquid, or by dissolving the dye intercalate material aqueous solution or the dye intercalate material polyhydric alcohol solution. It can be cured by adding a metal alkoxide to obtain a glassy solid that includes a dye intercalating material.

The radical polymerizable substance is a compound that undergoes a polymerization or crosslinking reaction in the presence of a radical polymerization initiator, and preferably a compound having at least one unsaturated double bond in one molecule is used. Examples include acrylate compounds, methacrylate compounds, allyl urethane compounds, unsaturated polyester compounds, styrene compounds, radical polymerizable group-modified silicone oils, and the like.
The radical polymerization initiator has a thermal polymerization initiator and a photopolymerization initiator and may be used depending on the application, but preferably a photopolymerization initiator, for example, a ketone system such as an acetophenone compound, a benzyl compound, or a thioxanthone compound A compound can be illustrated as a preferable thing.

  The cationically polymerizable substance is a compound that is polymerized by a cationic polymerization initiator or causes a crosslinking reaction. For example, an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, a spiro orthoester Examples thereof include a compound and a vinyl compound. Among these, an epoxy compound having a silicon atom is preferable.

  As a preferable thing of the epoxy compound which has the said silicon atom, it describes as a curable composition for optical materials in Unexamined-Japanese-Patent No. 2004-10849, for example. Specifically, it has an epoxy group, and at least three bonding elements include a silicon atom that is an oxygen atom, and a Si-R group (R is an alkyl group, a phenyl group, an alkylphenyl group, a phenylalkyl group, or R A part or all of the hydrogen atoms in the above are halogenated or deuterated, having an alkyl group, a phenyl group, an alkylphenyl group or a phenylalkyl group), and having no Si—OH group, a weight average molecular weight of 500 to 500 One million silicon-containing polymers (that is, macromonomers) can be exemplified.

Hereinafter, such a silicon-containing polymer will be described in detail.
The silicon-containing polymer has an epoxy group in its structure and a silicon atom bonded to at least three oxygen atoms.
The silicon-containing polymer has a Si—R group in its structure, and R is an alkyl group, a phenyl group, an alkylphenyl group, a phenylalkyl group, or a part or all of the hydrogen atoms in R are halogen. An alkyl group, a phenyl group, an alkylphenyl group, or a phenylalkyl group, which is substituted or deuterated. From the viewpoint of transparency in the near-infrared region, part or all of the hydrogen atoms in R are preferably halogenated or deuterated.
The halogenation is preferably fluorination, and specifically, 3,3,3-trifluoropropyl group, pentafluorophenyl group and the like are preferable. As the deuterated group, a deuterated phenyl group is preferable.

  The preferred weight average molecular weight of the silicon-containing polymer is 500 to 1,000,000, preferably 1,000 to 500,000 in terms of polystyrene. If it is less than 500, desirable physical properties cannot be obtained.

In the silicon-containing polymer, the number of epoxy groups depends on the molecular weight of the resulting silicon-containing polymer, and is not particularly limited. One piece per piece.
Moreover, it is preferable that the epoxy group in the silicon-containing polymer is bonded to a silicon atom without an oxygen atom.

  In addition, the silicon-containing polymer has one or two atoms selected from the group consisting of boron, magnesium, aluminum, phosphorus, titanium, iron, zirconium, niobium, tin, tellurium, tantalum, and germanium as atoms other than silicon. It may be contained above, and boron, aluminum, phosphorus, titanium, zirconium, tin, and germanium are particularly preferable. For introduction of these atoms, hydrolysis / condensation reaction may be carried out using alkoxysilane or chlorosilane and an alcoholate of another atom in combination or treatment with a complex of another atom.

(Method of introducing epoxy group into silicon-containing polymer)
(Hydrolysis / condensation reaction)
An epoxy group can be introduced into a silicon-containing polymer by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having an epoxy group.

(Hydrosilylation reaction)
An alkoxysilane having a silane group (Si-H) and / or a chlorosilane having a silane group (Si-H), or at least one of these polymers, and an epoxy compound having a vinyl group (for example, vinylcyclohexene oxide) Epoxy groups can be introduced into the silicon-containing polymer by a hydrosilylation reaction.
Alternatively, it has an alkoxysilane having a vinyl group (—CH═CH ₂ ) and / or a chlorosilane having a vinyl group (—CH═CH ₂ ), or at least one polymer thereof, and a silane group (Si—H). It can also be introduced by a hydrosilylation reaction with an epoxy compound.

More specifically, a polymer obtained by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having a silane group (Si—H) and an epoxy compound having a vinyl group are subjected to a hydrosilylation reaction. Is preferred.
In addition, a polymer obtained by hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane having a vinyl group (—CH═CH ₂ ), and an epoxy compound having a silane group (for example, glycidoxydimethylsilane) It can be introduced by subjecting it to a hydrosilylation reaction.
Any of these epoxy group introduction methods may be used, or may be used in combination.

(Method for producing silicon-containing polymer)
As described above, the silicon-containing polymer can be produced by the presence of alkoxysilane and / or chlorosilane having an epoxy group in the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane.
In this case, the hydrolysis / condensation reaction may be carried out only with alkoxysilane and / or chlorosilane having an epoxy group, but from the viewpoint of physical properties, the hydrolysis / condensation reaction may be performed by mixing with other alkoxysilanes. preferable.

Further, the silicon-containing polymer forms a polymer having a silane group in the presence of alkoxysilane having a silane group and / or chlorosilane having a silane group in the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane. To do. Thereafter, the polymer and an epoxy compound having a vinyl group (for example, vinylcyclohexene oxide) can be produced by subjecting the polymer to a hydrosilylation reaction.
Alternatively, in the hydrolysis / condensation reaction of alkoxysilane and / or chlorosilane, an alkoxysilane having a vinyl group and / or a chlorosilane having a vinyl group is present to form a polymer having a vinyl group, and then the polymer And an epoxy compound having a silane group can be subjected to a hydrosilylation reaction for production.

Also by a hydrosilylation reaction of silane groups (Si-H) and a vinyl group (-CH = CH _2), when obtaining the above silicon-containing polymer, performing a hydrosilylation reaction using a conventionally known catalyst such as a platinum catalyst That's fine.

  The epoxy compound used for introducing the epoxy group into the silicon-containing polymer by hydrosilylation reaction may be a compound having an epoxy group and a vinyl group or a compound having an epoxy group and a silane group. Specific examples include vinylcyclohexene oxide and glycidoxydimethylsilane.

  The hydrolysis / condensation reaction of alkoxysilane to obtain the silicon-containing polymer may be performed by a so-called sol-gel reaction. As such a sol-gel reaction, acid or base, etc. without solvent or in a solvent. The method of performing a hydrolysis and a condensation reaction with the catalyst of this is mentioned.

  The solvent used here is not particularly limited. Specifically, water, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, acetone, methyl ethyl ketone, dioxane, tetrahydrofuran, toluene and the like can be used. 1 type of these can be used, and 2 or more types can also be mixed and used.

The hydrolysis-condensation reaction of the alkoxysilane proceeds when the alkoxysilane is hydrolyzed with water to generate a silanol group (Si—OH) and the generated silanol groups or silanol groups and the alkoxy group are condensed.
In order to advance this reaction, it is preferable to add an appropriate amount of water. Water may be added to the solvent, or the catalyst may be added after dissolving in water. In addition, the hydrolysis reaction also proceeds due to moisture in the air or a small amount of moisture contained in the solvent.

  The catalyst such as acid or base used in the hydrolysis / condensation reaction is not particularly limited as long as it promotes the hydrolysis / condensation reaction. Specifically, inorganic acids such as hydrochloric acid, phosphoric acid, sulfuric acid and the like are used. Organic acids such as acetic acid, p-toluenesulfonic acid and monoisopropyl phosphate; inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide and ammonia; amine compounds such as trimethylamine, triethylamine, monoethanolamine and diethanolamine Titanium esters such as tetraisopropyl titanate and tetrabutyl titanate; Tin carboxylates such as dibutyltin laurate and tin octylate; Boron compounds such as trifluoroboron; Chlorination of metals such as iron, cobalt, manganese and zinc And metal carboxylates such as naphthenates or octylates; Mini um aluminum compound tris acetyl acetate, etc., and the like, also the use of these one may be used in combination of two or more. A preferred example is a method in which an acid catalyst is added and the reaction is allowed to proceed under acidic conditions (pH 7 or lower), and then a basic catalyst is added and the reaction is performed under basic conditions (pH 7 or higher).

When the hydrolysis / condensation reaction is performed, stirring is preferable, and the reaction can be accelerated by heating. The order of the hydrolysis / condensation reaction is not particularly limited. For example, when an alkoxysilane having an epoxy group is used to introduce an epoxy group, both the alkoxysilane having an epoxy group and another alkoxysilane are mixed. Alternatively, the hydrolysis / condensation reaction may be carried out, or the hydrolysis / condensation reaction may be carried out to some extent, and then the others may be added to further carry out the hydrolysis / condensation reaction.
In the case of using chlorosilane in addition to alkoxysilane, the hydrolysis condensation reaction may be performed in the same manner as alkoxysilane.

In order to obtain the silicon-containing polymer produced by the hydrolysis-condensation reaction, the reaction solvent, water, and catalyst may be removed. For example, after adding a solvent such as butanol to extract the solvent, the extraction solvent is reduced in a nitrogen stream. What is necessary is just to distill off.
In addition to the alkoxysilane and chlorosilane, the silicon-containing polymer may use a silicon dioxide condensate after removing sodium from sodium silicate by ion exchange or the like.

(Alkoxysilane, chlorosilane)
The alkoxysilane or chlorosilane used in the production of the silicon-containing polymer may have an alkoxy group that undergoes hydrolysis / condensation reaction in the molecule or may have a Si-Cl group. Specifically, trimethylmethoxy Silane, trimethylethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethoxymethylsilane, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyldimethoxysilane, methyldiethoxysilane, dimethylethoxysilane, Dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, diphenyldiethoxysilane , Phenyltriethoxysilane, vinyltrichlorosilane, vinyltris (βmethoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, γ- (methacryloyloxypropyl) trimethoxysilane, N-β (aminoethyl) γ-amino Instead of propyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane and their respective alkoxy groups, chlorinated products, and further groups other than these alkoxy groups Examples are those in which part or all of the hydrogen atoms are halogenated (particularly fluorinated) or deuterated, and one or more of these can be used.

In particular, from the viewpoint of transparency in the near-infrared region, it is preferable to use one that is partially or fully halogenated (particularly fluorinated) or deuterated. Specifically, deuterated phenyltrimethoxysilane, pentafluorophenyltriethoxysilane, (3,3,3-trifluoropropyl) trimethoxysilane and the like are preferably used. Further, for introduction of an epoxy group, those having a silane group (Si—H), a vinyl group (—CH═CH ₂ ), and a vinyl silane group (Si—CH═CH ₂ ) are preferable.

(Alkoxysilane having an epoxy group)
The alkoxysilane having an epoxy group used for introducing an epoxy group in the silicon-containing polymer may have an epoxy group in the molecule, specifically, γ-glycidoxypropyltrimethoxysilane, γ -Glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, etc., and one or two of these More than seeds can be used. These epoxy groups are preferably bonded to silicon atoms without any oxygen atoms in the middle.
In particular, from the viewpoint of photocurability, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltriethoxysilane are preferable.

(Chlorosilane having an epoxy group)
The chlorosilane having an epoxy group used for introduction of an epoxy group in the silicon-containing polymer used in the present invention may have an epoxy group in the molecule.
Such a silicon-containing polymer having an epoxy group can also be used as a mixture with other epoxy compounds.

  Examples of such an epoxy compound preferable for use in combination include an epoxy compound having a cyclohexene oxide structure. For example, 2,2-bis (3,4-epoxycyclohexyl) propane, 1,1, Examples thereof include 1,3,3,3-hexafluoropropyl-2,2-bis (3,4-epoxycyclohexyl) propane.

As the cationic polymerization initiator, any of those known as epoxy resin curing agents can be used. For example, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m - phenylenediamine, p, p'-diaminodiphenylmethane, p, p'-diaminodiphenyl sulfone, p, p'-diaminodiphenyl ether, aniline · _BF 3, p-toluidine · _BF 3, o-toluidine · BF _3, dimethylaniline · _BF 3, N-methylaniline _{· BF} 3, · N- ethylaniline BF 3, N, N'- dimethyl-aniline _· BF 3, N, N'- diethyl aniline · BF _3, ethylamine · _BF 3, n-butylamine · BF _3, piperidine · _BF 3, Phenylamine-BF _3, o-dimethylaminomethyl phenol, 2,4,6-tris (dimethylaminomethyl) phenol, an amine curing agent such as triethanolamine borate, polyamide resins, diacetone acrylamide complex, dicyandiamide Amide-based curing agents such as phthalic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, hexyl nadic anhydride, glutaric anhydride, pyromellitic anhydride, Examples thereof include acid anhydride-based curing agents such as phenylene-bis (3-butane-1,2-dicarboxylic acid) anhydride and tetrabromophthalic anhydride, and other curing agents such as phthalimide and imidazole complexes.

  The photocuring catalyst for photocuring may be any substance that releases a substance that initiates cationic polymerization upon irradiation with energy rays. Specifically, aryldiazonium salts, aryliodonium salts, arylsulfonium salts, sulfonylacetophenones And allene-ion complexes. Two or more of these curing catalysts can be used in combination.

The optical device of the present invention uses the dye functional material of the present invention. The dye functional material of the present invention is suitable as an optical device because the organic dye is stably dispersed in the resin material.
For example, an optical waveguide such as an optical amplifier can be preferably exemplified as the optical device.

The optical waveguide of the present invention uses the dye functional material of the present invention. Such an optical waveguide is suitable as an optical amplifier. That is, an optical amplifier can be obtained by using the dye functional material of the present invention as the core material of the optical waveguide.
Since the optical amplifier of the present invention contains a dye intercalating material in which an organic dye is intercalated in DNA (salt), it exhibits an extremely excellent light amplification effect. The reason for this is not clear, but in an ordinary optical amplifier, only the energy of the excitation light irradiated to the organic dye molecule is the light intensity when emitting the signal light corresponding to the signal light incident on the organic dye molecule. In the case of a dye intercalating material in which an organic dye is intercalated with DNA (salt), it is used not only for the excitation light irradiated to the organic dye but also with DNA (salt). This is thought to be because the excitation light energy received by the entire molecule is supplied to the organic dye.

Examples of the present invention will be described below to further explain the present invention, but the present invention is not limited to these.
[Production of curable substance (1)]
A silicon-containing macromonomer was synthesized according to the following procedure.
Reaction tank 1: 138.8 g (0.70 mol) of phenyltrimethoxysilane, 6.0 g (0.05 mol) of dimethyldimethoxysilane, 23.6 g (0.10 mol) of γ-glycidoxypropyltrimethoxysilane, After mixing 91.8 g of 0.032% phosphoric acid aqueous solution and stirring at 10 ° C. for 2 hours, 5.74 g of 0.5N sodium hydroxide aqueous solution was added.

  Reaction tank 2: 37.0 g (0.15 mol) of 3,4-epoxycyclohexylethyltrimethoxysilane and 16.2 g of ethanol were mixed, and 16.2 g of 0.032% phosphoric acid aqueous solution was added to the reaction solution. The solution was added dropwise over 5 minutes while being careful not to exceed 10 ° C., and stirred at 10 ° C. or lower for 2 hours. Thereafter, 1.01 g of 0.5N sodium hydroxide aqueous solution was added.

Mixing the reaction liquid of the above reaction tank 1 and reaction tank 2, adding 600 ml of toluene and 600 ml of ethanol, heating the outer bath temperature to 130 ° C., and removing water by azeotropy, The heat-condensation polymerization was carried out until the weight average molecular weight Mw was 1700 (analyzed by GPC, converted to polystyrene). 1780 g (12.0 mol) of triethyl orthoformate was added and heated to 130 ° C. After reaching 130 ° C., the mixture was heated and stirred for 1 hour. 90 g of adsorbent was added, and the mixture was heated and stirred at 100 ° C. for 1 hour. After removing the adsorbent by filtration, volatile components were removed at 120 ° C. and 3 mmHg, and 45 g of toluene and 1000 g of methanol were added to separate the two layers. Volatile components were removed from the lower layer at 110 ° C. and 3 mmHg to obtain 200 g of a silicon-containing macromonomer. As a result of analysis by GPC, the weight average molecular weight was 2800, and as a result of analysis by ¹ H-NMR, silanol groups (Si—OH) were not detected.

Further, as a result of analysis by ¹ H-NMR and infrared absorption spectrum, it was confirmed that the epoxy group was contained, and as a result of analysis by ²⁹ Si-NMR, it was confirmed that at least three bonding elements had a silicon atom which is an oxygen atom. As a result of analysis by ¹ H-NMR, it was confirmed to have a Si—R group, and as a result of analysis by ¹ H-NMR and ²⁹ Si-NMR, it was confirmed to have a Si—OR ′ group. Further, the phenyl group in the organic component excluding the silicon atom was 49.3% by mass, the methyl group in the organic component excluding the silicon atom was 1.3% by mass, and the epoxy equivalent measured by the potentiometric method was 584. Met.

  40 parts by mass of 2,2-bis (3,4-epoxycyclohexyl) propane, bis- [4- (bis (4-butoxyphenyl) sulfonio) phenyl] with respect to 50 parts by mass of the silicon-containing macromonomer A curable substance (1) was prepared by blending 0.3 parts by mass of sulfide hexafluoroantimonate and 10 parts by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

[Production of curable substance (2)]
A silicon-containing macromonomer was synthesized according to the following procedure.
Reaction tank 1: 50 g (0.25 mol) of phenyltrimethoxysilane, 121.5 g (1.01 mol) of dimethyldimethoxysilane, 149 g (0.63 mol) of γ-glycidoxypropyltrimethoxysilane, 0.032% 204.6 g of an aqueous phosphoric acid solution was mixed and stirred at 10 ° C. for 2 hours, and then 4.26 g of a 0.5N aqueous sodium hydroxide solution was added.

  Reaction tank 2: 155.2 g (0.63 mol) of 3,4-epoxycyclohexylethyltrimethoxysilane and 68.2 g of ethanol were mixed, and 68.2 g of 0.032% phosphoric acid aqueous solution was added to the reaction solution. The solution was added dropwise over 5 minutes while being careful not to exceed 10 ° C., and stirred at 10 ° C. or lower for 2 hours. Thereafter, 12.8 g of a 0.5N aqueous sodium hydroxide solution was added.

After mixing the reaction liquid in said reaction tank 1 and reaction tank 2, it heated to 45 degreeC and performed polycondensation for about 1.5 hours. After diluting the reaction liquid by adding 356.4 g of toluene, the stirring was stopped, and the lower layer containing many organic components separated into two layers was separated and extracted, and reflux dehydration was performed at 45 ° C. under reduced pressure for about 1 hour. 561 g (3.79 mol) of triethyl orthoformate was added and heated to 130 ° C. After reaching 130 ° C., the mixture was heated and stirred for 1 hour. After cooling with air and passing the reaction solution through a deionization filter, volatile components were removed at 60 ° C. and 3 mmHg, 100 g of toluene was added and dissolved, and 800 g of hexane was added to separate the two layers. Volatile components were removed from the lower layer at 60 ° C. and 5 mmHg to obtain a silicon-containing macromonomer. As a result of analysis by GPC, the weight average molecular weight (Mw) was 10,000, and as a result of analysis by ¹ H-NMR, silanol groups (Si—OH) were not detected.

Further, as a result of analysis by ¹ H-NMR and infrared absorption spectrum, it was confirmed that the epoxy group was contained, and as a result of analysis by ²⁹ Si-NMR, it was confirmed that at least three bonding elements had a silicon atom which is an oxygen atom. As a result of analysis by ¹ H-NMR, it was confirmed to have a Si—R group, and as a result of analysis by ¹ H-NMR and ²⁹ Si-NMR, it was confirmed to have a Si—OR ′ group. Further, the phenyl group in the organic component excluding the silicon atom is 7.7% by mass, the methyl group in the organic component excluding the silicon atom is 11.9% by mass, and the epoxy equivalent measured by the potentiometric method is 307%. Met.

  40 parts by mass of 2,2-bis (3,4-epoxycyclohexyl) propane, bis- [4- (bis (4-butoxyphenyl) sulfonio) phenyl] with respect to 50 parts by mass of the silicon-containing macromonomer 1.0 part by mass of sulfide hexafluoroantimonate and 10 parts by mass of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate were blended to prepare a curable substance (2).

[Production of DNA salt of quaternary ammonium having a hydrophobic group]
A 10% by mass aqueous solution of cetyltrimethylammonium chloride is added to a 0.5% by mass aqueous solution of sodium salt of deoxyribonucleic acid derived from white silkworm, the precipitate is filtered, washed with water and dried to obtain cetyltrimethylammonium DNA. A salt (hereinafter referred to as DNA-CTMA) was obtained.

[Example 1]
100 g of the above curable substance (1) as a curable substance for the polymer matrix is dissolved in a mixed solution of 300 ml of chloroform and 100 ml of ethanol, 0.45 g of DNA-CTMA, and trans-4- [4- ( 0.05 g of dibutylamino) styyl] -1-methylpyridinium iodide (hereinafter referred to as DBASMPI) was dissolved. This solution was designated as solution (A).

The curable material (2) as a clad material is laminated on a fired silicon substrate to a thickness of 30 μm by spin coating, irradiated with ultraviolet light (365 nm) with a light amount of 10 mW / cm ² for 400 seconds, and then heated at 90 ° C. for 15 minutes. did.
Subsequently, the solution (A) as a core material was laminated by a spin coating method, and the solvent was evaporated to form a layer having a thickness of 50 μm. Using a negative photomask, irradiated with ultraviolet light (365 nm) with a light amount of 10 mW / cm ² for 400 seconds, heated at 90 ° C. for 15 minutes, and developed with acetone: isopropanol having a mixing mass ratio of 1: 1, A pattern with a line width of 50 μm was produced by heating at 90 ° C. for 15 minutes. Further, the above curable substance (2) as the same cladding material is laminated by spin coating so as to have a thickness of 30 μm from the upper part of the previously formed pattern line, and ultraviolet rays (365 nm) with a light amount of 10 mW / cm ² are 200. After the second irradiation, the optical waveguide (1) of the present invention was produced on a silicon substrate by heating at 90 ° C. for 15 minutes.

  An optical amplification test was performed using this optical waveguide. When excitation light and signal light were made incident on this waveguide, the intensity of the outgoing signal light was amplified about 150 times. From this, the optical amplifier using the optical waveguide which is one form of the dye functional material of the present invention has extremely high amplification efficiency.

[Example 2]
The solution (A) was cast on a quartz glass substrate washed with acetone to a film thickness of 50 μm, and after removing the solvent in a dryer at 40 ° C. to form a film, ultraviolet light at 365 nm was applied with a light intensity of 10 mW / cm ² . And heated at 90 ° C. for 15 minutes using an oven to obtain the dye functional material (1) of the present invention.
This dye functional material (1) is exposed to each humidity at room temperature for 48 hours using a constant temperature and humidity chamber, and the weight increase rate (water absorption rate) and the change rate of the fluorescence quantum yield of the material at this time are measured. did. The results are shown in Table 1. As is clear from this result, the dye functional material of the present invention is excellent in stability and durability.

[Comparative Example 1]
For comparison, a material (comparative example) having a sex membrane only with DNA-CTMA was used in the same manner without using a polymer matrix.
That is, a solution was prepared by dissolving 10% by mass of DBASMPI in a mixed solvent of water / ethanol / chloroform (0.05 / 1 volume ratio) with respect to DNA-CTMA and DNA-CTMA. This solution is designated as solution (B).

The solution (B) was cast to obtain a dye functional material film in an amount equivalent to that in Example 2 as a DBASMPI mass (formed into a film due to the property of DNA itself). This material was used in the same manner as in Example 2.
The results are shown in Table 1. As is clear from this result, the material of the comparative example was inferior in stability and durability.

Example 3
An ethanol solution containing 10% by mass of tetraethoxysilane after adding 1% by mass of polyvinyl alcohol (molecular weight 100,000) as a dispersion stabilizer to the above solution (B) and further adding hydrochloric acid to adjust the pH to 5.0. Was added dropwise at room temperature with stirring, and the temperature was raised to 50 ° C. after the addition, whereby glass microparticles containing DNA-CTMA intercalated with DBASMPI were produced. The glass fine particles were separated, washed and dried to obtain the dye functional material (2) of the present invention.

When this dye functional material (2) was irradiated with ultraviolet rays, it showed strong fluorescence. The spectral width of the fluorescence this glass particles ^{0.45mJ / cm 2, 0.93mJ / cm} 2, 1.95mJ / cm 2, emitted by irradiating the ultraviolet rays of 2.25mJ / cm ^2, is, Normalized intensity At / au 0.4, it was about 53 nm, about 29 nm, about 14 nm, and about 7 nm, respectively, and the spectrum width became narrower as the irradiation energy increased, indicating that the laser oscillated. This is considered to be due to resonance oscillation in which light is confined in DNA.

Claims (9)

  A dye functional material, wherein a dye intercalating material in which an organic dye is intercalated with deoxyribonucleic acid and / or deoxyribonucleic acid salt is dispersed in a polymer matrix.   The dye functional material according to claim 1, wherein the polymer matrix is obtained by curing a curable substance.   The dye functional material according to claim 1 or 2, wherein the polymer matrix is obtained by curing a curable substance having a silicon atom.   The dye functional material according to any one of claims 1 to 3, wherein the polymer matrix is obtained by curing a photocurable resin having a polysiloxane structure and / or a thermosetting resin having a polysiloxane structure. .   The dye functional material according to any one of claims 1 to 4, wherein the deoxyribonucleic acid salt is a quaternary ammonium having a hydrophobic group.   The dye functional material according to claim 5, wherein the hydrophobic group is an alkyl group having 6 or more carbon atoms.   An optical device using the dye functional material according to any one of claims 1 to 6.   An optical waveguide using the dye functional material according to claim 1.   An optical amplifier using the dye functional material according to any one of claims 1 to 6.