JP4623982B2 - Organic-inorganic composite and method for producing the same - Google Patents

Description

  The present invention relates to a transparent organic-inorganic composite obtained by a sol-gel method, a method for producing the same, and an optical film using the composite.

  In the sol-gel method, a metal alkoxide compound and water are reacted to convert an alkoxy group contained in the metal alkoxide compound into a hydroxyl group, and at the same time, a polymer having a hydroxy metal group obtained by polycondensation is subjected to a dehydration reaction or desorption. In this method, a covalent bond is formed by an alcohol reaction to crosslink three-dimensionally. By allowing an organic polymer to coexist in the sol-gel reaction solvent, it becomes possible to synthesize a transparent organic-inorganic composite in which an organic polymer and silica gel are molecularly dispersed. Since the series of reports on the sol-gel method by Nakatsuji et al., Kyoto University (Y. Chujo, T. Saegusa, Adv. Polym. Sci., 100, 11, (1992)), there have been many studies on transparent organic-inorganic composites. Has been deployed.

The following three methods are known as methods for producing a transparent organic-inorganic composite by the sol-gel method.
The first technique is a technique for obtaining a transparent organic-inorganic composite by a sol-gel reaction between a non-reactive organic polymer having a hydrogen bond accepting group such as an amide group and tetraethoxysilane. For example, when tetraethoxysilane is used as a precursor of an inorganic component, in a repeating unit such as poly (2-methyl-2-oxazoline), poly (N-vinylpyrrolidone), poly (N, N-dimethylacrylamide), etc. Only when the sol-gel reaction is performed in a state where an organic polymer having an amidecarbonyl group is dissolved in an alcohol solvent, a transparent organic-inorganic composite with a wide composition range is synthesized. This is explained to be based on the homogeneous mixing of the organic polymer and silica gel at the molecular level due to the hydrogen bond interaction between the silanol residue in the silica gel matrix and the amide carbonyl group in the organic polymer. .

  On the other hand, it has been reported that an organic polymer (eg, polyurea, polyurethane, polyimide, polycarbonate, etc.) containing a functional group having hydrogen bond accepting ability other than an amide group can easily obtain a uniform complex with silica. However, since these functional groups have lower hydrogen bond acceptability than amide groups, the composition for obtaining a transparent organic-inorganic composite is limited (see, for example, Patent Documents 1 and 2).

  The first method is an extremely excellent method because a transparent organic-inorganic composite can be obtained by a simple operation. However, an organic polymer having a strong hydrogen bond-accepting functional group such as an amidecarbonyl group is used. There is a problem that the application range is limited. Furthermore, there is a problem that the first method is difficult to apply to an organic polymer having low solubility in alcohol.

  The second method is transparent by covalently bonding the organic polymer and silica gel by a sol-gel reaction between an organic polymer having an alkoxysilyl group at the side chain or terminal and tetraethoxysilane or tetramethoxysilane. This is a technique for obtaining a simple organic-inorganic composite. (For example, see Patent Documents 3 and 4).

  The transparent organic-inorganic composite obtained by the second method has an advantage that the organic polymer and the silica are covalently bonded, so that the bond is strong. However, in order to apply the second method, It is necessary to synthesize a novel organic polymer having an alkoxysilyl group. It is difficult to newly synthesize an alkoxysilyl group-containing polymer, which is disadvantageous in price. In addition, this method has a drawback that it cannot be applied to the synthesis of organic inorganic composites using commercially available organic polymers.

  The third method is a method using an organic polymer and a metal alkoxide (silsesquioxane) having a substituent that strongly interacts with the organic polymer. Specifically, in the case of a combination of polystyrene and phenyltrimethoxysilane (π-π interaction), a combination of polystyrenesulfonic acid and amino group-containing trialkoxysilane (cation-anion interaction), etc., a transparent organic-inorganic composite It has been reported that a body can be obtained (see, for example, Patent Document 5).

  The third method has an advantage that the application range of the organic polymer is wide as compared with the first and second methods. However, in the organic-inorganic composite obtained by the third method, the generated inorganic oxide is not silica but polysilsesquioxane. Therefore, the mechanical strength, heat resistance, thermal dimensions, which are the original advantages of the inorganic compound, are obtained. It is impossible to expect improvement in degree stability.

The three methods described above enable the synthesis of a transparent organic-inorganic composite. However, in order to obtain a transparent organic-inorganic composite by any of the methods, a strong interaction between the organic polymer and the inorganic substance is required. It was necessary to exist. Therefore, there is a problem that the combination of the organic polymer and the inorganic substance is limited. There is also a problem that it is difficult to synthesize an organic-inorganic composite using an organic polymer that does not dissolve in alcohol.
Therefore, even when there is no strong interaction between the organic polymer and the inorganic compound, or when the organic polymer does not dissolve in the alcohol, development of a new method for obtaining a transparent organic-inorganic composite has been desired. .
JP-A-5-310413 (Claims) JP-A-5-310994 (Claims) JP-A-11-255883 (Claim 1, [0036] to [0052], [0066] to [0075]) JP 2002-327024 A (Claim 1, [0065] to [0070] JP 2000-256539 A (Claims)

The present invention has been made in view of the above problems, and the object of the present invention is to provide an excellent solvent resistance even when there is no strong interaction between the organic polymer and the inorganic compound or when the organic polymer does not dissolve in the alcohol. An organic-inorganic composite having properties and a method for producing the same.
Another object of the present invention is to provide an optical film having excellent transparency and solvent resistance.

  The present inventor has intensively studied a method that can perform a sol-gel reaction even when the combination of an organic polymer and an inorganic compound has no interaction or does not dissolve in alcohol. The present inventor selected tetraethoxysilane as the metal alkoxide, aromatic polyester and polymethacrylic acid ester as the organic polymer that does not dissolve in alcohol, and studied the synthesis method of the organic-inorganic composite in various solvents. When a certain kind of solvent is used, it is found that a transparent organic-inorganic composite can be obtained even in the case of a combination having no strong interaction between the organic polymer and the inorganic compound, and the present invention is completed. It came to.

That is, the object of the present invention is achieved by the following organic-inorganic composite and the production method thereof.

The present invention is at least selected from the group consisting of an amide solvent, a urea solvent, a sulfoxide solvent, an amine solvent, and a phosphate solvent having a hydrogen bond accepting parameter (β value) of 0.6 to 1.0. A metal alkoxide sol-gel in a state where 5 to 30% by mass of an aromatic polyester or polymethacrylic acid ester is dissolved in an organic solvent containing at least 50% by mass in one organic solvent. Obtained by carrying out the reaction. Thereby, according to this invention, even in the case of the combination which does not have a strong interaction between an organic polymer and an inorganic compound, a transparent organic inorganic composite can be provided.

  Moreover, since the optical film of this invention is a film which consists of the said organic inorganic composite, according to this invention, the optical film which has both outstanding transparency and solvent resistance can be provided.

The organic-inorganic composite of the present invention and an optical film using the composite will be described below.
In the present specification, “to” is used as a meaning including numerical values described before and after the lower limit value and the upper limit value.

[Organic-inorganic composite and production method thereof]
<Organic solvent>
The organic solvent used in the present invention comprises an amide solvent, a urea solvent, a sulfoxide solvent, an amine solvent, and a phosphoric acid solvent having a hydrogen bond accepting parameter (β value) of 0.6 to 1.0. Contains at least one selected from the group. These organic solvents can form a strong hydrogen bond with the silanol group of the reaction intermediate product as compared with other organic solvents, so there is no strong interaction between the organic polymer and the inorganic compound. Is preferable for maintaining transparency.

  Examples of the amide solvent include dimethylacetamide, dimethylformamide, N-methylpyrrolidone, dimethylchloroacetamide and the like. Examples of urea solvents include tetramethylurea and tetraethylurea. Examples of the sulfoxide solvent include dimethyl sulfoxide, diphenyl sulfoxide, di-n-butyl sulfoxide and the like. Examples of the amine solvent include trimethylamine, pyridine, 4-methylpyridine, 2,6-dimethylpyridine, 2,4,6-trimethylpyridine, quinoline, 4-dimethylaminopyridine and the like. Examples of the phosphoric acid solvent include triethyl phosphoric acid, hexamethyl phosphoric triamide, triphenyl phosphine oxide, trimethyl phosphoric acid, trimethyl phosphine oxide, and the like.

  The organic solvent used in the present invention has an aspect consisting only of the amide solvent and an aspect consisting of a mixed solvent with other organic solvents. In the case where the organic solvent is composed only of the amide solvent, etc., it may be either a case where each solvent is used alone or a case where a plurality of solvents are mixed. In the case of an embodiment comprising a mixed solvent with a solvent other than the amide solvent, etc., at least one selected from an amide solvent, a urea solvent, a sulfoxide solvent, an amine solvent, and a phosphoric acid solvent in the organic solvent. It is preferable to contain 50 mass% or more with respect to the total mass of the organic solvent, more preferably 70 mass% or more, and even more preferably 90 mass% or more. By containing 50% by mass or more of an amide solvent or the like with respect to the total mass of the organic solvent, a strong hydrogen bond with the silanol group of the reaction intermediate product can be formed.

Hydrogen bond acceptor parameter of the organic solvent used in the present invention (hereinafter referred to as "β value") is state, and are 0.6 or more, more preferably 0.7 or more, to be 0.75 or more Further preferred. The β value is defined as a value measured by the method described on page 485 of MJ Kamlet, JLM Abboud, RW Taft, Prog. Phys. Org. Chem., 13 (1981). This is an index representing the hydrogen bond acceptability, and β values of standard organic solvents are listed in Table 35 of the above document. In the present invention, since the β value of the organic solvent is 0.6 or more, a strong hydrogen bond with the silanol group of the reaction intermediate product can be formed. The upper limit of the β value is 1.0, and the β value is preferably closer to 1.0.

  Examples of the organic solvent having a β value of 0.6 or more include amide-based solvents such as dimethylacetamide (β = 0.76), dimethylformamide (β = 0.69), or N-methylpyrrolidone (β = 0.77). ), Tetramethylurea (β = 0.78) which is a urea solvent, dimethyl sulfoxide (β = 0.76) which is a sulfoxide solvent, triethyl phosphoric acid (β = 0.77) which is a phosphate solvent, and the like It is preferable to use dimethylacetamide, N-methylpyrrolidone, tetramethylurea or triethylphosphoric acid, more preferably dimethylacetamide, N-methylpyrrolidone or tetramethylurea.

<Organic polymer>
The organic polymer used in the present invention is an aromatic polyester or polymethacrylic acid ester.
In addition, although 5 mass% or more is melt | dissolved in the said organic solvent as a prepolymer, the organic polymer (for example, insoluble polyimide, a thermosetting resin, etc.) which has a solubility of less than 5 mass% as a polymer is an organic polymer in this invention. It is not included in the range.

The organic polymer used in the present invention is most preferably a polyarylate resin.

  The organic polymer used in the present invention can be a single organic polymer or a combination of a plurality of organic polymers. Moreover, the organic polymer which consists of several monomer components, such as a random copolymer, a block copolymer, and a graft copolymer, can be used.

  The organic polymer used in the present invention can be dissolved in an amount of 5% by mass or more, preferably 7% by mass or more, more preferably 10% by mass or more, based on the total mass of the organic solvent. On the other hand, the upper limit of the solubility of the organic polymer may be within a range in which a sol-gel reaction with a metal alkoxide can be performed in an organic solvent, preferably 30% by mass or less, and more preferably 20% by mass or less. When the content of the organic polymer is 5% by mass or more, the drying load does not increase even when a large amount of solvent is evaporated during film production. On the other hand, when the content of the organic polymer is 30% by mass or less, the solution viscosity is not excessively increased and the solution can be stirred well.

<Metal oxide>
The metal oxide constituting the organic-inorganic composite of the present invention was obtained by reacting a metal alkoxide compound and water to convert an alkoxy group contained in the metal alkoxide compound into a hydroxyl group and simultaneously polycondensing it. It can be obtained by three-dimensionally crosslinking a polymer having a metal group by forming a covalent bond by dehydration or dealcoholization reaction. As a starting material for the sol-gel reaction, a metal complex compound may be used as an alternative to a metal alkoxide compound, or may be used in combination with a metal alkoxide compound.

  As the metal alkoxide compound, when only an alkoxy group is bonded to a metal element, that is, not only methoxide, ethoxide, isopropoxide, etc., but also a part of which is substituted with a methyl group, an ethyl group, etc., for example, monomethyl Also included are alkoxides, monoethyl alkoxides and the like. Furthermore, the metal complex compound includes not only a case where only an acetylacetone group is bonded to all metal atoms, but also a compound in which a part thereof is substituted with a methylalkoxy group, an ethylalkoxy group or the like.

  As the metal element forming the metal alkoxide compound or metal complex compound, it is preferable to use at least one metal selected from the group consisting of Si, Ti, Al and Zr.

Specific examples of the metal alkoxide compound include tetramethoxysilane [Si (OCH ₃ ) ₄ ], tetraethoxysilane [Si (OC ₂ H ₅ ) ₄ ], methyltriethoxysilane [(CH ₃ ) Si (OC ₂ H). ₅ ) ₃ ], methyltrimethoxysilane [(CH ₃ ) Si (OCH ₃ ) ₃ ], titanium tetraisopropoxide [Ti (O-iso-C ₃ H ₇ ) ₄ ], titanium acetylacetonate [Ti (CH ₃ COCHCOCH _{3) 4],} aluminum tri secondary butoxide _{[Al (O-sec-C 4} H 9) 4 ], zirconium n-butoxide _{[Zr (O-n-C 4} H 9) 4 ], zirconium acetylacetonate [Zr (CH ₃ COCHCOCH ₃ ) ₄ ] and the like are preferable. From the viewpoint of reaction rate and price, alkoxysilanes are preferred, and tetraethoxysilane is particularly preferred.

The metal complex compound used as an alternative to the metal alkoxide compound is an alcohol represented by the general formula R ¹⁰ OH (wherein R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms), and R ¹¹ COCH ₂ COR. ^{12 In the} formula, R ¹¹ is an alkyl group having 1 to 6 carbon atoms, and R ¹² is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 16 carbon atoms. Any metal can be suitably used without particular limitation. Within this category, two or more metal chelate compounds may be used in combination.

Particularly preferred as the metal chelate compound of the present invention is Al, Ti, Zr as the central metal.
In general formulas Zr (OR ¹⁰ ) _p1 (R ¹¹ COCHCOR ¹² ) _p2 , Ti (OR ¹⁰ ) _q1 (R ¹¹ COCHCOR ¹² ) _q2 and Al (OR ¹⁰ ) _r1 (R ¹¹ COCHCOR ¹² ) _r2 Those selected from the group of compounds represented are preferred.

R ¹⁰ and R ¹¹ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, specifically an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, phenyl group and the like. R ¹² may be an alkyl group having 1 to 6 carbon atoms as described above, or an alkoxy group having 1 to 16 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, or n-butoxy. Group, sec-butoxy group, tert-butoxy group, lauryl group, stearyl group and the like. Moreover, p1-r2 in a metal chelate compound represents the integer determined so that it may become 4 or 6-dentate coordination.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxy bis (ethylacetoacetate) titanium, diisopropoxy bis (acetylacetate) titanium, diiso Titanium chelate compounds such as propoxy bis (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropyl Poxyacetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetonate bis (ethyl) An aluminum chelate compound such as acetoacetate) aluminum. Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

Next, a specific method for obtaining silicon oxide from alkoxysilane will be described.
In the present invention, organosilane can be suitably used to obtain silicon oxide. Organosilane represents a silane compound having a functional group capable of giving silanol by hydrolysis in the molecule. In the metal oxide, a hydrolyzate and / or a part obtained by hydrolysis and condensation. It becomes a condensate and functions as a binder in the metal oxide.
In general, a compound represented by the formula (R) ₄ Si is preferably used. In the formula, R represents a hydrocarbon group (for example, an alkyl group, an alkenyl group, an alkynyl group, or an aryl group, and these groups may have a substituent), an alkoxyl group, an oxyacyl group, or a halogen atom.
Four Rs in one molecule may be the same as or different from each other within the scope of this definition, and can be freely selected and combined, but four do not become a hydrocarbon group at the same time. Preferably, no more than two hydrocarbon groups are simultaneously present in one molecule.

Of these organosilanes, alkoxysilanes are particularly preferably used. An example is an alkoxysilane represented by the general formula Si (OR ¹ ) _x (R ² ) _4-x . R ¹ in the alkoxysilane is preferably an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or n-butyl. Group, sec-butyl group, tert-butyl group, acetyl group and the like. R ² is preferably an organic group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group. Group, n-octyl group, tert-octyl group, n-decyl group, unsubstituted hydrocarbon group such as phenyl, vinyl group, allyl group, etc., γ-chloropropyl group, CF ₃ CH ₂ —, CF ₃ CH _{2 CH 2 -, C 3 F 7} CH 2 CH 2 CH 2 -, H (CF 2) 4 CH 2 OCH 2 CH 2 CH 2 -, γ- glycidoxypropyl group, .gamma.-mercaptopropyl group, 3,4 Examples thereof include substituted hydrocarbon groups such as an epoxycyclohexylethyl group and a γ-methacryloyloxypropyl group. x is preferably an integer of 2 to 4.

Specific examples of these alkoxysilanes are shown below.
Examples of x = 4 (hereinafter referred to as tetrafunctional organosilane) include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetraacetoxysilane, and the like. Is mentioned.

As x = 3 (hereinafter referred to as trifunctional organosilane), methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , Iso-propyltrimethoxysilane, iso-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , Γ-methacryloyloxypropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxysilane, vinyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxy Cyclohexylethyl _{triethoxysilane, CF 3 CH 2 CH 2 Si} (OCH 3) 3, C 2 F 5 CH 2 CH 2 Si (OCH 3) 3, C 2 F 5 OCH 2 CH 2 CH 2 Si (OCH 3) 3 _{, C 3 F 7 OCH 2 CH} 2 CH 2 Si (OC 2 H 5) 3, (CF 3) 2 CHOCH 2 CH 2 CH 2 Si (OCH 3) 3, C 4 F 9 CH 2 OCH 2 CH 2 CH 2 Si (OCH ₃ ) ₃ , H (CF ₂ ) ₄ CH ₂ OCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , 3- (perfluorocyclohexyloxy) propyltrimethoxysilane and the like can be mentioned.

Examples of x = 2 (hereinafter referred to as bifunctional organosilane) include dimethyldimethoxysilane, dimethyldiethoxysilane, methylphenyldimethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di- n- propyl diethoxy silane, di -iso- propyl dimethoxysilane, di -iso- propyl diethoxy silane, diphenyl dimethoxy silane, divinyl diethoxy _{silane, (CF 3 CH 2 CH 2} ) 2 Si (OCH 3) 2, ( C ₃ F ₇ OCH ₂ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) ₂ , [H (CF ₂ ) ₆ CH ₂ OCH ₂ CH ₂ CH ₂ ] ₂ Si (OCH ₃ ) ₂ , (C ₂ F ₅ CH ₂ CH ₂ ) ₂ Si (OCH ₃ ) _{2 and the} like.

  Said organosilane may be used individually by 1 type, and can also use 2 or more types together.

Next, the manufacturing method of the organic inorganic composite of this invention is demonstrated.
The organic-inorganic composite of the present invention contains at least one selected from the group consisting of an amide solvent, a urea solvent, a sulfoxide solvent, an amine solvent and a phosphoric acid solvent in an amount of 50% by mass or more based on the total mass of the organic solvent. On the base material, an organosilane prepared by the above-described method is added as a constituent component to a solution in which 5 to 30% by mass of an organic polymer is dissolved in an organic solvent containing It can be prepared by applying to and curing. In addition to these organosilanes, the following various compounds can be added to the solution as required.

(A) Hydrolysis / condensation catalyst (sol-gel catalyst)
(B) Chelate ligand compound (c) Water

  Hereinafter, various additives that can be used in combination will be described in detail.

(A) Sol-gel catalyst Various catalyst compounds can be used in the sol solution for the purpose of promoting hydrolysis / partial condensation reaction of organosilanes. The catalyst used is not particularly limited, and an appropriate amount may be used according to the constituent components of the used sol solution.
Generally effective sol-gel catalysts are the following compounds (a1) to (a5), and a preferable amount of these compounds can be added from these compounds. Further, two or more selected from these groups may be appropriately selected and used in combination as long as the mutual promoting effects are not inhibited.

(A1) Inorganic acid or organic acid Examples of the inorganic acid include hydrochloric acid, hydrogen bromide, hydrogen iodide, sulfuric acid, sulfurous acid, nitric acid, nitrous acid, phosphoric acid, phosphorous acid, and the like. Examples of organic acids include carboxylic acids (formic acid, acetic acid, propionic acid, butyric acid, succinic acid, cyclohexanecarboxylic acid, octanoic acid, maleic acid, 2-chloropropionic acid, cyanoacetic acid, trifluoroacetic acid, perfluorooctanoic acid, Benzoic acid, pentafluorobenzoic acid, phthalic acid, etc.), sulfonic acids (methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid), p-toluenesulfonic acid, pentafluorobenzenesulfonic acid, etc.), phosphoric acid / phosphonic acid (phosphoric acid) Dimethyl ester, phenylphosphonic acid, etc.), Lewis acids (boron trifluoride etherate, scandium triflate, alkyl titanic acid, aluminate, etc.), and heteropolyacids (phosphomolybdic acid, phosphotungstic acid, etc.).

(A2) Inorganic base or organic base Examples of the inorganic base include sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, and ammonia. Organic bases include amines (ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylamine, dibutylamine, tetramethylethylenediamine, piperidine, piperazine, morpholine, ethanolamine, diazabicycloundecene, quinuclidine, aniline. , Pyridine, etc.), phosphines (triphenylphosphine, trimethylphosphine, etc.), metal alkoxides (sodium methylate, potassium ethylate, etc.) and the like.

(A3) Metal chelate compound An alcohol represented by the general formula R ¹⁰ OH (wherein R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms) and R ¹¹ COCH ₂ COR ¹² (wherein R ¹¹ is carbon number 1-6 alkyl group, R ¹² is preferably not particularly limited as long as it is a metal that diketones as a ligand represented by an alkyl group or an alkoxy group having 1 to 16 carbon atoms having 1 to 5 carbon atoms) Can be used. Within this category, two or more metal chelate compounds may be used in combination.
Particularly preferred as the metal chelate compound of the present invention is one having Al, Ti, Zr as the central metal, and has the general formula Zr (OR ¹⁰ ) _p1 (R ¹¹ COCHCOR ¹² ) _p2 , Ti (OR ¹⁰ ) _q1 (R Those selected from the group of compounds represented by ¹¹ COCHCOR ¹² ) _q2 and Al (OR ¹⁰ ) _r1 (R ¹¹ COCHCOR ¹² ) _r2 are preferred and serve to promote the condensation reaction of the component (a).

R ¹⁰ and R ¹¹ in the metal chelate compound may be the same or different and each is an alkyl group having 1 to 6 carbon atoms, specifically, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, sec -Butyl group, tert-butyl group, n-pentyl group, phenyl group and the like. R ¹² may be an alkyl group having 1 to 6 carbon atoms as described above, or an alkoxy group having 1 to 16 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, or n-butoxy. Group, sec-butoxy group, tert-butoxy group, lauryl group, stearyl group and the like. Moreover, p1-r2 in a metal chelate compound represents the integer determined so that it may become a 4 or 6-dentate coordination.

  Specific examples of these metal chelate compounds include tri-n-butoxyethylacetoacetate zirconium, di-n-butoxybis (ethylacetoacetate) zirconium, n-butoxytris (ethylacetoacetate) zirconium, tetrakis (n-propylacetate). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetoacetate) zirconium, tetrakis (ethylacetoacetate) zirconium; diisopropoxybis (ethylacetoacetate) titanium, diisopropoxybis (acetylacetate) titanium, diisopropoxybis Titanium chelate compounds such as (acetylacetone) titanium; diisopropoxyethyl acetoacetate aluminum, diisopropoxy Acetylacetonate aluminum, isopropoxybis (ethylacetoacetate) aluminum, isopropoxybis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonate) aluminum, monoacetylacetonate bis (ethylacetate) And aluminum chelate compounds such as acetate) aluminum. Among these metal chelate compounds, tri-n-butoxyethyl acetoacetate zirconium, diisopropoxybis (acetylacetonato) titanium, diisopropoxyethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable. These metal chelate compounds can be used individually by 1 type or in mixture of 2 or more types. Moreover, the partial hydrolyzate of these metal chelate compounds can also be used.

(A4) Organometallic compound The type of the organometallic compound is not particularly limited, but an organic transition metal is preferable because of its high activity. Of these, tin compounds are particularly preferred because of their excellent stability and activity. Specific examples thereof include (C ₄ H ₉ ) ₂ Sn (OCOC ₁₁ H ₂₃ ) ₂ , (C ₄ H ₉ ) ₂ Sn (OCOCH = CHCOOC ₄ H ₉ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn ( Carboxylic acid type organotin compounds such as OCOC ₁₁ H ₂₃ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (OCOCH═CHCOOC ₄ H ₉ ) ₂ , Sn (OCOCC ₈ H ₁₇ ) ₂ ; (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₄ H ₉ ) ₂ Sn (SCH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ CH ₂ COOC ₈ H ₁₇ ) ₂ , (C ₈ H ₁₇ ) ₂ Sn (SCH ₂ COOC ₁₂ H ₂₅ ) ₂ or other mercaptide type or sulfide type organotin compounds, (C ₄ H ₉ ) ₂ SnO, (C ₈ H ₁₇ ) ₂ SnO or (C ₄ H _{9 ) 2 SnO, (C 8 H} 17) 2 organotin oxide and ethyl silicate maleic acid, such as SnO dimethyl, diethyl maleate, dioctyl phthalate What organotin compounds such as reaction products of the ester compound and the like.

(A5) Metal salts As metal salts, alkali metal salts of organic acids (for example, sodium naphthenate, potassium naphthenate, sodium octoate, sodium 2-ethylhexanoate, potassium laurate, etc.) are preferably used. The content of the metal salt in the solution of the sol-gel catalyst compound is 0.01 to 50% by mass, preferably 0.1 to 50% by mass, more preferably 0. 0% by mass with respect to the mass of the organosilane that is the raw material of the sol solution. 5 to 10% by mass.

(B) Chelate ligand compound When a metal complex compound is used in the sol solution, it is also preferable to use a compound having a chelate coordination ability from the viewpoint of adjusting the curing reaction rate and improving the liquid stability. Preferably used are β-diketones and / or β-ketoesters represented by the general formula R ¹⁰ COCH ₂ COR ^11, which act as a stability improver for the solution. That is, by coordinating with a metal atom in a metal chelate compound (preferably zirconium, titanium and / or aluminum compound) present in the accelerating liquid, the condensation reaction of component (a) by these metal chelate compounds is promoted. This is considered to suppress the action of controlling the rate of curing of the resulting film. R ¹⁰ and R ¹¹ are synonymous with R ¹⁰ and R ¹¹ constituting the metal chelate compound, but need not have the same structure when used.

  Specific examples of the β-diketones and / or β-ketoesters include acetylacetone, methyl acetoacetate, ethyl acetoacetate, acetoacetate-n-propyl, acetoacetate-i-propyl, acetoacetate-n-butyl, acetoacetate. Acetic acid-sec-butyl, acetoacetic acid-tert-butyl, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-nonanedione, 5-methyl Examples thereof include hexanedione. Of these, ethyl acetoacetate and acetylacetone are preferred, and acetylacetone is particularly preferred. These β-diketones and / or β-ketoesters may be used alone or in combination of two or more. Such β-diketone and / or β-ketoester is 2 mol or more, preferably 3 to 20 mol, per 1 mol of the metal chelate compound. If 2 mol or more of β-diketone and / or β-ketoester is used, the storage stability of the resulting composition can be maintained.

(C) Water To the preferred sol solution of the present invention, water is added for the hydrolysis / condensation reaction of the component (a). The usage-amount of water is 1.2-3.0 mol normally with respect to 1 mol of (a) organosilane components, Preferably it is about 1.3-2.0 mol. The sol liquid preferred in the present invention has a total solid content concentration of 0.1 to 50% by mass, preferably 1 to 40% by mass. When the solid component concentration exceeds 50% by mass, the storage stability of the solution is deteriorated, which is not preferable.

  In the organic-inorganic composite of the present invention, the mass of the inorganic component in the organic-inorganic composite is preferably 0.1 to 50% by mass, more preferably 1 to 30% by mass, and further preferably 5 to 20%. % By mass. When the mass of the inorganic component is less than or equal to this range, the effects of improving the mechanical strength, heat resistance, thermal dimensional stability, etc., which are the advantages of the inorganic compound, are hardly reflected in the organic-inorganic composite. On the other hand, when the mass of the inorganic component is not less than this range, the brittleness of the organic-inorganic composite deteriorates.

  The solution prepared as described above can be applied on a substrate and cured to obtain an organic-inorganic composite. The coating method and the curing method in the present invention are not particularly limited. Examples of the coating method include a band casting method, a drum casting method, a glass plate casting method, a dip coating method, and a spin coating method. The band casting method, the drum casting method, and the glass plate casting method can be used. It is preferable to use it. Examples of the curing method include a curing method by heating, a curing method by microwave irradiation, and the like. It is preferable to use a curing method by heating.

[Optical film]
The optical film of the present invention is a film comprising the organic-inorganic composite of the present invention. Although the thickness in particular of the film of this invention is not restrict | limited, Preferably it is 20-200 micrometers, More preferably, it is 50-150 micrometers, More preferably, it is 75-125 micrometers.

  When the thickness of the film of the present invention is 100 μm, the light transmittance at 550 nm is preferably 50% or more, more preferably 70% or more, and further preferably 85% or more. An organic-inorganic composite having a light transmittance of 85% or more at 550 nm is excellent in transparency, and therefore is preferably used as a substrate for transparent electrodes of image display elements such as circularly polarizing plates, liquid crystal display elements, touch panels, and organic EL elements. Can do.

  In the optical film of the present invention, a metal oxide is obtained by hydrolysis and polycondensation reaction by a sol-gel reaction in a state where an organic polymer is dissolved in an amide solvent, and a solution containing the metal oxide is applied and dried. Can be produced. Examples of the coating method include a band casting method, a drum casting method, a glass plate casting method, a dip coating method, and a spin coating method. The band casting method, the drum casting method, and the glass plate casting method can be used. It is preferable to use it. Examples of the curing method include a curing method by heating, a curing method by microwave irradiation, and the like. It is preferable to use a curing method by heating.

  The surface of the optical film of the present invention is treated by a method such as saponification, corona treatment, flame treatment, glow discharge treatment, etc., in order to enhance the adhesion with other layers or components depending on the application. Can do. Furthermore, an adhesive layer and an anchor layer may be provided on at least one side of the optical film. Also, on the optical film surface, a smoothing layer for smoothing, a hard coat layer for imparting scratch resistance, an ultraviolet absorbing layer for enhancing light resistance, and a surface roughening for improving the film transportability Various known functional layers can be provided depending on the purpose such as the layer.

  In the optical film of the present invention, a transparent conductive layer can be laminated on at least one side. As the transparent conductive layer, known metal films, metal oxide films, and the like can be applied. Among these, metal oxide films are preferable from the viewpoints of transparency, conductivity, and mechanical properties. For example, metal oxide films such as indium oxide, cadmium oxide and tin oxide to which tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium and the like are added as impurities, and zinc oxide and titanium oxide to which aluminum is added as impurities. Can be mentioned. Among them, an indium oxide thin film (ITO film) mainly containing tin oxide and containing 2 to 15% by weight of zinc oxide is excellent in transparency and conductivity, and can be preferably used.

[Image display element]
Although the use of the transparent organic-inorganic composite of the present invention is not particularly limited, since it has excellent optical properties, it can be suitably used as a substrate for a transparent electrode of an image display element. The term “image display element” as used herein means a circularly polarizing plate / liquid crystal display element, a touch panel, an organic EL element, or the like.

<Circularly polarizing plate>
When a transparent electrode substrate having a transparent conductive layer formed on the optical film of the present invention is prepared, a λ / 4 plate and a polarizing plate can be laminated on the transparent electrode substrate to prepare a circularly polarizing plate. In this case, the lamination is performed so that the slow axis of λ / 4 and the absorption axis of the polarizing plate are 45 °. As such a circularly polarizing plate, one that is stretched in the direction of 45 ° with respect to the longitudinal direction (MD) is preferably used. For example, those described in JP-A-2002-865554 can be suitably used. .

<Liquid crystal display element>
The reflective liquid crystal display device has a configuration including a lower substrate, a reflective electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, a transparent electrode, an upper substrate, a λ / 4 plate, and a polarizing film in order from the bottom. The transparent electrode substrate in which the transparent electrode layer is formed on the optical film of the present invention can be used as the transparent electrode and the upper substrate in the apparatus. In the case of color display, it is preferable to further provide a color filter layer between the reflective electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The transmissive liquid crystal display device includes, in order from the bottom, a backlight, a polarizing plate, a λ / 4 plate, a lower transparent electrode, a lower alignment film, a liquid crystal layer, an upper alignment film, an upper transparent electrode, an upper substrate, a λ / 4 plate, and a polarization It has the structure which consists of a film | membrane. Among these, when a transparent electrode substrate in which a transparent conductive layer is formed on the optical film of the present invention is produced, it can be used as the upper transparent electrode and the upper substrate. In the case of color display, it is preferable to further provide a color filter layer between the lower transparent electrode and the lower alignment film, or between the upper alignment film and the transparent electrode.

  The liquid crystal cell is not particularly limited, but more preferably TN (Twisted Nematic) type, STN (Supper Twisted Nematic) type or HAN (Hybrid Aligned Nematic) type, VA (Vertically Alignment) type, ECB type (Electrically Controlled Birefringence), OCB A type (Optically Compensatory Bend) and a CPA type (Continuous Pinwheel Alignment) are preferable.

<Touch panel>
The touch panel can be applied to those described in JP-A-5-127822, JP-A-2002-48913, and the like.

<Organic EL device>
The optical film of the present invention is provided with a gas barrier layer and TFT as necessary, and can be used for organic EL display applications as a substrate with a transparent electrode.
As a specific layer structure as an organic EL display element, anode / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / transparent cathode, anode / hole transport layer / light emitting layer / electron transport layer / transparent cathode , Anode / hole transport layer / light emitting layer / transparent cathode, anode / light emitting layer / electron transport layer / electron injection layer / transparent cathode, anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron Examples include injection layer / transparent cathode.

  When the optical film of the present invention is used for an organic EL device or the like, JP-A-11-335661, JP-A-11-335368, JP-A-2001-192651, JP-A-2001-192652, JP-A-2001-192653. JP-A-2001-335776, JP-A-2001-247859, JP-A-2001-181616, JP-A-2001-181617, JP-A-2002-181816, JP-A-2002-181617, JP-A-2002-056776 It is preferable to use in combination with the contents described in each gazette, and JP 2001-148291 A, JP 2001-221916 A, and JP 2001-231443 A.

  Hereinafter, it demonstrates in detail based on an Example. Here, although the present Example can implement the method of this invention effectively, this invention is not limited to these Examples.

[Example 1]
As the organic polymer, polyarylate resin “U-100” (manufactured by Unitika) was used. As the solvent, tetramethylurea (TMU: β = 0.78), N-methylpyrrolidone (NMP: β = 0.77), dimethylacetamide (DMAc: β = 0.76), ethanol (β = 0.0). 77), cyclohexanone (β = 0.53), acetone (β = 0.48), and dichloroethane (β = 0.00) were used.

  1 g of U-100 was added to 19.0 g of the above solvent to confirm solubility. As a result, when the solvent was TMU, NMP, cyclohexanone, or dichloromethane, it was uniformly dissolved by heating and became transparent (hereinafter referred to as “transparent uniform”). On the other hand, when the solvent was ethanol or acetone, it was not transparent and uniform even when heated.

  Add 0.77 g of tetraethoxysilane, 0.45 g of water, and 0.07 g of aluminum (III) diisopropoxide ethyl acetoacetate to the TMU solution, NMP solution, cyclohexanone solution, and dichloromethane solution that became transparent and uniform. And stirred at room temperature for 2 hours. As a result, in the case of the TMU solution, the NMP solution, and the cyclohexanone solution, it became transparent and uniform, but in the case of the dichloromethane solution, it was separated into two phases, and white turbidity considered to be based on the formation of silica particles was observed.

  The transparent and uniform TMU solution, NMP solution, and cyclohexanone solution were weighed in an amount of 15 g each, and cast on a glass petri dish with a diameter of 8.5 cm subjected to silane coupling treatment. The film was dried for an hour and further dried at 130 ° C. under reduced pressure for 2 days to obtain a film having a thickness of 100 μm. The light transmittance at 550 nm of this film was measured with a spectrophotometer. The obtained results are shown in Table 1.

From Table 1, films (samples 1 and 2) made of an organic-inorganic composite obtained from a TMU solution having β = 0.78 and an NMP solution having β = 0.77 were transparent. On the other hand, a film (sample 4) made of an organic-inorganic composite obtained from a cyclohexanone solution in which β = 0.53 was opaque.
From this, it can be seen that when U-100 is used as the organic polymer, a transparent organic-inorganic composite is obtained by a sol-gel reaction in a solvent having a β value of 0.6 or more.
The reason why a transparent organic-inorganic composite can be obtained by a sol-gel reaction in a solvent having a β value of 0.6 or more is not clear, but a transparent organic-inorganic composite is obtained from a polymer having tetraethoxysilane and an amide group. Is the mechanism by which the organic polymer and silica gel are mixed uniformly at the molecular level due to the hydrogen bond interaction between the silanol residue in the silica gel matrix and the amide carbonyl group in the organic polymer. From the analogy from "Silanol residue of silica gel oligomer generated by hydrolysis and condensation is stabilized by a solvent having high hydrogen bond acceptability (β ≧ 0.6), so in the solvent and in the drying process, The phase separation between polymer and silica is suppressed, and a transparent organic-inorganic composite material is obtained. ” Can guess.

[Example 2]
An organic-inorganic composite was synthesized in the same manner as in Example 1 except that polymethyl methacrylate (PMMA: average molecular weight 350,000; manufactured by Aldrich) was used in place of U-100 as the organic polymer. Films were prepared and optical properties were examined.

  1 g of PMMA was added to 19.0 g of the above solvent to confirm solubility. When the solvent was DMAc, acetone, or dichloromethane, it became transparent and uniform by heating. On the other hand, when the solvent was TMU, NMP, ethanol, or cyclohexanone, it was not transparent and uniform even when heated.

  Add 0.77 g of tetraethoxysilane, 0.45 g of water, 0.07 g of aluminum (III) diisopropoxide ethyl acetoacetate to the DMAc solution, acetone solution, and dichloromethane solution that became transparent and uniform. Stir for 2 hours. As a result, the DMAc solution and the acetone solution became transparent and uniform, but the dichloromethane solution was separated into two phases, and white turbidity considered to be based on the formation of silica particles was observed.

  15 g each of the DMAc solution and the acetone solution that became transparent and uniform were weighed and cast on a glass petri dish with a diameter of 8.5 cm subjected to silane coupling treatment, and dried at a temperature 20 ° C. lower than the boiling point of each solvent for 2 hours. Further, the film was dried at 80 ° C. under reduced pressure for 2 days to obtain a film having a thickness of 100 μm. The light transmittance at 550 nm of this film was measured with a spectrophotometer. The obtained results are shown in Table 2.

From Table 2, a film (sample 8) made of an organic-inorganic composite obtained from a DMAc solution with β = 0.76 was transparent, whereas it was obtained from an acetone solution with β = 0.48. The film (sample 10) made of the organic-inorganic composite was opaque.
Thus, when PMMA is used as the organic polymer, a transparent organic-inorganic composite is obtained by a sol-gel reaction in a solvent having a β value of 0.6 or more, as in the case of using U-100 as the organic polymer. I understood that.

[Example 3]
In Examples 1 and 2, Sample 1, Sample 2, and Sample 8 obtained as transparent organic-inorganic composites by sol-gel reaction were examined for solubility in dichloromethane. As a comparative example, Sample 12 and Sample 13 obtained by adding colloidal silica as a transparent organic-inorganic composite were used.

Sample 12 and sample 13 were prepared as follows.
(Sample 12)
After 1.0 g of U-100 was dissolved in 9.0 g of NMP, 0.37 g of MEK-ST (hydrophobic colloidal silica dispersion manufactured by Nissan Chemical; colloidal silica particle size of about 15 nm) was added to obtain a homogeneous solution. did. After 7.5 g of this solution was weighed and cast on a glass petri dish with a diameter of 8.5 cm subjected to silane coupling treatment, it was dried at 170 ° C. for 2 hours and further dried at 130 ° C. under reduced pressure for 2 days to obtain a thickness. A transparent film of about 100 μm was obtained.
(Sample 13)
After dissolving 1.0 g of PMMA in 9.0 g of acetone, 0.37 g of MEK-ST was added to obtain a homogeneous solution. After 7.5 g of this solution was weighed and cast on a glass petri dish with a diameter of 8.5 cm subjected to silane coupling treatment, it was dried at 80 ° C. for 2 hours, and further dried at 80 ° C. under reduced pressure for 2 days to obtain a thickness. A transparent film of about 100 μm was obtained.

  0.1 g each of Sample 1, Sample 2, and Sample 8 that became transparent organic-inorganic organic composites by the sol-gel method, and Sample 12 and Sample 13 that became transparent organic-inorganic organic composites by adding colloidal silica, After adding 4.9 g of dichloromethane and stirring at room temperature for 24 hours, the state of the sample was visually observed. The obtained results are shown in Table 3.

Samples 1, 2 and 8 obtained as transparent organic-inorganic composites by the sol-gel method did not dissolve in dichloromethane, which is a good solvent for U-100 and PMMA, whereas colloidal silica was added. Samples 12 and 13 obtained as transparent organic-inorganic composites were found to dissolve in dichloromethane.
From this, it was found that the transparent organic-inorganic composite obtained by the sol-gel method is excellent in solvent resistance.

  The fact that the transparent organic-inorganic composites obtained by the present invention by the sol-gel method are excellent in solvent resistance is that these organic-inorganic composites have an IPN-like structure, that is, both a silica and an organic polymer are continuous structures. This suggests the possibility of having

  Since the organic-inorganic composite of the present invention has excellent transparency and solvent resistance, it can be suitably used as an optical film material having transparency and solvent resistance. Moreover, since the optical film of this invention has the outstanding optical characteristic, it can utilize suitably as a board | substrate for transparent electrodes of various image display elements.

Claims (6)

An organic solvent having at least one selected from the group consisting of amide solvents, urea solvents, sulfoxide solvents, amine solvents, and phosphate solvents having a hydrogen bond acceptability parameter (β value) of 0.6 to 1.0 In an organic solvent containing 50% by mass or more with respect to the total mass of the above, 5-30% by mass of aromatic polyester or polymethacrylic acid ester is dissolved with respect to the total mass of the organic solvent. And / or an organic-inorganic composite comprising an organic polymer and a metal oxide, obtained by performing a sol-gel reaction of a metal complex compound. An organic solvent having at least one selected from the group consisting of amide solvents, urea solvents, sulfoxide solvents, amine solvents, and phosphate solvents having a hydrogen bond acceptability parameter (β value) of 0.6 to 1.0 In a state in which 5 to 30% by mass of polyarylate resin or polymethyl methacrylate is dissolved in an organic solvent containing 50% by mass or more with respect to the total mass of the organic solvent, the metal alkoxide compound and / or Alternatively, an organic-inorganic composite comprising an organic polymer and a metal oxide, obtained by performing a sol-gel reaction of a metal complex compound. The organic-inorganic composite according to claim 1 or 2, wherein the metal element forming the metal alkoxide compound or the metal complex compound is at least one selected from the group consisting of silicon, titanium, aluminum, and zirconium. An optical film comprising the organic-inorganic composite according to any one of claims 1 to 3 . The optical film according to claim 4 , wherein the light transmittance at a wavelength of 550 nm of the film having a thickness of 100 μm is 50% or more. An organic solvent having at least one selected from the group consisting of amide solvents, urea solvents, sulfoxide solvents, amine solvents, and phosphate solvents having a hydrogen bond acceptability parameter (β value) of 0.6 to 1.0 In a state where 5 to 30% by mass of aromatic polyester or polymethacrylic acid ester is dissolved in an organic solvent containing 50% by mass or more based on the total mass of The manufacturing method of the organic inorganic composite characterized by having the process of reacting.