JPH0656948A - Transparent solid resin having functional organic molecule incorporated therein and its production - Google Patents

Abstract

PURPOSE:To obtain a transparent solid resin which can be easily formed into a thin film and is useful in the field of information processing for, e.g. a molecular device, a recording material, and copy, by incorporating a specified organic molecule into a specified three-dimensional cured material. CONSTITUTION:An organic molecule exhibiting a nonlinear optical effect, a photoconductive phenomenon, a photochromic phenomenon, etc., is incorporated into a three-dimensional cured material formed by the radical polymerization of a polymerizable resin composition containing 30-95wt.% polyorganosilsesquioxane of formula I [wherein 50-97% of R1 to R2n are CH3, 3-50% thereof are a group having a (meth)acryloxy linkage, and the remainder are 2-3C alkyl or (substituted) phenyl; Ra to Rd are each OH or 1-3C alkoxy; and n is the degree of polymerization], 70-5wt.% (meth)acrylate and/or poly(meth)acrylate of formula II (wherein Re is H or CH3; R5 is a hydrocarbon residue or a residue of an ester of a polyhydric alcohol with a polybasic acid; and in is 1 or greater) (the total of the two constituents being 100wt.%), and a photosensitizer and/or a radical polymerization initiator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transparent solid resin in which organic molecules having a specific function are encapsulated and a method for producing the same. In more detail, organic molecules exhibiting nonlinear optical effect, photoconductivity phenomenon, photochromism phenomenon or photochemical hole burning phenomenon capable of storing and inputting / outputting information are encapsulated, and thin film formation is easy, and information processing such as molecular devices is possible. The present invention relates to a transparent solid resin useful as a composite in the field of (1) and a method for producing the same.

[0002]

2. Description of the Related Art Advances in electronic technology have deepened awareness of the usefulness of information recording,
There is an increasing demand for recording media having a larger capacity. From this point, optical memory has been attracting attention as a recording method that exceeds magnetic memory in terms of recording density.
Some have been put to practical use.

More recently, specific organic molecules encapsulated in a transparent solid medium can induce unique phenomena such as nonlinear optical effect, photoconductivity phenomenon, photochromism phenomenon and photochemical hole burning phenomenon by laser light. It is known that it is pointed out that the recording density may increase dramatically in the future.

As the above composite, for example, a material in which a dye molecule such as phthalocyanine is dispersed and encapsulated in a free molecular state in a silicate network structure has been reported. However, it is known that the formation of the composite by this method not only takes an extremely long time, but also tends to cause cracks when the film thickness exceeds a certain level. There are also restrictions on the type and concentration of organic molecules that can be encapsulated. That is, since the organic molecule having a specific function of the present invention has a low solubility by nature, a considerable amount of solvent must be used, and when the solvent volatilizes during the heat treatment for curing the film, the dye molecule However, since they have a low affinity for the silicate network structure, there is a problem such as bleeding out on the film surface.

On the other hand, as disclosed in JP-A-3-41154, an organic molecule having a specific function in a three-dimensional cured product formed by a heat condensation reaction of a ladder silicone oligomer having a hydroxyl group and an alkoxy group at the terminal. There has been proposed a transparent solid resin obtained by encapsulating. However, in this method for producing a transparent solid resin, the heating temperature is as high as 100 ° C. or higher, and it takes a long time to cure, so the encapsulated organic molecules bleed out on the surface, and deterioration due to heating and deterioration of durability function are caused. Is recognized.

As a transparent resin material, an acrylic resin is generally used, and the curing thereof is carried out by radical polymerization, so that it can be cured rapidly and at low temperature by means of UV irradiation or the like. However, when viewed from the object of the present invention of encapsulating the functional organic molecule in a transparent solid resin, the shrinkage during curing is large, and cracks or deformations are likely to occur at a certain thickness or more, and A thin film of less than a micron has some problems such as curing failure due to oxygen in the air and insufficient physical properties of the cured film, and is not adopted.

[0007] Therefore, an object of the present invention is to provide a transparent solid resin in which an organic molecule having a specific function is rapidly and easily encapsulated in a high concentration and uniformly, and particularly a thin film can be easily formed, and a method for producing the same. Especially.

[0008]

[Means for Solving the Problems] The inventors of the present invention have reached the present invention as a result of repeated research on organic silicon-based polymers that can be cured by radical polymerization in order to solve the above problems. That is, the present invention includes 1) (A) the following general formula (I)

[0009]

[Chemical 5]

(In the formula, R _{1 to} R _2n are each independently a substituent, 50 to 97% of the number of substituents of R _{1 to} R _2n is a methyl group, and 3 to 50% is a (meth) acryloxy group. A group having a bond, the remainder being an alkyl group having 2 to 3 carbon atoms, or an optionally substituted phenyl group,
The terminal groups Ra, Rb, Rc and Rd represent a hydroxyl group or an alkoxy group having 1 to 3 carbon atoms, and n is the degree of polymerization. ) A polyorganosilsesquioxane represented by the formula (B), the following general formula (II)

[0011]

[Chemical 6]

(Wherein Re is a hydrogen atom or a methyl group, Rf is a hydrocarbon residue or an ester residue composed of a polyhydric alcohol and a polybasic acid, and m is a number of 1 or more. A), and (C) a photosensitizer and / or a radical polymerization initiator, and (A) component and (B) component. The ratio of (A) component 3
A non-linear optical effect, a photoconductivity phenomenon, a photochromism phenomenon, or a photochemical phenomenon is contained in a three-dimensional cured body formed by radical polymerization of a polymerizable resin composition containing 0 to 95% by weight of component (B) and 70 to 5% by weight. A transparent solid resin in which organic molecules exhibiting a hole burning phenomenon are encapsulated, and 2) (A) the following general formula (I)

[0013]

[Chemical 7]

(Wherein R _{1 to} R _2n , Ra, Rb, Rc,
Rd and n have the same meanings as described above. ) A polyorganosilsesquioxane represented by the formula (B), the following general formula (II)

[0015]

[Chemical 8]

(Wherein Re, Rf and m have the same meanings as described above), and (meth) arylate and / or poly (meth) acrylate, and (C) photosensitizer and / or radical polymerization. An initiator is contained, and the ratio of the (A) component and the (B) component is the (A) component 3
(D) Nonlinear optical effect, photoconductivity phenomenon, photochromism phenomenon in a three-dimensional cured product formed by radical polymerization of a polymerizable resin composition containing 0 to 95% by weight of component (B) and 70 to 5% by weight of component (B). Or three-dimensionally characterized by dissolving or uniformly dispersing an organic solvent solution of organic molecules exhibiting a photochemical hole burning phenomenon, shaping it into a predetermined shape, removing the organic solvent, and then irradiating with ultraviolet rays to cure it. Provided is a method for producing a transparent solid resin in which an organic molecule exhibiting a nonlinear optical effect, a photoconductive phenomenon, a photochromism phenomenon, or a photochemical hole burning phenomenon is encapsulated in a cured body.

The organic molecule having a specific function used in the present invention is one which exhibits a physical and / or chemical change by absorbing a specific energy, and more specifically, a nonlinear optical effect, It is an organic compound that exhibits phenomena such as photoconductivity, photochromism, and photochemical hole burning. Specific examples of such an organic compound include 2-methyl-4-nitroaniline and 4-diethylamino-4'-
Nitrostilbenzene, 2- [butyl (4-((4-nitrophenyl) azo) phenyl) amino] ethanol,
3-methyl- (2,4-dinitrophenyl) -aminopropanol, N-4-nitrophenylpropanol and the like can be mentioned.

Examples of the compound exhibiting the photoconductivity phenomenon include metal-free phthalocyanine, titanyl phthalocyanine, and copper phthalocyanine.

Compounds exhibiting a photochromism phenomenon include 6-nitrospirobenzopyran, 2,5-dimethyl-3-furylfulgide, azobenzene, H ₂ -porphine, chlorin, H ₂ -phthalocyanine, quinizarin, dimethyl-S-tetrazine, Chlorophyll, phycocyanin, 2-methyl-4-nitroaniline, 4-dimethylamino-4'-nitrostilbenzene, 2- [4-((4-
Nitrophenyl) azo) phenyl] amino] pentanol and the like,

Compounds exhibiting the photochemical hole burning phenomenon include H ₂ -porphine, chlorin and H ₂
-Phthalocyanine, quinizarin, dimethyl-S-tetrazine, chlorophyll, phycocyanin, etc. are mentioned, but not limited to these compounds.

The polyorganosilsesquioxane of the component (A) used in the present invention is represented by the above general formula (I), and R _{1 to} R _2n in the formula may be the same group or different from each other. However, 50 to 97%, preferably 60 to 85%, of the number of substituents of R _{1 to} R _2n are methyl groups. When the methyl group is less than 50%, the hardness and heat resistance of the resin after curing become insufficient. Further, when the methyl group is 97% or more (when the group containing a (meth) acryloxy bond is less than 3%), solvent resistance and stain resistance are insufficient.
When the group containing a (meth) acryloxy bond is 50% or more,
The heat resistance and scratch resistance of the resin after curing become insufficient.

In R _{1 to} R _2n in the general formula (I), the remaining groups other than a methyl group and a group having a (meth) acryloxy bond are alkyl groups having 2 to 3 carbon atoms,
It is composed of an optionally substituted phenyl group. R ₁ ~ R _2n
If it contains an alkyl group having 4 or more carbon atoms, the hardness, heat resistance, and durability are deteriorated, which is not suitable for the purpose of the present invention. Examples of the substituent of the phenyl group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group or a group in which a part of hydrogen atoms bonded to carbon atoms of these groups are substituted with a halogen atom, a cyano group or the like. To be

In the present invention, the molecular weight of the polyorganosilsesquioxane as the component (A) is 1,000 to 100,000 in terms of number average molecular weight measured by using a gel permeation chromatography (GPC) apparatus and a standard molecular weight substance.
A degree is preferable.

Further, the terminal groups Ra, Rb, Rc and Rd of the polyorganosilsesquioxane of the general formula (I) represent an alkoxy group or a hydroxyl group derived from a raw material at the time of synthesis. It is also possible to enhance storage stability by capping with chlorosilane, trimethylmethoxysilane, or the like.

In the present invention, the (B) component (meth) acrylate or poly (meth) acrylate is represented by the above general formula (II), wherein Re is a hydrogen atom or a methyl group. All m Res existing in the same molecule do not have to be the same, and hydrogen atoms and methyl groups may be mixed.

Rf represents a hydrocarbon residue having a (meth) acrylic acid residue bonded to its carbon atom, or an ester residue composed of a polyhydric alcohol and a polybasic acid, and m is 1 or more. It is an integer.

The above-mentioned (meth) acrylate (m =
1) or poly (meth) acrylate (when m = 2 or more) can be produced by carrying out an esterification reaction of alcohols with acrylic acid or methacrylic acid under known conditions.

Here, specific examples of alcohols include:
Methanol, ethanol, ethylene glycol, diethylene glycol, 2,2,4-trimethyl-1,3-pentadiol, dipropylene glycol, propylene glycol, polypropylene glycol having an average molecular weight of about 150 to about 600, triethylene glycol, 1,
4-cyclohexanedimethanol, neopentyl glycol, 2,2-dimethyl-3-hydroxypropyl,
2,2-Dimethyl-3-hydroxypropanate, polyethylene glycol having an average molecular weight of about 150 to about 600, 2,2-bis [4- (2-hydroxyethoxy)
Phenyl] propane, 2,2-bis [4- (2-hydroxypropoxy) phenyl] propane, triethanolamine, 2,3-butanediol, tetraethylene glycol, 2,2-bis (4-hydroxyphenyl) propane, Glycerin, trimethylolpropane, 1,4-butanediol, polycaprolactone ester of trimethylolpropane, containing about 1.5 equivalents of caprolactone, about
3.6 Polycaprolactone ester of trimethylolpropane containing equivalent amount of caprolactone, 2-ethyl-1,3
-Hexanediol, 1,5-pentanediol, tripropylene glycol, 2,2-bis (4-hydroxycyclohexyl) propane, 1,2,6-hexanetriol, 1,3-propanediol, 1,6-hexanediol Etc. These alcohols are used alone or in combination of two or more.

In the present invention, when a poly (meth) acrylate having an ester residue composed of a polyhydric alcohol and a polybasic acid is produced, examples of the polyhydric alcohol include ethylene glycol, 1,2. -Propylene glycol, 1,6-hexanediol, glycerin, trimethylolpropane, 1,2,6-hexanetriol, sorbitol, pentaerythritol,
Examples include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol and the like.

On the other hand, specific examples of the polybasic acid include phthalic acid, tetrahydrophthalic acid, hexaahydrophthalic acid,
Isophthalic acid, terephthalic acid, hymic acid (End-
Bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid), succinic acid, adipic acid, dodecanoic acid, sebacic acid, maleic acid, itaconic acid, fumaric acid, pyromeric acid, trimellitic acid, etc. Examples thereof include polybasic acids or their anhydrides.

The preferred blending ratio of the component (A) and the component (B) in the transparent solid resin of the present invention is as follows.
Component (A) is 30 to 95% by weight, preferably 40 to 90
The content of the component (B) is 70 to 5% by weight, preferably 60 to 10% by weight. When the content of the component (A) is less than 30% by weight, the characteristics such as hardness, water resistance, heat resistance and durability due to the component (A) are insufficient, and when it exceeds 90% by weight, the crosslinking density becomes low and Poor chemical resistance and solvent resistance. If the content of the component (B) exceeds 70% by weight, the water resistance, hardness, and abrasion resistance of the cured film after (ultraviolet) curing will be poor, and the adverse effect of large curing shrinkage will appear. On the other hand, if the content of the component (B) is less than 5% by weight, the curing rate is slow even when irradiated with ultraviolet rays, and the cured coating film is fragile and cracks easily occur, which is not preferable.

The component (C) in the present invention is a photosensitizer and / or a radical polymerization initiator. As the photosensitizer, various conventionally known ones can be used. Specific examples include acetophenone, propiophenone, benzophenone, xanthol, fluorenone, benzaldehyde, fluorene, anthraquinone, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-.
Examples thereof include dimethoxybenzophenone. These photopolymerization initiators may be used alone or in combination of two or more.

In the present invention, it is also possible to enhance the ultraviolet curability by using a so-called sensitization aid such as a tertiary amine together with the above-mentioned photosensitizer. As the tertiary amine, various aliphatic and aromatic tertiary amines can be used, and specific examples thereof include N-dimethanolamine, triethanolamine, N-methyldiethanolamine, triethylamine, ethyl p-dimethylaminobenzoate. Etc.

As the radical polymerization initiator, various conventionally known compounds such as organic peroxides and diazo compounds can be used, and specific examples thereof include azobisisobutyronitrile, benzoyl peroxide and methyl ethyl ketone peroxide. Examples thereof include oxide, dicumyl peroxide, t-butyl perbenzoate and t-butyl hydroperoxide.

With these radical polymerization initiators,
A so-called accelerator that decomposes the radical polymerization initiator by a redox reaction to facilitate the generation of radicals can be used in combination. Examples of such an accelerator include lauryl mercaptan, N-butyl sulfide, cobalt naphthenate, manganese naphthenate, and vanadyl octoate.

The blending amount of the photosensitizer and / or radical polymerization initiator of the component (C) varies depending on the types of the components (A) and (B) and their blending ratio.
It is about 1 to 10 parts by weight based on 100 parts by weight of (B).

Further, various additives may be added to the curable resin composition of the present invention for the purpose of modifying the physical properties of the cured product or depending on the use of the cured product. Examples of these additives include thermal polymerization inhibitors (hydroquinone, p-methoxyphenol, etc.), color pigments (phthalocyanine blue, phthalocyanine green, titanium white, etc.), thickeners (silica, calcium carbonate, kaolin, clay, Colloidal silica, etc.) and various other UV absorbers, antioxidants, etc. are used.

In producing the transparent solid resin from the resin composition in the present invention, the above (A) and (b) are used.
And the functional organic molecule is uniformly dissolved or uniformly dispersed in the solution of the component (c) according to the purpose. The amount of the functional organic molecule varies depending on its type and use, so it cannot be said unconditionally, but it is 1 to 80 parts by weight, preferably 3 to 30 parts by weight, relative to 100 parts by weight of the total of (A) and (B). Is. In this case, it may be used after being diluted with a solvent in order to improve workability such as coating treatment or to control the film thickness. Further, a so-called reactive diluent can be used instead of the solvent.

The solvent used is propanol,
Alcohols such as butanol, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as cellosolve acetate and methyl cellosolve, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene. Is mentioned. You may use these solvents in mixture of 2 or more types. Also,
Reactive diluents used include N-vinylpyrrolidone, butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, isobornyl acrylate, dicyclopentenyloxyethyl acrylate, phenoxyethyl acrylate. A monofunctional compound is mentioned. You may use these reactive diluents in mixture of 2 or more types. The solvent and the reactive diluent may be mixed and used.

Curing of the resin composition of the present invention is carried out by radical polymerization. When a solvent is used, the solvent is removed and then radiation such as ultraviolet rays is irradiated at room temperature or at a relatively low temperature. It is carried out by heating at (40 to 100 ° C.) for a certain time (0.5 to 2 hours). Irradiation and heating may be used together if necessary.

[0041]

The resin composition of the present invention can be rapidly cured at room temperature or a relatively low temperature in a state in which functional organic molecules are encapsulated, so that the organic molecules are uniformly dispersed in the cured product and the performance is improved. It is effective in terms of stability and durability. At this time, since curing inhibition by air unlike acrylic resin is not observed at all, it is possible to cure an ultrathin film having a thickness of, for example, 1 μm or less.

After curing, the resin composition of the present invention has almost no energy absorption from the visible region to the ultraviolet region, which is convenient for exhibiting the function of the encapsulated organic molecule. It is particularly effective that the side chain of polyorganosilsesquioxane is methyl to create the above situation, and that polyorganosilsesquioxane is freely compatible with almost any organic solvent and has a specific function. It is convenient for complexing organic molecules having

[0043]

EXAMPLES The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.

Example 1 In the above general formula (I), R _{1 to} R _2n have a ratio of a methyl group, a γ-methacryloxypropyl group and a phenyl group of 60:10:30 and a number average molecular weight of 4,800. The polyorganosilsesquioxane of was synthesized by hydrolytic cocondensation of methyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane and phenyltrimethoxysilane. A curable resin composition having the following composition was prepared based on this polyorganosilsesquioxane.

[Composition] Polyorganosilsesquioxane 60 parts by weight Trimethylolpropane triacrylate 5 parts by weight N-vinylpyrrolidone 15 parts by weight Caprolactone-modified dipentaerythritol hexaacrylate 20 parts by weight benzophenone 1.5 parts by weight p-dimethylaminobenzoic acid Ethyl acid salt 1.5 parts by weight Isopropyl alcohol 30 parts by weight H ₂ -phthalocyanine 2 parts by weight

This solution was spin-coated on an aluminum plate and left at room temperature for 5 minutes to volatilize the solvent.
Ultraviolet irradiation with a dose of 1 J / cm ² was performed using a high-pressure water lamp. The thickness of the obtained transparent film was 1.5 μm, and the uniformity of H ₂ -phthalocyanine was extremely good.

Example 2 In the above general formula (I), R _{1 to} R _2n are polyorganosilsesquises having a ratio of methyl groups to γ-methacryloxypropyl groups of 85:15 and a number average molecular weight of 3,500. Oxane was synthesized by hydrolysis co-condensation of methyltrimethoxysilane and γ-methacryloxypropyltrimethoxysilane. Based on this polyorganosilsesquioxane, a curable resin composition having the following composition was prepared.

[Composition] 80 parts by weight of the above polyorganosilsesquioxane 10 parts by weight of pentaerythritol tetraacrylate 10 parts by weight of phenoxyethyl acrylate 5 parts by weight of benzophenone 2 parts by weight of ethyl p-dimethylaminobenzoate 40 parts by weight of isopropyl alcohol 6- Nitrospirobenzopyran 3 parts by weight

The above solution was coated on a polyimide film which had been surface-treated with an ethanol solution of aminopropyltriethoxysilane in advance, and allowed to stand at room temperature for 5 minutes, and then the same UV irradiation operation as in Example 1 was carried out to cure it. The thickness of the obtained hard coating was 0.8 μm, and the uniform dispersibility of 6-nitrospirobenzopyran was extremely good. It was confirmed by coloring that isomerization to merocyanine type occurred when this film was irradiated with ultraviolet rays of 340 nm.

Example 3 In the above general formula (I), R _{1 to} R _2n are polyorganosilsesquis having a ratio of methyl groups to γ-methacryloxypropyl groups of 70:30 and a number average molecular weight of 36,900. Oxane was synthesized according to the method of Example 1. Based on this polyorganosilsesquioxane, a curable resin composition having the following composition was prepared.

[Composition] Polyorganosilsesquioxane 45 parts by weight Ditrimethylolpropane tetraacrylate 35 parts by weight Acryloylmorpholine 20 parts by weight 2-Hydroxy-2-methyl-1-phenylpropan-1-one 4 parts by weight Methyl Isobutyl ketone 200 parts by weight

The above solution was coated on the surface of a copper phthalocyanine resin-dispersed positively charged photoreceptor layer, allowed to stand at room temperature for 10 minutes, and then irradiated with the same ultraviolet rays as in Example 1 to cure the same. The photosensitive member is prepared by diluting a photosensitive coating solution in which copper phthalocyanine is dispersed in a sand mill together with a polyester resin and xylene until the solid concentration is about 20%.
It is prepared by spray-coating on an aluminum drum and then thermally curing it, and the film thickness of the photoconductor layer is 25 μm. The thickness of the cured film of the present invention formed on the surface of the photoconductor layer is 1 μm, and the spectral sensitivity is completely equal to that of the photoconductor on which the cured film is not formed,
The durability evaluated by the number of times of repeated use capable of maintaining the amount of change in surface potential at a constant level improved five times.

[0053]

INDUSTRIAL APPLICABILITY The transparent solid resin of the present invention is a three-dimensional cured product which can be easily formed into a thin film and has hardness, and has high transparency from the visible region to the ultraviolet region and has a high hardness in the cured product. The organic molecules having a specific function can be uniformly encapsulated in high concentration, and are useful in the field of information processing such as molecular devices, recording materials and copying.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location // C09D 4/00 PEA 7921-4J

Claims (2)

[Claims] 1. (A) The following general formula (I): (In the formula, R _{1 to} R _2n are each independently a substituent,
50 to 97% of the number of substituents of _{1 to} R _2n is a methyl group,
3 to 50% is a group having a (meth) acryloxy bond, the rest is an alkyl group having 2 to 3 carbon atoms or an optionally substituted phenyl group, and a terminal group Ra,
Rb, Rc and Rd are hydroxyl groups or 1 carbon atom
~ 3 represents an alkoxy group, and n is the degree of polymerization. ) A polyorganosilsesquioxane represented by the formula (B), the following general formula (II): (In the formula, Re is a hydrogen atom or a methyl group, Rf is a hydrocarbon residue or an ester residue composed of a polyhydric alcohol and a polybasic acid, and m is a number of 1 or more.) (Meth) acrylate and / or poly (meth) acrylate represented by, and (C) a photosensitizer and / or a radical polymerization initiator are contained, and the ratio of the (A) component and the (B) component is (A) component 30-95
A non-linear optical effect, a photoconductive phenomenon, a photochromism phenomenon or a photochemical hole burning phenomenon is contained in a three-dimensional cured body formed by radical polymerization of a polymerizable resin composition containing 70 to 5% by weight of the component (B). Is a transparent solid resin in which organic molecules are encapsulated. 2. (A) The following general formula (I): (In the formula, R _{1 to} R _2n are each independently a substituent,
50 to 97% of the number of substituents of _{1 to} R _2n is a methyl group,
3 to 50% is a group having a (meth) acryloxy bond, the rest is an alkyl group having 2 to 3 carbon atoms or an optionally substituted phenyl group, and a terminal group Ra,
Rb, Rc and Rd are hydroxyl groups or 1 carbon atom
~ 3 represents an alkoxy group, and n is the degree of polymerization. ), A polyorganosilsesquioxane represented by the formula (B), the following general formula (II): (In the formula, Re is a hydrogen atom or a methyl group, Rf is a hydrocarbon residue or an ester residue composed of a polyhydric alcohol and a polybasic acid, and m is a number of 1 or more.) (Meth) acrylate and / or poly (meth) acrylate represented by, and (C) a photosensitizer and / or a radical polymerization initiator are contained, and the ratio of the (A) component and the (B) component is (A) component 30-95
(D) Non-linear optical effect, photoconductivity phenomenon, photochromism phenomenon or photochemical in a three-dimensional cured product formed by radical polymerization of a polymerizable resin composition containing 70 to 5% by weight of the component (B). In a three-dimensional cured product characterized by dissolving or uniformly dispersing an organic solvent solution of organic molecules exhibiting a hole burning phenomenon, shaping it into a predetermined shape, removing the organic solvent, and then irradiating it with ultraviolet rays to cure it. A method for producing a transparent solid resin in which organic molecules exhibiting a nonlinear optical effect, a photoconductive phenomenon, a photochromism phenomenon, or a photochemical hole burning phenomenon are encapsulated.