JP5072309B2 - Resin composition and method for producing the same - Google Patents

Description

The present invention relates to a resin composition and a method for producing the same. More specifically, the present invention relates to a resin composition useful as an optical application, an optical device application, a display device application, a mechanical component material, an electric / electronic component material, and the like, and a method for producing the same.

Thermosetting resin compositions are useful as, for example, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, etc., and also used as materials for paints and adhesives It is. Furthermore, the resin composition containing the inorganic substance not only can reduce the coefficient of thermal expansion, but also controls the appearance of the resin composition and its cured product by matching the refractive index of the inorganic substance and the resin. Since transparency can also be expressed, it is particularly useful as a material in electrical / electronic component materials and optical applications. For example, digital camera modules are being miniaturized, such as being mounted on mobile phones, and cost reduction is also required. Therefore, instead of inorganic glass, plastic lenses such as PMMA / PC and polycycloolefin are being used. In recent years, needs for in-vehicle use such as in-vehicle cameras and bar code readers for home delivery companies are increasing as new applications. When applied to these applications, long-term heat resistance is required in consideration of high temperature exposure in summer. Since heat resistance superior to that of conventional plastic materials is required, thermosetting materials have been studied.

Photoelasticity, which includes a matrix made of a transparent polymer resin having photoelastic birefringence and a large number of inorganic fine particles dispersed in the matrix, for materials used for conventional electrical / electronic component materials and optical applications. An optical resin material having reduced birefringence: the inorganic fine particles have a specific photoelastic birefringence and inorganic fine particles having a particle size, for example, the optical material (see, for example, Patent Document 1), average. A transparent material (for example, refer to Patent Document 2) composed of a particulate inorganic material and a vehicle having a particle size of 1 to 300 mμ and a content of 5 to 80% by weight, a specific metal element, and a size of 1 nm to 200 nm An organic-inorganic composite material containing some composite metal oxide nanoparticles (see, for example, Patent Document 3), an optical element containing an organic polymer and inorganic fine particles (see, for example, Patent Document 4), and A resin composition for an optical mounting material, which is a hydrolysis condensate of an alkoxide compound and / or a carboxylate compound and contains inorganic fine particles having an average radius of inertia of 50 nm or less is disclosed (for example, see Patent Document 5). ). However, these materials used for electrical and electronic parts and optical applications have sufficient long-term heat resistance and moisture resistance, and are used in harsh environments such as when used for a long time in a hot and humid environment. In addition, there is room for improvement in which the performance as a material such as excellent optical characteristics can be exhibited and the characteristics can be maintained.

In addition, regarding the method for producing a thermosetting resin composition, a thermosetting resin containing an alicyclic epoxy resin is dissolved and mixed in an alcohol organic solvent in which inorganic particles having a particle size of 70 nm or less are dispersed, and then this is mixed. A method for producing a thermosetting resin composition is disclosed in which after removing an alcohol organic solvent from a product, a curing agent is added and mixed (see, for example, Patent Document 6). However, when the thermosetting resin composition obtained by this production method is used for optical purposes, it is impossible to completely dissipate coarse inorganic particles and disperse them as primary particles. It will be scattered and transparency will fall. In addition, an epoxy resin composition containing inorganic fine particles having an average particle size of 50 nm or less is disclosed as an optical mounting resin composition (see, for example, Patent Document 7). Rayleigh scattering is an example of light scattering by particles shorter than the wavelength of light, and its light scattering property is expressed by Equation 1.

Equation 2 is given as a parameter related to the wavelength of k _s : scattering coefficient, n: number of particles, d: particle diameter, m: reflection coefficient, λ: wavelength scattering coefficient, and size of scattering particles.

D: Particle diameter, λ: Wavelength, α <0.4 suggests that light scattering is higher for light with a shorter wavelength from any of the Rayleigh scattering regions, but optical communication used for optical mounting applications The wavelength is in the near infrared region. Therefore, a resin that sufficiently suppresses light scattering due to Rayleigh scattering at a light wavelength in the visible light region, which is particularly targeted for optical applications, does not deteriorate visible light transmission, has excellent transparency, and has excellent performance. There was room for the device to be a composition.
JP 2005-208257 A (second page) JP-A 63-308069 (first page) JP 2005-146042 A (second page) JP 2004-286878 A (2nd page) JP 2006-131876 A (second page) JP 2004-346288 A (page 2) International Publication No. 2006/038735 Pamphlet

The present invention has been made in view of the above-mentioned present situation, exhibits excellent performance even in harsh use environments, has a heat resistance, moisture resistance, and excellent optical properties such as transparency, and a resin composition thereof The object is to provide a manufacturing method.

As a result of various studies on transparent resin compositions containing an organic resin, the present inventors have found that when a commercially available release agent is used, the viscosity of the coating solution increases. The present inventors have found a problem that curing is inhibited and a problem that the obtained cured product does not function as a lens, for example, when the compatibility with an organic (-inorganic composite) material is poor. The present inventors obtain a cured product suitable for various uses without causing such various problems by releasing the transparent organic resin composition with a strength of 40 kgf / cm ^2. I found out that I can do it. Further, it has been found that by containing a specific compound, a transparent organic resin composition having excellent releasability can be obtained, and it can be applied to a commonly used simple curing / molding method. That is, when curing to form a lens, for example, a (composite) material such as a transparent organic resin composition is usually cured with heat or light. For example, a heat latent cation generator is used. Thermosetting can be performed. In such a case, a thermal latent cation generator is added to an organic (-inorganic composite) material, mixed in one liquid, applied to a mold, and the lens is often taken out. Found that by adding a specific compound, a resin composition that can be applied and cured with a single solution can be obtained.

In addition, by having at least one glycidyl group and / or epoxy group as an organic resin, it exhibits heat resistance comparable to inorganic glass while having workability equivalent to that of a conventional thermosetting plastic material, When the heat latent cation generator is used, it has been found that the moisture resistance is drastically improved, and the inventors have conceived that the above problems can be solved brilliantly. It has also been found that such a resin composition can be suitably used for various applications such as optical applications, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, etc. is there.
The resin composition of the present invention is particularly useful as an optical element material. Some conventional optical element materials are manufactured from inorganic glass, and these optical element materials have the same optical properties even when exposed to high temperatures and humidity for a long time. The physical properties are required. When a general thermosetting material is exposed to a high temperature and high humidity for a long time, a subtle change in optical properties such as transparency appears and cannot be used. On the other hand, the present invention is a resin composition that not only exhibits excellent optical characteristics during device production, but also retains optical characteristics even in harsh usage environments.

That is, the present invention is a transparent organic resin composition containing an organic resin, and the transparent organic resin composition is selected from the group consisting of alcohols having 8 to 36 carbon atoms, carboxylic acids, carboxylic acid esters, and carboxylates. A transparent organic resin composition containing at least one compound.
The present invention is described in detail below.

The transparent organic resin composition contains at least one compound selected from the group consisting of alcohols having 8 to 36 carbon atoms, carboxylic acids, carboxylic acid esters, and carboxylates. A material containing such a compound is also called a mold release agent (or additive). By containing such a mold release agent, the mold can be easily peeled off when cured using a mold. In addition, since the appearance can be controlled and transparency can be expressed without damaging the surface of the cured product, it is particularly useful as a material for electrical / electronic component materials and optical applications.
The compound may be any compound having at least one compound selected from the group described above, and among these, alcohol, carboxylic acid and carboxylic acid ester are preferable, and carboxylic acid is more preferable.
The above compound has 8 to 36 carbon atoms, and may have any structure such as a straight chain, a branched chain, or a ring, and a branched one is preferable.
As said carbon number, it is an integer of 8-36. If it has a long chain of a certain amount in such a range, the effect of the present invention can be demonstrated, and excellent releasability can be exhibited without impairing functions such as transparency and workability of the resin composition. it can. In addition, it is relatively easy to obtain and can be economical. Preferably it is 8-20 as carbon number, More preferably, it is 10-18.

The said compound is at least 1 compound chosen from the group which consists of C8-C36 alcohol, carboxylic acid, carboxylic acid ester, and carboxylate, and the following are suitable as a specific example.
The alcohol having 8 to 36 carbon atoms is a monohydric or polyhydric alcohol, and may be linear or branched. Specifically, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl Alcohol, ceryl alcohol, myricyl alcohol, methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, 3.5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, dipentaerythritol 2-phenylethanol and the like are preferred. The alcohol is preferably an aliphatic alcohol, and more preferably octyl alcohol (octanol), lauryl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), and stearyl alcohol.
The carboxylic acid having 8 to 36 carbon atoms is a monovalent or polyvalent carboxylic acid, and includes 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, and tetradecanoic acid. Pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like are suitable. Preferred are octanoic acid, lauric acid, 2-ethylhexanoic acid, and stearic acid.

The carboxylic acid ester having 8 to 36 carbon atoms is (1) carboxylic acid ester obtained from the above alcohol and carboxylic acid, and (2) carbon such as methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol, etc. Carboxylic acid ester obtained by the combination of the number 1-7 alcohol and the above carboxylic acid, (3) a combination of the above alcohol with a carboxylic acid having 1 to 7 carbon atoms such as acetic acid, propionic acid, hexanoic acid, butanoic acid, etc. The resulting carboxylic acid ester is preferred. Among these, stearic acid methyl ester, stearic acid ethyl ester, octyl acetate and the like are preferable.
The carboxylate having 8 to 36 carbon atoms is a carboxylic acid obtained by a combination of the carboxylic acid and an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Sn. Salts and the like are preferred. Among these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.
Of the above-mentioned compounds, stearic acid compounds such as stearic acid and stearic acid esters, and alcohol compounds are more preferable, and stearic acid compounds are more preferable. Thus, as for the said transparent organic resin composition, the transparent organic resin composition containing a stearic acid type compound is also one of the preferable forms of this invention.

The transparent organic resin composition of the present invention contains an organic resin. The organic resin is not particularly limited as long as it exhibits the effects of the present invention. However, when the resin composition contains components other than the organic resin, the organic resin is excellent in compatibility with those components, and the component is an organic resin. It is preferable that it is uniformly dispersed. Such a transparent organic resin composition is preferably a curable resin or a thermoplastic resin, for example. For example, in plastic lens applications, processing is easier than with inorganic lenses, and the size and shape can be freely changed, making it suitable for mass production. At present, thermoplastic resins such as Zeonex are often used from the viewpoint of processability. In addition, a thermosetting resin is desired from the viewpoint of heat resistance, and is more preferably a curable resin in applications such as lenses that require heat resistance. Thermosetting resin is not currently popular because it involves difficulties in processing compared to thermoplastic resin, but in the present invention, for example, by using a specific release agent described later, A curable resin can also be suitably used.
As content of the said mold release agent, it is preferable that it is 10 mass% or less with respect to 100 mass% of resin compositions. If it exceeds 10% by mass, the resin may be difficult to cure. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

The curable resin is not particularly limited as long as it has curability and contains a resin having a high molecular weight to a molecular weight of an oligomer, and among them, it may be a thermosetting resin or a photocurable resin. Is preferred. Examples of the form of the curable resin include (1) a form comprising a liquid or solid curable resin, and (2) a liquid or solid curable resin and a curable compound or solvent having a lower molecular weight than the resin component (non- And (3) a form containing a liquid or solid non-curable resin and a curable compound having a lower molecular weight than the resin component. (3) As a form containing a liquid or solid non-curable resin and a curable compound having a lower molecular weight than the resin component, for example, an oligomer component of an acrylic resin such as PMMA and a (meth) acrylate monomer Can be listed.

As the curable resin, for example, a compound having at least one glycidyl group and / or an epoxy group, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and the like can be preferably used. Or it can also be used as a mixture of two or more. Among these, the organic resin preferably has at least one epoxy and / or glycidyl group. By having at least one epoxy and / or glycidyl group, it exhibits excellent heat resistance comparable to that of inorganic glass while having workability equivalent to that of conventional thermosetting plastic materials, and excellent molding and workability. The characteristic can be exhibited. Thus, the transparent organic resin composition having at least one glycidyl group and / or epoxy group is also one of the preferred embodiments of the present invention.

As the compound having at least one glycidyl group and / or epoxy group, the following compounds are suitable. Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin, and these bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc. High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction with other bisphenols; phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol And formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, hydroxybenzaldehyde Obtained by condensation reaction of polyhydric phenols obtained by condensation reaction of hydride, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. with epihalohydrin. Novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like with epihalohydrin, and the above bisphenols and tetramethyl Aromatic crystalline epoxy tree obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. High molecular weight polymers of the above; alicyclic glycols hydrogenated aromatic skeletons such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, glucose, fructose, lactose Aliphatic glycidyl ether type epoxide obtained by condensation reaction of mono / polysaccharides such as maltose and epihalohydrin (3,4-epoxycyclohexane) epoxy resin having an epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexyl carboxylate; condensation of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin Glycidyl ester type epoxy resin obtained by reaction; tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin. Among them, the aliphatic glycidyl ether type epoxy resin and the epoxy resin having an epoxycyclohexane skeleton are more preferably used for the purpose of suppressing the appearance deterioration during light irradiation.

In the present invention, a curable resin containing a non-curable component such as a thermoplastic resin and a low molecular weight curable compound can also be used. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer (AS resin), ABS resin made of acrylonitrile / butadiene / styrene, vinyl chloride resin, (meth) acrylic resin, polyamide resin, and acetal resin. , Polycarbonate resin, polyphenylene oxide, polyester, polyimide and the like. As the curable compound, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and a compound having at least one glycidyl group and / or epoxy group may be appropriately selected and used. . In addition, the polyhydric phenol compound which can be used suitably as an organic resin of this invention and the compound which has a polymerizable unsaturated bond are mentioned later.

The transparent organic resin composition preferably contains inorganic fine particles. Hereinafter, the transparent organic resin composition containing inorganic fine particles is also referred to as “organic-inorganic composite resin composition”. By containing inorganic fine particles, the coefficient of thermal expansion can be reduced, and by adjusting the refractive index of the inorganic substance and the resin, the appearance of the resin composition and its cured product can be controlled, and transparency can be expressed. It can be particularly useful as a material for electrical / electronic component materials and optical applications. Thus, the form in which the transparent organic resin composition is an organic-inorganic composite resin composition containing inorganic fine particles is also a preferred form of the present invention.

The inorganic fine particles (inorganic fine particles in the organic-inorganic composite resin composition) preferably have an average particle size of 400 nm or less, more preferably 1 nm to 400 nm. By having such a particle size distribution, the cured product of the resin composition of the present invention exhibits various excellent optical properties such as Rayleigh scattering in the visible light region is sufficiently suppressed, and is excellent in transparency. The resin composition can be suitably used for various applications such as applications, opto device applications, and display device applications. If the average particle size is less than 1 nm, the heat resistance, which is a characteristic of inorganic substances, may be adversely affected. On the other hand, if it exceeds 400 nm, visible light is scattered by the inorganic particles due to the large size of the inorganic particles, the transparency is lowered, and there is a possibility that it cannot be used for the various applications described above. As the particle size distribution of the inorganic fine particles, the primary particle size is preferably 1 nm to 100 nm, more preferably 1 nm to 50 nm, and particularly preferably 20 nm or less. The inorganic fine particles in the present invention preferably have an average particle size in the above range, and may contain fine particles of 1 nm or less. In addition, particles that are not in the form of particles, for example, polymers may be included. Such polymers are highly transparent if they are small, and are transparent even if secondary particles are formed. It becomes.

The primary particle size (average particle size, particle size distribution) of the inorganic fine particles can be determined from the inertia radius by the X-ray small angle scattering method and its scattering intensity. In the X-ray small angle scattering method, the fluctuation of the electron density in the non-uniform density region can change the scattering behavior during X-ray irradiation, so that the size of particles of 100 nm or less can be measured. The distribution state of the particles can be grasped as it is.

The X-ray small angle scattering method has an advantage that the dispersion state before curing can be grasped even when the resin is a dispersion medium. The measurement principle will be briefly described. Usually, the dispersion medium, which is an organic compound, and nano-sized inorganic fine particles originally have different densities, electronic states, and bonding modes, and fluctuations in electron density occur at the interface between them. When monochromatic X-rays pass through a mixture with non-uniform density, diffuse diffraction occurs in an extremely small angle region (2θ = 0 to 5 °) with respect to the incident direction. By analyzing this diffraction intensity pattern, the size and shape of the non-uniform density region can be determined, and the morphology of the organic / inorganic nanocomposite can be clarified. Here, when the particle size (size of the density non-uniform region) is uniform, the scattering intensity is expressed by the following expression (3) from the Guinier small-angle scattering intensity formula.

Q in Equation 1 is mathematically a Fourier transform of the space, and is a value (Å ⁻¹ ) proportional to the reciprocal of the distance, and is expressed by the following equation (4) as a function of the scattering angle. .

The Guinier plot is a plot of X-ray scattering intensity-q ² values. A region where the scattering intensity rapidly decreases due to an increase in the scattering angle is a small angle scattering region, and the width of the central peak is almost inversely proportional to the size of the nonuniform density region, that is, the radius of inertia of the primary particles. Therefore, if the scattering intensity increase / decrease behavior is applied to the Funkuchen method, tangent lines are drawn in order from the right end of the Guinier plot, and the inertia radius and the scattering intensity are calculated from the gradient of each tangent line, the primary particles can be calculated from their intensity ratio. The relative ratio of the distribution of inertia radii can be obtained.

As another method for measuring the particle size of the inorganic fine particles, a transmission electron microscope (TEM) can be suitably used. In TEM, the dispersed state of inorganic fine particles and individual particle diameters in the organic-inorganic composite resin composition can be evaluated. When the composition is a liquid resin, the liquid resin is used as a sample. When the composition is a solid or a molded product after curing, a thin film section is prepared using a microtome, and this is used as a sample. By observing a TEM image, it is possible to confirm the primary particle size, dispersion, and aggregation state of the inorganic fine particles.
Measurement of the radius of inertia by the X-ray small angle scattering method and observation by TEM are useful as methods for directly evaluating the primary particle size, particle size distribution, or dispersion state of the inorganic fine particles in the resin composition.
In addition, as a method for evaluating the dispersion state and dispersed particle size of inorganic fine particles in the composition, as an alternative method, when the resin composition is a liquid or a solvent-soluble resin, a dynamic light scattering particle size distribution measurement method Etc. can also be adopted. Usually, in order to use a sample diluted with a solvent to an appropriate concentration as a measurement sample, the dispersion state of the particles may change due to dilution, but it is easy to make a comparative comparative evaluation of the dispersion state and distribution. Useful in that it can be done.
As mentioned above, the evaluation method regarding the particle size (primary particle size, dispersed particle size) of the inorganic fine particles in the composition can be appropriately selected according to the purpose.

The transparent organic resin composition contains a curing agent, and the curing agent is preferably a thermal latent curing agent. The heat-latent curing agent is also called a heat-latent cation generator and a cationic polymerization initiator, and exhibits a substantial function as a curing agent when the resin composition reaches a curing temperature. By using such a heat-latent cation generator, for example, even when an organic resin that cures at room temperature is used, curing can be prevented from proceeding at room temperature. It becomes easy to handle. Moreover, the moisture resistance of the obtained resin composition is dramatically improved, and the excellent optical properties of the resin composition are maintained even in harsh usage environments, so that the resin composition can be suitably used for various applications. Normally, when water with a high refractive index is contained in a resin composition or its cured product, it causes turbidity, but since it can exhibit excellent moisture resistance, such turbidity is suppressed and it can be used for optical applications such as lenses. It can be used suitably. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns over yellowing and deterioration of strength due to prolonged ultraviolet irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. Excellent heat resistance over time.

Examples of the heat latent cation generator include the following general formula (1):
_{^{(R 1 a R 2 b R}} 3 c R 4 d Z) + m (AXn) -m (1)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and halogen elements. R ¹ , R ² , R ³ and R ⁴ is the same or different and represents an organic group, a, b, c and d are 0 or a positive number, and the sum of a, b, c and d is equal to the valence of Z. Cation (R ¹ _a R ² _b R ³ _c R ⁴ _d Z) ^{+ m} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element, and m is the net charge of the halide complex ion. N is the number of halogen elements in the halide complex ion It is preferable that it is represented by.

The heat-latent cation generator is not particularly limited as long as it has the above-described structure, but these generally generate cations at the curing temperature. The curing temperature is preferably 25 to 250 ° C. More preferably, it is 60-200 degreeC, More preferably, it is 80-180 degreeC.
Further, as a curing condition, the curing temperature may be changed stepwise. For example, after maintaining at a predetermined temperature and time in a mold for the purpose of improving productivity in producing a cured product of the resin composition, the resin composition is taken out from the mold and left in an air or inert gas atmosphere. Heat treatment is also possible. In this case, as the curing temperature, the holding temperature in the mold is 25 ° C to 250 ° C, more preferably 60 ° C to 200 ° C, still more preferably 80 ° C to 180 ° C, and the holding time is 10 seconds to 5 minutes, more preferably 30 ° C. Second to 5 minutes, more preferably 1 minute to 3 minutes.

Specific examples of the anion (AXn) ^-m of the general formula (1) include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexafluoro arsenates ^{(AsF 6-),} hexachloroantimonate (SbCl ^6-), and the like.
Further formula AXn (OH) ^- anions may be used which is represented by. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

Specific products of the above-described heat-latent cation generator include diazonium salt types: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries)
Iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries)
Sulfonium salt type: CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (manufactured by Adeka) ), Sun-Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San Apro)
Etc.

The present invention is also a transparent organic resin composition containing an organic resin, and the transparent organic resin composition is a transparent organic resin composition that is released at a strength of 40 kgf / cm ² or less.
In the said transparent organic resin composition, when it molds with the intensity | strength of 40 kgf / cm < ² > or less, when it peels easily in the said technical field, it can manufacture with sufficient productivity in a manufacturing process, and when continuous production of a transparent material is possible It means to be evaluated. If the mold release strength exceeds 40 kgf / cm ² , it cannot be produced with good productivity and may not be economical. The preferred peel strength, and at 20 kgf / cm ² or less, and more preferably at most 10 kgf / cm ² or less, still more preferably at most 1 kgf / cm ² or less, particularly preferably, 0.1 kgf / cm ² or less is there.
The peel strength is a necessary material hardness during continuous production of a transparent material, that is, a certain degree of material hardness (releasing to a strength of 40 kgf / cm ² or less) in a short time at a temperature of 150 ° C. or less at which a side reaction occurs. preferable. Such peel strength (material hardness) can be evaluated as follows, for example. The resin composition is cured to a SUS304 substrate shape at a height of 1 mm at 120 ° C. for 2.5 minutes, cooled to 30 ° C. within 30 s, and a cutter (manufactured by NTT Corporation, main body model number: L-500) at the interface between the resin and SUS304. The model number of the blade: BL-150P) can be pressed with a desired force (for example, a force with a peel strength of 40 kgf / cm ² ) to evaluate the ease of mold release. The force with a peel strength of 40 kgf / cm ² is calculated as a value when a load of 1.5 kg is applied to the interface between the resin of 2 cm in length and the SUS304 using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was set to 0.04 cm ² .

As a method for curing the transparent organic resin composition of the present invention, various methods such as thermosetting and photocuring can be suitably used. However, a curing agent and other materials as required may be added to the transparent organic resin composition. A method is preferably used in which the mixture is mixed to form one liquid, and the mixed liquid is applied and cured on a mold that matches the shape of the cured product, and then the cured product is removed from the mold. In such a method, it is preferable that the viscosity of the curable transparent organic resin composition mixed with a curing agent or the like is not significantly increased because it is easy to handle. That is, it is preferable that the viscosity of the curable transparent organic resin composition after storage for 3 days at 25 ° C. is 200% or less as compared to immediately after mixing. If it exceeds 200%, it may be difficult to apply the liquid to the mold, and the fluidity in the mold may be adversely affected. More preferably, it is 180% or less, More preferably, it is 150% or less. Thus, the transparent organic resin composition has a viscosity increase rate of a mixture of one liquid as a curable transparent organic resin composition, which is 200% or less after storage at 25 ° C. for 3 days, compared to immediately after mixing. A resin composition is also one preferred form of the present invention.

As a method for producing a cured product by curing the transparent organic resin composition, a commonly used method can be suitably used, and appropriately selected according to the type of the resin composition as described later. However, the method is preferably a method of producing a cured product by curing the transparent organic resin composition within 5 minutes. Specifically, the transparent organic resin composition is mixed with a curing agent and other materials as necessary to form one liquid, and the mixed liquid is applied to a mold that matches the shape of the cured product, for 5 minutes. It is preferable to cure within. By performing the curing using a mold in a short time, it is possible to make the method excellent in economic efficiency. Thus, a method for producing a cured product by curing the transparent organic resin composition, the production method comprising curing the transparent organic resin composition within 5 minutes to produce a cured product. A method for curing the composition is also one of the preferred embodiments of the present invention.
When the curing time (curing time using a mold) exceeds 5 minutes, the productivity is deteriorated. More preferably, it is within 3 minutes, More preferably, it is within 2 minutes, Most preferably, it is within 1 minute. Although it can set suitably as said hardening temperature according to the resin composition etc. to harden | cure, it is preferable that it is 80-200 degreeC. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC. Specifically, it is preferable to cure at 110 ° C. for 3 minutes.
In the said hardening method, it should just be the hardness which can be taken out from a metal mold | die and can maintain a shape, and the rate of a shape change when it extrudes with a force of 1 kgf / cm < ² > or more is 10% or less of hardening strength (hardness). Preferably there is. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, and still more preferably 0.01% or less. .

In the transparent organic resin composition of this invention, after making it harden | cure within 5 minutes as mentioned above, it is preferable to take out hardened | cured material from a metal mold | die and to perform a postcure (baking). By performing post-cure, the cured product has sufficient hardness and can be suitably used for various applications. Moreover, in post-cure, it is excellent in handleability from the point of further curing a cured product having a certain degree of hardness. Therefore, there is an advantage that a large amount of products can be post-cured in a small area because it is not necessary to use a mold.
In the post-cure, the curing temperature and the curing time can be appropriately set according to the resin composition to be cured. For example, the curing temperature is preferably 80 to 200 ° C. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC. The curing time for the post cure is preferably 1 to 48 hours, although it depends on the curing temperature. More preferably, it is 1-10 hours, More preferably, it is 2-5 hours.

Hereinafter, polyhydric phenol compounds and compounds having a polymerizable unsaturated bond that can be suitably used as the organic resin of the present invention will be described.
As the polyhydric phenol compound, those having a structure in which aromatic skeletons having at least one phenolic hydroxyl group are bonded via an organic skeleton having 2 or more carbon atoms can be suitably used. In the polyhydric phenol compound, the aromatic skeleton is an aromatic ring having at least one phenolic hydroxyl group. This aromatic skeleton is a part having a structure such as a phenol type, and a phenol type, a hydroquinone type, a naphthol type, an anthracenol type, a bisphenol type, a biphenol type and the like are preferable. Of these, the phenol type is preferred. Further, these sites having a phenol type structure or the like may be appropriately substituted with an alkyl group, an alkylene group, an aralkyl group, a phenyl group, a phenylene group, or the like.

In the above polyhydric phenol compound, the organic skeleton means a part that binds the aromatic ring skeletons constituting the polyhydric phenol compound and requires carbon atoms. The organic skeleton having 2 or more carbon atoms preferably has a ring structure. The ring structure is a structure having a ring such as an aliphatic ring or an aromatic ring, and the ring is preferably a cyclopentane ring, a cyclohexane ring, a benzene ring, a naphthalene ring, an anthracene ring or the like. Furthermore, the organic skeleton preferably has a ring structure containing a nitrogen atom such as a triazine ring or a phosphazene ring and / or an aromatic ring, and particularly preferably has a triazine ring and / or an aromatic ring. The polyhydric phenol compound may have an aromatic skeleton or an organic skeleton other than those described above, and the aromatic skeleton having at least one phenolic hydroxyl group is an organic skeleton having 1 carbon atom (methylene ) May be simultaneously bonded.

When the polyhydric phenol compound has a ring structure containing a nitrogen atom as an organic skeleton, the nitrogen atom content is preferably 1 to 50% by mass. If it is less than 1% by mass, the resulting resin composition may not have sufficient flame retardancy. If it exceeds 50% by mass, the physical properties and flame retardancy are sufficiently compatible. There is a risk of not becoming. More preferably, it is 3-30 mass%, More preferably, it is 5-20 mass%. In addition, a nitrogen atom content rate is a mass ratio of the nitrogen atom which comprises a polyhydric phenol compound when a polyhydric phenol compound is 100 mass%.

Examples of the polyhydric phenol compound that can be used in the present invention include a compound that forms an aromatic skeleton having at least one phenolic hydroxyl group (hereinafter also referred to as a compound that forms an aromatic skeleton), and an organic compound having 2 or more carbon atoms. It is preferable that the compound is produced from a reaction raw material containing a skeleton-forming compound (hereinafter also referred to as an organic skeleton-forming compound) as an essential component.

The reaction raw material includes a compound that forms an aromatic skeleton and a compound that forms an organic skeleton as essential components, includes other compounds that are used as necessary, and a solvent that is used as necessary to perform the reaction. Means a mixture containing In addition, the compound which forms aromatic skeleton, and the compound which forms organic skeleton can each use 1 type (s) or 2 or more types.

The compound that forms the aromatic skeleton may be a compound in which one or more phenolic hydroxyl groups are bonded to the aromatic ring, and a substituent other than one or two or more hydroxyl groups is bonded. May be. The compounds forming the aromatic skeleton include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, p-ethylphenol, mixed cresol, p-hydroxyethylphenol, and pn-propylphenol. , O-isopropylphenol, p-isopropylphenol, mixed isopropylphenol, o-sec-butylphenol, m-tert-butylphenol, p-tert-butylphenol, pentylphenol, p-octylphenol, p-nonylphenol, 2,3- Dimethylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 2,4-di-s-butylphenol, 3,5-dimethylphenol, 2,6-di-s-butylphenol 2,6-di-t-butylphenol, 3-methyl-4-isopropylphenol, 3-methyl-5-isopropylphenol, 3-methyl-6-isopropylphenol, 2-t-butyl-4-methylphenol, 3-Methyl-6-t-butylphenol, 2-t-butyl-4-ethylphenol and the like are preferable. Further, as the compound having two or more phenolic hydroxyl groups, for example, catechol, resorcin, biphenol, bisphenol A, bisphenol S, bisphenol F and the like are preferable, and polycyclic aroma such as α-naphthol and β-naphthol. Also suitable are compounds that form group skeletons.

As the compound that forms the organic skeleton, (1) an aromatic compound having any one of an α-hydroxyalkyl group, an α-alkoxyalkyl group, and an α-acetoxyalkyl group, (2) a compound having an unsaturated bond, (3) Compounds having a carbonyl group such as aldehydes and ketones, (4) Compounds having two or more of these specific active groups or active sites, (5) Amino group, hydroxyalkylamino group and di (hydroxyalkyl) amino group A compound having any of the above is preferred.

Examples of the aromatic compound (1) include p-xylylene glycol, p-xylylene glycol dimethyl ether, p-diacetoxymethylbenzene, m-xylylene glycol, m-xylylene glycol dimethyl ether, and m-diacetoxymethyl. Benzene, p-dihydroxyisopropylbenzene, p-dimethoxyisopropylbenzene, p-diacetoxyisopropylbenzene, trihydroxymethylbenzene, trihydroxyisopropylbenzene, trimethoxymethylbenzene, trimethoxyiropropylbenzene, 4,4'-hydroxymethylbiphenyl 4,4′-methoxymethylbiphenyl, 4,4′-acetoxymethylbiphenyl, 3,3′-hydroxymethylbiphenyl, 3,3′-methoxymethylbiphenyl, 3,3 ′ Acetoxymethylbiphenyl, 4,4′-hydroxyisopropylbiphenyl, 4,4′-methoxyisopropylbiphenyl, 4,4′-acetoxyisopropylbiphenyl, 3,3′-hydroxyisopropylbiphenyl, 3,3′-methoxyisopropylbiphenyl, 3, , 3'-acetoxyisopropylbiphenyl, 2,5-hydroxymethylnaphthalene, 2,5-methoxymethylnaphthalene, 2,5-acetoxymethylnaphthalene, 2,6-hydroxymethylnaphthalene, 2,6-methoxymethylnaphthalene, 2, 6-acetoxymethylnaphthalene, 2,5-hydroxyisopropylnaphthalene, 2,5-methoxyisopropylnaphthalene, 2,5-acetoxyisopropylnaphthalene, 2,6-hydroxyisopropylnaphthalene, 2 6-methoxy-isopropyl-naphthalene, 2,6-acetoxy-isopropyl naphthalene and the like.

As the compound (2) having an unsaturated bond, divinylbenzene, diisopropenylbenzene, trivinylbenzene, triisopropenylbenzene, dicyclopentadiene, norbornene, terpenes and the like are preferable. As the compound having a carbonyl group of (3) above, various aldehydes or ketones having 5 to 15 carbon atoms are suitable, and benzaldehyde, octanal, cyclohexanone, acetophenone, hydroxybenzaldehyde, hydroxyacetophenone, crotonaldehyde, cinnamaldehyde, Glyoxal, glutaraldehyde, terephthalaldehyde, cyclohexanedialdehyde, tricyclodecane dialdehyde, norbornane dialdehyde, suberaldehyde and the like are preferable.

In the compound having two or more specific active groups or active sites in the above (4), as the compound having a carbonyl group and an unsaturated bond, isopropenylbenzaldehyde, isopropenylacetophenone, citronellal, citral, perylaldehyde, etc. are preferable. It is. Examples of the compound having an α-hydroxyalkyl group or α-alkoxyalkyl group and an unsaturated bond include dihydroxymethyl styrene, dihydroxymethyl α-methyl styrene, dimethoxymethyl styrene, dimethoxymethyl α-methyl styrene, hydroxymethyl divinyl. Benzene, hydroxymethyldiisopropylbenzene, methoxymethyldivinylbenzene, methoxymethyldiisopropylbenzene and the like are suitable.

Examples of the compound having any one of the amino group, hydroxyalkylamino group and di (hydroxyalkyl) amino group of (5) above include melamine, dihydroxymethylmelamine, trihydroxymethylmelamine, acetoguanamine, dihydroxymethylacetoguanamine, Tetrahydroxymethylacetoguanamine, benzoguanamine, dihydroxymethylbenzoguanamine, tetrahydroxymethylbenzoguanamine, urea, dihydroxymethylurea, tetrahydroxymethylurea, ethylenediamine, dihydroxymethylethylenediamine, tetrahydroxymethylethylenediamine, hexaethylenediamine, dihydroxymethylhexaethylenediamine, tetrahydroxymethyl Hexaethylenediamine, p-xylylenediamine, -Dihydroxymethylaminobenzene, m-xylylenediamine, m-dihydroxymethylaminobenzene, 4,4'-oxydianiline, 4,4'-oxydihydroxymethylaniline, 4,4'-methylenedianiline, 4,4 '-Methylenedihydroxymethylaniline and the like are preferred. Among these, compounds having a triazine skeleton such as melamine, benzoguanamine, and acetoguanamine are preferable.

Examples of the reaction raw material include a compound that forms an aromatic skeleton (hereinafter also referred to as a raw material A) and a compound that forms at least one organic skeleton of the above (1) to (5) (hereinafter referred to as a raw material). B)) is preferably an essential component. More preferably, the raw material A, the compound forming the organic skeleton of at least any one of the above (1) to (4) (hereinafter also referred to as the raw material B1), and the organic skeleton of the above (5) are formed. The compound to be used (hereinafter also referred to as the raw material B2) is an essential component. The reaction order of the reaction raw materials in this case is to mix the raw material A, the raw material B1 and the raw material B2 in advance before starting the reaction, and to react the raw material B2 before the reaction between the raw material A and the raw material B1 is completed. Preferably, for example, the raw material A, the raw material B1, and the raw material B2 are reacted at the same time, or the raw material A and the raw material B2 are reacted in the first stage, and then the raw material B1 is further reacted in the second stage. . Thereby, a flame retardance can be improved more reliably and it can apply suitably to molding materials, adhesives, paints, etc., such as an electronic material. More preferably, after the raw material A and the raw material B2 are reacted in the first stage, the raw material B1 is further reacted in the second stage.

As a compounding molar ratio of the raw material A and the raw material B used when manufacturing the said polyhydric phenol compound, 1/1 or more are preferable and 10/1 or less are preferable. If the raw material A is less than 1/1, there is a risk of gelation during the production of the resin composition of the present invention. If the raw material A is more than 10/1, the flame retardancy of the resin composition is manifested. May be difficult. More preferably, since the resin composition can exhibit high strength at a high temperature, it is 1.3 / 1 or more and 8/1 or less. More preferably, it is 1.8 / 1 or more, and 5/1 or less.

The polyhydric phenol compound is preferably obtained by reacting the reaction raw material in the presence of a catalyst. The catalyst that can be used for the production of the polyhydric phenol compound may be any catalyst that can react with the reaction raw materials. When the raw material B1 is reacted in the above catalyst, the acid catalyst includes inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, methanesulfonic acid, organic sulfonic acid, boron trifluoride or a complex thereof. Solid acid catalysts such as super strong acids such as trifluoromethanesulfonic acid and heteropolyacid, activated clay, synthetic zeolite, sulfonic acid type ion exchange resin and perfluoroalkanesulfonic acid type ion exchange resin are suitable. Although the usage-amount of the catalyst in making the said raw material B1 react is set suitably by each acid intensity | strength, 0.001-100 mass% is preferable with respect to the raw material B1. As a catalyst which becomes homogeneous in these ranges, trifluoromethanesulfonic acid, methanesulfonic acid, boron trifluoride and the like are preferable, and the amount of use thereof is preferably 0.001 to 5% by mass. The amount of the heterogeneous ion exchange resin or activated clay is preferably 1 to 100% by mass.

In the case of reacting the raw material B2 in the catalyst, the basic catalyst includes alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, barium hydroxide and the like, ammonia, Preferred are primary to tertiary amines, hexamethylenetetramine, sodium carbonate and the like, and acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid and sulfonic acid, organic acids such as oxalic acid and acetic acid, Lewis acids, zinc acetate and the like Basic catalysts such as divalent metal salts are preferred. Further, it is preferable to remove impurities such as salts by neutralization and washing with water after the reaction of the raw material B2, if necessary. When amines are used as the catalyst, it is desirable not to remove impurities such as neutralization and water washing.

The polyhydric phenol compound is obtained by condensing the aromatic ring in the raw material A and the substituent in the raw material B. At this time, carboxylic acid, alcohol, water and the like are by-produced together with the polyhydric phenol compound. It will be. Carboxylic acid, alcohol, and water produced as by-products in this way can be distilled off under reduced pressure during or after the reaction, or by performing an operation such as azeotropy with a solvent without requiring a complicated process. It can be easily removed from the reaction product. The reaction product means a mixture containing all of the products obtained by reacting as described above, and is used as necessary in addition to the polyphenol compound, by-product carboxylic acid, alcohol, and water. The catalyst to be used and the solvent described later are included.

In the reaction conditions for the production of the polyhydric phenol compound, the reaction temperature is preferably a temperature at which by-product carboxylic acid, alcohol, water, and the like are volatilized and distilled off, and is 100 to 240 ° C. It is preferable. More preferably, it is 110-180 degreeC, More preferably, it is 130-160 degreeC. Thus, in the production of the polyhydric phenol compound, carboxylic acid and the like are by-produced, but can be easily removed from the reaction product. Although depending on the raw material used, the type and amount of the catalyst, the reaction temperature, etc., the reaction time is until the reaction between the raw material A and the raw material B is substantially completed, that is, carboxylic acid, alcohol, and water are generated. It is preferable that the time is zero, and it is preferably 30 minutes to 24 hours. More preferably, it is 1 to 12 hours.

As a reaction method in the production of the polyhydric phenol compound, the reaction may be performed in the presence of a solvent, and it is preferable to use an organic solvent inert to the reaction between the raw material A and the raw material B as the solvent. Xylene, monochlorobenzene, dichlorobenzene, and the like can be used. By using a solvent, the raw material can be dissolved in the solvent and homogenized. In addition, when reacting the raw material B1, it is preferable to carry out the reaction without solvent.

In the production of the polyhydric phenol compound, when removing by-products such as carboxylic acid, alcohol, and water and the solvent from the reaction product, the reaction product can be distilled off by distillation at the above temperature under a reduced pressure of 0.1 to 10 kPa. Is preferred. Since unreacted phenols may also be distilled off at this time, it is preferable to carry out after the reaction is substantially completed.

The compound having a polymerizable unsaturated bond may be any compound having a polymerizable unsaturated bond, but one or more selected from the group consisting of a (meth) acryloyl group, a vinyl group, a fumarate group, and a maleimide group. It is preferable that it is a compound which has these groups. That is, it is preferably at least one compound selected from the group consisting of a compound having a (meth) acryloyl group, a compound having a vinyl group, a compound having a fumarate group, and a compound having a maleimide group. In the present invention, the (meth) acryloyl group means an acryloyl group and a methacryloyl group, and when it has an acryloyl group, it has a vinyl group in the acryloyl group. Does not have an acryloyl group and a vinyl group, but has an acryloyl group. The fumarate group means a group having a fumarate structure, that is, a group having a fumarate ester structure.

Examples of the compound having the (meth) acryloyl group include (poly) ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, (poly) ether (meth) acrylate, alkyl (meth) acrylate, alkylene ( Examples include (meth) acrylate, (meth) acrylate having an aromatic ring, and (meth) acrylate having an alicyclic structure. Each of these can be used alone or in combination of two or more.

The (poly) ester (meth) acrylate is a (meth) acrylate having one or more ester bonds in the main chain. For example, alicyclic modified neopentyl glycol (meth) acrylate (“Nippon Kayaku Co., Ltd.” R-629 "or" R-644 "), caprolactone-modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, caprolactone-modified tetrahydrofur Monofunctional (poly) ester (meth) acrylates such as furyl (meth) acrylate;
Pivalate ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol of trimethylolpropane or glycerol Mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to pentaerythritol or ditrimethylolpropane Mono, di, tri or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol. Monool or poly (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol of dipentaerythritol A mono (meth) acrylate or poly (meth) acrylate of a polyhydric alcohol such as triol, tetraol, pentaol or hexaol;
Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, (poly) pentanediol, (poly) methylpentanediol, (poly) hexanediol, and malein Acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, het acid, hymic acid, chlorendic acid, dimer acid, alkenyl succinic acid, sebacic acid, Azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5- Potassium sulfoi Polyester polyols composed of polybasic acids such as phthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutamic acid, trimellitic acid, pyromellitic acid ( (Meth) acrylates; polyfunctional (poly) esters such as (meth) acrylates of cyclic lactone-modified polyester diols composed of the above diol components, polybasic acids, and ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone ( Meth) acrylates and the like are preferred.

The urethane (meth) acrylate is a (meth) acrylate having one or more urethane bonds in the main chain, and is a compound obtained by a reaction between a hydroxy compound having at least one (meth) acryloyloxy group and an isocyanate compound. Preferably it is.

Examples of the hydroxy compound having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylol Ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3 Phenoxy having various hydroxyl group, such as propyl (meth) acrylate (meth) acrylate compound or a ring-opening reaction product of (meth) acrylate compound and ε- caprolactone having the hydroxyl group are preferred.

Examples of the isocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane. Aromatic diisocyanates such as diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 3,3′-diethyldiphenyl-4,4′-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4, Aliphatic or alicyclic structures such as 4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Cyanates; Polyisocyanates such as one or more burettes of isocyanate monomers or isocyanurates obtained by trimerizing the above diisocyanate compounds; polyisocyanates obtained by urethanization reaction of these isocyanate compounds with various polyols, etc. are suitable. is there.

Examples of the polyol as a raw material for producing the polyisocyanate include (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) alkylene glycols such as (poly) tetramethylene glycol; ethylene glycol, Modified ethylene oxide of alkylene glycols such as propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol , Propylene oxide modified product, butylene oxide modified product, tetrahydrofuran modified product, ε-caprolactone modified product, γ-butyrolacto Modified products, δ-valerolactone modified products, methyl valerolactone modified products, etc .;
Hydrocarbon polyols such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol Aliphatic polyester polyols which are esterification reaction products of aliphatic dicarboxylic acids such as adipic acid and dimer acid and polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid and neopentyl Aromatic polyester polyols which are esterification reaction products with polyols such as glycols; polycarbonate polyols; acrylic polyols; polytetramethylene hexaglyce A polyhydric hydroxyl group compound such as ether (hexaglycerin modified tetrahydrofuran); mono- and polyhydric hydroxyl group-containing compounds of terminal ether groups of the polyhydric hydroxyl group-containing compounds; fumaric acid, phthalic acid , Polyhydric hydroxyl group-containing compounds obtained by esterification with dicarboxylic acids such as isophthalic acid, itaconic acid, adipic acid, sebacic acid and maleic acid; esters of polyhydric hydroxyl compounds such as glycerine and fatty acid esters of animals and plants A polyhydric hydroxyl group-containing compound such as monoglyceride obtained by an exchange reaction is preferred.

The epoxy (meth) acrylate is a (meth) acrylate obtained by reacting one or more epoxides with (meth) acrylic acid. Examples of the epoxide include (methyl) epichlorohydrin and hydrogenated bisphenol A. , Hydrogenated bisphenol S, hydrogenated bisphenol F, epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from ethylene oxide, propylene oxide-modified products, etc .; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Alicyclic epoxy resins such as bis- (3,4-epoxycyclohexyl) adipate; alicyclic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate;
Epichlorohydrin-modified bisphenol-type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, their ethylene oxide, propylene oxide-modified products, etc .; phenol novolac-type epoxy resin; cresol novolac-type epoxy resin; Epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting pentadiene with various phenols; Epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol, aromatic epoxides such as phenyl glycidyl ether;
(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol and other glycols (poly) glycidyl ether; glycols of alkylene oxide modified products (poly) Glycidyl ether; (poly) glycidyl ether of an aliphatic polyhydric alcohol such as trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; Alkylene-type epoxides such as (poly) glycidyl ethers of alkylene oxide-modified products of aliphatic polyhydric alcohols;
Glycidyl ester of carboxylic acid such as adipic acid, sebacic acid, maleic acid, itaconic acid, glycidyl ether of polyester polyol of polyhydric alcohol and polyhydric carboxylic acid; co-polymerization of glycidyl (meth) acrylate and methylglycidyl (meth) acrylate Preferred are aliphatic epoxy resins such as glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, and epoxidized polybutadiene.

The (poly) ether (meth) acrylate is a (meth) acrylate having one or more ether bonds in the main chain. For example, butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin-modified butyl (Meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) acrylate, 2-methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) Propylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyhydroxypropyl (meth) acrylic Monofunctional (poly) ethers (meth) acrylate, phenoxy (poly) ethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polyethylene glycol / polypropylene glycol mono (meth) acrylate, etc. ) Acrylates;
Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymers, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol and other hydrocarbon polyols, polytetramethylene Induced from polyvalent hydroxyl compounds such as hexaglyceryl ether (hexaglycerin modified tetrahydrofuran) and (meth) acrylic acid Polyfunctional (meth) acrylates are, neopentyl glycol 1 mol to 1 mol or more of ethylene oxide, propylene oxide, di (meth) acrylate of diol obtained by adding a cyclic ether such as butylene oxide and / or tetrahydrofuran;
Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; of alkylene oxide modified products of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S Di (meth) acrylate; di (meth) acrylate of alkylene oxide modified form of trisphenols; di (meth) acrylate of alkylene oxide modified form of hydrogenated trisphenols; alkylene oxide modified form of p, p'-biphenols Di (meth) acrylate of hydrogenated biphenols, alkylene oxide modified di (meth) acrylate; di (meth) acrylate of p, p'-dihydroxybenzophenone alkylene oxide modified; trimethylolpropane Is a mono-, di- or tri (meth) acrylate of a triol obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of glycerin;
Mono, di, tri or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of pentaerythritol or ditrimethylolpropane; Triol mono or poly (meth) acrylate triol, tetraol, pentaol, hexa obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of pentaerythritol Monofunctional (poly) ether (meth) acrylates or polyfunctional (poly) ether (meth) acrylates of polyhydric alcohols such as all are suitable.

The alkyl (meth) acrylate or alkylene (meth) acrylate has a main chain of linear alkyl, branched alkyl, linear alkylene group or branched alkylene group, and has a halogen atom and / or a hydroxyl group at the side chain or terminal. For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (Meth) acrylate, isopentyl (meth) acrylate, neopentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (Meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) Acrylate, neryl (meth) acrylate, geranyl (meth) acrylate, farnesyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, trans-2-hexene (meth) acrylate, etc. Functional (meth) acrylates;
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate 1,10-decanediol di (meth) acrylate hydrocarbon diol di (meth) acrylates;
Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Acrylate or poly (meth) acrylate, mono (meth) acrylate or poly (meth) acrylate of pentaerythritol, mono (meth) acrylate or poly (meth) acrylate of ditrimethylolpropane, mono (meth) acrylate or poly of dipentaerythritol Mono (meth) acrylates or poly (meth) acrylates of polyhydric alcohols such as triols, tetraols, hexaols of (meth) acrylates;
Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxyethyl (meth) acrylate; 2 , 3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, ethylene oxide modified tribromophenyl (meth) acrylate, ethylene oxide modified tetrabromobisphenol A di (meth) acrylate and other (meth) acrylates having a bromine atom;
Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) acrylate, hexa Fluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) Acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) ) Acrylate, 3- (having a perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) fluorine atoms, such as acrylates (meth) acrylates and the like.

The (meth) acrylate having an aromatic ring is a (meth) acrylate having an aromatic ring in the main chain or side chain, for example, monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl acrylate; bisphenol Diacrylates such as A diacrylate, bisphenol F diacrylate, and bisphenol S diacrylate are preferred.

The (meth) acrylate having the alicyclic structure is a (meth) acrylate having an alicyclic structure that may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain. For example, cyclohexyl ( (Meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclopentenyl (meth) ) Monofunctional (meth) acrylates having an alicyclic structure such as acrylate, norbornyl (meth) acrylate, bicyclooctyl (meth) acrylate, tricycloheptyl (meth) acrylate, and cholesteroid skeleton-substituted (meth) acrylate; water Di (meth) acrylates of hydrogenated bisphenols such as bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, di (meth) acrylates of hydrogenated trisphenols, di (meta) of hydrogenated p, p'-biphenols ) Acrylates; cyclic structures such as dicyclopentane-based di (meth) acrylates such as “Kayarad R684” (manufactured by Nippon Kayaku Co., Ltd.), tricyclodecane dimethylol di (meth) acrylate, bisphenol full orange hydroxy (meth) acrylate, etc. Polyfunctional (meth) acrylates; alicyclic acrylates having an oxygen atom and / or a nitrogen atom in the structure such as tetrahydrofurfuryl (meth) acrylate and morpholinoethyl (meth) acrylate are preferred.

Examples of the compound having the (meth) acryloyl group include poly (meta) such as a reaction product of (meth) acrylic acid polymer and glycidyl (meth) acrylate or a reaction product of glycidyl (meth) acrylate polymer and (meth) acrylic acid. ) Acrylic (meth) acrylate; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; Isocyanuric (meth) acrylate such as tris ((meth) acryloxyethyl) isocyanurate; Hexakis [((meth) (Acryloyloxyethyl) cyclotriphosphazene] and other phosphazene (meth) acrylates; (meth) acrylates having a polysiloxane skeleton; polybutadiene (meth) acrylates; melamine (meth) acrylates and the like may be used. Among these compounds having (meth) acryloyl groups, compounds having 1 to 6 (meth) acryloyl groups in one molecule are preferable.

As the compound having a vinyl group, the other end is substituted with a halogen atom, a hydroxyl group or an amino group, and the other end is substituted with a halogen atom, a hydroxyl group or an amino group. From the group consisting of an alkyl group, a cycloalkyl group, and an aromatic group, which may have a substituent, wherein the vinyl ether group is bonded to an alkylene group and may further have a substituent. Monovinyl ether, divinyl ether and polyvinyl ether having a structure in which one or more selected groups are bonded to one or more selected from the group consisting of an ether bond, a urethane bond and an ester bond Monovinyl ether, divinyl ether and Li vinyl ether also called) and the like. Each of these can be used alone or in combination of two or more.

Examples of the alkyl vinyl ether include methyl vinyl ether, hydroxymethyl vinyl ether, chloromethyl vinyl ether, ethyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, diethylaminoethyl vinyl ether, propyl vinyl ether, 3-hydroxypropyl vinyl ether, and 2-hydroxy. Propyl vinyl ether, 3-chloropropyl vinyl ether, 3-aminopropyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, 4-hydroxybutyl vinyl ether, isobutyl vinyl ether, 4-aminobutyl vinyl ether, pentyl vinyl ether, isopentyl vinyl ether, hexyl vinyl ether, 1,6- Hexanediol Vinyl ether, heptyl vinyl ether, 2-ethylhexyl vinyl ether, octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, isononyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, dodecyl vinyl ether, isododecyl vinyl ether, tridecyl vinyl ether, isotridecyl vinyl ether, pentadecyl vinyl ether , Isopentadecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, methylene glycol divinyl ether, ethylene glycol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexanediol dibi Ethers, trimethylolpropane trivinyl ether, pentaerythritol tetra vinyl ether.

Examples of the cycloalkyl vinyl ether include cyclopropyl vinyl ether, 2-hydroxycyclopropyl vinyl ether, 2-chlorocyclopropyl vinyl ether, cyclopropylmethyl vinyl ether, cyclobutyl vinyl ether, 3-hydroxycyclobutyl vinyl ether, 3-chlorocyclobutyl vinyl ether, Cyclobutyl methyl vinyl ether, cyclopentyl vinyl ether, 3-hydroxycyclopentyl vinyl ether, 3-chlorocyclopentyl vinyl ether, cyclopentyl methyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-aminocyclohexyl vinyl ether, cyclohexanediol model Vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether and the like.

Among the monovinyl ether, divinyl ether and polyvinyl ether, examples of the compound having an ether bond include ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, and triethylene glycol methyl vinyl ether. , Triethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol methyl vinyl ether, polyethylene glycol divinyl ether, propylene glycol methyl vinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol methyl vinyl ether, dipropylene Recall divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol methyl ether, tripropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol methyl ether, polypropylene glycol divinyl ether,
Tetramethylene glycol methyl vinyl ether, di (tetramethylene glycol) monovinyl ether, di (tetramethylene glycol) methyl vinyl ether, di (tetramethylene glycol) divinyl ether, tri (tetramethylene glycol) monovinyl ether, tri (tetramethylene glycol) methyl vinyl ether , Tri (tetramethylene glycol) divinyl ether, poly (tetramethylene glycol) monovinyl ether, poly (tetramethylene glycol) methyl vinyl ether, poly (tetramethylene glycol) divinyl ether, 1,6-hexanediol methyl vinyl ether, di (hexamethylene) Glycol) monovinyl ether, di (hexamethylene glycol) methyl vinyl ether, di (hexa) Tylene glycol) divinyl ether, tri (hexamethylene glycol) monovinyl ether, tri (hexamethylene glycol) methyl vinyl ether, tri (hexamethylene glycol) divinyl ether, poly (hexamethylene glycol) monovinyl ether, poly (hexamethylene glycol) methyl vinyl ether Poly (hexamethylene glycol) divinyl ether and the like are suitable.

Of the monovinyl ether, divinyl ether and polyvinyl ether, the compound having a urethane bond is a (poly) alkylene glycol monovinyl ether having at least one hydroxyl group in one molecule and at least one isocyanate group in one molecule. It is preferable that it is a compound obtained by the urethanation reaction of the compound which has this.

Examples of the monovinyl ether of (poly) alkylene glycol having at least one hydroxyl group in one molecule include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxy- 2-methylethyl vinyl ether, dipropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 1,6-hexanediol monovinyl ether and the like are suitable.

Examples of the compound having at least one isocyanate group in one molecule include m-isopropenyl-α, α-dimethylbenzyl isocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4 , 4'-diisocyanate, naphthalene diisocyanate and other aromatic isocyanates; propyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Preferred are aliphatic and alicyclic isocyanates such as silicate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate. In addition, polyisocyanates such as one or more dimers or trimers of a compound having at least one isocyanate group in one molecule may be used as a raw material for the compound having a urethane bond.

Among the monovinyl ether, divinyl ether and polyvinyl ether, the compound having a urethane bond is a compound having two or more isocyanate groups in one molecule among the compounds having at least one isocyanate group in one molecule. You may use the adduct body obtained by the urethanation reaction with various alcohols.

As the alcohols, compounds having at least one hydroxyl group in one molecule are suitable, and those having an average molecular weight of 100,000 or less are preferred. Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3- Methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethylol, 1,4-cyclohexanediol, spirogly , Tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid, dimethylolbutanoic acid, trimethylolethane, trimethylolpropane, glycerin, 3 -Methylpentane-1,3,5-triol, tris (2-hydroxyethyl) isocyanurate and the like are preferred. These can use 1 type (s) or 2 or more types.

As the alcohols, polyester polyols, polyether polyols, polycarbonate polyols and the like may be used. As said polyester polyol, what is obtained by reaction of the polyol component of the above-mentioned alcohol and carboxylic acid is preferable. As the carboxylic acid, various known and commonly used carboxylic acids, or acid anhydrides thereof can be used. For example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetic acid, highmic acid , Chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfo Of terephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, dimethyl- or diethyl ester of 5-sodium sulfoisophthalic acid, etc. Di-lower alkyl esters, o Sophthalic acid, 4-sulfophthalic acid, 1,10-decamethylene dicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexericarboxylic acid or pyromellitic An acid or an ester compound thereof with an acid anhydride or an alcohol such as methanol or ethanol is preferable. Moreover, you may use the lactone polyol obtained by the ring-opening reaction of (epsilon) -caprolactone and the above-mentioned polyol component.

Known polyether polyols can be used as the polyether polyol, for example, ether glycols such as polytetramethylene glycol, propylene oxide-modified polytetramethylene glycol, ethylene oxide-modified polytetramethylene glycol, polypropylene glycol, and polyethylene glycol; A polyether polyol obtained by ring-opening polymerization of a cyclic ether using a functional or higher polyol as an initiator is preferable.

The polycarbonate polyol is preferably obtained by a transesterification reaction between carbonate and various polyols. Examples of the carbonate include diphenyl carbonate, bischlorophenyl carbonate, dinaphthyl carbonate, phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate or 2-tolyl-4-tolyl-carbonate; and diaryl such as dimethyl carbonate or diethyl carbonate. Or a dialkyl carbonate etc. are suitable. As the polyol as a raw material for producing the polycarbonate polyol, the alcohols, polyester polyols, polyether polyols and the like are suitable.

Among the monovinyl ether, divinyl ether and polyvinyl ether, the compound having an ester bond is a monovinyl ether of alkylene glycol having at least one hydroxyl group in one molecule and a compound having at least one carboxyl group in one molecule. Those obtained by the esterification reaction of are preferred.

Examples of the monovinyl ether of alkylene glycol having at least one hydroxyl group in one molecule include (poly) alkylene glycol monovinyl ether having at least one hydroxyl group in one molecule in the above compound having a urethane bond. Is preferred.

As the compound having at least one carboxyl group in one molecule, known carboxylic acids and acid anhydrides thereof can be used. For example, formic acid, acetic acid, propionic acid, valeric acid, benzoic acid, maleic acid, Fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyl Adipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid; 5-sodium-sulfo Such as dimethyl- or diethyl ester of isophthalic acid -Di-lower alkyl esters of sodium-sulfoisophthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylene dicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthal An acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, or an acid anhydride thereof is preferable. Furthermore, among these carboxylic acids, a carboxylic acid obtained by a reaction between a compound having two or more carboxyl groups in one molecule and an alcohol in the above compound having a urethane bond can also be used.

As the compound having a fumarate group, for example, fumaric acid esters such as dimethyl fumarate and diethyl fumarate, an esterification reaction product of fumaric acid and a polyhydric alcohol, and the like are preferable. These can use 1 type (s) or 2 or more types.

Examples of the compound having a maleimide group include N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, Nn-butylmaleimide, N-tert-butylmaleimide, N-pentylmaleimide, N-hexylmaleimide, Monofunctional aliphatic maleimides such as N-laurylmaleimide, 2-maleimidoethyl-ethyl carbonate, 2-maleimidoethyl-isopropyl carbonate, N-ethyl- (2-maleimidoethyl) carbamate; alicyclics such as N-cyclohexylmaleimide Monofunctional maleimides; N-phenylmaleimide, N-2-methylphenylmaleimide, N-2-ethylphenylmaleimide, N- (2,6-diethylphenyl) maleimide, N-2-chlorophenylmaleimide, N- (4- Hydroxyfe A) aromatic monofunctional maleimides such as maleimide and N-2-trifluoromethylphenylmaleimide; N, N′-methylenebismaleimide, N, N′-ethylenebismaleimide, N, N′-trimethylenebismaleimide, Alicyclic bismaleimides such as N, N′-hexamethylene bismaleimide, N, N′-dodecamethylene bismaleimide, 1,4-dimaleimidocyclohexane; N, N ′-(4,4′-diphenylmethane) bismaleimide N, N ′-(4,4′-diphenyloxy) bismaleimide, N, N′-p-phenylenebismaleimide, N, N′-m-phenylenebismaleimide, N, N′-2,4-tri Renbismaleimide, N, N'-2,6-tolylenebismaleimide, N, N '-[4,4'-bis (3,5-dimethylphenyl) methane] Sumareimido, N, N'[4,4'-bis (3,5-diethyl-phenyl) methane] bismaleimide aromatic bismaleimides such as the like. These can use 1 type (s) or 2 or more types.

Other compounds that can be used as the compound having a polymerizable unsaturated bond include monofunctional (meth) acrylamides such as N-isopropyl (meth) acrylamide; polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide. Carboxylic acid vinyl derivatives such as vinyl acetate and vinyl cinnamate; styrene derivatives such as styrene and divinyl styrene; lauryl acrylate, isodecyl acrylate, isostearyl acrylate, lauryl alcohol ethoxy acrylate, epoxy stearyl acrylate, 2- (1- Methyl-4-dimethyl) butyl-5-methyl-7-dimethyloctyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenol polyalkoxy acrylate, Ruphenoxyethyl acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol polypropylene oxide modified acrylate, butoxypolypropylene glycol acrylate, tetrahydrofurfuryl alcohol lactone modified acrylate, lactone modified 2-hydroxyethyl acrylate, 2-ethylhexyl carbitol acrylate; 2-hydroxy-3 -Phenoxypropyl acrylate, acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicycle Acrylates such as lopentenyl acrylate, tricyclodecanyl acrylate, tricyclodecanyloxyethyl acrylate, isobornyloxyethyl acrylate;
Acrylamides such as acryloylmorpholine and diacetone acrylamide; N-vinylamides such as N-vinylpyrrolidone and N-vinylcaprolactam; Vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether; Maleimides such as chlorophenylmaleimide, cyclohexylmaleimide and laurylmaleimide Class: ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of ethylene oxide adduct of bisphenol A, bisphenol A Propylene oxide adduct diacrylate, tricyclodecane dimethylo Diacrylate, 2,2-di (glycidyloxyphenyl) propane acrylic acid adduct, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanate Examples thereof include nurate triacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, tris (hydroxypropyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, and ditrimethylolpropane triacrylate.

Below, the inorganic fine particle which can be used suitably for the resin composition of this invention is demonstrated.
The inorganic fine particles are not particularly limited as long as they are fine particles composed of an inorganic compound such as a metal or a metal compound. Inorganic components in the inorganic fine particles include metal oxides, hydroxides, (acid) nitrides, (acid) sulfides, carbides, halides, sulfates, nitrates, (basic) carbonates, (basic) Examples include acetate. Among these, a metal oxide (metal oxide) is preferable. The metal oxide means / includes the following. That is, it means a compound having a metal (M) as a metal component and a metalloxane (MO) bond as a main binding component. In addition, a single oxide composed of a single metal component, a composite oxide composed of a plurality of metal components, a solid solution oxidation in which a metal element different from metal element M and oxygen is dissolved in these metal oxides. Things are illustrated. Further, a metal oxide having a stoichiometric composition, a non-stoichiometric composition: for example, a metal element such as ZnO _(1-δ) , TiO _(2-δ) , NiO _(1-δ) or an oxygen element with respect to the stoichiometric composition Thus, an excess or deficient metal oxide having a non-stoichiometric composition can be preferably employed. The form of the metal oxide includes both crystalline and non-quality. Whether it is crystalline or amorphous, and whether the crystallinity is high or low can be usually evaluated by X-ray diffraction measurement. Hydrated metal oxides are also included in the metal oxide referred to in the present invention. Moreover, the thing which the residue, atom, and atomic group derived from the raw material in the manufacture process of metal oxide particle couple | bonded with a part of surface or internal metal atom or oxygen atom may be contained. Examples thereof include an organic group, a hydroxyl group, a nitrate group, a sulfate group, a halogen atom, a hydrogen atom, and an alkali metal atom (ion). Examples of the organic group include alkoxyl groups such as methoxy group and butoxy group; carboxyl groups such as ethanoyl group (acetoxy group) and propanoyl group; β-dicarbonyl group; β-ketoester group; alkyl group; cycloalkyl group; An aralkyl group or the like is preferably exemplified.

The inorganic fine particles include particles that have been surface-treated for the purpose of improving the affinity of the fine particles with the resin and improving the dispersibility. The surface treatment agent is not particularly limited, and various organic compounds, inorganic compounds, organometallic compounds, and the like are used for the purpose of introducing organic chains and polymer chains on the fine particle surfaces or controlling surface charge. For example,
1) Coupling agents; coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconium coupling agents; metal alkoxides and (partial) hydrolysis / condensates thereof; Organometallic compounds such as metal soaps;
2) Organic compounds such as organic amines, β-diketone compounds and carboxylic acids.
3) (Co) polymer-based polymers of vinyl monomers such as (meth) acrylic resin-based, polystyrene resin-based, polyolefin-based, vinyl acetate resin-based, acrylic silicone-based, in addition to conventionally known polymer dispersants; alkyds Resin polymer; Amino resin polymer; Epoxy resin polymer; Polyamide resin polymer; Polyimide resin polymer; Polyurethane resin polymer; Polyester resin polymer; Phenol resin polymer; Organopolysiloxane polymer; A polymer compound such as a fluororesin and a modified product thereof.
4) Various surfactants (such as cationic, anionic, amphoteric and nonionic).
5) Alkali metal ions and halogen ions.
Etc. are suitable.

The metal element (M) is arbitrary, but, for example, the metal element (M) is not particularly limited. For example, alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba, and Ra are used. Lanthanoid metal elements such as La and Ce; Actinide metal elements such as Ac; Group IIIa metal elements such as Sc and Y; Group IVa metal elements such as Ti, Zr and Hf; Group Va such as V, Nb and Ta Metal element; Group VIa metal element such as Cr, Mo, W; Group VIIa metal element such as Mn, Tc, Re; Group VIII metal element such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt Group Ib metal elements such as Cu, Ag and Au; Group IIb metal elements such as Zn, Cd and Hg; Group IIIb metal elements such as Al, Ga, In and Tl; Group IVb such as Si, Ge, Sn and Pb; Metal elements; V such as Sb and Bi Group metal element; Se, can be mentioned Group VIb metal element or the like of Te such, they may be present together one or more. Among these, it can select according to the electrical property, the optical property, the magnetic property, etc. which are the objectives of the composition. For example, among optical properties, Ti, Zr, In, Zn, La, Al, etc. are preferable when it is desired to obtain a resin composition having a high refractive index, and Si is desired when a composition having a low refractive index is desired. preferable.

The shape of the fine particles is not particularly limited. Specific examples of the shape include a spherical shape, an elliptical spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a cylindrical shape, a flake shape, a (hexagonal) plate shape, and the like.

As the inorganic fine particles, inorganic fine particles obtained by a liquid phase method, particularly metal oxide fine particles obtained by a liquid phase method described later are preferable. For example, inorganic fine particles composed of a hydrolysis condensate of an alkoxide compound and / or a carboxylate compound described later have a fine structure different from that of the inorganic fine particles obtained by the gas phase method. For example, when the inorganic fine particle contains a metal element or non-metal element such as Si, Al, P, Fe, Ag, Sn, Ti, V, Cr, Mn, Co, Cu, Zn, Sb, La, This can be confirmed by magnetic resonance (NMR) measurement. As an example, we describe the case of containing Si, tetrahedrons SiO ₄ atomic group around one Si atom is four oxygen atoms are coordinated to construction has a basic structure, SiO ₄ atomic Different groups have different microstructures depending on whether oxygen atoms are shared. When silica is produced by thermal decomposition of silicon halide or air oxidation of heat-reduced silica sand, all SiO ₄ atomic groups share oxygen atoms. Therefore, when Si-NMR measurement is performed, −120 to −100 ppm only Q ⁴ silica component having a peak top is observed. On the other hand, in the case of the hydrolysis condensate of the alkoxide compound and / or carboxylate compound, a SiO ₄ atomic group that does not share an oxygen atom appears, and has a peak top at −100 ppm to −90 ppm together with the Q ⁴ silica component. Q ³ silica component is also confirmed. Such NMR measurement can be an effective method for confirming whether inorganic fine particles are hydrolysis condensates of alkoxide compounds and / or carboxylate compounds, and further, what kind of performance is expected from inorganic fine particles. It is also possible to check whether the degree can be given.

As a blending method of the inorganic fine particles to the resin component for obtaining the organic-inorganic composite resin composition, an external addition method and an internal precipitation method are preferably used.
The external addition method of the inorganic fine particles, specifically, the addition form of inorganic fine particles to the resin composition and the dispersion will be described.
The inorganic fine particles / metal oxide particles are preferably mixed with the resin component in such a form that the particles are dispersed in a liquid medium. Examples of the medium include a solvent, a plasticizer, a monomer, and a liquid resin. As the solvent, water, organic solvent, mineral oil, vegetable oil, wax oil, silicone oil and the like are suitable.
The solvent dispersion includes surface-modified inorganic fine particles and further includes a solvent. Examples of the solvent in this case include the above-mentioned solvents. The content of the inorganic fine particles in the solvent dispersion is not particularly limited, but is preferably 10 to 70% by weight, more preferably 20 to 50% by weight of the entire solvent dispersion. It is easy to handle in the content of. Although there is no limitation in particular about content of the solvent in a solvent dispersion, Preferably it is 90-30 weight% of the whole solvent dispersion, More preferably, it is 80-50 weight%.

Organic solvents include alcohols, ketones, aliphatic and aromatic carboxylic esters, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, mineral oils, There may be mentioned vegetable oil, wax oil, silicone oil and the like.
The plasticizer dispersion is one that is dispersed in a plasticizer and includes the above-described inorganic fine particles, preferably surface-modified inorganic fine particles, and further contains a plasticizer. In this case, the plasticizer is not particularly limited. For example, phosphate ester plasticizers such as tributyl phosphate and 2-ethylhexyl phosphate; phthalate esters such as dimethyl phthalate, dibutyl phthalate and octyldecyl phthalate Plasticizers; Aliphatic-basic acid ester plasticizers such as butyl oleate and glycerol monooleate; Aliphatic dibasic acid plasticizers such as dibutyl adipate and di-2-ethylhexyl sebacate; Diethylene glycol Examples of conventionally known plasticizers such as divalent alcohol ester plasticizers such as dibenzoate and triethylene glycol di-2-ethylbutyrate; oxyacid ester plasticizers such as methyl acetylricinoleate and tributyl acetylcitrate Can do.
The monomer dispersion is dispersed in a polymerizable monomer serving as a resin component, and includes the above-described inorganic fine particles, preferably surface-modified inorganic fine particles, and further contains a monomer. The monomer used in the monomer dispersion is not particularly limited, and examples thereof include (meth) acrylic monomers such as (meth) acrylic acid and (meth) acrylic acid esters, and styrene monomers such as styrene, vinyltoluene and divinylbenzene. And conventionally known monomers such as vinyl monomers such as vinyl chloride and vinyl acetate.

As the particle size of the fine particles in the above-mentioned inorganic fine particle powder and fine particle dispersion for preparing the resin composition, a transparent resin composition having a fine particle size is obtained, and the compounding effect of the fine particles in the obtained resin composition (For example, the effect of reducing the coefficient of thermal expansion, the effect of improving the Abbe number, the effect of controlling the refractive index, etc.) is preferable. Specifically, the primary particle size of the fine particles is 1 nm to 400 nm, more preferably 100 nm. Hereinafter, it is more preferably 50 nm or less, particularly preferably 20 nm or less. The primary particle size of the fine particles is, for example, the above-described method of measuring the radius of inertia by the small-angle X-ray scattering method, the method of measuring the particle size of an arbitrary particle from an electron microscope, and the specific surface area diameter Ds measured by specific surface area measurement;
Ds = 6 / (ρ × S)
(However, ρ: true specific gravity of metal oxide-based particles, S: specific surface area (m ² / g) of metal oxide-based particles measured by BET method), or crystalline Can be determined by measuring the crystallite diameter by X-ray diffraction measurement.
The dispersed particle size of the fine particles in the inorganic fine particle powder and fine particle dispersion is preferably distributed in the primary particle size or a size close thereto, specifically, the average particle size is 400 nm or less, more preferably It is 70 nm or less, particularly preferably 30 nm or less. The dispersed particle size can be evaluated by a dynamic light scattering method, a centrifugal sedimentation method, or the like. The primary particle size and the dispersed particle size in the resin composition are preferably in the same range as in the case of the fine particle powder and fine particle dispersion, and can be evaluated by the small angle X-ray scattering method described above.
As such a range, it is preferable that it is the same range also in the resin composition.

Among the inorganic fine particles used in the external addition method, a liquid phase method, a gas phase method, or a solid phase method known in the art can be employed as a method for producing metal oxide particles. Specifically, the following are suitable.
[Gas phase method]
It is represented by a method of evaporating an inorganic or organic metal salt and usually thermally decomposing it at high temperature (oxidation) in the air. For example, a method of heating a metal halide to oxidize it into an oxide (for example, aluminum, silicon Gasification of halides such as titanium, and high-temperature vapor-phase oxidative decomposition with oxygen or water vapor is an industrial process for producing fine powders of alumina, silica, titanium oxide, etc.), oxidative pyrolysis of metal carbonyl compounds and organometallic compounds The method of doing is illustrated. Moreover, the method (for example, the industrial manufacturing method of French method ZnO) which heats a metal raw material (a metal, a mineral), and oxidizes metal vapor | steam at high temperature is illustrated.
[Solid phase method]
Examples thereof include a method in which a metal hydroxide or carbonate is heated and decomposed to obtain an oxide. An example is a method in which an intermediate of a metal oxide (hydrate) is obtained by a liquid phase method and then converted to an oxide in a gas phase or a solid phase. For example, a method in which a metal salt such as a metal carbonate is obtained by a decomposition precipitation method using an acid alkali and then decomposed by heating to obtain an oxide is suitable.

(Liquid phase method)
A precipitation method using an acid alkali, a hydrolysis / condensation method of an organometallic compound, a hydrolysis / condensation method of a metal halide, a hydrothermal reaction, or the like can be preferably employed.
Decomposition precipitation method with acid alkali: Reactions such as decomposition of an aqueous solution of a metal salt with an alkali, decomposition of a basic salt with an acid, and metathesis of a metal salt and a basic salt are exemplified. The method for producing silica particles by the neutralization reaction of an aqueous solution of water glass described later with an alkali is an example of a decomposition precipitation method with an acid alkali.
By these precipitation methods, a reaction solution of a metal oxide or oxide hydrate is usually obtained, but these can be preferably employed as a raw material for metal oxide fine particles of the present invention.
Of the above-mentioned various methods, except for the hydrolysis and condensation methods of organometallic compounds, usually after removing impurities by filtration and washing, pulverization and / or (solvent replacement and redispersion of powder in dispersion medium) It is preferable to use after dispersion.
In the case of the hydrolysis / condensation method of the organometallic compound, it can be processed into a desired form (powder, dispersion) from the obtained reaction solution without passing through the washing step.
Among these, the liquid phase method is more preferable.
In particular, after obtaining a reaction liquid of metal oxide (hydrate) fine particles by a liquid phase method, a consistent liquid phase process for preparing a mixture with a resin component without passing through a drying step is Subsequent aggregation can be avoided, which is preferable. Specifically, the reaction solution is concentrated as necessary, and removal of the solvent component in the reaction solution and substitution with a desired dispersion medium (resin component, monomer, solvent, etc.) are performed simultaneously, such as heating solvent replacement. A process is preferred.

Among the above-mentioned liquid phase methods of inorganic fine particles, a method for hydrolysis / condensation of an organometallic compound that can be preferably applied to an internal precipitation method will be described.
Among the organometallic compounds, alkoxide compounds (preferably metal alkoxides) and / or carboxylate compounds (preferably carboxylic acid metal salts) are suitable.

Below, the hydrolysis reaction and condensation reaction of an alkoxide compound and a carboxylate compound are shown.
M ′ (OR ¹ ) _a + aH ₂ O (hydrolysis) → M ′ (OH) _a + aR ¹ OH
M ′ (OH) _a → M ′ (OH) _b O _c → M′O _{2 / c} (condensate)
(In the formula, M ′ represents a metal element, R ¹ represents an alkyl group or an acyl group, and a, b, and c are arbitrary numerical values.)
As said alkoxide compound and carboxylate compound, following General formula (2);
M ′ (OR ² ) _n (2)
(Wherein M ′ represents a metal element, R ² represents an alkyl group or an acyl group, and n represents an integer of 1 to 7) and / or the following general formula (3);
(R ³ ) _m M ′ (OR ² ) _p (3)
(Wherein, M ′ and R ² are the same as those in the general formula (2). R ³ represents an organic group, and m and p represent integers of 1 to 6). .

As the alkyl group of R ^{2 in} the general formulas (2) and (3), an alkyl group having 1 to 5 carbon atoms is preferable, and an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, An i-butyl group, sec-butyl group, t-butyl group, n-pentyl group and the like are preferable. The acyl group R ^2, is a preferred acyl group having 1 to 4 carbon atoms, an acetyl group, a propionyl group, butynyl group and the like are preferable.

As the organic group of R ³ in the general formula (3), an organic group having 1 to 8 carbon atoms is preferable, and a methyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and other alkyl groups; 3-fluoropropyl group, 3-chloropropyl group, 3, 3 Halogenated alkyl groups such as 3-trichloropropyl group; mercapto group-containing alkyl groups such as 2-mercaptopropyl group; 2-aminoethyl group, 2-dimethylaminoethyl group, 3-aminopropyl group, 3-dimethylaminopropyl Amino group-containing alkyl groups such as phenyl group; phenyl group, methylphenyl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, chloropheny Aryl groups such as benzyl groups; aralkyl groups such as benzyl groups; epoxy group-containing organic groups such as 2-glycidoxyethyl groups, 3-glycidoxypropyl groups, 2- (3,4-epoxycyclohexyl) ethyl groups; An unsaturated group-containing organic group such as a vinyl group and 3- (meth) acryloxypropyl group is preferred.

The metal element M ′ in the general formulas (2) and (3) may be any element in the periodic table as long as the metal element can take the structure of the compound represented by the general formula (2) and the general formula (3). The same metal (M) as described above can be used. Preferably, IIIB group such as B, Al, Ga, In, Tl; IVB group such as C, Si, Ge, Sn, Pb; Ti, Zr, Zn, Ca, Na, Li, Te, Mg, Ni, Cr , Ba, Ta, Mo, Tb, Cs and the like.

In addition, as the alkoxide compound or the carboxylate compound, two or more kinds having different M ′ may be used in combination, or one containing two or more kinds of M ′ in combination. In particular, in optical applications, since insulation is required, it is preferable to select a material having low ion conductivity. As the metal element M ′, typical metal elements excluding alkali metals and alkaline earth metals, transitions Metal elements or non-metallic elements are preferred. Al or In is suitable as a typical metal element excluding alkali metal and alkaline earth metal, and Si is suitable as a nonmetallic element.

Examples of the alkoxide compound or carboxylate compound when M ′ is Si include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra- Tetraalkoxysilanes such as i-butoxysilane, tetra-sec-butoxysilane, tetra-t-butoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxy Silane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3,3,3-trifluoropropyltrime Xysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N- [3- (trimethoxysilyl) propyl] aniline, N- [3- (triethoxysilyl) propyl] aniline , Phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane, benzyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Sisilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane Trialkoxysilanes such as dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldiethoxysilane, di-i-propyldimethoxysilane, Dialkoxysilanes such as di-i-propyldiethoxysilane, diphenyldimethoxysilane and diphenyldiethoxysilane; tetraacyloxysilanes such as tetraacetyloxysilane and tetrapropionyloxysilane ; Triacyloxy silanes such as methyltrimethoxysilane acetyloxy silane, ethyltrimethoxysilane acetyloxy silane; dimethyl acetyl silane, di acyloxysilanes such as diethyl diacetyl silane and the like. Among these, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, and dimethyldiethoxysilane are preferable.

As the alkoxide compound when M ′ is other than Si, Cu (OCH ₃ ) ₂ , Zn (OC ₂ H ₅ ) ₂ , B (OCH ₃ ) ₃ , Al (OCH ₃ ) ₃ , Al (OC ₂ H) ₅ ) ₃ , Al (iso-OC ₃ H ₇ ) ₃ , Al (OC ₄ H ₉ ) ₃ , Ga (OC ₂ H ₅ ) ₃ , Y (OC ₄ H ₉ ) ₃ , Ge (OC ₂ H ₅ ) ₄ , Pb (OC ₄ H ₉ ) ₄ , P (OCH ₃ ) ₃ , Sb (OC ₂ H ₅ ) ₃ , VO (OC ₂ H ₅ ) ₃ , Ta (OC ₃ H ₇ ) ₅ , W (OC ₂ H ₅ ) ₆ , La (OC ₃ H ₇ ) ₃ , Nd (OC ₂ H ₅ ) ₃ , Ti (OCH ₃ ) ₄ , Ti (OC ₂ H ₅ ) ₄ , Ti (iso-OC ₃ H ₇ ) ₄ , Ti ( _{OC 4 H 9) 4, Zr} (OCH 3) 4, Zr (OC 2 H 5) 4 , Zr (OC ₃ H ₇ ) ₄ , Zr (OC ₄ H ₉ ) _{4 and} other single metal alkoxides; La [Al (iso-OC ₃ H ₇ ) ₄ ] ₃ , Mg [Al (iso-OC ₃ H _{7) ) 4] 2, Mg [Al} (sec-OC 4 H 9) 4] 2, Ni [Al (iso-OC 3 H 7) 4] 2, (C 3 H 7 O) 2 Zr [Al (OC 3 H _{7) 4] 2, Ba [} Zr (OC 2 H 5) 9] composite metal alkoxides such as ₂ are suitable.
The hydrolysis / condensation reaction of the alkoxide compound and / or the carboxylate compound can be carried out by bringing these compounds into contact with water, usually in an organic solvent. Alcohol is preferred as the organic solvent. In order to proceed with the hydrolysis / condensation reaction, a hydrolysis catalyst is usually allowed to coexist. As the catalyst for obtaining metal oxide fine particles used in the external addition method, an inorganic acid such as hydrochloric acid and nitric acid, an acid catalyst such as carboxylic acid such as acetic acid, and a basic catalyst such as ammonia and amine are preferable. Depending on the type of the metal element M ′, it can be appropriately selected. The reaction temperature is usually preferably 0 to 120 ° C, more preferably 10 to 100 ° C.
A catalyst and conditions suitable for the internal addition method will be described later.

Next, the silicon-based oxide fine particles and the production method thereof will be described.
Specific examples of the silicon-based oxide particles (dispersion) include, in addition to silica particles mainly composed of SiO ₂ , an organic group such as an alkyl group bonded to a part of silicon, for example, polymethyl Organosiloxane-based particles such as silsesquioxane-based particles: General formula (4) R _m SiO _(4-m) / 2 is preferably exemplified.
The silica particles are preferably a) a method using water glass as a starting material, and b) those obtained by hydrolysis / condensation reaction of a hydrolyzable silicon compound.
a) A method of mixing water glass with an inorganic acid such as nitric acid or hydrochloric acid in an aqueous medium (one of the decomposition and precipitation methods using the acid-alkali), or by bringing a water glass aqueous solution into contact with an ion exchange resin. A method of ion exchange between an alkali metal component and proton (ion exchange method) is preferably used. According to this method, colloidal silica particles are produced.
From the obtained reaction solution (fine silica particles are produced, and the former method dissolves inorganic acid radicals and alkali metal salts), if necessary, desalting treatment is performed to partially remove the solvent components. By doing so, an aqueous dispersion of concentrated silica particles is obtained. The solvent can be replaced with a desired solvent by a known method (heating solvent replacement, centrifugation, redispersion, etc.).
b) In the general formula (2), the silicon compound in the case of M ′ = Si is hydrolyzed and condensed in a water-containing organic solvent, preferably a water-containing alcohol, preferably in the presence of a hydrolysis catalyst. Is obtained. The catalyst is preferably an inorganic acid such as hydrochloric acid or nitric acid, an acid catalyst such as carboxylic acid such as acetic acid, or a basic catalyst such as ammonia or amine, and particularly preferably a basic catalyst.
By concentrating and / or replacing the obtained reaction solution of silica particles with a desired organic solvent, a fine particle dispersion of silica particles can be obtained.

Organosiloxane-based particle: ... General formula (4) R _m SiO _(4-m) / 2 production method example At least one of the silicon compounds in the case of M ′ = Si in the general formula (3), or the general formula In the same manner as (b) above, at least one kind of silicon compound in the case of M ′ = Si in the formula (3) and at least one kind of silicon compound in the case of M ′ = Si in the general formula (2) It can be obtained by hydrolysis and condensation.
As an example of a commercially available Si-based oxide particle dispersion, an organosilica sol manufactured by Nissan Chemical is suitable.

As a method for producing inorganic fine particles used in the present invention, a method of obtaining inorganic fine particles by hydrolyzing and condensing an alkoxide compound and / or a carboxylate compound in a liquid medium containing the above-described resin component (internal) The precipitation method) is preferred. An organic-inorganic hybrid is obtained by obtaining a hydrolyzed condensate in a liquid medium containing a resin component, and inorganic fine particles are finely dispersed in a matrix resin. Thus, the resin composition of the present invention can be obtained. The organic-inorganic hybrid thus obtained exhibits excellent curability and flame retardancy.

Hereinafter, the internal precipitation method will be described. In the internal precipitation method, the raw materials described in the above description of the hydrolysis / condensation method of the organometallic compound can be suitably used.
As a specific method for producing the inorganic fine particles (internal precipitation method), first, a liquid medium containing a resin, preferably a solution containing a resin, is prepared, and an alkoxide compound and / or carvone is added to the solution. An acid salt compound and water or a solvent containing it may be added to perform a hydrolysis reaction and a condensation reaction. The liquid medium containing the resin component has at least one structure selected from the group consisting of an ether bond, an ester bond, and a nitrogen atom as the resin component and a solvent, a plasticizer, or a lubricant. It is preferable to use the compound which has.

Examples of the compound having an ether bond include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, ethyl vinyl ether, butyl vinyl ether, anisole, phenetole, butyl phenyl ether, pentyl phenyl ether, methoxy toluene, and benzyl ethyl. Ether, diphenyl ether, dibenzyl ether, peratrol, propylene oxide, 1,2-epoxybutane, dioxane, trioxane, furan, 2-methylfuran, tetrahydrofuran, tetrahydropyran, thionel, 1,2-dimethoxyethane, 1,2-di Ethoxyethane, 1,2-dibutoxyethane, glycerin ether, crown ether, methylal, acetal, methyl cellosol , Ethyl cellosolve, butyl cellosolve, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol, Triethylene glycol monomethyl ether, tetraethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol methyl ether, propylene glycol dimethyl ether, propylene glycol propyl ether Propylene glycol butyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, tripropylene glycol, tripropylene glycol monomethyl ether, 2- Methoxyethanol, 2-ethoxyethanol, 2- (methoxymethoxy) ethanol, 2-isopropoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 2-phenoxyethanol, 2- (Benzyloxy) ethanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, etc. are preferred It is.

Examples of the compound having an ester bond include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-acetate Butyl, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, isopentyl propionate , Ethylene glycol monoacetate, diethylene glycol monoacetate, monoacetin, diacetin, triacetin, monobutyrin, dimethyl carbonate, diethyl carbonate, dipropyl carbonate Dibutyl carbonate, butyric acid ester, isobutyric acid ester, isovaleric acid ester, stearic acid ester, benzoic acid ester, ethyl cinnamate, abietic acid ester, adipic acid ester, γ-butyrolactone, Shu Acid esters, malonic acid esters, maleic acid esters, tartaric acid esters, citric acid esters, sebacic acid esters, phthalic acid esters, ethylene diacetate and the like are suitable.

Examples of the compound containing the nitrogen atom include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, Benzonitrile, α-tolunitrile, formamide, N-methylformamide, N, N-dimethylformamide, N, N-diethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, N, N-diethylacetamide, 2 -Pyrrolidone, N-methylpyrrolidone, ε-caprolactam and the like are preferred.

Examples of the compound having a plurality of structures selected from the group consisting of the ether bond, ester bond and nitrogen atom include N-ethylmorpholine, N-phenylmorpholine, methyl cellosolve acetate, ethyl cellosolve acetate, propyl cellosolve acetate, and butyl cellosolve acetate. , Phenoxyethyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether Acetate, dipropylene glycol methyl ether acetate, dipropylene glycol ethyl ether acetate, dipropylene glycol propyl ether acetate, dipropylene glycol butyl ether acetate, tripropylene glycol methyl ether acetate are preferable.

The amount of the solvent used is preferably 5 parts by weight or more, more preferably 500 parts by weight or less, based on 100 parts by weight of the resin. More preferably, it is 20 parts by weight or more and 200 parts by weight or less. As said other solvent, methanol, ethanol, etc. are suitable.

In the hydrolysis and condensation reaction conditions in the liquid medium containing the resin, the reaction temperature is preferably 0 to 120 ° C. More preferably, it is 10-100 degreeC, More preferably, it is 20-80 degreeC. The reaction time is preferably 30 minutes to 24 hours. More preferably, it is 1 to 12 hours. As reaction conditions in the case of preparing the inorganic fine particles, the reaction temperature may be appropriately set depending on the inorganic fine particles to be prepared, and the reaction pressure may be increased as normal pressure, but in the present invention, for example, the reaction temperature is 100 ° C. or less, preferably 50 to 100 ° C., more preferably 70 to 100 ° C., the reaction pressure to normal pressure, and the reaction time to 4 to 10 hours.

The method for producing the organic-inorganic composite resin composition (internal precipitation method) is preferably produced by hydrolysis and condensation of a metal alkoxide and / or carboxylic acid metal salt in the presence of water. Further, in such a production method, the remaining metal alkoxide and / or carboxylic acid metal salt is added to a reaction solution obtained by hydrolyzing and condensing a part of two or more kinds of metal alkoxide and / or carboxylic acid metal salt. It is more preferable that the production method includes hydrolysis and condensation.
The metal alkoxide and carboxylic acid metal salt have different reaction rates for hydrolysis and condensation depending on the type and number of organic groups bonded to the metal element, and are generally low-polar organic groups that are σ-bonded to the metal without using a hetero element. The reaction rate is lower as the number of organic groups bonded to each other or the number of organic groups bonded through a hetero element such as O and N decreases. When metal alkoxides and / or carboxylic acid metal salts having different reaction rates are added all at once, only the metal alkoxide and / or carboxylic acid metal salt having a high reaction rate are hydrolyzed and condensed in the initial stage of the reaction. The composition of the carboxylic acid metal salt is changed, and only the metal alkoxide and / or the carboxylic acid metal salt having a slow reaction rate are hydrolyzed and condensed in the later stage of the reaction. For this reason, the hydrolyzed and condensed product has not only a raw material composition but also a nonuniform particle size, a large refractive index distribution, and the resin composition is likely to cause Rayleigh scattering during visible light transmission.

As the above production method, among two or more kinds of metal alkoxides and / or carboxylic acid metal salts, a compound having a low hydrolysis and condensation rate is added, and after hydrolysis and condensation are advanced to a predetermined reaction rate, hydrolysis is performed. It is preferable to add a compound having a high decomposition and condensation rate, followed by hydrolysis and condensation. Thereby, the raw material composition and particle size of the obtained hydrolysis and condensate are likely to be uniform, and the resin composition is less likely to cause Rayleigh scattering during visible light transmission. As the number of hydrolysis and condensation reactions of two or more kinds of metal alkoxides and / or carboxylic acid metal salts, it is most preferable to divide into the number of raw materials to be used. You may divide into the mixture of a body and a compound with a slow reaction rate into two.

About the reaction rate of the said hydrolysis and condensation, it can carry out by various methods. An example of a metal alkoxide and / or carboxylic acid metal salt is an alkoxysilane. In the case of alkoxysilane, the alkoxysilyl skeleton is hydrolyzed to become silanol, and dehydration condensation between silanols or dealcoholization condensation between silanol and alkoxysilyl skeleton proceeds to form siloxane condensation. Therefore, for example, it is possible to follow the change in the reaction rate by quantifying unreacted silane by gas chromatography, quantifying alkoxyl groups by NMR, or quantifying silanol by FT-IR.
Whether to perform the next step of the hydrolysis and condensation reaction is preferably determined by determination with an unreacted metal alkoxide and / or carboxylic acid metal salt by gas chromatography, and the residual ratio is preferably 50 to 0%, more preferably It is 40 to 0%, more preferably 30 to 0%. The measurement conditions for gas chromatography may be known and publicly used conditions.

In the hydrolysis and condensation reaction, a metal chelate compound can be used to accelerate the reaction. These can use 1 type (s) or 2 or more types. Such a catalyst is preferable in the hydrolysis / condensation reaction in the internal precipitation method. The metal chelate _{^{compound, Zr (OR 4) q (}} R 5 COCHCOR 6) 4-q, Ti (OR 4) r (R 5 COCHCOR 6) 4-r, _{^{and, Al (OR 4) s (}} R 5 COCHCOR ⁶ ) One or more compounds selected from the group consisting of _4-s and partial hydrolysates thereof are preferred.

R ⁴ and R ⁵ in the metal chelate compound are the same or different and represent an organic group having 1 to 6 carbon atoms, and R ⁶ represents an organic group having 1 to 6 carbon atoms or an alkoxyl group having 1 to 16 carbon atoms. And q and r are integers of 0 to 3, and s is an integer of 0 to 2. Examples of the organic group having 1 to 6 carbon atoms in R ⁴ and R ⁵ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t- A butyl group, n-pentyl group, n-hexyl group, phenyl group and the like are preferable. Moreover, as a C1-C16 alkoxyl group in R < ⁶ >, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, sec-butoxy group, t-butoxy group Groups etc. are preferred.

Examples of the metal chelate compound include tri-n-butoxy / ethyl acetoacetate zirconium, di-n-butoxy / bis (ethyl acetoacetate) zirconium, n-butoxy / tris (ethyl acetoacetate) zirconium, tetrakis (n-propylacetate). Acetate) zirconium, tetrakis (acetylacetonato) zirconium, zirconium chelate compounds such as tetrakis (ethylacetoacetate) zirconium; di-i-propoxy bis (ethylacetoacetate) titanium, di-i-propoxy bis (acetylacetate) Titanium chelate compounds such as titanium, di-i-propoxy bis (acetylacetonato) titanium; di-i-propoxy ethylacetoacetate aluminum, di-i- Ropoxy acetylacetonato aluminum, i-propoxy bis (ethylacetoacetate) aluminum, i-propoxy bis (acetylacetonate) aluminum, tris (ethylacetoacetate) aluminum, tris (acetylacetonato) aluminum, monoacetylacetate Aluminum chelate compounds such as nart bis (ethylacetoacetate) aluminum are preferred. Among these, tri-n-butoxy ethyl acetoacetate zirconium, di-i-propoxy bis (acetylacetonate) titanium, di-i-propoxy ethyl acetoacetate aluminum, and tris (ethyl acetoacetate) aluminum are preferable.

The amount of the metal chelate compound used is preferably 30 parts by weight or less with respect to 100 parts by weight of the compound represented by the general formula (2) and / or the compound represented by the general formula (3). If it exceeds 30 parts by weight, the surface appearance of the molded product may be deteriorated. More preferably, it is 20 parts by weight or less, and still more preferably 10 parts by weight or less.

Another description of the organic-inorganic composite resin composition is as follows. It is common to both the internal precipitation method and the external addition method.
The resin composition of the present invention preferably contains the inorganic fine particles in an amount of 1% by mass or more, more preferably 5% by mass or more and 50% by mass or less, and more preferably 40% by mass or less. By setting it as 1 mass% or more, the improvement effect of the flame retardance and thermal property of the resin composition obtained will fully express. When it exceeds 50 mass%, there exists a possibility that it may become high viscosity and a composition cannot be mixed uniformly.

In addition to the resin and inorganic fine particles described above, the resin composition of the present invention includes a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, an antioxidant, an ultraviolet absorber, a light Stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers and organic fillers, adhesion improvers such as coupling agents, thermal stabilizers, Antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-color separation agent, emulsifier, anti-slip / scratch agent Further, it may contain an anti-skinning agent, a desiccant, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid) and the like.

Hereinafter, the method for curing the resin composition of the present invention will be described. For curing the resin composition of the present invention, a conventionally known method can be employed depending on the properties of the resin used.
When the resin component of the resin composition of the present invention contains a compound having at least one glycidyl group and / or epoxy group, a cured product can be obtained by thermosetting using a curing agent. As the curing agent, it is preferable to use the thermal latent cation generator described above. Examples of the curing agent other than the heat latent cation generator include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, and methylnadic acid; Various phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, terpene phenol resin; various phenols and various such as hydroxybenzaldehyde, crotonaldehyde, glyoxal Various phenol resins such as a polyhydric phenol resin obtained by a condensation reaction with aldehydes; one or more of BF ₃ complexes, sulfonium salts, imidazoles and the like can be used. It is also a preferred embodiment that the compound having at least one glycidyl group and / or epoxy group is cured with a polyhydric phenol compound described later.

In the curing of the resin composition containing the compound having at least one glycidyl group and / or epoxy group, a curing accelerator can be used. For example, triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine One or more organic phosphorus compounds such as tris (dimethoxyphenyl) phosphine are suitable. As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC.

When the resin component of the resin composition of the present invention contains a polyhydric phenol compound, a cured product can be obtained by thermosetting using a curing agent. Examples of the curing agent include compounds having at least two glycidyl groups and / or epoxy groups, and examples of the compound having at least two glycidyl groups and / or epoxy groups include two or more on average in one molecule. An epoxy resin having a glycidyl group and / or an epoxy group is preferable, and an epibis type glycidyl ether type epoxy resin obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, and bisphenol S with an epihalohydrin; phenol, cresol , Phenols such as xylenol, resorcin, catechol, bisphenol A, bisphenol F and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, dicyclopentadiene, terpe Novolak / aralkyl type glycidyl ether type epoxy resins obtained by condensation reaction of polyphenols obtained by condensation reaction of coumarin, paraxylylene dimethyl ether, dichloroparaxylene and the like with epihalohydrin; tetrahydrophthalic acid, hexane Glycidyl ester type epoxy resin obtained by condensation reaction of hydrophthalic acid, benzoic acid and epihalohydrin; Glycidyl ether type epoxy resin obtained by condensation reaction of hydrogenated bisphenol or glycols and epihalohydrin; Hindatoin or cyanuric acid and epihalohydrin Amine-containing glycidyl ether type epoxy resins obtained by condensation reactions; aromatic polycyclic epoxy resins such as biphenyl type epoxy resins and naphthalene type epoxy resins are suitable. . Moreover, the compound which has an epoxy group in a molecule | numerator by addition reaction with these epoxy resins, polybasic acids, and / or bisphenols may be sufficient. These can use 1 type (s) or 2 or more types.

The blending mass ratio of the polyhydric phenol compound and the epoxy resin curing agent (polyhydric phenol compound / epoxy resin curing agent) is preferably 30/70 or more, and 70/30 or less. It is preferable that If it is less than 30/70, the mechanical properties and the like of the cured product formed may be reduced, and if it exceeds 70/30, the flame retardancy may be insufficient. More preferably, it is 35/65 or more and 65/35 or less. A curing accelerator may be used for the curing. Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2,4,6-tris (dimethylaminomethyl). ) Amines such as phenol, benzylmethylamine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) An organic phosphorus compound such as tributylphosphine, triphenylphosphine, and tris (dimethoxyphenyl) phosphine is preferable.

Examples of the curing method in the case of containing a compound having a polymerizable unsaturated bond as the resin component of the resin composition of the present invention include a curing method by irradiation with active energy rays and a curing method by heat. The resin composition has an intrinsic spectral sensitivity in the range of 200 to 400 nm, and can be polymerized by irradiation with ultraviolet rays or visible rays having a wavelength of 180 to 500 nm in the absence of a photopolymerization initiator. Since light having wavelengths of 308 nm, 313 nm, and 365 nm is effective for curing, a curing method by irradiation with active energy rays is preferable. Further, the resin composition of the present invention can be cured in air and / or in an inert gas.

The resin composition containing the compound having a polymerizable unsaturated bond can be cured by irradiation with an active energy ray other than the above-described ultraviolet ray or visible ray, and generates a radically active species as the active energy ray. In addition to the ultraviolet rays or visible rays described above, ionizing radiation such as electron beams, α rays, β rays, and γ rays, microwaves, high frequencies, infrared rays, laser beams, and the like are suitable. The absorption wavelength of the compound that generates radically active species may be selected as appropriate.

Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, and a short arc. A lamp, helium / cadmium laser, argon laser, excimer laser, sunlight and the like are suitable. The irradiation time of ultraviolet light or visible light having a wavelength of 180 to 500 nm may be appropriately set according to the wavelength irradiation amount of the active energy ray, but is preferably 0.1 microsecond to 30 minutes, and preferably 0.1 millisecond to 1 minute. Is more preferable.

In the curing by irradiation with the active energy ray, a known and usual photopolymerization initiator may be added and cured in order to perform the curing reaction more efficiently. As a compounding quantity of the said photoinitiator, it is preferable that it is 0.1 mass part-10 mass parts with respect to 100 mass parts of curable resin components of this invention. If it is less than 0.1 parts by mass, photopolymerization may not proceed efficiently, and if it exceeds 10 parts by mass, there is no further effect of improving the curing rate, and conversely, curing may be insufficient. is there.

Examples of the photopolymerization initiator include an intramolecular bond cleavage type photopolymerization initiator and an intramolecular hydrogen abstraction type photopolymerization initiator. Examples of the intramolecular bond cleavage type photopolymerization initiator include diethoxyacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4-thio). Methylphenyl) propan-1-one ("Irgacure 907" manufactured by Ciba-Geigy), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl-1- Phenylpropan-1-one (Merck "Darocur 1173"), 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy "Irgacure 184"), 1- (4-Isopropylphenyl) -2-hydroxy-2-methyl Propan-1-one (Merck "Darocur 1116"), benzyldimethyl ketal “Irgacure 651” manufactured by Ciba-Geigy Co., Ltd.), oligo {2-hydroxy-2-methyl-1- “4- (1-methylvinyl) phenyl” propane} (Esacure KIP100 manufactured by Ramberty), 4- (2-acryloyl) -Oxyethoxy) phenyl-2-hydroxy-2-propyl ketone (acetphenone series such as “ZLI3331” manufactured by Ciba-Geigy Co., Ltd., benzoin derivatives such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin alkyl, 1-hydroxycyclohexyl phenyl Mixture of ketone and benzophenone ("Irgacure 500" manufactured by Ciba-Geigy), 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF), bisacyl phosphite Acylphosphine oxides such as oxides (“CGI1700” manufactured by Ciba Geigy), benzyl and benzyl derivatives, methylphenylglyoxyesters, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (Nippon Yushi) BTTB manufactured by the company is suitable.

Examples of the intramolecular hydrogen abstraction type photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate and alkyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4. Benzophenone series such as '-methyl-diphenyl sulfide, acrylated benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 2- Thioxanthone series such as isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Michler ketone, aminobenzophenone series such as 4,4'-diethylaminobenzophenone, 10 -Butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferred.

Examples of other compounds that can be used as the photopolymerization initiator include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- [ 4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and its derivatives, 4-dimethylaminobenzoate ester, 1,1-di Alkoxyacetophenone, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone, thioxanthone and Thioki Tontone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl) -2,4 , 4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylphenyl) -phenylphosphine oxide and the like are suitable.

As the photopolymerization initiator, a photocationic polymerization initiator can also be used. Examples of the photocationic polymerization initiator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chloro. Phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide Bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) be Zen] -Fe- hexafluorophosphate, diaryliodonium hexafluoroantimonate and the like. These can be easily obtained from the market. For example, SP-150, SP-170 (manufactured by Asahi Denka); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide) CD-1012 (manufactured by Sartomer) and the like are suitable. Among these, it is preferable to use an onium salt as the photocationic polymerization initiator. Moreover, as an onium salt, it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.

In the curing by irradiation with the active energy ray, it is preferable to use a photosensitizer in combination. It is preferable that the compounding quantity of the said photosensitizer is 0.1-20 mass% with respect to 100 mass% of resin compositions of this invention. If the amount is less than 0.1% by mass, the photopolymerization may not proceed efficiently. If the amount exceeds 20% by mass, the ultraviolet ray may be prevented from being transmitted into the coating film and curing may be insufficient. . More preferably, it is 0.5-10 mass%.

Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethylamino). ) Amines such as ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate and the like are suitable.

In the curing of the resin composition containing the polymerizable unsaturated compound, an additive may be further added and cured, and the additive has a curing accelerator, a reactive diluent, and an unsaturated bond. No saturated compounds, pigments, dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers and Adhesion improvers such as organic fillers, coupling agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners -Anti-sagging agents, anti-coloring agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, desiccants, IR cut agents, antifouling agents, antistatic agents, conductive agents (electrostatic aids), etc. are suitable is there.

The resin composition of the present invention can obtain a cured product by the above-described curing method, and such a cured product is excellent in various optical properties. For example, the haze of the cured product is preferably 20% or less. Thus, the resin composition in which the degree of haze of the cured product of the resin composition is 20% or less is also a preferred embodiment of the present invention. The haze of the cured product is preferably 18% or less, and more preferably 15% or less. As the transparency, it is preferable that the light transmittance in the visible light region (region having a wavelength of 360 to 780 nm) is 75% or more. The light transmittance of the cured product is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 87% or more.
The turbidity of the cured product is preferably 5 or less. More preferably, it is 2 or less, More preferably, it is 1 or less.
In the cured product, a wide range of numerical values is required for the refractive index and Abbe number of the cured product depending on the optical design of the applied optical system. The light transmittance of the cured product can be measured by a method according to JIS K7361-1, the turbidity can be measured by JIS K7136, and the refractive index / Abbe number can be measured by a method according to JIS K7142.
The PCT moisture absorption of the cured product varies depending on the curing conditions, but by optimizing the curing conditions. It is preferably 1.0% or less, more preferably 0.5% or less, and still more preferably 0.2% or less.

As for the heat resistance of the cured product, it is preferable that the appearance is not changed at all, such as generation of cracks, and the change rate of total light transmittance and haze is 20% or less. More preferably, the change rate of the total light transmittance and haze is 15% or less, and more preferably 10% or less.
Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged UV irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. Excellent heat resistance over time.

As described above, the cured product exhibits excellent transparency and optical characteristics, and can be suitably used for various applications such as optical applications, optical device applications, display device applications, and the like. Specifically, eyeglass lenses, camera lenses, filters, diffraction gratings, prisms, light guides, light beam condensing lenses and light diffusion lenses, watch glasses, transparent glasses such as cover glasses for display devices, cover glasses, etc. Optical applications: Photosensors, photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical fiber adhesives, and other opto-device applications; LCD, organic EL, PDP, etc. Display device substrates such as display device substrates, color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, and antifogging films are suitable.
The shape of the cured product can be appropriately set depending on the application, and is not particularly limited, and examples thereof include forms such as deformed products, films, sheets, pellets, and the like.

The resin composition of the present invention and the production method thereof have the above-described configuration, exhibit excellent performance even in harsh usage environments, have heat resistance and moisture resistance, and have excellent optical properties such as transparency, optical This is a resin composition useful as a use, an opto-device use, a display device use, a machine part material, an electric / electronic part material, and the like, and a production method thereof.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.

Synthesis Example 1 (Synthesis of nanocomposite A)
Liquid hydrogenated bisphenol A epoxy resin (trade name “Epicoat YX8000”, manufactured by Japan Epoxy Resin Co., Ltd.) 403 g, solid hydrogenated bisphenol A epoxy resin 268.66 g (trade name “Epicoat YL7170”, manufactured by Japan Epoxy Resin Co., Ltd.) and 671.66 g of butanol were charged and stirred well at 80 ° C. to make uniform. Thereafter, the temperature was lowered to 50 ° C., and 167.45 g of phenyltrimethoxysilane, 133.06 g of 3-glycidoxypropyltrimethoxysilane, and 212.24 g of tetramethoxysilane were added and stirred uniformly. Thereafter, 133.15 g of water was added and stirred uniformly. Thereafter, 13.71 g of trimethyl borate was added, stirred uniformly, and heated. After stirring at 85 to 90 ° C. for 6 hours, methanol, water and butanol were distilled off as volatile components under reduced pressure, and after cooling, nanocomposite A which was a colorless transparent viscous liquid was obtained. The yield at 1020 g and 40 ° C. was 203 Pa · s.

Synthesis Example 2 (Synthesis of nanocomposite B)
425.92 g of liquid hydrogenated bisphenol A epoxy resin (trade name “Epicoat YX8000”, manufactured by Japan Epoxy Resin Co., Ltd.) in a 3 L flask with a gas inlet, a condenser tube and a stirring rod, and a liquid hydrogenated bisphenol A epoxy 283.95 g of resin (trade name “Epicoat YL7170”, manufactured by Japan Epoxy Resin Co., Ltd.) and 382.24 g of butanol were charged and stirred well at 80 ° C. to make uniform. Thereafter, the temperature was lowered to 50 ° C., 103.24 g of phenyltrimethoxysilane, 82.03 g of 3-glycidoxypropyltrimethoxysilane, and 132.08 g of tetramethoxysilane were added and stirred uniformly. Thereafter, 82.09 g of water was added and stirred uniformly. Thereafter, 8.45 g of trimethyl borate was added, stirred uniformly, and heated.
After stirring at 85 to 90 ° C. for 6 hours, methanol, water and butanol were distilled off as volatile components under reduced pressure, and after cooling, nanocomposite B which was a colorless transparent viscous liquid was obtained. The yield was 962 g and the viscosity at 40 ° C. was 105 Pa · s.

Synthesis example 3 (sample C)
168 g of hydrogenated bisphenol A (Japan Epoxy Resin, YX-8000, epoxy equivalent 205) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-20 nm, solid content 30%) 240 g at 80 ° C. Evaporated (finally 30 minutes under 30 torr). The yield was 249.7 g and the viscosity was 38 Pa · s.

(Resin composition)
Heat was applied as necessary (80 ° C., etc.) so that the release agent (stearic acid, etc.) was in a predetermined amount (0.5%, etc.) relative to the total weight, and was uniformly mixed. After cooling to 50 ° C., the mixture was uniformly mixed so as to be 1% of a cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-80L, etc.).
(Molded body)
Heat was applied to the resin composition as needed (50 ° C. or the like), a vacuum defoaming treatment was performed, and the resin composition was cured at 110 ° C. for 5 hours to obtain a 1 mm thick cast plate.
Physical properties

<Transparency (turbidity, permeability)>
Transparency (1): Evaluated using a turbidimeter (Nippon Denshoku Co., Ltd., NDH2000).
(Curing liquid): The resin solution was poured into a cell having an optical path length of 1 cm, and the haze was evaluated.
(Curing product): The haze of a 1 mm molded body was evaluated.
(Evaluation): Haze 5 or more was evaluated as x, less than 5, 2 or more, Δ, and less than 2 as ◯.
Transparency (2): Evaluation was performed using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100).
(Curing liquid): The resin solution was poured into a cell having an optical path length of 1 cm, and the transmittance was evaluated.
(Hardened product) The transmittance of a molded product of 1 mm was evaluated.
(Evaluation): A transmittance of 75% or more was evaluated as 〇, and a value less than 75 was evaluated as ×.
<Viscosity change rate>
The viscosity of the resin composition at 40 ° C. and rotation speed D = 1 / s was evaluated with an R / S rheometer (Brickfield, USA). When the viscosity was 20 Pa · s or more, an RC25-1 measuring jig was used, and when it was less than 20, an RC50-1 jig was used. The viscosity of the resin composition was evaluated immediately after synthesis. For storage stability, the change in viscosity of the resin composition after storage at 20 ° C. for 3 days is evaluated, and what is the viscosity relative to 100% of the viscosity of the resin before addition of the initiator / release agent? Was evaluated.

<Hardness>
As a necessary condition for continuous production of transparent materials, a certain degree of material hardness is achieved in a short time at a temperature of 150 ° C. or less at which side reactions occur. The resin composition is cured at a height of 1 mm on a SUS304 substrate at 120 ° C. for 2.5 minutes, cooled to 30 ° C. within 30 s, and the hardness is examined by applying a load of 706.5 g to a cylindrical glass rod with a diameter of 3 mm. It was. When a load of 706.5 g is applied to the diameter of 3 mm, a force of 1 kgf / cm ² is obtained.
○: No change in shape (change in shape of 10% or less),
Δ: There is a change in the shape of the gel solidified (the change in shape is 10% or more),
X: Liquid and not cured <Adhesiveness>
As a necessary condition for continuous production of transparent materials, a certain degree of material hardness is achieved in a short time at a temperature of 150 ° C. or less at which side reactions occur. The resin composition is cured to a SUS304 substrate shape at a height of 1 mm at 120 ° C. for 2.5 minutes, cooled to 30 ° C. within 30 s, and a cutter (manufactured by NTT Corporation, main body model number: L-500) at the interface between the resin and SUS304. The model number of the blade: BL-150P) was pressed with a force of 40 kgf / cm ² to evaluate the ease of release. The force with a peel strength of 40 kgf / cm ² is calculated as a value when a load of 1.5 kg is applied to a 2 cm long resin and SUS304 interface using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was set to 0.04 cm ² .
The strength was evaluated in five stages.
5 (strong, difficult to peel)>4>3>2> 1 (weak, easy to peel)
<Remaining on substrate>
The cured resin remaining on the SUS304 surface was visually confirmed during the adhesion evaluation.
○: No remaining, ×: Remaining

In Table 1, the curing agent and the release agent are as follows.
(Curing agent)
Cationic polymerization initiator: Sun-Aid SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.), aromatic sulfonium saltCation polymerization initiator: Sun-Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd.), aromatic sulfonium salt (separated) Mold)
Mold with INT-1850HT (manufactured by Axel), mixture of glycerides and organic phosphate ester and fatty acid copolymer Footent 100 (manufactured by Neos Co., Ltd.), fluorinated surfactant, anionic, sulfonic acid Na salt / ftergent 212MH (manufactured by Neos Co., Ltd.), fluorinated surfactant, nonionic, one end Rf group / one end CH3 type footgent 310 (manufactured by Neos Co., Ltd.), fluorinated surfactant, cationic, ammonium salt, footagent 207S (manufactured by Neos Co., Ltd.), nonionic, one terminal Rf group / one terminal stearyl alcohol type, stearin Acid / stearic acid Mg
・ Lauric acid (dodecanoic acid)
・ Octanoic acid ・ 2-ethylhexanoic acid ・ 2-ethyl-1-hexanol

Claims (7)

A transparent organic resin composition containing an organic resin,
The transparent organic resin composition contains at least one compound selected from the group consisting of alcohols having 8 to 20 carbon atoms, carboxylic acids, carboxylic acid esters, and carboxylates with respect to 100% by mass of the transparent organic resin composition. 0.1 to 5% by mass , and containing a thermal latent curing agent,
The organic resin has at least one glycidyl group and / or epoxy group, and is a transparent organic resin composition. The organic resin includes a compound having at least one glycidyl group and / or epoxy group,
The transparent organic resin composition according to claim 1, wherein the compound having at least one glycidyl group and / or epoxy group is an aliphatic glycidyl ether type epoxy resin and / or an epoxy resin having an epoxycyclohexane skeleton. object. The alcohol having 8 to 20 carbon atoms is an aliphatic alcohol,
The carboxylic acid having 8 to 20 carbon atoms is 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearin. Acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid and / or behenic acid,
The carboxylic acid ester having 8 to 20 carbon atoms is a carboxylic acid ester obtained by a combination of the carboxylic acid having 8 to 20 carbon atoms and the alcohol having 8 to 20 carbon atoms, an alcohol having 1 to 7 carbon atoms, Carboxylic acid ester obtained by a combination with the carboxylic acid having 8 to 20 carbon atoms and / or carboxylic acid ester obtained by a combination of the carboxylic acid having 1 to 7 carbon atoms and the alcohol having 8 to 20 carbon atoms And
The carboxylate is obtained by combining the carboxylic acid having 8 to 20 carbon atoms with amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn and / or Sn. The transparent organic resin composition according to claim 1, wherein the transparent organic resin composition is a salt. The transparent organic resin composition according to any one of claims 1 to 3, wherein the transparent organic resin composition is an organic-inorganic composite resin composition containing inorganic fine particles. The at least 1 compound chosen from the group which consists of said C8-C20 alcohol, carboxylic acid, carboxylic acid ester, and carboxylate salt is a stearic acid type compound, The any one of Claims 1-4 characterized by the above-mentioned. transparent organic resin composition according to. The transparent organic resin composition, a transparent organic resin composition according to any one of claims 1 to 5, characterized in that to release at an intensity of 40 kgf / cm ^2. The transparent organic resin composition is characterized in that, as a curable transparent organic resin composition, the viscosity increase rate of a mixture in one liquid becomes 200% or less after storage at 25 ° C for 3 days compared to immediately after mixing. Item 7. The transparent organic resin composition according to any one of Items 1 to 6.