JP4290726B2 - Method for producing organic-inorganic composite resin composition and organic-inorganic composite resin composition - Google Patents

Description

The present invention relates to an organic-inorganic composite resin composition and an optical member. More specifically, the present invention relates to an organic-inorganic composite 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 an optical member thereof.

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 conventional plastic materials is required, thermosetting materials are being studied.

Regarding the method for producing a thermosetting resin composition, a thermosetting resin containing an alicyclic epoxy resin is dissolved and mixed in an organic solvent in which inorganic particles having a particle size of 70 nm or less are dispersed, and then from this A method for producing a thermosetting resin composition is disclosed in which a curing agent is added and mixed after removing an organic solvent (see, for example, Patent Document 1). However, in the thermosetting resin composition obtained by such a production method, when used in optical applications, coarse inorganic particles are completely eliminated and sufficiently dispersed as primary particles, and visible light is inorganic particles. There is a demand for sufficient transparency without being scattered by light. Specifically, a resin comprising a dispersion in which dry silica is dispersed in a solvent and an alicyclic epoxy is disclosed. In such a case, impurities such as flexibility, fracture resistance, thickening suppression effect, mixing of bead mills, and the like are disclosed. There was room for improvement in preventing contamination and improving transparency.
Also, an epoxy resin molded body molded by curing a composition comprising at least an epoxy resin and inorganic oxide particles, wherein inorganic oxide particles having an average particle size of 50 nm or less are dispersed in the molded body. There is disclosed an epoxy resin molded body characterized in that it is characterized (for example, see Patent Document 2). Here, wet silica and an epoxy resin are disclosed, but bisphenol A (Abbe number 34.1) is used as the epoxy resin. In such a case, there has been room for improvement in which the silica concentration is sufficient, the viscosity increase during solvent degassing is suppressed, and the material strength and optical characteristics are improved. Accordingly, there has been a demand for a device having basic performance such as heat resistance, which can improve optical characteristics and can be suitably applied to various optical members.
JP 2004-346288 A (page 2) JP 2004-250521 A (2nd page)

The present invention has been made in view of the above situation, and can be continuously produced without gelation during production, and has excellent basic performance such as heat resistance, and is excellent in optical properties such as transparency. An object of the present invention is to provide a resin composition and an optical member thereof.

The inventors of the present invention have studied various methods for producing an organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component. When the solvent is degassed in the presence of a specific component, the present invention gels during production. I found it difficult. In addition to high strength and heat resistance, both transparency and Abbe's number are high, and optical properties such as refractive index are excellent. Continuous production of resin compositions that can be suitably used for optical applications, etc. I found what I could do. Moreover, in such a manufacturing method, it has the above-mentioned outstanding optical characteristics by using a specific organic resin component and inorganic fine particle component, specifically, an alicyclic curable substance and a wet inorganic dispersion. It has been found that a thermosetting resin can be obtained. The organic-inorganic composite resin composition obtained by the production method of the present invention has been found to be able to perform complicated processing that cannot be performed at low cost, and particularly in the case of using a thermosetting resin, It has been conceived that it can have heat resistance that cannot be achieved and can solve the above-mentioned problems. Furthermore, such organic-inorganic composite resin compositions are used in various applications such as optical applications such as lenses, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, and molding materials. It has also been found that the present invention can be suitably applied to various uses, and the present invention has been achieved.

That is, the present invention is a method for producing an organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component, wherein the production method comprises a step of preparing a mixture containing inorganic fine particles, an organic resin and a solvent; A degassing step of degassing the solvent from the mixture, wherein the degassing step is a method for producing an organic-inorganic composite resin composition performed in the presence of a high-boiling component.
The present invention is described in detail below.

The method for producing an organic-inorganic composite resin composition of the present invention includes (1) a step of preparing a mixture containing inorganic fine particles, an organic resin and a solvent, and (2) a degassing step of degassing the solvent from the mixture. It is a waste.
The preparation step of (1) is not particularly limited as long as a mixture containing the above three components can be prepared, and it is sufficient that the three components are uniformly mixed, and an arbitrary addition (mixing) order and mixing method are used. Can do. Furthermore, the said mixture may contain the other component.
As the solvent, methanol, ethanol, isopropanol, butanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, acetonitrile, chloroform, toluene, xylene and the like are preferable. More preferred are isopropanol, butanol, methyl ethyl ketone, and toluene.
As said preparation process, it is preferable to prepare at 100 degrees C or less.
In the above preparation step, the ratio of the organic resin component, the inorganic fine particle component, and the solvent is (organic resin component + inorganic fine particle component) / (organic resin component + inorganic fine particle component + solvent) = 10 to 90% by mass. Is preferred. More preferably, it is 15-60 mass%.

The degassing step (2) is performed in the presence of a high boiling point component. By deaeration in the presence of a high-boiling component, the inorganic fine particle component can be made high in concentration, and an organic-inorganic composite resin composition having high transparency and high Abbe number can be obtained. Moreover, the thickening of a mixture can be suppressed effectively and continuous production becomes possible. The term “in the presence of a high-boiling component” only requires a period during which the high-boiling component coexists in the deaeration process, and the coexistence period is a partial period even during the entire period of the deaeration process. However, the entire period is preferable to prevent thickening.
The method for adding the high boiling point component is not particularly limited as long as the effects of the present invention are exhibited, and may be added all at once, may be added dropwise, or may be divided additions. Among these, batch addition is preferable. Moreover, it does not specifically limit as addition time (or addition start time) of a high boiling point component, For example, (1) It is after completion | finish of a preparation process, and before the start of a deaeration process, (2) It may be in the preparation step, or (3) in the deaeration step. Among these, (1) is preferable for preventing thickening. Thus, a production method in which the high-boiling point material is added before degassing the solvent after mixing the inorganic fine particle component (inorganic material) and the organic resin component (organic material) is also one of the preferred embodiments of the present invention. .

The amount of the high boiling point component added is 0.01 to 10% by mass with respect to 100% by mass of a mixture of the organic resin component, the inorganic fine particle component, the solvent before degassing, the high boiling point component and other components as required. It is preferable that More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%.
When the amount of the high-boiling component added is in the above range, the effect of suppressing gelation is sufficient, and the ratio of the high-boiling component remaining in the composition after completion of deaeration is a preferable range described later. It is preferable that the composition is easily obtained at a relatively low temperature in a short time. On the other hand, even if the addition amount of the high-boiling component exceeds 10% by mass, the gelling suppression effect is exhibited, but the ratio of the high-boiling component remaining in the composition after completion of deaeration is preferably the upper limit described later. A composition exceeding the value can be easily obtained, and properties such as mechanical strength of the cured product obtained by molding and curing the obtained composition may be insufficient. When the amount of the high-boiling component added exceeds 10% by mass, the heating temperature at the time of deaeration is increased in order to keep the ratio of the high-boiling component remaining in the composition after completion of deaeration to a preferable range described later. Or the deaeration time needs to be long, the viscosity of the resulting composition increases, and the molding processability may deteriorate, which is also not economically preferable.

Note that the high boiling point component remains in the composition at the end of the degassing step. The proportion is preferably 0.01 to 10% by mass in 100% by mass of the mixture at the end of the degassing step. More preferably, it is 0.01-5 mass%, More preferably, it is 0.5-3 mass%.
When the ratio of the high-boiling components remaining in the composition after completion of the degassing is in the above range, the homogeneity, transparency, and mechanical properties of a cured product obtained by molding and curing the obtained composition Since it is easy to obtain what is excellent in strength, it is preferable. On the other hand, when it exceeds 10 mass%, when the obtained composition is molded and cured, the mechanical strength of the obtained cured product may be insufficient.
The residual amount of the high-boiling component can be measured by gas chromatography (GC).
The measurement conditions are as follows.
(GC measurement conditions)
Column: “DB-17” manufactured by GL Sciences Inc.
Carrier gas: Helium flow rate: 1.44 mL / min

In the said deaeration process, if it is the conditions which can deaerate a solvent, it will not specifically limit, However, It is preferable that it is the conditions which suppress decomposition | disassembly of an organic resin component, hardening reaction, and aggregation of an inorganic fine particle component excessively. Specifically, the deaeration temperature is preferably 200 ° C. or less. More preferably, it is 100 degrees C or less, More preferably, it is 80 degrees C or less. The deaeration time is preferably 72 hours or less. More preferably, it is 24 hours or less, More preferably, it is 2 hours or less. Although the normal pressure may be sufficient as the pressure in a deaeration process, it is preferable that it is 200 torr or less, and it is more preferable that it is 100 torr or less.
In the degassing step, the end of the degassing step is when the solvent content is 5% by mass or less with respect to 100% by mass of the mixture at that time. The content of the solvent at the end of the degassing step is more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

The high boiling point component is preferably an alcohol having a boiling point of 100 ° C. or higher. If the alcohol has a boiling point of less than 100 ° C., the mixture may not be sufficiently thickened. As the high-boiling component, alcohol having a boiling point of 120 ° C. or higher is more preferable, alcohol having a boiling point of 150 ° C. or higher is more preferable, and alcohol having a boiling point of 190 ° C. or higher is particularly preferable.
Examples of the high-boiling point alcohol include primary, secondary, and tertiary alcohols, and primary and secondary alcohols are usually preferably used. Examples of the alcohol include aliphatic saturated alcohols, aliphatic cyclic alcohols, aliphatic unsaturated alcohols, glycols, glycol ether / glycol esters, aromatic alcohols, and heterocyclic alcohols. Of these, aliphatic saturated alcohols, aliphatic cyclic alcohols, aliphatic unsaturated alcohols, and glycols are preferable, and aliphatic saturated alcohols and aliphatic cyclic alcohols are more preferable.
As the aliphatic saturated alcohol, the alkyl group may be either linear or branched, and primary alcohol, secondary alcohol, and tertiary alcohol can be used. Secondary alcohols are preferred, and primary alcohols are particularly preferred. The number of carbon atoms is preferably 4 to 36, more preferably 4 to 18, especially 5 to 18, and most preferably 6 to 12. Moreover, as an aliphatic cyclic alcohol, a C6 or more thing is preferable, and a C6-C36 thing is especially preferable.

Examples of alcohols that can be suitably used in the present invention are shown below.
(1) Aliphatic saturated alcohols having 4 or more carbon atoms <aliphatic primary alcohols having 4 to 36 carbon atoms>
1-butanol, 1-amyl alcohol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-penta Carbon number 4 to 4 such as detanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol, 1-eicosanol, 1-docosanol, 1-tetracosanol, 1-hexacosanol, 1-octacosanol 36 linear aliphatic primary alcohols,
Branched form having 4 to 36 carbon atoms such as isobutyl alcohol, isoamyl alcohol, isohexanol, isooctanol, 2-ethylhexanol, isononanol, 2-methyloctanol, isodecanol, isooctadecanol, 2-decyl-1-tetradecanol Aliphatic primary alcohol,
Aliphatic saturated primary alcohol having 4 to 36 carbon atoms, such as
<C4-C36 aliphatic saturated secondary alcohol>
C4-C36 aliphatic saturated secondary alcohols such as 2-butanol (sec-butyl alcohol), 2-hexanol, 2-octanol;
Aliphatic saturated alcohols having 4 to 36 carbon atoms, such as

(2) Aliphatic cyclic alcohols Aliphatic cyclic alcohols having 6 to 36 carbon atoms such as cyclohexanol, 4-methylcyclohexanol, 4-ethylcyclohexanol, 4-t-butylcyclohexanol and the like.
(3) Aliphatic unsaturated alcohols Aliphatic unsaturated alcohols such as crotyl alcohol and propargyl alcohol.
(4) Glycols C2-C36 such as ethylene glycol, propylene glycol, butanediol, pentyl glycol, neopentyl glycol, hexanediol, octyl glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, thiodiglycol, spiroglycol, etc. Glycols.
(5) Glycol ethers / glycol esters Glycol ethers / glycol esters such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, and ethylene glycol monoacetate.
(6) Aromatic and heterocyclic alcohols Aromatic alcohols such as benzyl alcohol and cinnamyl alcohol.
Heterocyclic alcohols such as furfuryl alcohol.

In the production method of the present invention, the produced organic-inorganic composite resin composition contains an organic resin component and an inorganic fine particle component. As the organic resin component and the inorganic fine particle component, those described below are preferably used. it can. Moreover, all the description regarding an organic inorganic composite resin composition, such as another component and a hardening method, can be applied suitably to the manufacturing method of the said organic inorganic composite resin composition. The organic resin component is particularly preferably an alicyclic epoxy compound, and the method for producing an organic-inorganic composite resin composition in which the organic resin component is an alicyclic epoxy compound is also a preferred embodiment of the present invention. One.

The present invention is also an organic-inorganic composite resin composition obtained from the above production method. In the above production method, deaeration is performed in the presence of a high-boiling component, and the high-boiling component remains in the composition. Therefore, the organic-inorganic composite resin composition contains the high-boiling component. As described above, as a preferable form of the high boiling point component, as described above, the organic resin component (for example, alicyclic curable substance) containing high boiling point material (high boiling point alcohol) and the inorganic fine particle component (for example, high boiling point alcohol) , An inorganic dispersion) is preferable. Thus, alcohol having a boiling point of 100 ° C. or higher (preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 190 ° C. or higher), an organic resin component (eg, thermosetting material) A transparent resin composition containing an inorganic fine particle component (for example, an inorganic oxide) is also a preferred embodiment of the present invention.

The organic-inorganic composite resin composition is produced in the presence of a high-boiling component. According to such a production method, gelation is suppressed during production, thickening can be effectively suppressed, and continuous production becomes possible. Furthermore, the obtained organic-inorganic composite resin composition has a viscosity in a range suitable for workability and is excellent in handleability. The viscosity immediately after production of the organic-inorganic composite resin composition is preferably 0.01 to 10,000 Pa · s. If it is less than 0.01 Pa · s, there is a risk of leakage from the mold during molding, and if it exceeds 10,000 Pa · s, it is difficult to handle the material (the obtained organic-inorganic composite resin composition). There is a risk. More preferably, it is 1-1000 Pa.s, More preferably, it is 5-100 Pa.s.
The organic-inorganic composite resin composition also does not significantly increase the viscosity after production, effectively suppresses thickening, and exhibits excellent storage stability after production. The viscosity after the production of the organic-inorganic composite resin composition is preferably 140% or less after being stored at 4 ° C. for 1 day as compared to immediately after the production. When the viscosity after storage for 1 day at 4 ° C. exceeds 140%, the storage stability is not excellent and there is a possibility that it cannot be suitably used for various applications. The viscosity after storage for 1 day at 4 ° C. is more preferably 130% or less, and still more preferably 120% or less.
The viscosity after storage for 6 days at 4 ° C. is preferably 240% or less. If the viscosity after storage for 6 days at 4 ° C. exceeds 240%, the viscosity may vary during handling due to a change in viscosity, and stable molding may be difficult. More preferably, the viscosity after storage at 4 ° C. for 6 days is 200% or less, and more preferably 180% or less.
As described above, the organic-inorganic composite resin composition has (1) a form in which the viscosity immediately after production is 0.01 to 10,000 Pa · s, and (2) a viscosity after storage at 4 ° C. for 1 day as compared with that immediately after mixing. It is preferable that the form is 140% or less, and (3) the form is such that the viscosity after storage at 4 ° C. for 6 days is 240% or less as compared to immediately after mixing.
The viscosity of the organic-inorganic composite resin composition can be measured and evaluated by the following method.
<Viscosity measurement / evaluation method>
The viscosity of the organic-inorganic composite resin composition at 40 ° C. and rotation speed D = 1 / s is evaluated with an R / S rheometer (manufactured by Brookfield, USA).
When the viscosity is 20 Pa · s or more, an RC25-1 measuring jig is used, and when the viscosity is less than 20, an RC50-1 jig is used.
When the viscosity at the time point of D = 1 / s cannot be measured, the value of D = 5-100 / s is extrapolated and evaluated as the viscosity of the resin composition.

The organic resin component is not particularly limited as long as it exhibits the effects of the present invention, but it is preferable that the organic resin component is excellent in compatibility with the inorganic fine particle component and the component is uniformly dispersed in the organic resin.
The organic resin component 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 as organic resin components in terms of processability. Thermosetting resins are not widely used at present because of difficulties in processing compared to thermoplastic resins, but in the present invention, for example, by using a specific release agent described later, etc. A curable resin can also be used suitably. For example, in the case of continuous production using a mold, a thermosetting resin can be suitably used. There is also a method of dissolving a soluble resin in a solvent and applying it to remove the solvent to obtain a molded body, but if the solvent is included in continuous production such as a mold, the solvent remains inside the mold There is a possibility that bubbles are generated inside the molded body. On the other hand, in the case of thermosetting resin, a molded body can be obtained without being dissolved in a solvent when molding with a mold or the like. Therefore, in the thermosetting resin which does not substantially use a solvent, bubbles are not generated in the molded body, which is advantageous from this point. 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.

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. The form of the curable resin includes, for example, (1) a form comprising a liquid or solid curable resin, and (2) a liquid or solid curable resin and a curable compound having a lower molecular weight than the resin component or a solvent (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, a (meth) acrylate monomer, etc. The form to do can be mentioned.

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, an alicyclic compound, and the like can be suitably used. These compounds can be used alone or as a mixture of two or more. Among these, it is preferable that it is an alicyclic compound (alicyclic curable material) at the point with the high inhibitory effect of the gelatinization in the deaeration process by coexistence of a high boiling component. By using the alicyclic material, the Abbe number can be improved, the optical characteristics can be improved, and it can be suitably used for various applications.
Examples of the alicyclic compounds include alicyclic glycols obtained by hydrogenating aromatic skeletons such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, and naphthalenediol described below; 3,4-epoxycyclohexylmethyl-3 Cycloaliphatic epoxy resins such as 1,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate; cycloaliphatic epoxides such as triglycidyl isocyanurate-containing epoxy resins; alicyclic modification Neopentyl glycol (meth) acrylate (“R-629” or “R-644” manufactured by Nippon Kayaku Co., Ltd.); tetrahydrofurfuryl (meth) acrylate, morpholinoethyl (meth) acrylate, etc. / Or alicyclic ring with nitrogen atom Acrylate; Alicyclic monofunctional maleimides such as N-cyclohexylmaleimide; N, N′-methylenebismaleimide, N, N′-ethylenebismaleimide, N, N′-trimethylenebismaleimide, N, N′-hexa Preferred are alicyclic bismaleimides such as methylene bismaleimide, N, N′-dodecamethylene bismaleimide, 1,4-dimaleimidocyclohexane; hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and the like. Among these, more preferred are alicyclic epoxy compounds; hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, and the like, and still more preferred are alicyclic epoxy compounds. That is, a resin composition in which an epoxy is contained in an alicyclic curable material is preferable, and a resin composition in which the alicyclic curable material (curable material) essentially includes an alicyclic epoxy is more preferable. As described above, an organic-inorganic composite resin composition in which the organic resin component is an alicyclic epoxy compound is also a preferred embodiment of the present invention. The content of the alicyclic epoxy compound is not particularly limited as long as it is contained in the organic resin component, but it is preferably 40% by mass or more in the total organic components. More preferably, it is 60% by mass or more, still more preferably 80% by mass or more, and particularly preferably substantially all are alicyclic epoxy compounds.

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, which will be described later, may be appropriately selected and used. That's fine. A compound having at least one glycidyl group and / or epoxy group, a polyhydric phenol compound, and a compound having a polymerizable unsaturated bond that can be suitably used as the organic resin of the present invention will be described later.

In the organic resin component, the Abbe number is preferably 45 or more. An Abbe number of 45 or more means that “the average value of the Abbe number of all organic resin components is 45 or more”, and an organic resin component having an Abbe number of less than 45 is included. Good. By setting the Abbe number to 45 or more (the average value of Abbe numbers of all organic resin components is 45 or more), when the organic-inorganic composite resin composition is used for optical applications, the dispersion of light is reduced and the resolution is increased. The optical properties can be improved. If it is less than 45, for example, there is a risk of bleeding when used in a spectacle lens, and sufficient optical characteristics may not be exhibited, so that it may not be a material suitable for various optical applications. In the organic resin component, the Abbe number can be set to 45 or more by appropriately combining suitable forms described later. The Abbe number is preferably 47 or more, and more preferably 50 or more. The organic resin component is not particularly limited as long as it has an Abbe number of 45 or more (the average value of the Abbe numbers of all organic resin components is 45 or more). For example, an organic resin having an Abbe number of 45 or more is a total organic component. It is preferable that 40 mass% or more is contained. More preferably, the ratio of the organic resin having an Abbe number of 45 or more is 60% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight (substantially all of which have an Abbe number of 45 or more. Stuff).

The organic resin component preferably contains an organic resin having a molecular weight of 700 or more. When the organic resin component contains an organic resin having such a molecular weight, when the organic-inorganic composite resin composition is cured, it can have a sense of unity, and the strength at the time of peeling can be improved and cracked. And a suitable material hardness can be obtained. The molecular weight of the organic resin contained as an essential component in the organic resin component is preferably 700 to 10,000. If the molecular weight exceeds 10,000, the organic-inorganic composite resin composition may not have sufficient transparency.
Among the organic resin components, those that require an organic resin having a molecular weight of 700 or more are suitable, but a component having a molecular weight of 700 or more (organic resin) may be contained in the organic resin component by 30% by mass or more. preferable. Further, from the viewpoint of ease of molding, it is preferable that the component of 700 or more (specifically, 700 to 10,000) is 90% by mass or less. More preferably, it is 35-80 mass% as content of the organic resin whose molecular weight is 700 or more, More preferably, it is 40-70 mass%. Thus, a resin composition comprising 30 to 90% by mass of an organic resin component having a molecular weight of 700 or more is also a preferred embodiment of the present invention. In addition, as a measuring method of the molecular weight of organic resin, it is as follows.

<Measurement method of molecular weight>
The molecular weight of the cyclic moiety and the long-chain hydrocarbon group-containing polymer compound can be measured, for example, using gel permeation chromatography (trade name “HLC-8220GPC” manufactured by Tosoh Corporation) under the following conditions.
(Molecular weight measurement conditions)
Column: “TSK-GEL SUPER HZM-N 6.0 * 150” x 4 manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Flow rate: 0.6 mL / min Temperature: 40 ° C.
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

The organic-inorganic composite resin composition contains inorganic fine particle components. By containing inorganic fine particles, the Abbe number of the organic-inorganic composite resin composition can be increased, and the coefficient of thermal expansion can be reduced. In addition, by adjusting the refractive index of the inorganic substance and the resin, it is possible to control the appearance of the resin composition and its cured product and to develop transparency, and it is particularly useful as a material in electrical / electronic component materials and optical applications. Can be. Furthermore, a mold release effect can be exhibited by including an inorganic fine particle component. Specifically, when a thermosetting resin (particularly an epoxy material) is included as an organic resin component, for example, the organic resin component has an adhesive effect, and such an organic-inorganic composite resin composition is cured. There is a risk of bonding to the mold. By adding an appropriate amount of the inorganic fine particle component, a mold release effect is observed, and the inorganic fine particle component is easily peeled off from the mold.
The inorganic fine particle is not particularly limited as long as it is a fine particle composed of an inorganic compound such as a metal or a metal compound, but is preferably a metal oxide, and is preferably silica. Specifically, organosilica sol MEK-ST manufactured by Nissan Chemical Industries, Ltd. is preferable. Details of the inorganic fine particles will be described later. Thus, a resin composition comprising a curable substance having a molecular weight of 600 or more and silica particles is also a preferred embodiment of the present invention.

The inorganic fine particle component preferably contains inorganic fine particles (hereinafter also simply referred to as “wet inorganic fine particles”) obtained by a wet method.
When the inorganic fine particles are fine particles containing silica, they are obtained by performing silica precipitation by neutralization or decomposition reaction with an acid or alkali metal salt of a sodium silicate aqueous solution. The inorganic fine particle component is not particularly limited as long as wet inorganic fine particles are essential, and may contain, for example, inorganic fine particles produced by a dry method. The content of wet inorganic fine particles in 100% by mass of the inorganic fine particle component is preferably 10 to 100% by mass. More preferably, it is 50-100 mass%, More preferably, it is 80-100 mass%. It is particularly preferred that substantially all inorganic fine particle components are wet inorganic fine particles. Thus, the form in which the inorganic fine particles are wet materials is also one of the preferred forms of the present invention. Moreover, as an organic resin component contained in an organic inorganic composite resin composition, it is suitable that it is an alicyclic epoxy compound. That is, an organic-inorganic composite resin composition comprising an organic resin component and an inorganic fine particle component, wherein the inorganic fine particle component essentially comprises inorganic fine particles obtained by a wet method, An organic-inorganic composite resin composition in which the resin component is essentially an alicyclic epoxy compound is also one preferred form of the present invention.
The inorganic fine particle component can be suitably blended in the resin component using either the external addition method or the internal precipitation method. Among these, the external addition method is more preferable because there is no fear of reaction with the resin. The inorganic fine particle component thus blended is preferably dispersed with a primary particle size in the organic-inorganic composite resin composition. That is, the inorganic fine particles are preferably in the form of a dispersion (inorganic fine particle dispersion). More preferably, the inorganic fine particles are wet silica dispersions. When the inorganic fine particle component is dispersed with a primary particle size, the organic-inorganic composite resin composition is not cloudy, and the organic-inorganic composite resin composition can be suitably used for various applications. If it becomes the same size as visible light due to secondary particles, etc., the organic-inorganic composite resin composition may become turbid and the Abbe number may be reduced.

In the organic-inorganic composite resin composition of the present invention, a cured product having excellent transparency can be provided. However, when the transparency is improved, the performance as an optical member is improved, and the optical application and the optical device application are performed. The resin composition can be suitably used for various applications such as display device applications. In order to improve transparency, 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, it is 100 nm or less, More preferably, it is 50 nm or less, Most preferably, it is 20 nm or less.
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 using such a particle size distribution, the cured product of the resin composition of the present invention can exhibit various excellent optical properties such as Rayleigh scattering in the visible light region being sufficiently suppressed and excellent transparency. it can.
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, when the thickness exceeds 400 nm, the visible light is scattered by the inorganic fine particles due to the large inorganic fine 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 shape of particles, for example, a polymer-like material may be included. Such a polymer-like material is highly transparent if it is small, and even if secondary particles are formed, it is more visible than visible light. Since the particles are small, the organic-inorganic composite resin composition becomes transparent. As the organic-inorganic composite resin composition (resin composition) containing such inorganic fine particles, (1) a form comprising silica and an epoxy material having a particle size of 100 nm or less, and (2) curing having a molecular weight of 600 or more A form comprising a functional material and inorganic fine particles having a particle size of 100 nm or less is preferable.
The Rayleigh scattering in the visible light region needs to be considered as light scattering by particles shorter than the wavelength of light when the resin composition is used for optical applications. The light scattering characteristic of Rayleigh scattering is expressed by the following equation (1).

k _s : scattering coefficient, n: number of particles, d: particle diameter, m: reflection coefficient, λ: a parameter relating to the wavelength of the wavelength scattering coefficient and the size of the scattering particle, the following equation (2) is exemplified.

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 transmittance, has excellent transparency, and has other excellent performance. There is a demand for a composition.

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 density nonuniformity 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 are 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 inorganic fine particle component is preferably inorganic fine particles having a pH of 4 to 11 at 25 ° C. when dispersed at 15% by mass in the solution. When forming a resin such as the organic-inorganic composite resin composition of the present invention, the solvent is degassed. Usually, however, the viscosity of the solvent increases and gelation may occur, resulting in poor productivity. When inorganic fine particles having the above pH are used, the viscosity is high when degassing the solvent because the pH is high, and gelation does not occur. In particular, when an alicyclic epoxy compound is used as the organic resin component, gelation is suppressed without ring opening of the ring structure portion within the above pH range. In addition, the temporal stability of the resin is improved. Furthermore, when the resin composition is cured, since the solvent does not volatilize at the time of curing, continuous production is possible and it can be suitably used for various applications. The pH range is more preferably 4-7. By setting it as such a range, coloring of an organic inorganic composite resin composition can be suppressed more fully.

The pH of the inorganic fine particles is a value measured by using a HORIBA pH meter at 25 ° C., adjusting the inorganic fine particles to 15% by mass, the organic solvent to 35% by mass, and water to 50% by mass. . Since the pH value varies depending on the concentration of inorganic fine particles, the amount of organic solvent, the amount of water, and the measurement temperature, it is preferable to adjust the sample with the above composition and measure the pH value.
As the organic solvent, methanol, ethanol, isopropanol (IPA), butanol, methyl ethyl ketone (MEK), N, N-dimethylacetamide (DMAC), acetone, acetonitrile, ethylene glycol, methyl isobutyl ketone (MIBK) and the like are preferable. More preferred are MEK, methanol, ethanol, isopropanol (IPA) and butanol, and still more preferred is MEK.
By using such an organic solvent in the above range, the dispersibility of the inorganic fine particles is improved, and the pH of the inorganic fine particles can be measured.
As said water, it is preferable to use neutral ion-exchange water of pH 7. By mixing water at the above ratio, the pH of the inorganic fine particles can be accurately measured.
More preferably, it is 4-9 as pH of the said inorganic fine particle, More preferably, it is 4-6.

The organic-inorganic composite resin composition of the present invention includes the organic resin component and the inorganic fine particle component, but the organic resin component is 40 to 99% by mass with respect to a total of 100% by mass of the organic resin component and the inorganic fine particle component. The inorganic fine particle component is preferably contained in an amount of 1 to 60% by mass. By setting it as such content, it can be set as an organic inorganic composite resin composition with high transparency and an Abbe number. In particular, when a thermosetting resin is used as the organic resin component, it is possible to overcome the heat resistance that cannot be achieved by a thermoplastic resin, and it is possible to perform complicated and inexpensive processing that cannot be achieved by glass. More preferably, the content is 60 to 90% by mass of the organic resin component and 10 to 40% by mass of the inorganic fine particle component, and more preferably 70 to 90% by mass of the organic resin component and 10 to 10% of the inorganic fine particle component. 30% by mass. Particularly preferably, the inorganic fine particle component is 15 to 30.
In the organic-inorganic composite resin composition of the present invention, an inorganic material having a pH of 4 to 9 (preferably 4 to 6) at 25 ° C. when dispersed as 15% by mass in a solution and an average particle size of less than 100 nm. A form that is a resin composition comprising fine particles and an alicyclic curable material is preferred. In such a form, the Abbe's number can be improved by using an alicyclic material, and since the solvent does not volatilize at the time of curing, continuous production is possible, and since inorganic fine particles can be dispersed, transparency and heat resistance High optical resin can be produced. Since the pH is high, there is an advantage that the degree of thickening is low in the process of degassing the solvent when forming the resin, the possibility of causing gelation is small, and the aging stability of the resin is improved.
In the organic-inorganic composite resin composition of the present invention, as a preferred form, the organic resin component contains an organic resin having an Abbe number of 45 or more in the total organic component of 40% or more (preferably 60 or 80% or more), Silicon oxide) in an amount of 10 to 40% (preferably 15 to 30), more preferably 40% or more (80% or more) of an alicyclic material and 10% or more of wet silica. More preferably, the alicyclic epoxy is 40% (80%) or more and the wet silica dispersion is 10% or more. Thus, the organic-inorganic composite resin produced using the organic-inorganic composite resin composition (transparent resin composition) comprising the alicyclic cured product and the weakly acidic wet silica dispersion, and the inorganic fine particles in the pH range described above. A method for producing the composition is also one of the preferred embodiments of the present invention.

In the organic-inorganic composite resin composition, the ratio of the compound having an unsaturated bond is preferably 10% by mass or less. Examples of the compound having an unsaturated bond include an aromatic ring (for example, a phenyl group) in an organic resin component, an alkenyl group having a double bond, and the like. The compound having an unsaturated bond is included in any of the organic resin component, inorganic fine particles, and other components added as necessary. Since the compound having such an unsaturated bond generally lowers the Abbe number, if the content of the unsaturated bond exceeds 10% by mass, the Abbe number of the organic-inorganic composite resin composition is not sufficiently large. However, for example, when used as a lens, the blur of light increases, and there is a possibility that it cannot be suitably used for various applications.
More preferably, the proportion of the compound having an unsaturated bond is 8% by mass or less in 100% by mass of the organic-inorganic composite resin composition (organic resin component, inorganic fine particles and other components as required), and more preferably. 6 mass% or less. Particularly preferably, it is not substantially contained. That is, a form that is not included in any of the organic resin component, the organic resin component, the inorganic fine particles, and other components added as necessary is preferable.
The compound having such an unsaturated bond preferably has a content in the above range even in a cured product obtained by curing the organic-inorganic composite resin composition. As described above, a resin composition and a cured product having a double bond property (aromatic ring or the like) content of 10% or less in the resin are also a preferred embodiment of the present invention.

It is preferable that the organic-inorganic composite resin composition also includes a component having flexibility (flexible component). By including a flexible component, an organic-inorganic composite resin composition having a sense of unity can be obtained. As the flexible component, both (1) a form that is a flexible component made of a compound different from the organic resin component, and (2) a form in which one of the organic resin components is a flexible component are suitable. Can be applied. Specifically, a compound having an oxyalkylene skeleton represented by-[-(CH ₂ ) n-O-] m- (n is 2 or more, m is an integer of 1 or more. Preferably, n is 2 -12, m is an integer of 1 to 1000. More preferably, n is 3 to 6 and m is an integer of 1 to 20); a polymer epoxy resin (for example, hydrogenated bisphenol (Japan Epoxy Resin Co., Ltd.) YL-7170, epoxy equivalent 1000, solid hydrogenated epoxy resin); liquid rubber such as liquid nitrile rubber, polymer rubber such as polybutadiene, fine particle rubber having a particle size of 100 nm or less, etc. Among these, more preferable. It is a compound containing a curable functional group at the terminal, side sheath, main chain skeleton, etc. Thus, the flexible component is an organic-inorganic composite resin composition containing a curable functional group. Of the present invention The above-mentioned “curable functional group” is “a functional group that cures with heat or light, such as an epoxy group or a glycidyl group (a group that causes the resin composition to undergo a curing reaction)”. Say.
As the flexible component, a compound containing a curable functional group can be suitably applied. Among the compounds containing a curable functional group, a compound containing an epoxy group is particularly preferable.
The content of the flexible component is 40 to 99% by mass of the organic resin component and 1 to 60% by mass of the inorganic fine particle component in a total of 100% by mass of the organic resin component, the inorganic fine particle component and the flexible component. It is preferable to contain 0.01 to 10% by mass of a flexible component. That is, a resin composition having a flexible component of 10% or less is preferable. More preferably, it is 0.1-5 mass% as content of a flexible component, More preferably, it is 0.5-1 mass%.
As described above, the organic-inorganic composite resin composition of the present invention includes an organic resin component and inorganic fine particles, and preferably includes a flexible component. That is, (1) a form composed of an alicyclic curable substance and an inorganic dispersion containing a flexible material (preferably epoxy), (2) a flexible material (flexible component) and curability A form comprising a material and inorganic fine particles having a particle size of 100 nm or less is also a preferred form of the present invention.

The organic-inorganic composite resin composition of the present invention preferably has a bending resistance of 60 MPa or more when cured at 120 ° C. for 2 minutes. As described later, the organic-inorganic composite resin composition is preferably cured within 5 minutes using a mold, and then the cured product is taken out of the mold and post-cured (baked). In this case, the bending strength of the cured product refers to the strength of the cured product obtained after curing for 2 minutes at 120 ° C. using a mold before post-cure (baking).
Thus, an organic-inorganic composite resin composition containing an inorganic fine particle component and an organic resin component, the organic-inorganic composite resin composition containing a flexible component and cured at 120 ° C. for 2 minutes An organic-inorganic composite resin composition in which the bending strength of the cured product is 60 MPa or more is also a preferred embodiment of the present invention.
The organic-inorganic composite resin composition preferably has a viscosity of 10,000 Pa · s or less. More preferably, it is 1000 Pa.s or less, More preferably, it is 100 Pa.s or less.

The organic-inorganic composite resin composition is also an organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component, and the organic-inorganic composite resin composition comprises two or more organic resins and inorganic fine particles. Is preferably prepared in a solvent of 5% by mass or less. By preparing in such a form, it becomes possible to produce a thermosetting resin that can be continuously produced, has a sense of unity, has high strength, and has high transparency and heat resistance, and has a transmittance of 80% or more at 500 nm. A thermosetting material useful as a lens material (optical material) can be provided.
The amount of the solvent is 5% by mass or less of the solvent in 100% by mass of the mixture (a mixture of two or more organic resins, inorganic fine particles, and a solvent (and other components as necessary)). If it exceeds 5 mass%, foaming or strength reduction of the molded product may occur. More preferably, it is 3 mass% or less as a solvent amount, More preferably, it is 1 mass% or less. From the viewpoint of suppressing an increase in the viscosity of the resin composition as one of the preferred embodiments of the present invention, it is preferable to leave 0.05 to 5% by mass of the solvent in 100% by mass of the mixture (resin composition). More preferably, it is 0.1-3 mass% as a residual amount of a solvent, More preferably, it is 0.5-2 mass%. In the present invention, for example, by simultaneously evaporating a high boiling point solvent or the like, the solvent can be brought to the above range in a short period of time, and an organic-inorganic composite resin composition can be suitably obtained. As the solvent, 2-ethyl-1-hexanol, dodecanol and the like are preferable.

The two or more organic resins are preferably an organic-inorganic composite resin composition containing two or more organic resins having a molecular weight of 700 or more and less than 700. Essentially having a molecular weight of 700 or more (high molecular weight organic resin, polymer material) and less than 700 (low molecular weight organic resin), the effect of reducing the viscosity during production and improving the mechanical strength of the product is achieved. Will be obtained.

The organic-inorganic composite resin composition preferably contains a polymer material and a low-molecular material, but as a preparation method thereof, a low-molecular material and inorganic fine particles (and other components as required) And a method of adding a polymer material after distilling off the solvent (solvent), and a mixture (low molecular material, inorganic fine particles, polymer material and solvent (and other components as required)) The mixture is preferably prepared so that the solvent is 5% by mass or less in 100% by mass. During the formation of the resin (organic-inorganic composite resin composition), the solvent is distilled off. Usually, the polymer material forms a chemical bond or a physical bond with the inorganic fine particles by heating at this time. Although the viscosity of a composite resin composition will rise, a suitable resin composition can be obtained by mixing as mentioned above, without the viscosity of an organic inorganic composite resin composition rising. Further, the familiarity of the high molecular weight material with the resin composition can be improved. Thus, a method for producing an organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component, the production method comprising mixing two or more organic resins and inorganic fine particles, and finally A method for producing an organic-inorganic composite resin composition including a step of preparing with 5% by mass or less of a solvent is also one of preferred embodiments of the present invention. More preferable as such a production method is a form in which the two or more kinds of organic resins essentially have a molecular weight of 700 or more (polymer material) and less than 700 (low molecular material). . More preferably, the mixing step is a mode in which at least a part of the solvent is removed from the mixture containing the low molecular material, the inorganic fine particles, and the solvent, and then the polymer material is added.

The organic resin having a molecular weight of 700 or more, the molecular weight measurement method, and the inorganic fine particle component contained in the organic-inorganic composite resin composition are preferably the same as described above.
The ratio of those having a molecular weight of 700 or more and less than 700 is preferably [700 or more / (whole resin composition)] = 30 to 90. More preferably, it is 35-80, More preferably, it is 40-70. Specific examples of the organic resin will be described later.
The two or more organic resins are preferably two or more epoxy compounds. Among these, it is preferable to include an alicyclic epoxy. In addition, as described above, the inorganic fine particle component is preferably silica. Thus, a resin composition in which two or more epoxies are mixed with silica in a solvent of 5% or less is also a preferred embodiment of the present invention.

Hereinafter, a compound having at least one epoxy and / or glycidyl group, a polyhydric phenol compound, and a compound having a polymerizable unsaturated bond that can be suitably used as the organic resin of the present invention will be described. Since the organic resin component preferably has a small amount of unsaturated bonds, those having an unsaturated bond such as an aromatic ring of a polyhydric phenol compound have an unsaturated bond of 10% by mass or less of the organic-inorganic composite resin composition. It is preferable to be included.
The organic resin preferably has at least one epoxy and / or glycidyl group. By having at least one epoxy and / or glycidyl group, it has heat resistance comparable to that of inorganic glass while having workability equivalent to that of a conventional thermosetting plastic material, and has excellent molding and workability. The characteristic can be exhibited. Thus, the organic-inorganic composite 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.

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 site that combines 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, and 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 carry out 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 carbonyl groups such as aldehydes and ketones, (4) Compounds having two or more of these specific active groups or active sites, (5) Amino groups, hydroxyalkylamino groups and di (hydroxyalkyl) amino groups 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 (4) above, as the compound having a carbonyl group and an unsaturated bond, isopropenyl benzaldehyde, isopropenyl acetophenone, citronellal, citral, perillaldehyde, 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 in (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.

As the reaction raw material, 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. And a compound (hereinafter also referred to as a raw material B2) to be an essential component. As a reaction sequence of the reaction raw materials in this case, the raw material A, the raw material B1, and the raw material B2 are mixed in advance before starting the reaction, and the raw material B2 is reacted 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 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. . 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.

It is preferable that the polyhydric phenol compound is 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 preferable. 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.

When the raw material B2 is reacted 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. The 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. As described above, 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. The reaction time depends on the raw material used, the type and amount of the catalyst, the reaction temperature, etc., but 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 to make it disappear, and it is preferable to set it as 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. At this time, since unreacted phenols may also be distilled off, it is preferably carried 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 mole of trimethylolpropane or glycerin 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-decamethylene dicarboxylic 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 diol component, polybasic acid, 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; one or more burettes of isocyanate monomers, or polyisocyanates such as isocyanurates obtained by trimerizing the above diisocyanate compounds; polyisocyanates obtained by urethanation 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 Polyhydric hydroxyl group compounds such as ruether (tetrahydrofuran modified from hexaglycerin); mono- and polyhydric hydroxyl group-containing compounds of terminal ether groups of the above polyvalent hydroxyl group-containing compounds; the above polyvalent 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 thereof; 3,4-epoxycyclohexylmethyl, bis- (3,4-epoxycyclohexyl) ) Cycloaliphatic epoxy resins such as adipate; Cycloaliphatic 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 polyhydric 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) acrylates, bisphenol fluorenedioxyhydroxy (meth) acrylates, 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 a (meth) acryloyl group, 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.

Of the monovinyl ether, divinyl ether, and polyvinyl ether, the compound having a urethane bond is a compound having at least one isocyanate group in one molecule and having two or more isocyanate groups in one molecule. Adduct bodies obtained by urethanation reaction between the alcohol and various alcohols may be used.

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-decamethylenedicarboxylic 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.

As the polyether polyol, known and conventional ones can be used, 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 suitable.

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; 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 Suitable are acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, cyclohexanedicarboxylic acid, and acid anhydrides thereof. 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-dimaleimide cyclohexane; 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-vinylpyrrolidone, N-vinylcaprolactam, etc. N-vinyl amides; vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether; maleimides such as chlorophenylmaleimide, cyclohexylmaleimide and laurylmaleimide; ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, Dipropylene glycol diacrylate, neopentyl glycol hydroxypivalate Acrylate, diacrylate of ethylene oxide adduct of bisphenol A, diacrylate of propylene oxide adduct of bisphenol A, tricyclodecane dimethylol diacrylate, acrylic acid adduct of 2,2-di (glycidyloxyphenyl) propane, trimethylol Propane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, triacrylate of tris (2-hydroxyethyl) isocyanurate, diacrylate of tris (2-hydroxyethyl) isocyanurate, tris (hydroxypropyl) ) Isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropanthate Acrylate, and the like.

Below, the inorganic fine particle which can be used suitably for the resin composition of this invention is demonstrated. In addition, by combining suitably the preferable form of the inorganic microparticles | fine-particles described in this specification, as mentioned above, 25 degreeC of the solution which is 15 mass% of inorganic microparticles, 35 mass% of organic solvents, and 50 mass% of water. In the preferred embodiment of the present invention, such as those having a pH of 4 to 11 at.
The inorganic fine particles are not particularly limited as long as they are fine particles composed of inorganic compounds such as metals and metal compounds. Inorganic components in inorganic fine particles include metal oxides, hydroxides, (acid) nitrides, (acid) sulfides, carbides, halides, sulfates, nitrates, (basic) carbonates, (basic) Examples include acetate and the like. 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) , Ni _(1-δ) O or oxygen element has a stoichiometric composition. On the other hand, a metal oxide having a non-stoichiometric composition that is excessive or deficient can also be preferably used. 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; Polyalkylene glycol 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 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 of Sb, Bi, etc. 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, optical property, 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 elliptic spherical shape, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a column shape, a rod shape, a cylindrical shape, a flake shape, and a (hexagonal) plate shape.

As the inorganic fine particles, inorganic fine particles obtained by a liquid phase synthesis method, particularly metal oxide fine particles obtained by a liquid phase synthesis 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 synthesis method. For example, when the inorganic fine particles contain 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 or not they share oxygen atoms. 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 oils, wax oils, silicone oils and the like.
The plasticizer dispersion is one that is dispersed in a plasticizer and includes the above-mentioned 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 plasticizers such as tributyl phosphate and 2-ethylhexyl phosphate; phthalate esters such as dimethyl phthalate, dibutyl phthalate and octyldecyl phthalate Plasticizers; Aliphatic-basic ester plasticizers such as butyl oleate and glycerin monooleate; Aliphatic dibasic ester plasticizers such as dibutyl adipate and di-2-ethylhexyl sebacate; Diethylene glycol Examples of conventionally known plasticizers such as dihydric 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. For example, (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 that is fine is obtained, and the blending effect of 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.) are 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 diameter 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 ( nm);
Ds = 6000 / (ρ × S)
(However, ρ: true specific gravity of metal oxide-based particles, S: specific surface area of metal oxide-based particles (m ² / g) 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 to a 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 diameter and the dispersed particle diameter 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.
Such a range is preferably the same range in the resin composition.

Among the inorganic fine particles used in the above external addition method, the production method thereof is obtained by a liquid phase synthesis method that can ensure transparency among known liquid phase synthesis methods, gas phase synthesis methods, and solid phase synthesis methods. The obtained fine particles are referred to as wet particles (wet inorganic fine particles) in the present application. In the organic-inorganic composite resin composition of the present invention, wet inorganic fine particles are essential, and for example, inorganic fine particles obtained by a vapor phase synthesis method or a solid phase synthesis method may be included. Thus, a form in which all inorganic fine particle components are wet inorganic fine particles is preferable.
The wet inorganic fine particles are suitable as a raw material for the composition of the present application without being subjected to a drying step, and can be provided as a liquid containing inorganic fine particles.
That is, the inorganic fine particles of the present invention may be those synthesized by a liquid phase synthesis method, and among them, those synthesized by a liquid phase synthesis method and not subjected to a drying step are preferable.
It does not pass through the process of making it dry powder until it is used as a raw material of the composite resin composition of this application (organic-inorganic composite resin composition) from the synthesis | combination (production | generation) (liquid phase synthesis method) of fine particles. Represents a so-called all-wet process. For example, consistent liquid phase process, liquid process. Moreover, the process of reducing a wet cake state is included in the range of a wet process. Naturally, one of the organic resin components which are constituent components of the composite resin composition of the present application includes those dispersed from the fine particle synthesis reaction solution without undergoing a drying process, and included in the wet inorganic fine particles. The liquid material includes a wet cake, a solvent dispersion, a liquid resin dispersion, and the like.
As the vapor phase synthesis method and solid phase synthesis method of metal oxide fine particles that can be suitably used among the inorganic fine particles, the following are suitable.
[Gas phase synthesis method]
It is represented by a method in which an inorganic or organic metal salt is vaporized and usually thermally decomposed at high temperature (oxidation) in the air. 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 synthesis method]
There is a method in which a metal hydroxide or carbonate is heated to decompose to obtain an oxide. An example is a method in which an intermediate of a metal oxide (hydrate) is obtained by a liquid phase synthesis 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.

Next, a liquid phase synthesis method of wet metal oxide fine particles that are useful among the wet inorganic fine particles that are essential components of the present invention will be described.
(Liquid phase synthesis method)
A precipitation method such as an acid-alkali decomposition method, an organic metal compound hydrolysis / condensation method, a metal halide hydrolysis / condensation method, or a hydrothermal reaction may 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 the raw material for metal oxide fine particles of the present invention.
Among 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 the powder in a 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 from the obtained reaction liquid into a desired form (powder, dispersion) without going through the washing step.
After obtaining a reaction solution of metal oxide (hydrate) fine particles by the liquid phase synthesis method, a consistent liquid phase process is prepared that is mixed with the resin component without passing through the drying step. Aggregation can be avoided, which is preferable. Specifically, the reaction solution is concentrated as necessary, and the solvent component in the reaction solution is removed and replaced with a desired dispersion medium (resin component, monomer, solvent, etc.) at the same time, such as heating solvent replacement. A process is preferred.

Among the above-mentioned liquid phase synthesis methods of inorganic fine particles, an organometallic compound hydrolysis / condensation method 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 1,3-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 group such as benzyl group; aralkyl group such as benzyl group; epoxy group-containing organic group such as 2-glycidoxyethyl group, 3-glycidoxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl group; 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, wet process silicon-based oxide fine particles that are particularly useful among the metal 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 containing SiO ₂ as a main component, 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 above-described decomposition and precipitation methods using an acid alkali) or a water glass aqueous solution in 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 subjected to hydrolysis and condensation reaction 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 silica particle reaction liquid 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 an industrially available silicon 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 includes at least one structure selected from the group consisting of the resin component and a solvent, a plasticizer, or a lubricant, an ether bond, an ester bond, and a nitrogen atom. It is preferred to use compounds having

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 set as appropriate depending on the inorganic fine particles to be prepared, and the reaction pressure may be increased as normal pressure. 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, and subsequently 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, not only the raw material composition but also the particle size of the hydrolyzed and condensed product is non-uniform, the refractive index distribution becomes large, and the resin composition tends to cause Rayleigh scattering during visible light transmission.

As the above production method, among two or more kinds of metal alkoxide and / or carboxylic acid metal salt, 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 the number 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 form 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). Zirconium chelate compounds such as acetate) zirconium, tetrakis (acetylacetonato) zirconium, 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 (ethyl acetoacetate) 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.

Other explanations of the organic-inorganic composite resin composition are 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. If it exceeds 50% by mass, the viscosity may be increased and the composition may not be mixed uniformly.

In addition to the resin and inorganic fine particles described above, the resin composition of the present invention includes a release agent, a curing agent, a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, a pigment, a dye, and an antioxidant. Adhesives such as additives, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers, organic fillers, coupling agents, etc. Improving agent, heat stabilizer, antibacterial / antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, An emulsifier, slip / scratch prevention agent, anti-skinning agent, desiccant, antifouling agent, antistatic agent, conductive agent (electrostatic aid) and the like may also be contained.

As the release agent (or additive), a normal release agent can be suitably used, but it is selected from the group consisting of alcohols having 8 to 36 carbon atoms, carboxylic acids, carboxylic acid esters, and carboxylates. Preferably, the compound is at least one compound. By containing such a mold release agent, when cured using a mold, the mold can be easily peeled off, the appearance is controlled without damaging the surface of the cured product, and transparency is improved. Since it can be expressed, 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, and 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, seryl 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. Octanoic acid, lauric acid, 2-ethylhexanoic acid and stearic acid are preferred.

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) In the 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. Of these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.
Among 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 organic inorganic composite resin composition, the organic inorganic composite resin composition containing a stearic acid type compound is also one of the preferable forms of this invention.
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 curing agent is preferably a heat latent curing agent. The heat-latent curing agent is also called a heat-latent cation generator or a cationic polymerization initiator, and exhibits a substantial function as a curing agent when a curing temperature is reached in the resin composition. 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 resin composition obtained is drastically improved, the excellent optical properties of the resin composition are maintained even in harsh usage environments, and 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 thermal 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, 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 a net charge of a halide complex ion. N is the number of halogen elements in the halide complex ion It is preferable that it is what is represented by this.

The heat-latent cation generator is not particularly limited as long as it has the above-mentioned structure, but generally these 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 Examples include arsenate (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-mentioned heat latent cation generator include diazonium salt types: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemicals)
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 organic-inorganic composite resin composition of the present invention is preferably one that is released with a strength of 40 kgf / cm ² or less. In the above-mentioned organic-inorganic composite resin composition, releasing with a strength of 40 kgf / cm ² or less means that it can be easily peeled in the technical field and can be manufactured with high productivity in the manufacturing process, and continuous production of the resin composition can be achieved. It means that it is evaluated as possible. 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, as a necessary condition during continuous production of a transparent material, a certain degree of material hardness (releasing at 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 having 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 a 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 .

As the curing method of the organic-inorganic composite resin composition of the present invention, various methods such as thermosetting and photocuring can be suitably used. A method is preferably used in which the materials are mixed to form one liquid, the liquid mixture is applied to a mold that matches the shape of the cured product and cured, and then the cured product is removed from the mold. In such a method, it is preferable that the viscosity of the curable organic-inorganic composite 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 organic-inorganic composite 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, as for the said organic inorganic composite resin composition, the viscosity increase rate of the mixture by 1 liquid as a curable organic inorganic composite resin composition will be 200% or less compared with immediately after mixing after storage at 25 degreeC for 3 days. An organic-inorganic composite resin composition is also one preferred form of the present invention.

As a method for producing a cured product by curing the organic-inorganic composite resin composition, a commonly used method can be suitably used, and it is appropriately selected according to the type of the resin composition as described later. However, it is preferable that the organic-inorganic composite resin composition is cured within 5 minutes to produce a cured product. Specifically, the organic-inorganic composite 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. It is preferable to cure within minutes. By performing curing using a mold in a short time, it is possible to obtain a method with excellent economic efficiency. Thus, a method for producing a cured product by curing the organic-inorganic composite resin composition, wherein the production method is an organic method for producing a cured product by curing the organic-inorganic composite resin composition within 5 minutes. A method for curing the inorganic composite resin composition is also one of the preferred embodiments of the present invention.
When the said hardening time (hardening time using a metal mold | die) exceeds 5 minutes, productivity will worsen. 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 the force of 1 kgf / cm < ² > or more is 10% or less of hardening intensity (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 organic-inorganic composite resin composition of the present invention, it is preferable that the cured product is taken out of the mold and post-cured (baked) after being cured within 5 minutes using the mold as described above. 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, the curing method of the organic-inorganic composite resin composition of the present invention will be further 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, the above-described thermal latent cation generator is preferably used. 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 two 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.

As a resin component of the resin composition of this invention, when a polyhydric phenol compound is contained, it can be set as hardened | cured material by thermosetting using a hardening | 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, bisphenol S and epihalohydrin; phenol, cresol , Phenols such as xylenol, resorcin, catechol, bisphenol A, bisphenol F and formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, dicyclopentadiene, terpe , A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by condensation reaction of a polyphenol obtained by the condensation reaction of coumarin, paraxylylene dimethyl ether, dichloroparaxylene and the like with an 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 glycol 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 where the resin component of the resin composition of the present invention contains a compound having a polymerizable unsaturated bond 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 irradiating with ultraviolet light or visible light 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.

As a light generation source of ultraviolet or visible light having a wavelength of 180 to 500 nm, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, mercury-xenon lamp, excimer lamp, 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 depending on 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 preferable.

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 (Asahi Denka); Irgacure 261 (Ciba-Geigy); UVR-6974, UVR-6990 (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. Further, as the onium salt, it is preferable to use at least one of a triarylsulfonium salt and a diaryliodonium 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 it is less than 0.1% by mass, photopolymerization may not proceed efficiently, and if it exceeds 20% by mass, ultraviolet rays may be prevented from penetrating 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 turbidity (haze) of the cured product is preferably 20% or less. Thus, the resin composition in which the turbidity of the cured product of the resin composition is 20% or less is also a preferred embodiment of the present invention. The turbidity of the cured product is more preferably 10% or less, still more preferably 5% or less, and particularly preferably 1% or less. As the transparency, the light transmittance in the visible light region (region having a wavelength of 360 to 780 nm) is preferably 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.
In the above cured product, a wide range of numerical values are 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 turbidity is 20% or less. More preferably, the total light transmittance and the change rate of turbidity are 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 over 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.

Since the cured product can exhibit excellent transparency and optical properties as described above, the organic-inorganic composite resin composition of the present invention is suitable for various uses such as optical use, opto device use, display device use and the like. Can be used. Thus, the curable material for optical members (the curable material using the resin composition) constituted by the organic-inorganic composite resin composition is also one aspect of the present invention. The curable material for optical members is a curable optical material formed from the organic-inorganic composite resin composition, and is a heat / photocurable optical material that is cured by heat or light (thermosetting optical material or photocuring). Optical material). Such a curable material for an optical member preferably has an Abbe number of 45 or more and a transmittance of 60% or more at a wavelength of 500 nm. When the Abbe number and the transmittance are within such ranges, a curable material for optical members having high transparency and resolution and excellent optical characteristics is obtained. More preferably, it is 55 or more as an Abbe number of the curable material for optical members, More preferably, it is 60 or more. More preferably, it is 80% or more as a transmittance | permeability of the curable material for optical members, More preferably, it is 85% or more. Moreover, since the said curable material for optical members (transparent optical material) is comprised with the said organic inorganic composite resin composition, the bending strength at the time of hardening for 2 minutes at 120 degreeC may be 60 Mpa or more. preferable. The bending strength is as described above.

The present invention is also an optical member obtained by curing the curable material for an optical member. As such an optical member (cured product formed by the organic-inorganic composite resin composition), among the above-described curable materials for optical members, the content of double bond (such as an aromatic ring) is contained in the resin. A cured product of 10% or less is preferred. When the compound having a double bond such as an aromatic ring is 10% by mass or less in the organic-inorganic composite resin composition, the optical properties such as refractive index are excellent, and it can be suitably used for optical applications.
The Abbe number and transmittance of the optical member are preferably the same as those in the curable material for optical members. Since it is a cured product having such a high Abbe number, it can be used in the following various applications.
Specific uses of the cured products include spectacle lenses, camera lenses such as (digital) cameras, mobile phones, and vehicle cameras, filters, diffraction gratings, prisms, light guides, light beam condensing lenses, and light diffusion lenses. , Optical applications such as watch glass, transparent glass such as cover glass for display devices, and cover glass; photosensors, photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, and light splitting Applications for optical devices such as glassware, optical fiber adhesives; LCD, organic EL and PDP display element substrates, color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, antifogging A display device such as a film is suitable.
The shape of the cured product can be appropriately set depending on the application, and is not particularly limited. Examples of the shape of the molded product such as a deformed product, a film, a sheet, and a pellet are also included.

The resin composition of the present invention and the optical member thereof have the above-described configuration, can be continuously produced, have excellent basic performance such as heat resistance, and have excellent optical properties such as transparency, optical use, and optical device use. Organic-inorganic composite resin compositions useful as display device applications, mechanical component materials, electrical / electronic component materials, and the like, and optical members 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%”.

Example 1 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 203.5 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid 30%) 290.7 g and 1-butanol 5.8 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 299.1 g and the viscosity was 37 Pa · s. Moreover, MEK-ST used as the raw material silica corresponds to the wet inorganic fine particles of the present invention.

Example 2 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 203.5 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 290.7 g and 2-ethyl-1-hexanol 5.8 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 300.6 g, and the viscosity was 30 Pa · s.

Example 3 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 203.5 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 290.7 g and 2-ethyl-1-hexanol 5.8 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 90 ° C. for 1 hour. The yield was 300.0 g, and the viscosity was 68 Pa · s.

Example 4 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 203.5 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 290.7 g and 1-dodecanol 5.8 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 301.1 g and the viscosity was 18 Pa · s.

Example 5 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 203.5 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 290.7 g and 1-hexadecanol 5.8 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 301.9 g and the viscosity was 17 Pa · s.

Example 6 (YX-8000 / SiO ₂ (MEK-ST) = 80/20 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 269.1 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 224.2 g and 1-hexadecanol 6.7 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 350.5 g and the viscosity was 1.6 Pa · s.

Example 7 (YX-8000 / SiO ₂ (MEK-ST) = 60/40 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 153.6 g, organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 341.3 g and 1-hexadecanol 5.1 g were mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 269.6 g and the viscosity was 1099 Pa · s.

Example 8 (828 EL / SiO ₂ (MEK-ST) = 70/30 (wt%))
203.5 g of bisphenol A (manufactured by Japan Epoxy Resin, Epicoat 828EL, epoxy equivalent 184 to 194), 290.7 g of organosilica sol (manufactured by Nissan Chemical Industries, Ltd., MEK-ST, particle size 10 to 15 nm, solid content 30%), And 1-hexadecanol 5.8g was mixed so that it might become uniform, and the vacuum distillation of the solvent was performed at 65 degreeC for 5.5 hours. The yield was 299.9 g and the viscosity was 27 Pa · s.

Example 9
In Example 2, each raw material was mixed in the same manner except that 50 g of 2-ethyl-1-hexanol was used instead of 5.8 g of 2-ethyl-1-hexanol, and the solvent was distilled under reduced pressure at 65 ° C. As a result of performing the last 5.5 hours, the yield was 344 g, and the added 2-ethyl-1-hexanol contained about 10% by mass or more. Then, the resin composition with a yield of 302 g and a viscosity of 500 Pa · s was obtained by further performing vacuum distillation at 70 ° C. for 20 hours.

Comparative Example 1 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
203.5 g of hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (30% min.) 290.7 g was mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 297.1 g, and the viscosity was 118 Pa · s.

Comparative Example 2 (YX-8000 / SiO ₂ (MEK-ST) = 70/30 (wt%))
203.5 g of hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 290.7 g was mixed uniformly, and the solvent was distilled off under reduced pressure at 90 ° C. for 1 hour. The yield was 295.9 g and the viscosity was 144 Pa · s.

Comparative Example 3 (YX-8000 / SiO ₂ (MEK-ST) = 80/20 (wt%))
272.7 g of hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (Min. 30%) 227.3 g was mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 351.4 g, and the viscosity was 5 Pa · s.

Comparative Example 4 (YX-8000 / SiO ₂ (MEK-ST) = 60/40 (wt%))
Hydrogenated bisphenol A (Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) 155.2 g and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10-15 nm, solid (30% min) 344.8 g was mixed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 266.6 g, and the viscosity was> 15000 Pa · s.

Comparative Example 5 (828 EL / SiO ₂ (MEK-ST) = 70/30 (wt%))
205.9 g of bisphenol A (Japan Epoxy Resin, Epicoat 828EL, epoxy equivalent 184 to 194) and organosilica sol (Nissan Chemical Industries, MEK-ST, particle size 10 to 15 nm, solid content 30%) 294.1 g Mixing was performed uniformly, and the solvent was distilled off under reduced pressure at 65 ° C. for 5.5 hours. The yield was 302.3 g and the viscosity was 146 Pa · s.

Comparative Example 6 (YX-8000 = 100 (wt%))
Hydrogenated bisphenol A (manufactured by Japan Epoxy Resin, Epicoat YX-8000, epoxy equivalent 205, liquid hydrogenated epoxy resin) was used as the resin composition.

(Preparation of curing resin composition)
To the resin compositions [Synthesis Examples 1 to 8], stearic acid as a release agent was uniformly mixed at 80 ° C. so as to be 0.5 parts with respect to 100 parts of the resin composition.
After cooling to 50 ° C., a cationic polymerization initiator (manufactured by Sanshin Chemical Industry Co., Ltd., Sun-Aid SI-80L) was added to 1 part with respect to 100 parts of the resin composition and mixed uniformly.
(Molded body)
Heat is applied to the curable resin composition as necessary (50 ° C., etc.), followed by vacuum defoaming treatment, followed by film formation. When bubbles are generated due to the presence of a solvent, Curing was performed at 110 ° C. for 5 hours to obtain a cast plate having a thickness of 1 mm.
The following physical properties were evaluated for the obtained resin composition and molded body.
The results are shown in Table 1.

<Viscosity>
The viscosity of the resin composition before adding the release agent and curing agent at 40 ° C. and rotation speed D = 1 / s was evaluated with an R / S rheometer (manufactured by Brookfield, 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.
About the thing which cannot measure the viscosity at the time of D = 1 / s, the value of D = 5-100 / s was extrapolated and evaluated as the viscosity of a resin composition.
<Evaluation of refractive index and Abbe number>
Evaluation was performed using a refractometer (DR-M2 manufactured by Atago Co., Ltd.).
(Hardened product) The refractive index and Abbe number of a 1 mm molded product were evaluated.

From the results in Table 1, it is possible to suppress an increase in the viscosity of the resin composition during synthesis by adding a solvent (high boiling point component), and to suppress a viscosity increase during storage over time. Became clear.
From the results in Table 2, it has been clarified that the addition of a solvent (high boiling point component) does not greatly affect the optical physical properties, shows a high Abbe number, and can be suitably used for various applications such as optical applications. Note that Comparative Example 6 uses hydrogenated bisphenol A alone and does not contain inorganic fine particles.

In the above-described Examples and Comparative Examples, 1-dodecanol, 1-butanol, 1-hexadecanol, and 2-ethyl-1-hexanol are used as the high-boiling components, and the alicyclic epoxy compound ( YX-8000), epoxy compound (828EL), wet inorganic fine particles (MEK-ST) are used as inorganic fine particles, and a step of preparing a mixture containing inorganic fine particles, an organic resin and a solvent, and a solvent from the mixture If it is a manufacturing method including the deaeration process deaerated in the presence of a high-boiling component, the mechanism for suppressing the increase in the viscosity of the organic-inorganic composite resin composition is the same. Therefore, if these steps are essential, it can be said that the advantageous effects of the present invention are manifested. In the case where at least alcohol having a boiling point of 100 ° C. or higher is used as a high-boiling component, an alicyclic epoxy compound is used as an organic resin component, and wet silica is used as wet inorganic fine particles, the examples and comparative examples described above are sufficient. The advantageous effects of the invention are proved and the technical significance of the present invention is supported.

Claims (5)

A method for producing a liquid organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component,
The production method includes a degassing step of degassing the solvent from the mixture containing the inorganic fine particle component, the organic resin component and the solvent, and the degassing step is performed in the presence of a high boiling point component,
The high boiling point component is an alcohol having a boiling point of 100 ° C. or higher,
The organic resin component is an alicyclic epoxy compound, a hydrogenated epoxy resin, or an epibis type glycidyl ether type epoxy resin. A method for producing a liquid organic-inorganic composite resin composition containing an organic resin component and an inorganic fine particle component,
The production method includes a degassing step of degassing the solvent from the mixture containing the inorganic fine particle component, the organic resin component and the solvent, and the degassing step is performed in the presence of a high boiling point component,
The high boiling point component is an alcohol having a boiling point of 100 ° C. or higher,
The organic resin component is an alicyclic epoxy compound, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, or an epibis type glycidyl ether type epoxy resin. Production method. The degassing step is performed such that a ratio of the high boiling point component remaining in 100% by mass of the mixture at the end of the degassing step is 0.01 to 10% by mass. 2. A method for producing a liquid organic-inorganic composite resin composition according to 2. The said manufacturing method is a method of manufacturing the liquid organic inorganic composite resin composition whose viscosity at the measurement temperature of 40 degreeC is 0.01-10000 Pa.s, In any one of Claims 1-3 characterized by the above-mentioned. The manufacturing method of liquid organic inorganic composite resin composition of description. The amount of the high-boiling component added is 0.01 to 10% with respect to 100% by mass of the mixture of the inorganic fine particle component, the organic resin component, the organic solvent before degassing, the high-boiling component and other components contained as necessary. It is mass%, The manufacturing method of the liquid organic inorganic composite resin composition in any one of Claims 1-4 characterized by the above-mentioned.