JP4398500B2 - Resin composition and optical member - Google Patents

Description

The present invention relates to a resin composition and an optical member. More specifically, the present invention relates to a resin composition useful as an optical application, an optical device application, a display device application, a machine 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. 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 uses, long-term heat resistance is required in consideration of high temperature exposure in summer. Since heat resistance superior to that of conventional plastic materials is required, thermosetting materials have been studied.

Such a curable material is also required to have excellent workability and handleability of a cured product after being cured. For example, when used for an optical member such as a lens, precise workability is required, and further, it is required to have high strength and excellent handleability. However, conventional glass lenses have low strength, and plastic lenses and the like do not have sufficient workability and high strength at the same time, and there is room for improvement in materials constituting curable materials. there were.

By the way, what contains an inorganic component is also disclosed regarding the thermosetting resin composition. For example, (a) colloidal silica dispersed in an organic solvent, (b) an alicyclic polyepoxy compound and (c) a metal chelate compound are contained as essential components, and the blending ratio of the components (a) and (b) Is a solid content ratio of (a) component 5 to 85% by weight and (b) component 95 to 15% by weight, and (c) component is a total of 100 parts by weight of the solids of component (a) and component (b) An organic solvent-based thermosetting composition containing 0.01 to 30 parts by weight per unit is disclosed (see, for example, Patent Document 1). According to this, a resin using a material having a high molecular weight is provided, but there is room for improvement in terms of transparency and productivity.
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 by the above-mentioned (for example, see Patent Document 2). Here, wet silica and epoxy resin are disclosed, but bisphenol A type epoxy resin (Abbe number 34.1) is used as the epoxy resin. In such a case, there is room for improvement in optical characteristics, for example, in reducing the blur of light and obtaining a high Abbe number. Accordingly, there has been a demand for a material having basic performance such as heat resistance, which improves optical characteristics and can be suitably applied to various optical members.
Japanese Patent No. 28657741 (first page) JP 2004-250521 A (2nd page)

The present invention has been made in view of the above-mentioned present situation, is rich in processability as a resin composition, has high strength in a cured product after curing the resin composition, and does not crack at the time of release. It aims at providing the optical member formed by hardening | curing the resin composition which is excellent in handleability, etc., and the resin composition.

The inventors of the present invention have studied various resin compositions containing an organic resin component, and pay attention to the fact that they are useful as materials in various applications such as optical applications. When a specific organic resin component is used, the transparency is high. The resin composition before curing and the cured product obtained by curing the resin composition are easy to mold, have excellent processing characteristics, and have high strength and excellent handleability. Therefore, it has been found that the resin composition can be suitably used for optical applications and the like. Specifically, the ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution in the resin composition is 15 to 90% by mass with respect to the total amount of the organic resin component. In other words, in the resin composition By having the ratio of the organic resin component having a molecular weight of less than 700 in the molecular weight distribution of 10 to 85% by mass with respect to the total amount of the organic resin component, it has excellent moldability and high strength. It has been found that it can be handled easily. By using a polymer resin material having a molecular weight of 700 or more, it has excellent strength, and by using a low molecular resin material having a molecular weight of less than 700, the viscosity of the curable resin composition can be reduced. It is possible to perform complicated processing that cannot be performed with glass at a low cost. In particular, when a thermosetting resin is used, it has been conceived that it can have a heat resistance that cannot be achieved by a thermoplastic resin, and can solve the above-mentioned problems. Furthermore, it can be suitably applied to 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. As a result, the present invention has been achieved.

That is, the present invention is a resin composition containing an organic resin component, and the resin composition has a ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution of 15 to 90% by mass with respect to the total amount of the organic resin component. It is the resin composition which comprises.
The present invention is described in detail below.

The resin composition of the present invention contains an organic resin component. Thus, the resin composition containing an organic resin component can make the cured product excellent in handleability after curing. For example, when it is used as an optical material such as a lens, it has advantages such as resistance to cracking compared to the case where glass or the like is used as a lens.
The said resin composition may contain other components other than an organic resin component, and it does not specifically limit as a component which comprises a resin composition. The resin composition preferably contains 40% by mass or more of an organic resin component in 100% by mass of the resin composition. More preferably, it is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
In addition, in the present specification, in the case of simply “curing”, not only a case where it becomes hard by polymerizing components constituting the resin composition such as a curable resin composition, but also a thermoplastic resin, etc. This includes the case where the material is once softened and then hardened. The term “curing” refers to the property of curing by polymerizing the components constituting the resin composition.

The said resin composition comprises 15-90 mass% of the ratio of the organic resin component of molecular weight 700 or more in the molecular weight distribution in a resin composition with respect to the organic resin component total amount. In other words, the ratio of the organic resin component having a molecular weight of less than 700 in the molecular weight distribution in the resin composition comprises 10 to 85% by mass with respect to the total amount of the organic resin component. That is, the ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution in the resin composition is 15 to 90% by mass with respect to the total amount of the organic resin components, and the organic having a molecular weight of less than 700 in the molecular weight distribution. The ratio of the resin component is 10 to 85% by mass with respect to the total amount of the organic resin component. Thus, by making an organic resin component having a molecular weight of 700 or more (hereinafter also referred to as “high molecular weight component”) and an organic resin component having a molecular weight less than 700 (hereinafter also referred to as “low molecular weight component”) essential. The effect of reducing the viscosity during production and improving the mechanical strength of the product can be obtained. That is, it is possible to satisfy both characteristics such as excellent processing characteristics (viscosity and flowability) of the resin composition and excellent mechanical strength of the cured product of the resin composition. When only the high molecular weight component is used as the organic resin component, the viscosity of the resin composition increases. Moreover, when it is only a low molecular-weight component, it will become hard but brittle, and will become easy to break. This problem is remarkable when the low molecular weight component is a curable resin, particularly a polyfunctional epoxy compound. As in the present invention, by using a low molecular weight component and a high molecular weight component in combination, the moldability can be improved, cracking is difficult, and handleability can be improved. Further, regarding the cure shrinkage when curing the resin composition, since the high molecular weight component is smaller than the low molecular weight component, it is preferable to contain a large amount of the high molecular weight component, and the content of the high molecular weight component and the low molecular weight component. By adjusting, the curing shrinkage rate can also be adjusted. These high molecular weight components and low molecular weight components may have the same composition or different compositions. For example, FIGS. 1 (a) and 1 (b) are schematic diagrams showing the molecular weight distribution, where the vertical axis shows the amount of the compound and the horizontal axis shows the molecular weight, but shown in FIG. 1 (a). Thus, it may be a molecular weight distribution having a maximum value of one peak that spans both a region having a molecular weight of less than 700 and a region having a molecular weight of 700 or more, and as shown in FIG. A molecular weight distribution having a peak maximum value in each of a region less than 700 and a region greater than 700 may be used.

In the molecular weight distribution, the resin composition has at least one maximum value of molecular weight peak in a region having a molecular weight of less than 700, and has at least one maximum value of molecular weight peak in a region having a molecular weight of 700 or more. It is preferable. Thus, when each of the region having a molecular weight of less than 700 and the region having a molecular weight of 700 or more has the maximum value of the molecular weight peak, the molecular weight of the organic resin component constituting the resin composition is biased between the low molecular weight side and the high molecular weight side. Will occur. In such a case, the effect obtained by including the low molecular weight component and the effect obtained by including the high molecular weight component can be more remarkably exhibited. In the molecular weight distribution, the two peaks having the maximum value may partially overlap as shown in FIG. 1B or may be completely separated without overlapping. Moreover, the composition of the compounds resulting from the maximum values of the two peaks may be the same or different.
The resin composition preferably includes at least one organic resin component having a weight average molecular weight of 700 or more and at least one organic resin component having a weight average molecular weight of less than 700. Thus, by including 2 types from which a weight average molecular weight differs, the effect acquired by including a low molecular weight component and the effect acquired by including a high molecular weight component can be exhibited more notably. In addition, a weight average molecular weight is averaged by 1 type comprised by the same composition.

Moreover, it is preferable that the total amount of the organic resin component whose weight average molecular weight is 700 or more is 15-90 mass% with respect to the total amount of an organic resin component. In other words, the total amount of the organic resin component having a weight average molecular weight of less than 700 is preferably 10 to 85% by mass with respect to the total amount of the organic resin component. Thus, by including two kinds of compounds having different weight average molecular weights, the effect obtained by including the low molecular weight component and the effect obtained by including the high molecular weight component can be more remarkably exhibited.
In addition, the molecular weight of the organic resin component in a resin composition and the ratio of the organic resin component in molecular weight distribution can be measured by the method shown below.

<Measurement method of molecular weight and molecular weight distribution>
The molecular weight of a compound contained in the organic resin component, for example, an organic resin component having a molecular weight of less than 700, an organic resin component having a molecular weight of less than 700, and the like can be determined as follows. The ratio of the high molecular weight component is the ratio (S1 / S2) of the S1 and the total region S2 of the high molecular weight region having a molecular weight of 700 or more determined from the GPC (gel permeation chromatography) molecular weight calibration curve. Is a ratio (S0 / S2) between S0 of the low molecular side region having a molecular weight of less than 700 and the entire region S2. For example, it can be measured under the following conditions using gel permeation chromatography (trade name “HLC-8220GPC” manufactured by Tosoh Corporation).

(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.
The point of molecular weight 700 was determined by using a polystyrene oligomer (trade name “TSK Standard Polystyrene”, manufactured by Tosoh Corporation) as a standard sample, and creating a molecular weight calibration curve under the GPC conditions using this standard sample. The content of the above organic resin component and the organic resin component having a molecular weight of less than 700 was determined by the following method using this calibration curve: First, the chromatogram of the resin composition to be measured under the above GPC conditions. When a perpendicular is drawn from the point of molecular weight 700 on the calibration curve, the area S1 of the high molecular weight side region surrounded by the perpendicular, the baseline and the peak waveform, and the total peak waveform area surrounded by the chromatogram and the baseline The ratio (S1 / S2) of S2 was the content (wt%) having a molecular weight of 700 or more in the total resin composition. The content (wt%) having a molecular weight of less than 700 is a ratio region of the area S0 of the low molecular weight side region surrounded by the perpendicular line, the baseline and the peak waveform, and the total peak waveform area S2 surrounded by the chromatogram and the baseline. This is the ratio (S0 / S2) between S0 of the low molecular side region having a molecular weight of less than 700 and the entire region S2.
FIG. 2 shows a chart showing a GPC analysis result and a calibration curve for one embodiment of the resin composition of the present invention. In the GPC analysis, the organic resin component in the resin composition can be measured, and the ratio of the organic resin component having a molecular weight of 700 or more with respect to the total amount of the organic resin component can be obtained by the above method using the GPC analysis result.

As described above, it is possible to analyze the contents of an organic resin component having a molecular weight of 700 or more and an organic resin component having a molecular weight of less than 700 by GPC. For analysis of its constituent components, etc., by combining a fractionation device such as FC-8010, AS8071 manufactured by Tosoh Corporation with the GPC device, the component of the target molecular weight in the resin composition is fractionated, and its specific molecular weight By conducting structural / quantitative analysis by NMR analysis, IR analysis, elemental analysis, etc., the components of the resin composition can be analyzed.

The organic resin component is preferably, for example, a curable resin or a thermoplastic resin. 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. A thermoplastic resin such as Zeonex is preferably used as the organic resin component from the viewpoint 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. Moreover, in the curable resin, the effect of the present invention combining the high molecular weight component and the low molecular weight component is remarkable.

The curable resin is not particularly limited as long as it has curability, and among them, a thermosetting resin or a photocurable resin is preferable. Examples of the form of the curable resin include (1) a form made of a liquid or solid curable resin, and (2) a form containing a liquid or solid curable resin and a solvent (non-curable). Can be mentioned. (3) Examples include a liquid or solid non-curable resin, an organic resin component having a molecular weight of 700 or more, and an organic resin component having a molecular weight of less than 700. Examples of the form containing (3) a liquid or solid non-curable resin, an organic resin component having a molecular weight of 700 or more and an organic resin component having a molecular weight of less than 700 include an oligomer component of an acrylic resin such as PMMA and (meta ) A form containing an acrylate monomer or the like.

As the curable resin, for example, a compound having at least one epoxy group, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, an alicyclic compound, a hydrogenated compound, and the like can be suitably used. These compounds can be used alone or as a mixture of two or more. In the present specification, the “epoxy group” means a group containing an oxirane ring which is a 3-membered ether. Specifically, a glycidyl group containing an epoxy group or an epoxy group structure is preferred. As the epoxy group, an epoxy group such as an epoxycyclohexyl group, a glycidyl group such as a glycidyl ether group, a glycidyl ester group, or the like can be preferably used. Among these, it is preferable to include at least one of an alicyclic compound (alicyclic curable material) and a hydrogenated compound (hydrogenated curable material). By using an alicyclic compound or a hydrogenated compound, the optical properties such as Abbe number and refractive index can be adjusted more easily, and the optical properties can be made excellent and suitable for various applications. Can be used.
Examples of the alicyclic compound and hydrogenated compound include alicyclic glycols obtained by hydrogenating an aromatic skeleton such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc., which will be described later; 3,4-epoxy Cycloaliphatic epoxy resins such as cyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis- (3,4-epoxycyclohexyl) adipate; cycloaliphatic epoxides such as heterocycle-containing epoxy resins such as triglycidyl isocyanurate; In structures such as alicyclic modified neopentyl glycol (meth) acrylate (“R-629” or “R-644” manufactured by Nippon Kayaku Co., Ltd.); tetrahydrofurfuryl (meth) acrylate, morpholinoethyl (meth) acrylate, etc. Oxygen atom and / or nitrogen source Alicyclic acrylate having N; cyclohexylmaleimide and other alicyclic monofunctional maleimides; N, N′-methylenebismaleimide, N, N′-ethylenebismaleimide, N, N′-trimethylenebismaleimide, N , N′-hexamethylene bismaleimide, N, N′-dodecamethylene bismaleimide, 1,4-dimaleimidocyclohexane, etc .; hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol S type epoxy compound, Hydrogenated epoxy compounds such as hydrogenated bisphenol F type epoxy compounds are preferred. Among these, more preferred are alicyclic epoxy compounds and / or hydrogenated epoxy compounds, and even more preferred are alicyclic epoxy compounds. The hydrogenated epoxy compound is a hydrogenated product of an epoxy compound. For example, an aromatic polyfunctional compound such as a bisphenol A type epoxy resin, a hydrogenated bisphenol S type epoxy resin, or a hydrogenated bisphenol F type epoxy resin. A hydrogenated product of a glycidyl ether compound is preferable.

The curable resin is preferably an epoxy compound having an epoxy group. Although content of an epoxy compound is not specifically limited, It is preferable that it is 40 mass% or more in a total organic resin component. More preferably, it is 60% by mass or more, still more preferably 80% by mass or more, and particularly preferably, substantially all are epoxy compounds.
From the above, the organic resin component contained in the curable resin composition includes an alicyclic epoxy material in which an epoxy is contained in an alicyclic curable material and / or a hydrogenation in which an epoxy is contained in a hydrogenated curable material. An epoxy material is preferred. That is, it is more preferable that the resin composition has at least one of an alicyclic epoxy compound and a hydrogenated epoxy compound. In addition, an alicyclic epoxy compound is an alicyclic compound containing an epoxy group, and similarly, a hydrogenated epoxy compound is a hydrogenated compound containing an epoxy group.
As described above, a resin composition in which the organic resin component essentially includes an alicyclic epoxy compound and / or a hydrogenated epoxy compound is also one of the preferred embodiments of the present invention. The content of the alicyclic epoxy compound and / or hydrogenated epoxy compound is not particularly limited as long as it is contained in the organic resin component, but the preferable content in the total organic resin component is the above-described epoxy compound. It is the same as the content of.
Moreover, as an epoxy equivalent with respect to the resin composition total amount, it is preferable that it is 100-3000. When the epoxy equivalent exceeds 3000, the thermal expansion coefficient of the cured product (for example, a lens or the like) increases. If it is less than 100, the cured product may be mechanically brittle. As an epoxy equivalent with respect to the resin composition total amount, More preferably, it is 110-1400, More preferably, it is 150-1000. The “epoxy equivalent with respect to the total amount of the resin composition” is determined by dividing the total mass of the resin composition by the number of moles of epoxy groups contained in the resin composition.

As the alicyclic epoxy compound, an epoxy resin having an epoxycyclohexane skeleton, an epoxy resin in which an epoxy group is added to a cyclic aliphatic hydrocarbon directly or via a hydrocarbon group, and the like are preferable. More preferably, the alicyclic epoxy compound is a resin having an epoxycyclohexane group. As the hydrogenated epoxy compound, a hydrogenated product of an aromatic polyfunctional glycidyl ether compound such as a bisphenol type epoxy resin is suitable. More preferably, the hydrogenated epoxy compound is a complete or partial hydrogenated product of an aromatic epoxy compound.

In the present invention, as the curable resin, a resin containing a non-curable component such as a thermoplastic resin and a low molecular weight curable compound may be suitably 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 epoxy group described later may be appropriately selected and used. A compound having at least one 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.

When the organic resin component is applied to an optical member having a high Abbe number, the Abbe number is preferably 45 or more. The Abbe number of 45 or more means that “the average value of the Abbe numbers of all organic resin components is 45 or more”, and an organic resin component having an Abbe number of less than 45 is included. Also good. By setting the Abbe number to 45 or more (the average value of the Abbe numbers of all organic resin components is 45 or more), when the resin composition is used for optical applications, the light dispersion is reduced, the resolution is increased, and the optical characteristics are increased. It can be made excellent. 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 more preferably 47 or more, and still more preferably 50 or more.
The organic resin component preferably 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 all organic. It is preferable that 40 mass% or more is contained in a component. 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 includes an organic resin component having a molecular weight of 700 or more. When the organic resin component contains an organic resin having such a molecular weight, when the resin composition is cured, it can have a sense of unity, and the strength at the time of peeling is improved, and it is not cracked. Material hardness.
The organic resin component contains 15 to 90% by mass of an organic resin having a molecular weight of 700 or more in 100% by mass of the organic resin component. If the component (organic resin) having a molecular weight of 700 or more is less than 15 % by mass in the organic resin component, the strength when the resin composition is cured may not be sufficient, and if it exceeds 90% by mass There is a risk that the ease of molding will not be sufficient. The content of the organic resin having a molecular weight of 700 or more is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 70% by mass.
The molecular weight of an organic resin having a molecular weight of 700 or more, which is included as an essential component in the organic resin component, is preferably 700 to 10,000. If the molecular weight exceeds 10,000, the resin composition may not have sufficient transparency. More preferably, it is 1000-5000 as a molecular weight of the said high molecular weight component, More preferably, it is 2000-4000.
The epoxy equivalent of the high molecular weight component is preferably 130 to 5000. More preferably, it is 180-2500, More preferably, it is 350-2000. The “epoxy equivalent of the high molecular weight component” is obtained by dividing the total mass of the high molecular weight component by the number of epoxy groups. As the high molecular weight component having a molecular weight of 700 or more, for example, alicyclic epoxy compounds, hydrogenated epoxy compounds, aromatic epoxy compounds and the like can be suitably used. Specifically, YL-7170, YX-8034, E H PE-3150, etc. already described, but these are epoxy compounds containing 15% by mass or more of the high molecular weight component having a molecular weight of 700 or more. It can be suitably used as a raw material for the polymer component in the resin composition of the present invention. Furthermore, YL-7170 and E H PE-3150 have a weight average molecular weight of 700 or more, and can be preferably employed as a raw material for the polymer component.

The organic resin component includes an organic resin component having a molecular weight of less than 700. When the organic resin component contains an organic resin having such a molecular weight, a low-viscosity curable resin composition can be obtained, and the moldability of the curable resin composition can be improved. The molecular weight of the organic resin contained as an essential component in the organic resin component is preferably 150 to 700. If the molecular weight is less than 150, there is a risk of swelling of the molded product due to volatilization during molding.
In the organic resin component, the content of the organic resin having a molecular weight of less than 700 is preferably 10 to 70% by mass in 100% by mass of the organic resin component. If components having a molecular weight of less than 700 (organic resin) is less than 10 wt% in the organic resin component, carry the risk ease of molding is not sufficient, and if more than 70 wt%, the resin composition Ru danger strength is not sufficient at the time of curing the. The content of the organic resin having a molecular weight of less than 700 is preferably 20 to 65% by mass, and more preferably 30 to 60% by mass.
As the raw material of the organic resin component having a molecular weight of less than 700 in the resin composition described above, for example, YX8000 and YX8034 are preferable as the hydrogenated epoxy compound, Celoxide 2021P is preferable as the alicyclic epoxy compound, and Ogsol PG100 is preferable as the aromatic epoxy compound. Illustrated.

The curable resin composition can be suitably used as an optical member. By adjusting the contents of the high molecular weight component and the low molecular weight component, the optical properties such as the Abbe number and the refractive index can be adjusted. Can be adjusted. Thereby, for example, a high Abbe optical member and a low Abbe optical member can be manufactured. Hereinafter, a preferable embodiment as a high Abbe optical member and a preferable embodiment as a low Abbe optical member will be described.

As the high Abbe optical member, it is preferable that both the low molecular weight component and the high molecular weight component contain a hydrogenated epoxy compound and / or an alicyclic epoxy compound because the Abbe number is high. Preferably, as the low molecular weight component and the high molecular weight component, 80% by mass or more of the low molecular weight component and the high molecular weight component is a hydrogenated epoxy compound and / or an alicyclic epoxy compound. Of the low molecular weight components, it is particularly preferred that 80% by mass or more is hydrogenated and / or alicyclic, and among the high molecular weight components, 80% by mass or more is hydrogenated and / or alicyclic. Moreover, when manufacturing a high Abbe optical member, it is more preferable to use the above-mentioned organic resin having an Abbe number of 45 or more. The content of the organic resin having an Abbe number of 45 or more with respect to 100% by mass of the organic resin component is preferably in the above-described range.
Moreover, it is also a preferable form that both the low molecular weight component and the high molecular weight component are hydrogenated epoxy compounds, and that both the low molecular weight component and the high molecular weight component are alicyclic epoxy compounds.

Moreover, when using as a high Abbe optical member, it is preferable that the amount of unsaturated bonds in a composition and hardened | cured material is 10 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. In addition, the compound which has an unsaturated bond will be contained in either an organic resin component or the other component added as needed. Since the compound having such an unsaturated bond generally decreases the Abbe number, if the content of the unsaturated bond exceeds 10% by mass, the Abbe number of the resin composition does not become sufficiently large. When used as a lens, there is a possibility that the blur of light becomes large and it cannot be used suitably for various applications. More preferably, the proportion of the compound having an unsaturated bond is 8% by mass or less, more preferably 6% by mass or less in 100% by mass of the resin composition (organic resin component and other components as required). is there. Particularly preferably, it is not substantially contained. That is, a form that is not included in any of the organic resin component 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 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. Such a curable resin composition can be suitably used as, for example, a high Abbe lens with low wavelength dispersion.

Since the low Abbe optical member is cured in a short time, it is preferable that both the low molecular weight component and the high molecular weight component contain a hydrogenated epoxy compound and / or an alicyclic epoxy compound. Moreover, it is preferable that 10 mass% or more of aromatic epoxy compounds are included for Abbe number control. More preferably, it is preferably 30% by mass or more. The content range of the aromatic epoxy compound in the total organic resin component is preferably 10 to 50% by mass, and more preferably 30 to 50% by mass or more. The aromatic epoxy compound is preferably one of low molecular weight components. The aromatic epoxy compound is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin having a bisphenol skeleton, or an aromatic compound having a conjugated structure having 7 or more carbon atoms.

In the said curable resin composition and the hardened | cured material formed by hardening | curing this curable resin composition, it is preferable that the amount of unsaturated bonds exceeds 10 mass%. According to this, it can be suitably used as an optical member that is required to have a low Abbe number and a high refractive index. Similarly, also for the resin composition, the proportion of the compound having an unsaturated bond is preferably more than 10% by mass. Furthermore, it is preferable that at least one of the low molecular weight components is an aromatic compound having a conjugated structure having 7 or more carbon atoms. The conjugated structure composed of 7 or more carbon atoms is one having 7 or more carbon atoms belonging to an atomic group constituting one conjugated unit. Taking a conjugated double bond as an example, the conjugated unit includes at least two double bonds and one single bond. However, in the present invention, all the double bonds and single bonds that can be conjugated are included. The number of carbon atoms is counted as a single conjugated unit, and when a bond structure including the unit is shown, a group of portions related to resonance is called one conjugated unit. Therefore, the low Abbe optical member, and a as a low molecular weight component hydrogenated and / or cycloaliphatic and aromatic epoxy compounds (carbon atoms containing 7 or more conjugated structure), hydrogenated as high molecular weight component And / or the form containing an alicyclic is preferable. A preferred form of the conjugated unit will be described later.

Specific examples of the aromatic compound having a conjugated structure composed of 7 or more carbon atoms include the following chemical formulas (1-1) to (1-8):

It is preferable that it has either of the structures represented by these. That is, a fluorene skeleton represented by the chemical formula (1-1) (a conjugated structure composed of 13 carbon atoms) and an anthracene ring represented by the chemical formula (1-2) (constructed by 14 carbon atoms) Conjugated structure), a dibenzothiophene ring represented by the above chemical formula (1-3) (a conjugated structure composed of 12 carbon atoms), and a carbazole represented by the above chemical formula (1-4) (12 A conjugated structure composed of carbon atoms), a stilbene represented by the chemical formulas (1-5-1) and (1-5-2) (conjugated structure composed of 14 carbon atoms), and the chemical formula (1 -6) biphenyl (conjugated structure composed of 12 carbon atoms), naphthalene ring represented by the above chemical formula (1-7) (conjugated structure composed of 10 carbon atoms) Preferably it has one of the. Among these, those having a skeleton structure such as fluorene and carbazole, and those having an anthracene ring and a dibenzothiophene ring are more preferable. That is, it is one of the preferred embodiments of the present invention that the conjugated structure requires at least one structure selected from a fluorene skeleton, an anthracene ring, a dibenzothiophene ring, and a carbazole skeleton. Any conjugated structure may be used as long as it has the skeleton or ring structure described above. Moreover, a structure in which bisphenol is bonded to the fluorene skeleton represented by the above chemical formula (1-8) (a conjugated structure composed of 25 carbon atoms) and the like are more preferable.
Note that having in the skeleton structure means that these structures may have a substituent within a range having a resonance structure.

In addition, specific examples of how to count the conjugated structures of the above-described compounds are as follows.
For example, in the fluorene structure represented by the following formula (a), 6-membered rings are connected even in the thick line portion. As a result, since the middle five-membered ring sandwiched between the aromatic rings also has a resonance structure, the carbon surrounded by the dotted circle is part of the conjugated structure, and there are 13 conjugated structures. Furthermore, when the fluorene structure and the benzene ring are directly bonded as in the structure represented by the following formula (b), the conjugated structure is further expanded, and the number of conjugated structures in the structure is 25.
On the other hand, in the case of a compound having a structure such as bisphenol A represented by the following formula (c), the central carbon itself is bonded to the aromatic ring as in the fluorene structure, but the central carbon itself. Is not part of the ring structure and does not have a conjugated structure. In this case, one conjugated structure has 6 carbon atoms.

In the case of a linear compound, the number of carbon atoms constituting one conjugated structure is counted as 7 in both cases of the structures shown in the following formulas (d) and (e).

As a method for preparing a resin composition containing an organic resin component having a molecular weight of 700 or more (high molecular weight component) and an organic resin component having a molecular weight of less than 700 (low molecular weight component), it is necessary after dispersing the low molecular weight component in a solvent. Depending on the method, a method of adding the high molecular weight component after mixing with other components and distilling off the solvent (solvent) is preferred. In 100% by mass of a dispersion in which a low molecular weight component is dispersed in a solvent, or a mixture (a mixture including a solvent) in which a low molecular weight component is mixed with other components as necessary, the solvent is 5% by mass or less. The prepared form is preferred. By mixing as described above, a suitable resin composition can be obtained without increasing the viscosity of the resin composition. Further, the familiarity of the high molecular weight component with the resin composition can be improved. Thus, it is a method for producing a curable resin composition containing an organic resin component, in which the organic resin component (low molecular weight component) having a molecular weight of less than 700 is dispersed in a solvent, A method for producing a resin composition comprising a step of mixing at least part of an organic resin component (high molecular weight component) having a molecular weight of 700 or more and finally preparing with 5% by mass or less of a solvent is also provided. It is one of the preferred embodiments of the invention.

The amount of the solvent is 5% by mass of solvent in 100% by mass of a mixture (a mixture of an organic resin component having a molecular weight of 700 or more and an organic resin component having a molecular weight of less than 700 and, if necessary, another organic resin component and a solvent). % Or less. 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. On the other hand, from the viewpoint of suppressing an increase in viscosity during the production of a resin composition using a solvent (at the time of desolvation) as one of the preferred embodiments of the present invention, a mixture (resin composition) of 0.05 to 5% by mass of a solvent is used. Thing) It is preferable to leave in 100 mass%. 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 a resin composition can be suitably obtained. As the solvent, high boiling alcohols such as 2-ethyl-1-hexanol and dodecanol are preferable. A specific example of the high boiling alcohol will be described later. The residual amount of such high boiling alcohol is preferably 0.01 to 2% by mass.

The resin composition preferably also includes a component having flexibility (flexible component). By including a flexible component, a 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 ) _n1 —O—] _m1 − (n1 is an integer of 2 or more, m1 is an integer of 1 or more. Preferably, n1 is 2 -12, m1 is an integer from 1 to 1000. More preferably, n1 is from 3 to 6 and m1 is an integer from 1 to 20.) Polymer epoxy resin (for example, hydrogenated bisphenol (Japan Epoxy Resin Co., Ltd.) YL-7170, epoxy equivalent 1400, 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, and the like. It is a compound containing a curable functional group at the terminal, side sheath, main chain skeleton, etc. Thus, the above-mentioned flexible component is also a resin composition containing a curable functional group. The above-mentioned “curable functional group” refers to “functional group that cures with heat or light, such as an epoxy group or an oxetane group (a group that causes a resin composition to undergo a curing reaction). ".

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 includes 40 to 99% by mass of the organic resin component and 0.01 to 40% by mass of the flexible component in a total of 100% by mass of the organic resin component and the flexible component. It is preferable. A resin composition having a flexible component of 40% or less is preferable. More preferably, it is 0.1-30 mass% as content of a flexible component, More preferably, it is 0.5-20 mass%.
The 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 200 Pa.s or less, Most preferably, it is 10-200 Pa.s. The lower limit of the viscosity is preferably 1 Pa · s or more, more preferably 5 Pa · s or more, and further preferably 10 Pa · s or more.

As a method for curing the resin composition of the present invention, various methods such as heat curing and photocuring can be suitably used. However, the resin composition may be mixed with a curing agent and other materials as required. A method is preferably used in which the liquid mixture is cured in a mold that matches the shape of the cured product, and then the cured product is removed from the mold. In such a method, it is preferable that the viscosity of the curable 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 resin composition after storage at 25 ° C. for 3 days is 200% or less as compared to immediately after mixing. If it exceeds 200%, the injection of the liquid into the mold may be difficult, and the fluidity in the mold may be adversely affected. More preferably, it is 180% or less, More preferably, it is 150% or less. Thus, the resin composition is also a resin composition in which the viscosity increase rate of the mixture in one liquid as a curable resin composition is 200% or less after storage at 25 ° C. for 3 days compared to immediately after mixing. This is one of the preferred embodiments of the present invention.

The resin composition of the present invention contains an organic resin component, and suitable examples of the organic resin component are as described above. That is, curable resins such as a compound having at least one epoxy group, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and an alicyclic compound are preferable, and among them, an alicyclic compound is preferable.
Hereinafter, compounds having at least one epoxy group, polyhydric phenol compounds, and compounds having a polymerizable unsaturated bond that can be suitably used as the organic resin of the present invention will be described. 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 in the resin composition. It is suitable that it is contained in.
The organic resin preferably has at least one epoxy group. By having at least one epoxy group, it exhibits heat resistance comparable to that of inorganic glass while exhibiting excellent properties such as excellent molding and workability while having workability equivalent to that of conventional thermosetting plastic materials. be able to. As described above, the resin composition having at least one epoxy group is also one of the preferred embodiments of the present invention.

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

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

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.

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.

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

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

Other compounds that can be used as the compound having a polymerizable unsaturated bond include monofunctional (meth) acrylamides such as N-isopropyl (meth) acrylamide; polyfunctional (meth) acrylamides such as methylenebis (meth) acrylamide. Carboxylic acid vinyl derivatives such as vinyl acetate and vinyl cinnamate; styrene derivatives such as styrene and divinyl styrene; lauryl acrylate, isodecyl acrylate, isostearyl acrylate, lauryl alcohol ethoxy acrylate, epoxy stearyl acrylate, 2- (1- Methyl-4-dimethyl) butyl-5-methyl-7-dimethyloctyl acrylate, phenoxyethyl acrylate, phenoxyethoxyethyl acrylate, phenol polyalkoxy acrylate, Ruphenoxyethyl acrylate, nonylphenol ethylene oxide modified acrylate, nonylphenol polypropylene oxide modified acrylate, butoxypolypropylene glycol acrylate, tetrahydrofurfuryl alcohol lactone modified acrylate, lactone modified 2-hydroxyethyl acrylate, 2-ethylhexyl carbitol acrylate; 2-hydroxy-3 -Phenoxypropyl acrylate, acrylic acid dimer, ω-carboxy-polycaprolactone monoacrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicycle Acrylates such as lopentenyl acrylate, tricyclodecanyl acrylate, tricyclodecanyloxyethyl acrylate, isobornyloxyethyl acrylate; acrylamides such as acryloylmorpholine, diacetone acrylamide; N-vinylpyrrolidone, N-vinylcaprolactam, etc. N-vinyl amides; vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether; maleimides such as chlorophenyl maleimide, cyclohexyl maleimide and lauryl maleimide; ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, Dipropylene glycol diacrylate, neopentyl glycol hydroxypivalate Acrylate, diacrylate of bisphenol A ethylene oxide adduct, diacrylate of bisphenol A propylene oxide adduct, 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.

The curable resin composition of the present invention preferably contains an inorganic fine particle component in addition to the above-described resin and the like. When the resin composition contains an inorganic fine particle component and an organic resin component, the resin composition can further be high in strength, can be continuously produced, can be easily molded, and has high transparency. Both the transparency and the Abbe number are high, and the optical properties such as the refractive index are excellent. In particular, the resin composition can be suitably used for optical applications that require a high Abbe number. The resin composition of the present invention can perform complicated processing that cannot be performed with glass at low cost, and has heat resistance that cannot be achieved with a thermoplastic resin, particularly when a thermosetting resin is used. 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. In addition, the resin composition containing an inorganic substance can reduce the coefficient of thermal expansion, and by controlling the appearance of the resin composition and its cured product by adjusting the refractive index of the inorganic substance and the resin, transparency Therefore, it is particularly useful as a material in electrical / electronic component materials and optical applications.
The present invention is also an organic-inorganic composite resin composition comprising an organic resin component and an inorganic fine particle component, wherein the organic resin component is an organic-inorganic composite resin composition comprising an organic resin component having a molecular weight of 700 or more. is there. Even in this case, it is a more preferable form that the organic resin component contains an organic resin component having a molecular weight of less than 700. As for the content of the organic resin component having a molecular weight of less than 700, preferred compounds, etc., the viscosity of the resin composition can be reduced. The organic resin component having a molecular weight of 700 or more is preferably contained in an amount of 15 to 90% by mass with respect to the total amount of the organic resin component. More preferably, it is 30-90 mass%. Even when an organic resin component having a molecular weight of less than 700 is not contained, by containing inorganic fine particles, the coefficient of thermal expansion can be lowered, and further, the effect of increasing the Abbe number of the resin composition can be obtained. it can. 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, which 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, for example, when a thermosetting resin (particularly an epoxy material) is included as an organic resin component, the organic resin component has an adhesive effect, and when such a resin composition is cured, it becomes a mold. There is a risk of adhesion. By adding an appropriate amount of the inorganic fine particle component, a mold release effect can be seen and it can be easily peeled off from the mold.

When the resin composition contains inorganic fine particles, the content of the flexible component is 40 to 99 mass% of the organic resin component in a total of 100 mass% of the organic resin component, the inorganic fine particle component, and the flexible component. %, 1 to 60% by mass of the inorganic fine particle component, and 0.01 to 40% by mass of the flexible component. A resin composition having a flexible component of 40% or less is preferable. More preferably, it is 0.1-30 mass% as content of a flexible component, More preferably, it is 0.5-20 mass%.
As described above, the resin composition of the present invention contains an organic resin component and inorganic fine particles, and preferably contains 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 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 the resin such as the resin composition of the present invention is formed, the solvent is deaerated. Usually, however, the viscosity of the solvent increases and gelation may occur, resulting in poor productivity. When the inorganic fine particles having the above pH are used, since the pH is high, the thickening at the time of solvent degassing is small, and no gelation occurs. In particular, when an alicyclic epoxy compound and / or a hydrogenated 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. More preferably, it is 4-9 as pH of the said inorganic fine particle, More preferably, it is 4-7, Most preferably, it is 4-6. By setting it as such a range, coloring of a resin composition can be suppressed more fully. In addition, when the resin composition includes a compound having an unsaturated bond, that is, the resin composition includes an organic resin component and inorganic fine particles, and the organic resin component requires a compound having an unsaturated bond. When used in a low Abbe optical member, the proportion of the compound having an unsaturated bond is preferably 100% by mass of the resin composition (organic resin component, inorganic fine particles and other components as required), It is 10 mass% or less. More preferably, it is 8 mass% or less, More preferably, it is 6 mass% or less. Particularly preferably, it is not substantially contained.

The pH of the inorganic fine particles is a value measured 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.
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 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 material having a molecular weight of 700 or more and silica particles is also one of the preferred embodiments 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 particle is a fine particle containing silica, it is obtained by performing silica precipitation by neutralization or decomposition reaction with an acid or alkali metal salt of a sodium silicate aqueous solution. That is, as the resin composition, a resin composition containing wet inorganic fine particles and an alicyclic compound as essential is preferable. Thus, a resin composition containing 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, and the organic resin A resin composition in which the component is essentially an alicyclic epoxy compound and / or a hydrogenated epoxy compound is also a preferred embodiment of the present invention.
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.
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 blended in this way is preferably dispersed in the resin composition with a primary particle size. That is, the inorganic fine particles are preferably in the form of a dispersion (inorganic fine particle dispersion). More preferred is a wet silica dispersion. When the inorganic fine particle component is dispersed with a primary particle size, the resin composition is not cloudy, and the resin composition can be suitably used for various applications, but the primary particles aggregate to form secondary particles. And when it becomes a magnitude | size comparable to visible light, there exists a possibility that a resin composition may become muddy and an Abbe number may become small.

In the curable resin composition of this invention, the cured | curing material which was more excellent in transparency can be given by containing an inorganic fine particle. And if transparency is improved, the performance as an optical member will improve and it will become a curable resin composition which can be used suitably for various uses, such as an optical use, an opto device use, a display device use. In order to improve transparency, the inorganic fine particles (inorganic fine particles in the 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 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 resin composition becomes transparent. As a 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) a curable material having a molecular weight of 700 or more A form containing inorganic fine particles having a particle diameter of 100 nm or less is preferable.
The particle size distribution of the inorganic fine particles (inorganic fine particles in the resin composition) is 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. More preferably, the primary particle size is 1 nm to 100 nm, more preferably 1 nm to 50 nm as the particle size distribution of the inorganic fine particles.
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 the 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.

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 dispersion state of inorganic fine particles and individual particle diameters in the 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 so as to obtain an appropriate fine particle concentration, the dispersion state of the fine 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 described 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.

In the case of the curable resin composition containing the organic resin component and the inorganic fine particle component, the organic resin component is 40 to 99% by mass and the inorganic fine particle component is 100% by mass in total of the organic resin component and the inorganic fine particle component. It is preferable to contain 1-60 mass%. By setting it as such content, it can be set as the resin composition by which transparency and the Abbe number were controlled. 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 15-30.

In the resin composition of the present invention, inorganic fine particles having a pH of 4 to 9 (preferably 4 to 6) at 25 ° C. when dispersed as 15% by mass in the solution, and an average particle size of less than 100 nm, A form that is a resin composition comprising an alicyclic curable material and / or a hydrogenated curable material is preferable. In such a form, the Abbe number can be improved by using an alicyclic curable material and / or a hydrogenated curable material, and since there is no volatilization of the solvent during curing, continuous production is possible. Since it can be dispersed, it is possible to produce optical resins with high transparency and heat resistance. 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 present invention, a resin composition comprising an organic resin component and an inorganic fine particle component, the inorganic fine particle component essentially comprises inorganic fine particles obtained by a wet method, A form in which the resin component is a resin composition having an Abbe number of 45 or more is also preferable. In the resin composition of the present invention, as a preferable form, an organic resin having an Abbe number of 45 or more is contained as an organic resin component in an amount of 40% or more (preferably 60 or 80% or more) in the total organic component, and wet inorganic (silicon (Oxide) content is 10 to 40% (preferably 15 to 30), and more preferable form is 40% or more (80% or more) of alicyclic curable material and / or hydrogenated curable material, It is a form comprising 10% or more of wet silica, and more preferred forms include 40% (80%) or more of alicyclic epoxy compound and / or hydrogenated epoxy compound and 10% or more of wet silica dispersion. It is a form. Thus, it manufactures using the resin composition (transparent resin composition) which consists of an alicyclic epoxy compound and / or a hydrogenated epoxy compound, and a weakly acidic wet silica dispersion, and the inorganic fine particle of the pH range mentioned above. A method for producing a resin composition is also one of the preferred embodiments of the present invention.

In addition, by combining suitably the preferable form of the inorganic microparticles | fine-particles described in this specification, etc. 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. As the inorganic fine particles, metal oxides containing metal elements such as silicon, titanium, zirconium, indium, tin, lanthanum, and yttrium as metal components, and those essentially containing organopolysiloxane are suitable. Depending on the above, preferred inorganic fine particles can be appropriately selected. For example, for low refractive index optical members (high Abbe optical members), metal oxide particles having a refractive index of 1.5 or less are preferable. For example, metal oxides containing silicon as a metal component (for example, silica particles). Etc. are suitable. For high refractive index optical members (low Abbe optical members), metal oxide particles having a refractive index of 1.9 or more are preferable. For example, from the group consisting of titanium, zirconium, indium, tin, lanthanum, and yttrium. Metal oxide particles containing a selected metal element as a metal component are preferred. Inorganic components in the inorganic fine particles include metal oxides, hydroxides, (acid) nitrides, (acid) sulfides, carbides, halides, sulfates, nitrates, (basic) carbonates, (basic) Examples include acetate 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, non-stoichiometric composition: for example, a metal element such as ZnO _(1-δ) , TiO _(2-δ) , Ni _(1-δ) O or an 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 employed. The form of the metal oxide includes both crystalline and non-quality. Whether it is crystalline or amorphous, and whether the crystallinity is high or low can be usually evaluated by X-ray diffraction measurement. Hydrated metal oxides are also included in the metal oxide referred to in the present invention. Moreover, the thing which the residue, atom, and atomic group derived from the raw material in the manufacture process of metal oxide particle couple | bonded with a part of surface or internal metal atom or oxygen atom may be contained. Examples thereof include an organic group, a hydroxyl group, a nitrate group, a sulfate group, a halogen atom, a hydrogen atom, and an alkali metal atom (ion). Examples of the organic group include alkoxy groups such as methoxy group and butoxy group; carboxyl groups such as ethanoyl group (acetoxy group) and propanoyl group; β-dicarbonyl group; β-ketoester group; alkyl group; cycloalkyl group; An aralkyl group or the like is preferably exemplified.

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

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

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

As the inorganic fine particles, inorganic fine particles obtained by a liquid phase 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 oxygen atoms are shared. When silica is produced by thermal decomposition of silicon halide or air oxidation of heat-reduced silica sand, all the 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 the inorganic fine particles are hydrolyzed condensates of alkoxide compounds and / or carboxylate compounds. 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 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 mass, more preferably 20 to 50% by mass 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 mass% of the whole solvent dispersion, More preferably, it is 80-50 mass%.

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; phthalates such as dimethyl phthalate, dibutyl phthalate and octyldecyl phthalate Plasticizers; aliphatic-basic acid ester plasticizers such as butyl oleate and glycerol monooleate; aliphatic dibasic acid plasticizers such as dibutyl adipate and di-2-ethylhexyl sebacate; diethylene glycol Examples of conventionally known plasticizers such as 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 having a fine particle size is obtained, and the compounding effect of the fine particles in the obtained resin composition (For example, the effect of reducing the coefficient of thermal expansion, the effect of improving the Abbe number, the effect of controlling the refractive index, etc.) is preferable. Specifically, the primary particle size of the fine particles is 1 nm to 400 nm, more preferably 100 nm. Hereinafter, it is more preferably 50 nm or less, particularly preferably 20 nm or less. The primary particle 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 (m ² / g) of metal oxide-based particles measured by BET method), or crystalline Can be determined by measuring the crystallite diameter by X-ray diffraction measurement.
The dispersed particle size of the fine particles in the inorganic fine particle powder and fine particle dispersion is preferably distributed in the primary particle size or a size close thereto, specifically, the average particle size is 400 nm or less, more preferably It is 70 nm or less, particularly preferably 30 nm or less. The dispersed particle size can be evaluated by a dynamic light scattering method, a centrifugal sedimentation method, or the like. The primary particle size and the dispersed particle size in the resin composition are preferably in the same range as in the case of the fine particle powder and fine particle dispersion, and can be evaluated by the small angle X-ray scattering method described above.
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 resin composition of the present invention, it is preferable that wet inorganic fine particles are essential. For example, inorganic fine particles obtained by a gas phase synthesis method or a solid phase synthesis method may be included. As described above, 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, which is obtained without passing through 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 go through the process of dry powder until it is used as a raw material of the composite resin composition (resin composition) of the present application from the synthesis (generation) of fine particles (liquid phase synthesis method) without passing through a dry product, This is 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 of evaporating an inorganic or organic metal salt and usually thermally decomposing it at high temperature (oxidation) in the air. For example, a method of heating a metal halide to oxidize it into an oxide (for example, aluminum, silicon Gasification of halides such as titanium, and high-temperature vapor-phase oxidative decomposition with oxygen or water vapor is an industrial process for producing fine powders of alumina, silica, titanium oxide, etc.), oxidative pyrolysis of metal carbonyl compounds and organometallic compounds The method of doing is illustrated. Moreover, the method (for example, the industrial manufacturing method of French method ZnO) which heats a metal raw material (a metal, a mineral), and oxidizes metal vapor | steam at high temperature is illustrated.
[Solid-phase synthesis method]
Examples thereof include a method in which a metal hydroxide or carbonate is heated and decomposed to obtain an oxide. An example is a method in which an intermediate of a metal oxide (hydrate) is obtained by a liquid phase 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 using an acid alkali, a hydrolysis / condensation method of an organometallic compound, a hydrolysis / condensation method of a metal halide, a hydrothermal reaction, or the like can be preferably employed.
Decomposition precipitation method with acid alkali: Reactions such as decomposition of an aqueous solution of a metal salt with an alkali, decomposition of a basic salt with an acid, and metathesis of a metal salt and a basic salt are exemplified. The method for producing silica particles by the neutralization reaction of an aqueous solution of water glass described later with an alkali is an example of a decomposition precipitation method with an acid alkali.
By these precipitation methods, a reaction solution of a metal oxide or oxide hydrate is usually obtained, but these can be preferably employed as a raw material for metal oxide fine particles of the present invention.
Of the above-mentioned various methods, except for the hydrolysis and condensation methods of organometallic compounds, usually after removing impurities by filtration and washing, pulverization and / or (solvent replacement and redispersion of powder in dispersion medium) It is preferable to use after dispersion.
In the case of the hydrolysis / condensation method of the organometallic compound, it can be processed into a desired form (powder, dispersion) from the obtained reaction solution without passing through the washing step.
After obtaining a reaction solution of metal oxide (hydrate) fine particles by a liquid phase synthesis method, a consistent liquid phase process is prepared that is mixed with a resin component without passing through a drying step. Aggregation can be avoided, which is preferable. Specifically, the reaction solution is concentrated as necessary, and removal of the solvent component in the reaction solution and substitution with a desired dispersion medium (resin component, monomer, solvent, etc.) are performed simultaneously, such as heating solvent replacement. A process is preferred.

Among the liquid phase synthesis methods of the inorganic fine particles, an organic metal compound hydrolysis / condensation method that can be preferably applied to the 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 (1);
M ′ (OR ² ) _n2 (1)
(Wherein M ′ represents a metal element, R ² represents an alkyl group or an acyl group, and n2 represents an integer of 1 to 7) and / or the following general formula (2);
(R ³ ) _m2 M ′ (OR ² ) _p (2)
(Wherein, M ′ and R ² are the same as those in the general formula (1). R ³ represents an organic group, and m2 and p represent an integer of 1 to 6). .

As the alkyl group of R ^{2 in} the general formula (1) and the general formula (2), an alkyl group having 1 to 5 carbon atoms is preferable, and an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. Group, 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 (2), an organic group having 1 to 8 carbon atoms is preferable, and a methyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and other alkyl groups; 3-fluoropropyl group, 3-chloropropyl group, 3, 3 Halogenated alkyl groups such as 3-trichloropropyl group; mercapto group-containing alkyl groups such as 2-mercaptopropyl group; 2-aminoethyl group, 2-dimethylaminoethyl group, 3-aminopropyl group, 3-dimethylaminopropyl Amino group-containing alkyl groups such as phenyl group; phenyl group, methylphenyl group, ethylphenyl group, methoxyphenyl group, ethoxyphenyl group, fluorophenyl group, chloropheny Aryl 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.

As the metal element M ′ in the general formula (1) and the general formula (2), any element of the periodic table can be used as long as it is a metal element capable of taking the structure of the compound represented by the general formula (1) and the general formula (2) However, the same metal (M) as described above may be employed. 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 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. Moreover, in order to advance a 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. It is preferable that reaction temperature is 0-120 degreeC normally, More preferably, it is 10-100 degreeC.
A catalyst and conditions suitable for the internal addition method will be described later.

Next, silicon 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 (dispersions) include polyorganosiloxane-based materials in which an organic group such as an alkyl group is bonded to a part of silicon in addition to silica particles containing SiO ₂ as a main component. Particles. As the polyorganosiloxane, a conventional polyorganosiloxane can be employed, and a non-particulate polyorganalsiloxane can also be suitably used. For example, linear silicone compounds such as polydimethylsiloxane, polymethylphenylsiloxane, polydiphenylsiloxane, polysilsesquioxane compounds such as polymethylsilsesquioxane, polyphenylsilsesquioxane, carboxyl group modification, alcohol modification And modified silicone compounds such as amine modification, polyether modification, and epoxy modification. When polyorganosiloxane is contained in the resin composition, the content thereof is preferably in the range of 0.01 to 10% by mass, more preferably 0.1 to 2% by mass, based on the total mass of the resin composition. The range of is preferable. The polyorganosiloxane can be applied to both high Abbe optical members and low Abbe optical members.
For example, as polyorganosiloxanes such as polyorganosiloxane particles such as polymethylsilsesquioxane particles, general formula (3);
R _m3 SiO _(4-m3) / 2 (3)
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-mentioned decomposition and precipitation methods using an acid-alkali) or by bringing a water glass aqueous solution into contact with an ion exchange resin. A method of ion exchange between an alkali metal component and proton (ion exchange method) is preferably used. According to this method, colloidal silica particles are produced.
From the resulting reaction liquid (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 (1), the silicon compound in the case of M ′ = Si is hydrolyzed and condensed in a water-containing organic solvent, preferably a water-containing alcohol, preferably in the presence of a hydrolysis catalyst. Is obtained. The catalyst is preferably an inorganic acid such as hydrochloric acid or nitric acid, an acid catalyst such as carboxylic acid such as acetic acid, or a basic catalyst such as ammonia or amine, and particularly preferably a basic catalyst.
By concentrating and / or replacing the obtained silica particle reaction liquid with a desired organic solvent, a fine particle dispersion of silica particles can be obtained.

Polyorganosiloxanes such as organosiloxane-based particles, etc. General formula (3) Example of production method of R _m3 SiO _(4-m3) / 2 At least one kind or at least one kind of silicon compound in the case of M ′ = Si in the general formula (2) and at least one kind of silicon compound in the case of M ′ = Si in the general formula (1) are the above (b). It is obtained by (co) hydrolysis / condensation in the same manner as.
As an example of an industrially available silicon-based oxide particle dispersion, an organosilica sol manufactured by Nissan Chemical is suitable.

As a method for producing inorganic fine particles and non-particulate polyorganosiloxane used in the present invention, an alkoxide compound and / or a carboxylate compound is hydrolyzed and dissolved in a liquid medium containing the organic resin component described above. A method of condensing to obtain inorganic fine particles (internal 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.

Another description of the resin composition is as follows. It is common to both the internal precipitation method and the external addition method.
The resin composition of the present invention preferably contains the inorganic fine particles in an amount of 1% by mass or more, more preferably 5% by mass or more and 50% by mass or less, and more preferably 40% by mass or less. By setting it as 1 mass% or more, the improvement effect of the flame retardance and thermal property of the resin composition obtained will fully express. If it exceeds 50% by mass, the viscosity may be increased and the composition may not be mixed uniformly. When polyorganosiloxane (particulate or non-particulate) is used instead of inorganic fine particles, the above-mentioned range is preferable.

The resin composition is preferably in the form of two or more organic resins and inorganic fine particles 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, 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. Thus, a resin composition containing an organic resin component and an inorganic fine particle component, wherein the resin composition is prepared by preparing two or more organic resins and inorganic fine particles in a solvent of 5% by mass or less. A thing is also one of this invention. The same method can be suitably used when polyorganosiloxane (particulate or non-particulate) is used instead of inorganic fine particles.

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 preferred embodiment 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 a resin composition can be suitably obtained. As the solvent, 2-ethyl-1-hexanol, dodecanol and the like are preferable. The same applies when polyorganosiloxane (particulate or non-particulate) is used instead of inorganic fine particles.

The above resin composition contains a high molecular weight component and a low molecular weight component, and it is one of the preferred forms that further contains inorganic fine particles. These preparation methods include low molecular weight components and inorganic fine particles ( And other components as needed), and after distilling off the solvent (solvent), a method of adding a high molecular weight component is preferred. The mixture (low molecular weight component, inorganic fine particles, high molecular weight component, solvent (and In a mixture of 100% by mass with other components) if necessary, a form prepared by adjusting the solvent to 5% by mass or less is preferable. During the formation of the resin (resin composition), the solvent is distilled off. Normally, the viscosity of the resin composition is increased by heating such that the high molecular weight component forms a chemical bond or a physical bond with the inorganic fine particles. However, by mixing as described above, a suitable resin composition can be obtained without increasing the viscosity of the resin composition. Further, the familiarity of the high molecular weight material with the resin composition can be improved. Thus, a method for producing a resin composition comprising 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 solvent of 5 mass. A method for producing a resin composition including a step of preparing at a% or less is also one of the preferred embodiments of the present invention. More preferable as such a production method is a form in which the above two or more organic resins essentially require a molecular weight of 700 or more (high molecular weight component) and a molecular weight of less than 700 (low molecular weight component). . 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 weight component, the inorganic fine particles, and the solvent, and then the high molecular weight component is added. The same method can be suitably used when polyorganosiloxane (particulate or non-particulate) is used instead of inorganic fine particles.

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 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)] × 100 = 15 to 90%. More preferably, it is 30 to 90%, still more preferably 35 to 80%, and particularly preferably 40 to 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 them, it is preferable to include an alicyclic epoxy compound and / or a hydrogenated epoxy compound, particularly an alicyclic epoxy compound. That is, it is preferable to use a high molecular weight epoxy compound as the high molecular weight component and a low molecular weight epoxy compound as the low molecular weight component. Further, as described above, the inorganic fine particle component is preferably silica. Thus, a resin composition in which two or more types of epoxy compounds are mixed with silica in a solvent of 5% or less is also a preferred embodiment of the present invention. The same method can be suitably used when polyorganosiloxane (particulate or non-particulate) is used instead of inorganic fine particles.

The method for producing the resin composition of the present invention is not particularly limited as long as the resin composition can be produced. For example, (1) a mixture containing inorganic fine particles (or polyorganosiloxane), an organic resin and a solvent. And (2) a degassing step of degassing the solvent from the mixture.
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 same method can also be used when polyorganosiloxane that is not particulate is used instead of the inorganic fine particle component.

The degassing step (2) is preferably performed in the presence of a high-boiling component. By deaeration in the presence of a high-boiling component, the inorganic fine particle component (or non-particulate polyorganosiloxane) can be increased in concentration, and a resin composition having both high transparency and high Abbe number can be obtained. it can. 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 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 process or (3) in the degassing process. Among these, (1) is preferable for preventing thickening. Thus, the production method of adding the high boiling point material before degassing the solvent after mixing the inorganic substance such as the inorganic fine particle component or non-particulate polyorganosiloxane and the organic substance such as the organic resin component is also the present invention. It is one of the preferable forms.

The amount of the high-boiling 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 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%.
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%. Further, when using non-particulate polyorganosiloxane instead of the inorganic fine particle component, the same amount of the high boiling point component can be preferably used.
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

The degassing step is not particularly limited as long as the solvent can be degassed, but it is preferably a condition that suppresses excessive decomposition of the organic resin component, curing reaction, and aggregation of the inorganic fine particle component. 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 same method can be preferably used when non-particulate polyorganosiloxane is used instead of the inorganic fine particle component. Further, an inorganic fine particle component and a non-particulate polyorganosiloxane may be used in combination.

As the high boiling point component, alcohol having a boiling point of 100 ° C. or higher such as 2-ethyl-1-hexanol, dodecanol, butanol and the like is preferable. More preferred is an alcohol having a boiling point of 120 ° C. or higher (specifically, 2-ethyl-1-hexanol or dodecanol), and still more preferred is an alcohol having a boiling point of 150 ° C. or higher. Thus, the composition whose high boiling point material is alcohol is preferable. Among alcohols having a boiling point of 120 ° C. or higher, 2-ethyl-1-hexanol and dodecanol are more preferable, and 2-ethyl-1-hexanol is more preferable. An alcohol having a boiling point of less than 100 ° C is preferably an alcohol having a boiling point of 100 ° C or higher because the thickening of the mixture may not be sufficiently prevented. A method for producing a resin composition in which the high-boiling component is an alcohol having a boiling point of 100 ° C. or higher is also one preferred form of the present invention. Among alcohols having a boiling point of 120 ° C. or higher, alcohols having a boiling point of 150 ° C. or higher are more preferable, and alcohols having a boiling point of 190 ° C. or higher are more preferable.

The resin composition of the present invention is preferably produced by the method described above. That is, a method for producing a resin composition containing an organic resin component and an inorganic fine particle component, the production method comprising a step of preparing a mixture containing inorganic fine particles, an organic resin component and a solvent, and a solvent from the mixture. A method for producing a resin composition comprising a deaeration step of deaeration, wherein the deaeration step is performed in the presence of a high-boiling component is also a preferred embodiment of the present invention.
In the said manufacturing method, although the resin composition manufactured contains an organic resin component and an inorganic fine particle component, the above-mentioned thing can be used suitably as an organic resin component and an inorganic fine particle component. Moreover, all the description regarding a resin composition, such as another component and a hardening method, can be applied suitably to the manufacturing method of the said resin composition. The organic resin component is particularly preferably an alicyclic epoxy compound and / or a hydrogenated epoxy compound, and most preferably an alicyclic epoxy compound. A method for producing a resin composition is also one of the preferred embodiments of the present invention. A form using non-particulate polyorganosiloxane in place of the inorganic fine particle component is also a preferred form. Further, an inorganic fine particle component and a non-particulate polyorganosiloxane may be used in combination.

The resin composition of the present invention is preferably obtained from the above production method. In this case, in the above production method, degassing is performed in the presence of a high-boiling component, and the high-boiling component is contained in the composition. Since it remains, a high boiling point component is contained in the resin composition. 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. As described above, 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 (for example, a thermosetting material). A transparent resin composition containing an inorganic fine particle component (for example, an inorganic oxide) is also one preferred form of the present invention.

The resin composition of the present invention has a release agent, a curing agent, a curing accelerator, a reactive diluent, and an unsaturated bond in addition to the above-described resin and inorganic fine particles (or non-particulate polyorganosiloxane). 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 -An anti-sagging agent, an anti-coloring agent, an emulsifier, an anti-slip / scratch agent, an anti-skinning agent, a desiccant, an antifouling agent, an antistatic agent, and a conductive agent (electrostatic aid) may 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 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. As the alcohol, aliphatic alcohols are preferable, and octyl alcohol (octanol), lauryl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), and stearyl alcohol are more preferable.
The carboxylic acid having 8 to 36 carbon atoms is a monovalent or polyvalent carboxylic acid, and includes 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, and tetradecanoic acid. Pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like are suitable. Preferred are octanoic acid, lauric acid, 2-ethylhexanoic acid, and stearic acid.

The carboxylic acid ester having 8 to 36 carbon atoms is (1) carboxylic acid ester obtained from the above alcohol and carboxylic acid, and (2) carbon such as methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol, etc. Carboxylic acid ester obtained by the combination of the number 1-7 alcohol and the above carboxylic acid, (3) 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. Among 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, the resin composition containing a stearic acid compound is also one of the preferred embodiments of the present 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%.

Examples of the curing agent include various ones such as polymerization initiators such as thermal latent curing agents and photolatent curing agents, and acid anhydride curing agents. When a polymerization initiator is used, it can be cured in a short time, and thus is suitable for manufacturing a thin film material or a small thin film such as an imaging lens. Moreover, when using an acid anhydride hardening | curing agent, since the temperature at the time of hardening can be strictly controlled, it is suitable when manufacturing a thick film and a molded object.
Examples of the acid anhydride curing agent include phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, succinic anhydride, dodecynyl succinic anhydride, dichlorosuccinic anhydride, maleic anhydride, methyl nadic anhydride, anhydrous Pyromellitic acid, methylhexahydrophthalic anhydride, methylcyclohexene dicarboxylic acid anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, alkylstyrene-maleic anhydride copolymer And acid anhydrides such as tetrabromophthalic anhydride, polyazeline acid anhydride, chlorendic acid anhydride, and benzophenone tetracarboxylic anhydride. Among these, those that are liquid at room temperature are preferable from the viewpoints of workability during production, characteristics after curing, productivity, and the like.

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

As the heat latent cation generator, the following general formula (4);
_{^{(R 4 d R 5 e R}} 6 f R 7 g Z) + k (AX n3) -k (4)
(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 a halogen element. R ⁴ , R ⁵ , R ⁶ and R ⁷ is the same or different and represents an organic group, d, e, f and g are 0 or a positive number, and the sum of d, e, f and g is equal to the valence of Z. Cation (R ⁴ _d R ⁵ _e R ⁶ _f R ⁷ _g Z) ^{+ k} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, and B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. X represents a halogen element, and k is the net charge of the halide complex ion. K 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 removed 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 (AX _n3 ) ^{-k in} the general formula (4) include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexa Examples thereof include fluoroarsenate (AsF ⁶⁻ ) and hexachloroantimonate (SbCl ⁶⁻ ).
Furthermore, an anion represented by the general formula AX _n3 (OH) ^— can also be used. 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 resin composition of the present invention is preferably one that is released with a strength of 40 kgf / cm ² or less. In the said resin composition, when it molds with the intensity | strength of 40 kgf / cm < ² > or less, it peels easily in the said technical field, it can manufacture with sufficient productivity by a manufacturing process, and it is evaluated that continuous production of a resin composition can be performed. Means that If the mold release strength exceeds 40 kgf / cm ² , it cannot be produced with good productivity and may not be economical. The preferred peel strength, and at 20 kgf / cm ² or less, and more preferably at most 10 kgf / cm ² or less, still more preferably at most 1 kgf / cm ² or less, particularly preferably, 0.1 kgf / cm ² or less is there.
The peel strength is a necessary material hardness during continuous production of a transparent material, that is, a certain degree of material hardness (releasing to a strength of 40 kgf / cm ² or less) in a short time at a temperature of 150 ° C. or less at which a side reaction occurs. preferable. Such peel strength (material hardness) can be evaluated as follows, for example. The resin composition is cured to a SUS304 substrate shape at a height of 1 mm at 120 ° C. for 2.5 minutes, cooled to 30 ° C. within 30 s, and a cutter (manufactured by NTT Corporation, main body model number: L-500) at the interface between the resin and SUS304. The model number of the blade: BL-150P) can be pressed with a desired force (for example, a force with a peel strength of 40 kgf / cm ² ) to evaluate the ease of mold release. The force with a peel strength of 40 kgf / cm ² is calculated as a value when a load of 1.5 kg is applied to the interface between the resin of 2 cm in length and the SUS304 using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was set to 0.04 cm ² .

As a method for curing the resin composition of the present invention, various methods such as heat curing and photocuring can be suitably used. However, the resin composition may be mixed with a curing agent and other materials as required. A method is preferably used in which 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 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 resin composition after storage at 25 ° C. for 3 days is 200% or less as compared to immediately after mixing. If it exceeds 200%, it may be difficult to apply the liquid to the mold, and the fluidity in the mold may be adversely affected. More preferably, it is 180% or less, More preferably, it is 150% or less. Thus, the resin composition is also a resin composition in which the viscosity increase rate of the mixture in one liquid as a curable resin composition is 200% or less after storage at 25 ° C. for 3 days compared to immediately after mixing. This is one of the preferred embodiments of the present invention.

As a method for producing a cured product by curing the resin composition, a commonly used method can be suitably used, and can be appropriately selected according to the type of the resin composition as described later. However, it is preferable that the resin composition is cured within 5 minutes to produce a cured product. Specifically, the 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 within 5 minutes. It is preferable to cure. 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 resin composition, the production method is also a curing method for a resin composition in which the resin composition is cured within 5 minutes to produce a cured product. Moreover, it is one of the preferable forms of this 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 a force of 1 kgf / cm < ² > or more is 10% or less of hardening strength (hardness). Preferably there is. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, and still more preferably 0.01% or less.

In the 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 method for curing the 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 epoxy group, a cured product can be obtained by thermosetting using a curing agent. As the curing agent, it is preferable to use the thermal latent cation generator described above. Examples of the curing agent other than the thermal 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 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 epoxy group, a curing accelerator can be used, for example, triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, tris (dimethoxyphenyl). ) One or more organic phosphorus compounds such as phosphine are suitable. As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC.

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

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

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

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

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

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

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

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 (manufactured by Asahi Denka); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide) CD-1012 (manufactured by Sartomer) and the like are suitable. Among these, it is preferable to use an onium salt as the photocationic polymerization initiator. Moreover, as an onium salt, it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.

In the curing by irradiation with the active energy ray, it is preferable to use a photosensitizer in combination. It is preferable that the compounding quantity of the said photosensitizer is 0.1-20 mass% with respect to 100 mass% of resin compositions of this invention. If 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, it is preferable that the light transmittance in the visible light region (region having a wavelength of 360 to 780 nm) is 75% or more. The light transmittance of the cured product is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 87% or more.
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 there is no change in appearance such as generation of cracks, and the change rate of total light transmittance and turbidity is 20% or less.
More preferably, the change rate of the total light transmittance and turbidity is 15% or less, and more preferably 10% or less.
Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns 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. Therefore, the resin composition does not cause yellowing or strength reduction. Excellent heat resistance over time.

Since the cured product can exhibit excellent transparency and optical properties as described above, the resin composition of the present invention is preferably used for various applications such as optical applications, optical device applications, display device applications, and the like. Can do.
Thus, the curable material for optical members (the curable material using the resin composition) constituted by the resin composition is also one aspect of the present invention.
The curable material for optical members is a curable optical material formed from the resin composition, and is a heat / photocurable optical material that is cured by heat or light (thermosetting optical material or photocurable optical material). ) Is preferable.
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.

It is preferable that the curable material for optical members has a bending strength of 50 MPa or more when cured at 150 ° C. for 5 minutes. In the curable material for an optical member of the present invention, the resin composition contains a proportion of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution of 15 to 90% by mass with respect to the total amount of the organic resin component. Thus, the bending strength can be 50 MPa or more. In the curable material for optical members of the present invention, if the bending strength of the cured product when cured at 150 ° C. for 5 minutes is 50 MPa or more, cracking occurs during mold release using molding. Although it is difficult, if it is less than 50 MPa, cracking is likely to occur during mold release. The bending strength is more preferably 60 MPa or more, still more preferably 80 MPa or more, and particularly preferably 100 MPa or more.
As described above, the curable material for an optical member 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 5 minutes at 150 ° C. using a mold before post-cure (baking). Thus, the ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution of the resin composition is 15 to 90% by mass with respect to the total amount of the organic resin component, and is cured at 150 ° C. for 5 minutes. A resin composition having a bending strength of 50 MPa or more when cured is also one of the preferred embodiments of the present invention. The 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. Further, as the resin composition, a form containing an inorganic fine particle component (or non-particulate polyorganosiloxane) or a flexible component is also a preferred form. In such a case, the resin composition was cured under the above conditions. The bending strength is preferably 50 MPa or more.

The curable material for an optical member preferably has a bending strength of 40 MPa or more when cured at 150 ° C. for 10 minutes. The curable material for optical members of the present invention can have a bending strength of 40 MPa or more by being constituted by a resin composition in which an organic resin component and an inorganic fine particle component are appropriately combined. The bending strength is more preferably 60 MPa or more, still more preferably 80 MPa or more, and particularly preferably 100 MPa or more.
As described above, the curable material for an optical member 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 10 minutes at 150 ° C. using a mold before post-cure (baking). Thus, the ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution of the resin composition is 15 to 90% by mass with respect to the total amount of the organic resin component, and is cured at 150 ° C. for 10 minutes. A resin composition having a bending strength of 40 MPa or more when cured is also one of the preferred embodiments of the present invention.
The 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 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 from the above resin composition), a high Abbe optical member and a low Abbe optical member each have a preferable form. As the high Abbe optical member, among the above-described curable materials for optical members, a cured product having a double bond (aromatic ring or the like) content of 10% by mass or less in the resin is preferable. When the compound having a double bond such as an aromatic ring is 10% by mass or less in the resin composition, the optical properties such as the 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 for the following various applications.
Specific uses of the cured products include spectacle lenses, (digital) cameras, camera lenses such as 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; photo sensors, photo switches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical split Applications for optical devices such as LCDs, 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. , 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%”.

Synthesis example 1
_{(YX-8000 / YL7170 / SiO} 2 = 65/25/10 (wt%))
168 g of hydrogenated bisphenol A type epoxy resin JER YX8000 (manufactured by Japan Epoxy Resin, epoxy equivalent 205, weight average molecular weight 430) and organosilica sol MEK-ST (manufactured by Nissan Chemical Industries, particle size 10-15 nm, solid content 30%) 240 g was mixed uniformly, and the solvent was distilled off under reduced pressure using an evaporator at 80 ° C. to obtain 249.7 g of a resin composition 1. 34.7 g of resin composition 1, 25 g of hydrogenated bisphenol A type epoxy resin JER YL7170 (manufactured by Japan Epoxy Resin, epoxy equivalent 1400, weight average molecular weight 5550), and 41.6 g of JER YX8000 were each weighed and 140 ° C. And mixed uniformly. The yield was 101.3 g and the viscosity was 80 Pa · s. (Resin composition for Example 1)

Synthesis example 2
_{(YX-8000 / YL7170 / SiO} 2 = 45/245/10 (wt%))
34.7 g of resin composition 1, 45.1 g of hydrogenated bisphenol A type epoxy resin JER YL7170 (manufactured by Japan Epoxy Resin, epoxy equivalent 1400), and 21.6 g of JER YX8000 were weighed and evenly at 140 ° C. It mixed so that it might become. The yield was 100.2 g and the viscosity was 420 Pa · s. (Resin composition for Example 2)

Synthesis example 3
(YX-8034 / SiO ₂ = 90/10 (wt%))
168 g of hydrogenated bisphenol A type epoxy resin JER YX8034 (manufactured by Japan Epoxy Resin, epoxy equivalent 277, weight average molecular weight 580) and organosilica sol MEK-ST (manufactured by Nissan Chemical Industries, particle size 10-15 nm, solid content 30%) 240 g was mixed so as to be uniform, and the solvent was distilled off under reduced pressure using an evaporator at 80 ° C. The yield was 250.1 g and the viscosity was 65 Pa · s. (Resin composition for Example 3)

Synthesis example 4
(YX-8000 / SiO ₂ = 90/10 (wt%))
168 g of hydrogenated bisphenol A type epoxy resin JER YX-8000 (manufactured by Japan Epoxy Resin, epoxy equivalent 205) and organosilica sol MEK-ST (manufactured by Nissan Chemical Industries, particle size 10-15 nm, solid content 30%) 62.0 g Were mixed in a uniform manner, and the solvent was distilled off under reduced pressure at 80 ° C. using an evaporator. The yield was 187.0 g, and the viscosity was 65 Pa · s. (Resin composition for Comparative Example 1)

Synthesis example 5
34.7 parts of liquid epoxy resin ceroxide-2021P (alicyclic epoxy resin epoxy equivalent 131, weight average molecular weight 260, manufactured by Daicel Chemical Industries, Ltd.) as an epoxy resin in a four-necked flask equipped with a gas inlet, a condenser, and a stirring rod EHPE-3150 (alicyclic epoxy resin epoxy equivalent 131, weight average molecular weight 3520, Daicel Chemical Industries, Ltd.) 25 parts, Ogsol PG100 (aromatic epoxy resin, weight average molecular weight 530, Osaka Gas Chemical Co., Ltd.) 40 parts are charged. Stir well at 140 ° C. until uniform. Thereafter, KF-6004 as a silicon compound (modified silicone oil introduced with organic groups having polyoxyethylene chains and polyoxypropylene chains at both ends, weight average molecular weight 7.7621 × 10 ⁴ , manufactured by Shin-Etsu Silicone) 3 parts were added and stirred uniformly. Thereby, the resin composition for Example 4 was prepared.
In the resin composition, as shown in Table 1, the molecular weight distribution of the organic resin component is 76.5% by weight of the organic resin component having a molecular weight of less than 700 and 23.5% by weight of the organic resin component having a molecular weight of 700 or more. Among the organic resin components having a molecular weight of less than 700, the aromatic epoxy compound was 34% by weight and the alicyclic epoxy compound was 42.5% by weight.

Synthesis Example 6
40 g of Celoxide-2021P, 60 g of EHPE-3150, and 0.3 g of KF-6004 were weighed and mixed uniformly at 140 ° C. to prepare a resin composition for Example 5. Conditions such as temperature at the time of mixing are the same as those in Synthesis Example 5.

Synthesis example 7
100 g of Celoxide-2021P and 0.3 g of KF-6004 were weighed and mixed uniformly at 140 ° C. to prepare a resin composition for Comparative Example 2. Conditions such as temperature at the time of mixing are the same as those in Synthesis Example 5.

Synthesis example 8
100 g of Celoxide-2021P, 0.3 g of KF-6004, and 0.3 g of KF-6004 were weighed and mixed uniformly at 140 ° C. to prepare a resin composition for Comparative Example 3. Conditions such as temperature at the time of mixing are the same as those in Synthesis Example 5.

In the molecular weight distribution of the organic resin component of each resin composition obtained in Synthesis Examples 1, 2, 3, 5, and 6, in any resin composition, in each region having a molecular weight of 700 or more and less than 700. And had a maximum value of molecular weight peak.

(Preparation of curing resin composition)
To the above 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 wt% with respect to the total weight.
On the other hand, for the resin compositions obtained in Synthesis Examples 1 to 4, after cooling to 50 ° C., a cationic polymerization initiator (San-Aid SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) is based on the total weight. It added so that it might become 1 wt%, and it mixed so that it might become uniform.
For the resin compositions obtained in Synthesis Examples 5 and 7, after cooling to 50 ° C., 0.6 wt% of cationic polymerization initiator (San-Aid SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) with respect to the total weight. % And mixed to be uniform.
For the resin compositions obtained in Synthesis Examples 6 and 8, after cooling to 50 ° C., 0.2 wt% of the cationic polymerization initiator (San-Aid SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) with respect to the total weight. % And mixed to be uniform.

<Viscosity>
The viscosity at 40 ° C. and rotation speed D = 1 / s of the resin compositions obtained in Synthesis Examples 1 to 8 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.

<Measurement of molecular weight>
Under the above GPC measurement conditions, the resin compositions obtained in Synthesis Examples 1 to 8 were measured, and the proportion of organic resin components having a molecular weight of 700 or more was determined.
The content ratios of the compounds in the resin compositions obtained in Synthesis Examples 1 to 8 are shown in Table 1 below.

In Table 1, parts by weight of each component in the resin composition represent a relative weight ratio.

Next, the strength of the cured products obtained by curing the resin compositions obtained in Synthesis Examples 1 to 8 was evaluated by the method described below.
<Evaluation of strength (bending strength and elastic modulus)>
(Curing plate): Heat the resin composition as necessary (45 ° C., etc.), vacuum defoaming treatment, pour into a mold and cure in an oven at 150 ° C. for 5 minutes, and a resin with a thickness of 3 mm A cured plate was obtained.
(Strength measurement): Thermal properties and mechanical properties (bending strength / elastic modulus) were measured according to JIS K6911.

Moreover, the evaluation test of the refractive index of the hardened | cured material which hardened the resin composition obtained by the synthesis examples 1-6 by the method shown below, an Abbe number, transparency, and the intensity | strength at the time of peeling was done.
<Strength test during peeling>
As a necessary condition for continuous production of a molded body, a certain degree of material hardness is achieved in a short time at a temperature of 200 ° C. or less at which a side reaction occurs. The resin composition is cured at a height of 1 mm on a SUS304 substrate at 140 ° C. for 2 minutes, and 40 kgf of a cutter (manufactured by NTT Corporation, main body model number: L-500, blade model number: BL-150P) at the interface between the resin and SUS304. The material strength at the time of mold release was evaluated by pressing with a force of / cm ² . The force with a peel strength of 40 kgf / cm ² is calculated as a value when a load of 1.5 kg is applied to a 2 cm long resin and SUS304 interface using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was set to 0.04 cm ² .
The evaluation of releasability is indicated by ○ and ×.
○: Hard to crack ×: Easy to crack

<Transparency>
Transparency: The turbidity meter (Nippon Denshoku make, NDH2000) evaluated.
Heat was applied to the resin composition as necessary (45 ° C. or the like), and after that, it was poured into a mold and cured in an oven at 110 ° C. for 5 hours to obtain a cured product having a thickness of 1 mm. Refractive index and Abbe number were also evaluated using this molded body.

<Evaluation of refractive index and Abbe number>
Evaluation was performed using a refractometer (DR-M2 manufactured by Atago Co., Ltd.).
Table 2 below shows the results of the above evaluations on the cured products formed using the resin compositions of Synthesis Examples 1 to 8.

Moreover, about the resin composition adjusted using the synthesis examples 1-3 and the synthesis examples 5-6, the hardening evaluation conditions were changed and the strength evaluation test was done. The evaluation method is shown below, and the evaluation results are shown in Table 3 below.
<Evaluation of strength (bending strength and elastic modulus)>
(Curing plate): Heating the resin composition as necessary (45 ° C., etc.), vacuum defoaming treatment, pouring into a mold and curing in an oven at 150 ° C. for 10 minutes, 3 mm thick resin A cured plate was obtained.
(Strength measurement): Thermal properties and mechanical properties (bending strength / elastic modulus) were measured according to JIS K6911.

Synthesis Example 9
90 g of hydrogenated bisphenol A type epoxy resin JER YL-7170 and 33.4 g of organosilica sol MEK-ST were mixed, and then the solvent was distilled off under reduced pressure using an evaporator at 80 ° C. to obtain a resin composition. Obtained. The yield was 115 g (resin composition for Comparative Example 4). In the resin composition, the content of silica particles derived from MEK-ST was 10% by weight, and the content of the organic resin component having a molecular weight of less than 700 in the molecular weight distribution was 5% by weight. Further, the resin composition had almost no fluidity at normal temperature.

Comparative Example 4
To the resin composition obtained in Synthesis Example 9, in the same manner as in Synthesis Examples 1 to 8, at 80 ° C., stearic acid was added to 0.5 wt% as a release agent, and after cooling to 50 ° C. A curable resin composition was prepared by adding a cationic polymerization initiator (Sun-Aid SI-80L) to 1 wt% with respect to the total weight.
The obtained curable resin composition, like other curable resin compositions, was tried to be molded to evaluate the strength of the cured molded body, to evaluate the transparency, etc., but the fluidity was insufficient. I could n’t.

FIG. 1 is a schematic diagram showing a molecular weight distribution in a resin composition. (A) is a form in which one peak extends over both a region having a molecular weight of less than 700 and a region having a molecular weight of 700 or more. (B) is the form which has the maximum value of a peak in each of the area | region which is less than 700, and the area | region which is 700 or more. FIG. 2 is a chart showing GPC analysis results and calibration curves for one embodiment of the resin composition of the present invention.

Claims (20)

A resin composition for an optical member molded body containing an organic resin component,
The resin composition contains 15 to 90% by mass of an organic resin component having a molecular weight of 700 or more in the molecular weight distribution with respect to the total amount of the organic resin component, and an organic resin component having a molecular weight of less than 700 in the molecular weight distribution in the total amount of the organic resin component. 10 to 85% by mass with respect to
The organic resin component of the above molecular weight 700, an alicyclic epoxy compound and / or a hydrogenated epoxy compound only containing,
The organic resin component having a molecular weight of less than 700 includes an alicyclic epoxy compound and / or a hydrogenated epoxy compound,
The resin composition further includes a release agent,
The release agent is at least selected from the group consisting of an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, and a carboxylate having 8 to 36 carbon atoms. A resin composition for optical member molded bodies , which is a single compound . The resin composition for optical member molded bodies according to claim 1 , wherein the resin composition further contains a heat-latent cation generator. The said optical member molded object is a lens, The resin composition for optical member molded objects of Claim 1 or 2 characterized by the above-mentioned. The resin composition has, in its molecular weight distribution, a maximum value of at least one molecular weight peak in a region having a molecular weight of less than 700, and a maximum value of at least one molecular weight peak in a region having a molecular weight of 700 or more. The resin composition for optical member molded bodies according to any one of claims 1 to 3 . The resin composition contains at least one more than 700 of the organic resin component is a weight average molecular weight, and, according to claim 1-4, characterized in that the weight-average molecular weight is comprised of at least one organic resin component is less than 700 The resin composition for optical member molded bodies according to any one of the above. 6. The molded optical member according to claim 5 , wherein the resin composition has a total amount of organic resin components having a weight average molecular weight of 700 or more of 15 to 90% by mass based on the total amount of organic resin components. use resin composition. The resin composition, an optical member molded body resin composition according to any one of claims 1 to 6, characterized in that it comprises an organic resin component 40 to 99 mass%. The resin composition for optical member molded bodies according to any one of claims 1 to 7 , wherein the resin composition has an aromatic epoxy compound ratio of 10% by mass or less. The resin composition, an optical member molded body resin composition according to any one of claims 1 to 7, wherein the ratio of the aromatic epoxy compound is in excess of 10 mass%. The organic resin component is less than the molecular weight 700, according to claim 1 to 7, 9 an optical member molded body resin composition according to any one of which comprises an aromatic epoxy compound. The resin composition for optical member molded bodies according to claim 10 , wherein the aromatic epoxy compound essentially comprises an aromatic compound having a conjugated structure composed of 7 or more carbon atoms. The resin composition for optical member molded bodies according to any one of claims 1 to 11, wherein the resin composition is prepared by preparing two or more organic resin components in a solvent of 5 mass% or less. It said resin composition further the resin composition in 100% by mass, the optical member molded body according to any one of claims 1 to 1 2, characterized in that it comprises 0.01 to 10 mass% of high-boiling alcohol use resin composition. The high-boiling alcohol, claims 1 to 3 optical member molded body resin composition, wherein the boiling point of the alcohol of more than 120 ° C.. Curable material for optical member molded body characterized by being constituted by an optical element molded body resin composition according to any one of claims 1 to 14. The optical member molded body for a curable material, the flexural strength of the cured product when cured 5 minutes at 0.99 ° C. is cured optical member molded body according to claim 15, wherein a is more than 50MPa Sex material. The optical member characterized by comprising curing the curable material for the optical member molded product according to claim 15 or 16. The optical member according to claim 17, wherein the optical member is a high Abbe optical member. The optical member according to claim 17, wherein the optical member is a low Abbe optical member. A method for producing a resin composition for an optical member molded article comprising an organic resin component and a release agent,
The production method includes an alicyclic epoxy compound and / or a hydrogenated epoxy compound, an organic resin component having a weight average molecular weight of 700 or more, and an alicyclic epoxy compound and / or a hydrogenated epoxy compound. Including a step of mixing at least one organic resin component having a weight average molecular weight of less than 700 and a release agent,
In the mixing step, the ratio of the organic resin component having a molecular weight of 700 or more in the molecular weight distribution in the resin composition is 15 to 90% by mass with respect to the total amount of the organic resin component, and the molecular weight in the molecular weight distribution in the resin composition is less than 700. The organic resin component having a weight average molecular weight of 700 or more and the organic resin component having a weight average molecular weight of less than 700 are mixed so that the ratio of the organic resin component is 10 to 85% by mass with respect to the total amount of the organic resin component,
The release agent is at least selected from the group consisting of an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, and a carboxylate having 8 to 36 carbon atoms. The manufacturing method of the resin composition for optical member molded objects characterized by being one compound.

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