JP2009298995A - Composite particle, resin composition, and cured product thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: composite particles capable of producing a resin composition having excellent transparency and a high refractive index from them by enhancing dispersibility of inorganic fine particles in the resin composition; a resin composition containing the composite particles and resin components; and a cured product produced by curing the resin composition. <P>SOLUTION: The composite particle having an organic group on the surface includes a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of an inorganic fine particle. There are also provided a resin composition containing the composite particle and a cured product thereof. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to composite particles, a resin composition, and a cured product thereof. More specifically, the present invention relates to composite particles suitably contained in a resin composition useful for optical applications such as lens units and optical device applications, a resin composition containing the composite particles, and a cured product thereof.

Resin compositions are used as so-called plastic materials for machine part materials, electrical / electronic parts materials, automobile parts materials, civil engineering and building materials, molding materials, and the like, and are also used as materials for paints and adhesives. In recent years, plastic molding materials have attracted attention from the viewpoints of light weight and workability, and application has been attempted in various fields. One example is the application to the field of optical technology. In this field, for example, a digital camera module is mounted on a mobile phone. Instead of glass, plastic lenses such as PMMA / PC and polycycloolefin are being used. Furthermore, as new applications, there is a growing need for in-vehicle use such as in-vehicle cameras and barcode readers for home delivery companies.

Thus, application of a resin composition as a plastic molding material or the like to the optical field has been studied. However, in addition to being able to adapt to recent miniaturization and weight reduction, high performance in optical properties, mechanical strength, and heat resistance is required, but depending on conventional plastic materials, it is possible to achieve this high required performance could not. For example, in a plastic lens, there has been a demand for a resin composition excellent in transparency, mechanical strength, and heat resistance, and a cured product obtained by curing the resin composition.

One of the methods for controlling the optical properties, mechanical strength, heat resistance, etc. of the resin composition is to include inorganic particles in the resin composition. For example, regarding a method for producing a thermosetting resin composition, a thermosetting resin containing an alicyclic epoxy resin is dissolved and mixed in an organic solvent in which inorganic particles having a particle size of 70 nm or less are dispersed. A method for producing a thermosetting resin composition in which a curing agent is added and mixed after removing an organic solvent from the product is disclosed (for example, see Patent Document 1).
JP 2004-346288 A (page 2)

Addition of inorganic particles to the resin as described above is an effective means for the purpose of controlling the refractive index of lenses, improving mechanical strength, improving heat resistance, etc., but the dispersion of inorganic particles is not sufficient. However, there are problems that the effect of addition is not sufficiently exhibited and the transparency is not sufficient. For example, the inorganic particles that have become coarse due to agglomeration etc. are completely disappeared and sufficiently dispersed as primary particles, and there is room for contrivance in ensuring sufficient transparency without scattering visible light by the inorganic particles. was there. Further, in order to obtain excellent transparency, it is necessary to use fine inorganic particles of 0.1 μm or less, but as the particle diameter becomes finer, it is difficult to disperse with primary particles.

Furthermore, the resin usually has a refractive index of about 1.4 to 1.6, and in order to obtain a material having a higher refractive index than this, it is essential to add inorganic particles, particularly inorganic particles having a high refractive index. However, the higher the refractive index, the larger the difference in the refractive index from the resin. Therefore, what has a very high dispersibility that can be dispersed at a nano level and without aggregation is desired. For example, high-refractive-index metal oxide particles having a refractive index of 2 or more, such as titanium oxide and zirconium oxide, are known as nano-level high refractive index inorganic particles. It was high and it was difficult to disperse in resin at the nano level. In addition, as a technique for improving dispersibility, products having improved dispersibility such as aqueous sol or organic solvent sol have been developed. When an aqueous sol or organic solvent sol is used, the oxide itself In addition to the problem that the refractive index of the particles decreases due to the low crystallinity of the particles and the presence of a large amount of a dispersant for imparting dispersibility, the composition is prepared by blending with a resin. Further, the dispersibility was not sufficient in terms of causing secondary aggregation. As described above, in resin applications, particularly in optical resin applications, the development of fine particles with excellent dispersibility that can control optical physical properties such as refractive index while being excellent in transparency, especially in the field of lenses, etc. There has been an urgent need to develop fine particles that can provide excellent high refractive index materials.

The present invention has been made in view of the above situation, and has excellent dispersibility while having the properties of inorganic fine particles, that is, when dispersed in a resin composition or the like, has excellent transparency, It is an object to provide composite particles that can have a high refractive index, a resin composition containing the composite particles and a resin component, and a cured product obtained by curing the resin composition. is there.

The present inventor has examined inorganic fine particles added to a resin composition that can be suitably used for various plastic material applications, particularly optical applications. When the inorganic fine particles are contained in the resin composition, It has been noted that the transparency of the resin composition and its cured product is affected by the dispersibility of the inorganic fine particles in the resin composition. In order to prevent and further improve the transparency of the resin composition containing the inorganic fine particles and the cured product thereof, the surface of the inorganic fine particles has a conjugated aromatic skeleton having 7 or more carbon atoms. We have found that this can be achieved by using composite particles. That is, such composite particles have the properties of inorganic fine particles and have excellent dispersibility. For example, the composite particles can improve dispersibility in the resin component constituting the resin composition, and have transparency. It can be set as the improved resin composition. The effect of the present invention is particularly remarkable when inorganic fine particles having a high refractive index are used, or when fine particles are used as the inorganic fine particles, and more than 7 conjugated aromatics It has been found that since it has a skeleton on the surface, it can be suitably used for a resin composition or the like for which a high refractive index is desired. That is, the composite particles of the present invention can be suitably used for optical members that are required to have high transparency and refractive index, thereby conceiving that the above problems can be solved brilliantly, The present invention has been achieved.

That is, the present invention provides composite particles having a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of inorganic fine particles, a resin composition comprising the composite particles and a resin component, and curing the resin composition. Is a cured product.
The present invention is described in detail below.

The composite particles in the present invention have a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of the inorganic fine particles. That is, the composite particles include inorganic fine particles and a conjugated aromatic skeleton having 7 or more carbon atoms introduced on the surface thereof. The composite particles have a conjugated aromatic skeleton having 7 or more carbon atoms (hereinafter, also simply referred to as “conjugated aromatic skeleton”) on the surface of the inorganic fine particles. For example, the resin composition The dispersibility of the resin composition and the transparency of the resin composition and its cured product can be improved. Further, since the surface of the inorganic fine particle has a conjugated aromatic skeleton having 7 or more carbon atoms, the resin composition having a high refractive index can be obtained due to the conjugated bond.
The medium in which the composite particles are dispersed is preferably a resin component, whereby a resin composition having excellent optical properties, mechanical strength properties, heat resistance, and the like can be obtained. There is no particular limitation as long as the effect of improving dispersibility can be obtained. For example, when dispersed in an organic solvent or the like, the dispersibility can be improved, and the composite particles of the present invention can be suitably used.

As the above-mentioned “having on the surface” form, a form attached and / or bonded to the surface is preferable. For example, the composite particles having a conjugated aromatic skeleton are preferably in a form that does not leave even when washed with an organic solvent (for example, hexane, methanol, etc.) that can dissolve the conjugated aromatic skeleton. As an example, a compound containing a conjugated aromatic skeleton is attached to the surface of an inorganic fine particle (it may not be chemically bonded to an element constituting the surface of the inorganic fine particle), A form in which an element constituting the surface and an organic group containing the conjugated aromatic skeleton are chemically bonded (covalently bonded) is preferable.
In the composite particle of the present application, the content of the “conjugated aromatic skeleton having 7 or more carbon atoms” on the surface is not particularly limited, but the ash content in the composite particle is 100% by mass, and the carbon number is 7 or more. The conjugated aromatic skeleton is preferably 2% by mass or more from the viewpoint of excellent effect (dispersibility improvement effect) by having the organic skeleton. Moreover, it is preferable that it is 30 mass% or less. Even if it exceeds 30% by mass, the effect of improving dispersibility is difficult to further increase, and there is a possibility that the ratio of those that are detached from the inorganic fine particles by washing is increased. The content of the “conjugated aromatic skeleton having 7 or more carbon atoms” is more preferably in the range of 3 to 20% by mass, particularly preferably in the range of 5 to 15% by mass, for the reasons described above. It is. “Ash” is the amount of organic matter remaining on the surface of the inorganic fine particles after the composite particles are heated in an air atmosphere. More specifically, by TG-DTA (thermogravimetric-differential thermal analysis), it remains on the surface of the inorganic fine particles when the temperature is raised from 25 ° C. to 800 ° C. at a temperature rising rate of 10 ° C./min in an air atmosphere. It is the amount of organic matter.
The content of the conjugated aromatic skeleton having 7 or more carbon atoms, which does not leave even when washed with an organic solvent, is the same as the range described above. Of the conjugated aromatic skeleton having 7 or more carbon atoms on the surface, the higher the proportion of the conjugated aromatic skeleton having 7 or more carbon atoms on the surface that does not leave even after washing, the more preferable.

When the composite particles having the conjugated aromatic skeleton are in a form that does not leave even when washed with an organic solvent capable of dissolving the conjugated aromatic skeleton, the conjugated aromatic skeleton can be dissolved as one guideline. In a preferred embodiment, when 1 part of the composite particles is added to 100 parts by weight of the organic solvent and stirred for 12 hours using an organic solvent, the conjugated aromatic skeleton remains on the surface of the inorganic fine particles. is there. More specifically, when 1 part of the composite particles is added to 100 parts by mass of the organic solvent and the mixture is stirred for 12 hours at a temperature of 50 ° C. and a stirring speed of 100 rpm, a conjugated aromatic skeleton is formed on the surface of the inorganic fine particles. Is preferably left. For example, it is preferable that the organic component containing a conjugated aromatic skeleton on the surface of the inorganic fine particles in the state before washing is 100% by mass, and the extraction amount of the organic component extracted after washing is 10% by mass or less. It is. As the organic solvent for washing, hexane and methanol are preferable.

The composite particles are not particularly limited as long as they contain inorganic fine particles and a conjugated aromatic skeleton introduced on the surface of the inorganic fine particles, and may contain other components. For example, an organic component other than the conjugated aromatic skeleton may be attached or bonded to the surface of the inorganic fine particles.
The composite particles are preferably made of a single inorganic fine particle. That is, it is preferable that a plurality of primary particles are not aggregated due to aggregation or the like. For example, when the composite particles are observed with a transmission electron microscope, an image composed of inorganic fine particles is observed. The inorganic fine particles are preferably dispersed without agglomeration, and the particle diameter of the composite particles is And the number average particle size of the particle size is preferably 1 μm or less, more preferably 100 nm or less, and still more preferably 20 nm or less. Especially preferably, it is 15 nm or less.
The composite particles preferably have a refractive index of 1.6 or more. By setting the refractive index of the composite particles to 1.6 or more, the refractive index of the resin composition containing the composite particles and the cured product thereof can be further improved. The refractive index of the composite particles is more preferably 1.8 or more, and further preferably 2.0 or more. Moreover, since the content of the composite particles in the resin composition can be reduced by using composite particles having a high refractive index, the transparency can be further improved.

The composite particle of the present invention is not particularly limited as long as it has the conjugated aromatic skeleton on the surface of inorganic fine particles containing an inorganic element. As said inorganic type microparticles | fine-particles, it is preferable that the average particle diameter of a primary particle is 1 micrometer or less. When the average particle diameter exceeds 1 μm, sufficient transparency may not be obtained. More preferably, it is 100 nm or less, More preferably, it is 20 nm or less, Most preferably, it is 15 nm or less.

The primary particle diameter is a number average particle diameter obtained from a TEM image (transmission electron microscope observation image); E. T.A. The specific surface area diameter obtained by the method; the crystallite diameter obtained by the powder X-ray diffraction measurement method; Especially, the number average particle diameter obtained from a TEM image is preferable.
The shape of the inorganic fine particles is not limited to a spherical shape, and is, for example, an elliptical sphere, a cube, a rectangular parallelepiped, a pyramid, a needle, a column, a rod, a cylinder, a flake, a plate (for example, a hexagonal plate). For example, a flake shape such as a string shape or the like is preferable.
The inorganic fine particles preferably have a refractive index of 1.6 or more. When the refractive index of the inorganic fine particles is 1.6 or more, the refractive index of the resin composition containing the inorganic fine particles and the cured product thereof can be further improved. The refractive index of the inorganic fine particles is more preferably 1.8 or more, and further preferably 2.0 or more. Further, since the content of the inorganic fine particles in the resin composition can be reduced, the transparency can be further improved.

The composite particle is not particularly limited as long as it is a fine particle having the conjugated aromatic skeleton on the surface of an inorganic fine particle constituted by containing an inorganic element, but as an inorganic fine particle constituted by containing an inorganic element. Metal oxide fine particles, metal oxynitride fine particles, metal oxycarbide fine particles, metal oxysulfide fine particles, metal nitride fine particles, metal carbide fine particles, metal sulfide fine particles, metal telluride fine particles, metal selenide fine particles, metal fine particles Etc. Among these, those having a large number of metal hydroxyl groups on the surface are preferable, and specifically, a group consisting of metal oxide fine particles, metal oxynitride fine particles, metal oxycarbide fine particles, metal oxysulfide fine particles, and metal fine particles. It is preferably at least one selected from the group. More preferably, it is preferably at least one selected from the group consisting of metal oxide fine particles, metal oxynitride fine particles, metal oxycarbide fine particles, and metal oxysulfide fine particles. More preferred are metal oxide fine particles.

The inorganic fine particles are preferably metal oxide fine particles. By being a metal oxide fine particle, it can be used more suitably for applications that require transparency. Further, by reducing the particle size, for example, the inorganic fine particles are more suitable in the case of dispersing in the resin composition.
The metal oxide fine particles preferably contain at least one metal element selected from the group consisting of titanium, zirconium, zinc, lanthanum, yttrium, indium, tin and niobium. The metal oxide fine particles containing these metal elements can have a higher refractive index. Therefore, the resin composition comprising composite particles having the conjugated aromatic skeleton on the surface of the inorganic fine particles can have a higher refractive index. For example, it is particularly preferred when used as an optical member such as a lens for a camera, an antireflection film, or a light extraction layer used in an organic EL (electroluminescence) used in equipment requiring a high refractive index. Such metal oxide fine particles may be a single oxide (an oxide composed of a kind of metal element and oxygen), a solid solution form, or a composite oxide form. May be. The composite oxide is in the form of oxide fine particles containing two or more metal elements and oxygen. More preferably, it is a metal oxide fine particle containing a kind of metal element and oxygen. The metal element preferably contains zirconium, titanium, zinc and / or niobium as the metal element from the viewpoint of increasing the refractive index. In the present invention, the dispersibility in the resin composition can be improved by having a conjugated aromatic skeleton on the surface of the inorganic fine particles, but the effect of the present invention is introduced on the surface of the inorganic fine particles. If the effect of the present invention can be obtained with a kind of inorganic fine particles having a conjugated aromatic skeleton on the surface (for example, zirconium oxide fine particles) It is obvious that the effects of the present invention can be obtained with other metal elements. That is, the effect of the present invention can be obtained as long as the metal element has a conjugated aromatic skeleton on the surface. Note that zirconium oxide, which is one of metal oxides, is preferable in that it has a high refractive index of about 2.0 to 2.3, although the refractive index varies depending on the crystal system. Further, it is a preferred metal oxide not only with a high refractive index but also with a wide light transmission range, excellent chemical stability, and no photocatalytic activity. That is, it is one of the more preferable forms that the metal oxide fine particles are fine particles of zirconium oxide.

The conjugated aromatic skeleton means an aromatic skeleton including a conjugated structure having 7 or more carbon atoms in one conjugated unit. In other words, it is an aromatic skeleton having 7 or more carbon atoms belonging to an atomic group constituting one conjugated unit and having at least one such conjugated structure. The conjugated unit is preferably one having a conjugated double bond. Thus, when the aromatic skeleton is bonded to the surface of the inorganic fine particles, the cured product having a high refractive index when the resin composition containing the composite particles and the resin component is cured. Can do. The aromatic skeleton is an organic skeleton containing an aromatic ring. If the conjugated aromatic skeleton is an aromatic skeleton composed of atoms belonging to an atomic group constituting the conjugated structure, the form, etc. It is not particularly limited. Note that the conjugated unit includes at least two double bonds and one single bond, taking a conjugated double bond as an example. When the number of carbon atoms is counted as a single conjugated unit and a bond structure including the unit is shown, a group of portions related to resonance is called one conjugated unit. A preferred form of the conjugated unit will be described later.

Examples of the conjugated aromatic skeleton 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), dibenzothiophene ring represented by the above chemical formula (1-3) (conjugated structure composed of 12 carbon atoms), carbazole skeleton represented by the above chemical formula (1-4) (12) A conjugated structure composed of carbon atoms), a stilbene skeleton represented by the chemical formulas (1-5-1) and (1-5-2) (conjugated structure composed of 14 carbon atoms), and the chemical formula Biphenyl skeleton represented by (1-6) (a conjugated structure composed of 12 carbon atoms), naphthalene ring represented by the above chemical formula (1-7) (constituted by 10 carbon atoms) It is preferred to have at least one member selected from the group consisting of among conjugated structure) it was. In the case of increasing the refractive index, among these, a fluorene skeleton, anthracene ring, dibenzothiophene ring, carbazole skeleton, stilbene skeleton, biphenyl skeleton and naphthalene ring are preferable. That is, the composite particle in which the conjugated aromatic skeleton essentially includes at least one structure selected from the group consisting of a fluorene skeleton, an anthracene ring, a dibenzothiophene ring, a carbazole skeleton, a stilbene skeleton, a biphenyl skeleton, and a naphthalene ring. Is also one of the preferred embodiments of the present invention. Among these, more preferably, at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is essential.
Any conjugated aromatic skeleton may be used as long as it has the skeleton or ring structure described above. In addition, as represented by the above chemical formula (1-8), a structure in which bisphenol is bonded to a fluorene skeleton (a conjugated structure composed of 25 carbon atoms) and the like are more preferable.

In addition, specific examples of how to count the number of carbon atoms constituting the conjugated unit such as the above-described compound 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, carbon surrounded by a dotted circle is also part of the conjugated structure, and the number of carbon atoms constituting one conjugated structure is 13 It becomes a piece. Further, 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 carbon atoms constituting one conjugated 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 is bonded to the aromatic ring as in the fluorene structure, but the central carbon itself. Is not a 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 where the structures are represented by the following formulas (d) and (e).

The composite particle has a conjugated aromatic skeleton on the surface of the inorganic fine particle. As a form in which the inorganic fine particle and the organic group having the conjugated aromatic skeleton are bonded, M-O-Q A form formed by bonding in the form of (M represents a metal element constituting the surface of the inorganic fine particles. Q represents an organic group containing a conjugated aromatic skeleton having 7 or more carbon atoms) is preferable. Preferred metal element M is the same as the metal element constituting the metal oxide fine particles described above. Q may be in the form of an organic group in which no substituent is bonded to the conjugated aromatic skeleton, or in the form in which a substituent is bonded to the conjugated aromatic skeleton. As a more preferable form of M—O—Q bonding, an atom (terminal atom of Q) bonded to oxygen among atoms constituting the organic group Q is carbon or silicon.
In addition, although the form of the bond has been described here, as described above, the conjugated aromatic skeleton may be attached to the surface of the inorganic fine particles, and is limited to those that are chemically bonded. It is not a thing.

The composite particle preferably has a form in which an organic group containing the conjugated aromatic skeleton and a silicon atom is bonded to an atom constituting the surface of the inorganic fine particle. Further, it is more preferable that the conjugated aromatic skeleton is bonded to the atoms constituting the surface of the inorganic fine particles through an organic chain containing silicon atoms. For example, when a composite particle having the conjugated aromatic skeleton on the surface of the inorganic fine particle is obtained by performing a surface treatment, a hydrolyzable group bonded to a silicon atom and a conjugated aromatic skeleton having 7 or more carbon atoms By using a hydrolyzable silicon compound having, an organic group containing a stable conjugated aromatic skeleton can be uniformly bonded to the surface of the inorganic fine particles. Thus, the composite particle has an organic group on the surface of the inorganic fine particle, and the inorganic fine particle is a conjugated aromatic having 7 or more carbon atoms through an organic chain containing a silicon atom. A composite particle having a skeleton on the surface of the inorganic fine particles is also one of the preferred embodiments of the present invention. In the present specification, the “organic chain” means a divalent organic group having a structure in which two or more (preferably three or more, more preferably four or more) atoms are linked. is there.

The form of the organic group bonded to the surface of the inorganic fine particles is not particularly limited as long as it contains a conjugated aromatic skeleton having 7 or more carbon atoms. For example, the following formula (2-1) To (2-4);

(In the formula, R represents an organic group containing a conjugated aromatic skeleton having 7 or more carbon atoms. R ¹ and R ² are the same or different and are an alkyl group, an aryl group, or an aralkyl group. L ¹ , L ² and L ³ are the same or different and each represents a divalent organic group which is an organic chain.

The composite particle has a conjugated aromatic skeleton on the surface of the inorganic fine particle. As a method of having a conjugated aromatic skeleton on the surface of the inorganic fine particle as described above, the inorganic fine particle is surfaced. There is a method in which an organic group containing a conjugated aromatic skeleton is bonded to the surface of the inorganic fine particles by treatment. For example, a surface treatment method may be mentioned by mixing a solution containing a hydrolyzable silicon compound (A) containing a conjugated aromatic skeleton having 7 or more carbon atoms and inorganic fine particles and stirring them.
That is, the present invention is a composite particle obtained by subjecting inorganic fine particles to a surface treatment, and the composite particle essentially comprises a hydrolyzable silicon compound (A) containing a conjugated aromatic skeleton having 7 or more carbon atoms. The inorganic fine particles are also surface-treated. The composite particles are those in which the inorganic fine particles are surface-treated, so that the affinity with the resin or the like is increased and the dispersibility is improved.
The surface treatment method will be described in detail below.

With respect to the method for producing composite particles by introducing the conjugated aromatic skeleton into the surface of the inorganic fine particles, for example, (1) a hydrolyzable silane compound containing a conjugated aromatic skeleton having 7 or more carbon atoms. (2) A hydrolyzable silicon compound having a reactive group (I) is introduced into the surface of the inorganic fine particles, and then the reactive group (I) and a conjugated fragrance having 7 or more carbon atoms. A method of reacting a compound having a group skeleton and a reactive group (II), (3) a method of utilizing a reaction between a metal hydroxyl group on the surface of inorganic fine particles and a reactive group, etc. are preferable. Among these (1) to (3), the surface treatment with a hydrolyzable silane compound having a conjugated aromatic skeleton having 7 or more carbon atoms shown in (1) is more preferable. Below, the method of said (1)-(3) is explained in full detail.

Examples of (1) surface treatment with a hydrolyzable silane compound having a conjugated aromatic skeleton having 7 or more carbon atoms include, for example, (A), (B), (C ), (D), (E), (H) in FIG. 2, (K) in FIG. 3, etc., a method of bonding the hydrolyzable silane compound to the metal element constituting the surface of the inorganic fine particles 1. Can be mentioned. 1, 2 and 3 illustrate the method (1). 1, 2 and 3 are the same or different and each represents an R ³ O group, a hydrogen atom, a halogen atom or a hydroxyl group, and R ³ represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. R represents an organic group containing a conjugated aromatic skeleton. R ^p represents a hydrogen atom or a methyl group. X is more preferably an R ³ O group. R is more preferably an organic group containing a skeleton represented by the chemical formulas (1-1) to (1-8) described above. L is the same or different and represents a divalent organic group which is an organic chain. The organic chain 2 conceptually represents a divalent organic group, and the organic chains 2 shown in FIGS. 1 to 11 do not have the same structure. For example, the organic chain 2 in the compound (I) in FIG. 3 and the organic chain 2 in the compound (J) may be the same or different. Similarly, in any of FIGS. 1 to 11, the form of the organic chain 2 may be the same or different.
As shown in (f-1) to (f-3) of FIG. 1, a compound in which a hydroxyl group is bonded to R and a compound in which a chlorine atom, an isocyanate group, an epoxy group, or the like is bonded to a silicon atom of SiX ₃ By reacting, a compound in which SiX ₃ and R indicated by (A) to (C) in FIG. 1 are connected by a divalent organic group is generated, and surface treatment of inorganic fine particles is performed with this compound. A method of forming composite particles in a form in which R and inorganic fine particles are combined with an organic chain 2 by bonding with atoms constituting the surface of the inorganic fine particles 1, as shown in FIG. By hydrosilylating with a group-bonded compound and H-SiX ₃ , a compound in which SiX ₃ and R shown by (D) in FIG. 1 are linked by an alkylene group is generated, and inorganic fine particles are formed by this compound. 1 surface treatment, the inorganic fine particles 1 A method of forming composite particles having R on the surface of inorganic fine particles by bonding with atoms constituting the surface, as shown in FIG. 1 (h), vinyl group on SiX ₃ with respect to R-SiR ¹ R ² H 1 is reacted to form a compound indicated by (E) in FIG. 1, and the surface of the inorganic fine particles 1 is constituted by surface treatment of the inorganic fine particles 1 with this compound (E). And a method of forming composite particles having R on the surface of the inorganic fine particles. R ¹ and R ² are the same as those described above. Further, as shown in FIG. 2, compound (H) is obtained by copolymerizing compound (F) in which a vinyl group is bonded to R in FIG. 2 and a compound containing SiX ₃ shown in (G) in FIG. And a method of producing composite particles having R on the surface of the inorganic fine particles by reacting (H) with the inorganic fine particles 1. In addition, as shown in FIG. 3, a compound (K) is formed by reacting a compound having a thiol group bonded to R represented by (I) via an organic chain with a compound having SiX ₃ represented by (J). And the method of manufacturing the composite particle which has R on the inorganic type fine particle surface by making this (K) react with an inorganic type fine particle is also mentioned. In addition, about the organic chain 2 mentioned above, it changes suitably by the compound etc. which react with inorganic type microparticles | fine-particles, The organic chain 2 in above-mentioned FIGS. 1-3 and FIGS. It may be the same or different.

The surface treatment is preferably performed with a hydrolyzable silicon compound containing a hydrolyzable group and a conjugated aromatic skeleton having 7 or more carbon atoms. More preferably, the reaction is performed with a hydrolyzable silicon compound (A) containing a hydrolyzable group bonded to a silicon atom and a conjugated aromatic skeleton having 7 or more carbon atoms. For example, as a method for introducing the organic group R containing a conjugated aromatic skeleton having 7 or more carbon atoms, a method of surface treatment with a hydrolyzable silicon compound containing R is preferable. In this case, M-O-Si-LR (M represents a metal element, R represents an organic group containing 7 or more conjugated aromatic skeletons. L represents a divalent organic chain. It is preferable to be a bonding form represented by an organic group. Note that R may be in the form of an organic group in which no substituent is bonded to the conjugated aromatic skeleton, or may be in the form of a substituent bonded to the conjugated aromatic skeleton. The conjugated aromatic skeleton contained in R preferably has a skeleton represented by the above formulas (1-1) to (1-8). In the case of increasing the refractive index, the conjugated aromatic skeleton must have at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, a carbazole skeleton, a stilbene skeleton, an anthracene ring, and a dibenzothiophene ring. More preferably, it is a composite particle. Among these, at least one of a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is more preferable. Any conjugated aromatic skeleton can be used as long as it has the skeleton or ring structure described above. As represented by the above chemical formula (1-8), bisphenol is present in the fluorene skeleton. A bonded structure is mentioned as a more preferable form.

(1) Surface treatment with a hydrolyzable silane compound having a conjugated aromatic skeleton having 7 or more carbon atoms (hereinafter also referred to as “hydrolyzable silicon compound (A)”), More preferable methods include the following methods.
As the hydrolyzable silicon compound (A), the following formula:
R _n1 SiX _(4-n1)
(In the formula, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. X is the same or different and is an R ³ O group, a hydrogen atom, a halogen atom or a hydroxyl group. R ³ Are the same or different and each represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and n1 represents a number of 1 to 3). In such a hydrolyzable silicon compound (A), R and Si may have a conjugated aromatic skeleton having 7 or more carbon atoms directly bonded to the Si atom or bonded via an organic chain. You may do it. Preferably, it is the form couple | bonded through the organic chain.

Examples of those in which the silicon atom and the conjugated aromatic skeleton are bonded via the organic chain include the following formula:
R- (L _h SiX _(4-h) ) _i
(In the formula, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. L is the same or different, and any structure excluding the conjugated aromatic skeleton having 7 or more carbon atoms. X is the same or different and represents an R ³ O group, a hydrogen atom, a halogen atom or a hydroxyl group, and R ³ is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. H is a number of 1 to 3, and i is a number of 1 or more). R ³ is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and particularly preferably a methyl group and / or an ethyl group. A preferred value for h is 1. A preferred value for i is 1 or 2, more preferably 1.

Examples of the form in which the organic chain L is bonded to R (form of RL) include the following formulas (3-1) to (3-3);

(Wherein, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms) is preferable. The organic chain L is preferably represented by the formula (3-1).

Below, the preferable manufacturing method of a hydrolysable silicon compound (A) is demonstrated. As a manufacturing method of a hydrolyzable silicon compound (A), following formula;

(Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more), or

(Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more), or

(Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more), or

(In the formula, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. J represents an integer of 1 or more.) . In the above formula, R— (OH) _j represents the following formula:

It is more preferable that it is either the compound which has a conjugated aromatic skeleton represented by these. Such a reaction is simple, and the composite particles produced are stabilized by subjecting the inorganic fine particles to a surface treatment using the silane compound. Among the above reactions, the following formula:

It is more preferable that it is a silane compound obtained by reaction shown by these.

One of the preferred embodiments of the composite particles is one that is surface-treated with a hydrolyzable silicon compound (B) having a radical polymerizable group. As the hydrolyzable silicon compound (B), the following general formula (4);
R ⁴ _k SiX _4-k (4)
(Wherein R ⁴ represents an organic group having a radically polymerizable group, k represents an integer of 1 to 3, and X represents a hydrolyzable group). R ⁴ is preferably an organic group containing at least one selected from the group consisting of a methacryloxy group, an acryloxy group, a vinyl group, and a styryl group.

Examples of the organic group (R ⁴ ) containing the radical polymerizable group include the following general formulas (5), (6) and (7);
^{_{CH 2 = C (-R 5)}} -COOR 6 - (5)
(Here, R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an optionally substituted divalent organic group having 1 to 20 carbon atoms.)
^{_{CH 2 = C (-R 7)}} - (6)
(Here, R ⁷ represents a hydrogen atom or a methyl group.)
^{_{CH 2 = C (-R 8)}} -R 9 - (7)
(Wherein R ⁸ represents a hydrogen atom or a methyl group, and R ⁹ represents a divalent organic group having 1 to 20 carbon atoms which may have a substituent). And the like as preferred organic groups.

Examples of the organic group containing the radical polymerizable group of the general formula (5) include an acryloxy group and a methacryloxy group. Examples of the silicon compound of the general formula (4) having the organic group include: γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacryloxypropyltriacetoxysilane, γ-methacryloxyethoxy Propyltrimethoxysilane (also referred to as γ-trimethoxysilylpropyl-β-methacryloxyethyl ether), γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-acryloxypropiyl And rumethyldimethoxysilane. These may be used alone or in combination of two or more.

Examples of the radical polymerizable group-containing organic group of the general formula (6) include a vinyl group and an isopropenyl group. Examples of the silicon compound of the general formula (4) having the organic group include vinyl. Examples include trimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, and vinylmethyldiacetoxysilane. These may be used alone or in combination of two or more. Examples of the radical polymerizable group-containing organic group of the general formula (7) include a 1-alkenyl group or a vinylphenyl group, an isoalkenyl group, an isopropenylphenyl group, and the like. Examples of the silicon compound 4) include 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-decenyltrimethoxysilane, γ-trimethoxysilylpropyl vinyl ether, ω- Examples include trimethoxysilylundecanoic acid vinyl ester, p-trimethoxysilylstyrene, 1-hexenylmethyldimethoxysilane, 1-hexenylmethyldiethoxysilane, and the like. These may use only 1 type or may use 2 or more types together.

The surface treatment performed by the hydrolyzable silicon compound (B) having a radical polymerizable group is a hydrolyzable silicon compound (A) having a hydrolyzable group and a conjugated aromatic skeleton having 7 or more carbon atoms. The surface treatment may be performed simultaneously with the surface treatment, or after the surface treatment performed with the hydrolyzable silicon compound (A), the surface treatment may be performed using the hydrolyzable silicon compound (B). A surface treatment performed by the hydrolyzable silicon compound (B) using a hydrolyzable silicon compound having a radical polymerizable group, a conjugated aromatic skeleton having 7 or more carbon atoms, and a hydrolyzable group; The surface treatment performed with the hydrolyzable silicon compound (A) can also be performed in a lump. Among such methods, suitable methods for producing composite particles having the conjugated aromatic skeleton on the surface of the inorganic fine particles include a hydrolyzable group, a conjugated aromatic skeleton having 7 or more carbon atoms, and A surface treatment performed simultaneously with the surface treatment performed with the hydrolyzable silicon compound (A), or after the surface treatment performed with the hydrolyzable silicon compound (A), the surface is formed using the hydrolyzable silicon compound (B). This is a method of processing.

As the surface treatment using the hydrolyzable silicon compound (A), (surface treatment amount of hydrolyzable silicon compound (A) (addition amount standard)) / (inorganic fine particles) × 100 = 0.1 to 100 It is preferable to carry out with the quantity used as (wt%). More preferably, it is 1-70 (wt%), More preferably, it is 5-50 (wt%). The surface treatment amount on the basis of the addition amount is an amount used when the inorganic fine particles are surface-treated, and is different from the amount of organic groups bonded to the surface of the inorganic fine particles. As the surface treatment method, a method of stirring in an organic solvent in which inorganic fine particles and hydrolyzable silicon compound (A) are present is preferable. More preferably, stirring is performed in the presence of moisture. Moreover, the method of heating the organic solvent in which inorganic type microparticles | fine-particles and a hydrolyzable silicon compound (A) exist is preferable. As temperature to heat, 50 degreeC or more is preferable, More preferably, it is 80 degreeC or more. Moreover, as a preferable upper limit of the temperature to heat, it is 300 degrees C or less, More preferably, it is 200 degrees C or less.
More preferably, it is a method of heating with stirring. The heating time is preferably 0.1 to 24 hours, and more preferably 0.5 to 4 hours. As stirring time, it is preferable that it is 0.1 to 24 hours, More preferably, it is 0.5 to 4 hours. When heating with stirring, the time for stirring and heating is the same.

As the surface treatment using the hydrolyzable silicon compound (B), (surface treatment amount of hydrolyzable silicon compound (B) (addition amount standard)) / (inorganic fine particles) × 100 = 0.1-50 It is preferable to carry out with the quantity used as (wt%). Moreover, the method of performing a surface treatment by making it coexist with a hydrolysable silicon compound (A) is preferable. Moreover, you may process with a hydrolysable silicon compound (B) after processing with a hydrolysable silicon compound (A). Moreover, you may process with a hydrolysable silicon compound (A) after processing with a hydrolysable silicon compound (B).

Next, (2) after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group and a compound having a conjugated aromatic skeleton and having a reactive group (II) A method of reacting will be described. The reactive group (I) is a reactive group possessed by an organic group bonded to atoms constituting the surface of the inorganic fine particles, and the reactive group (II) is a conjugated aromatic skeleton having 7 or more carbon atoms. It is a reactive group contained in the compound containing (R). That is, the method for producing a composite particle by introducing the conjugated aromatic skeleton onto the surface of the inorganic fine particles introduces a hydrolyzable silicon compound having a conjugated aromatic skeleton reactive group (I), A method of reacting a reactive group with a compound having a conjugated aromatic skeleton and having a reactive group (II) is also preferred. The reactive group (I) is preferably at least one group selected from the group consisting of Si-H group, vinyl group, (meth) acryloxy group, isocyanato group, amino group, epoxy group and oxetane group. The reactive group (II) is preferably at least one group selected from the group consisting of vinyl group, Si—H group, thiol, hydroxyl group, carboxyl group, amino group and epoxy group.
Suitable combinations of reactive group (I) and reactive group (II) are summarized in Table 1 below.

As shown in (a) of Table 1, when the reactive group (I) is a Si-H group and the reactive group (II) is a vinyl group, for example, by performing the reaction shown in FIG. Composite particles having a conjugated aromatic skeleton on the surface of inorganic fine particles can be produced. 4 to 10 illustrate the method (2). The composite particles can be produced by reacting a compound in which a vinyl group is bonded to R in FIG. 4 with inorganic fine particles 1 in which hydrogenated silicon is bonded through an organic chain 2. As shown in (a) of Table 1, when the reactive group (I) is a vinyl group and the reactive group (II) is a Si—H group, the reaction shown in FIG. 5 is performed. Thus, the composite particles can be produced. The compound represented by (M) in FIG. 5 can be produced, for example, by introducing vinyltrimethoxysilane into the inorganic fine particles 1. The organic chain 2 may be a divalent organic group containing carbon and hydrogen, and is not particularly limited.

As shown in (c) of Table 1, when the reactive group (I) is a (meth) acryloxy group and the reactive group (II) is a vinyl group, as shown in FIG. The composite particles can be produced by copolymerization with a monomer. In addition, when the reactive group (I) is a (meth) acryloxy group and the reactive group (II) is a thiol as shown in (D) of Table 1, as shown in FIG. Thus, the composite particles can be obtained. The compound represented by (P) in FIGS. 6 and 7 can be produced, for example, by reacting inorganic fine particles with methacryloxypropyltrimethoxysilane.

As shown in Table (1), when the reactive group (I) is an isocyanato group and the reactive group (II) is a group having an active hydrogen such as a hydroxyl group, a carboxyl group, or an amino group, By the reaction as shown in FIG. Further, as shown in (f) of Table 1, when the reactive group (I) is an amino group and the reactive group (II) is a carboxyl group or an epoxy group, the reaction shown in FIG. The composite particles can be obtained. About the compound shown by (N) in FIG. 9, it can carry out by making aminopropyl trimethoxysilane react, for example.

As shown in (x) in Table 1, the reactive group (I) is an epoxy group and / or an oxetane group, and the reactive group (II) is a group having active hydrogen such as a carboxyl group or a hydroxyl group. In this case, the composite particles can be produced by a reaction as shown in FIGS. 10-1 and 10-2. In FIGS. 10-1 and 10-2, R ¹⁹ is an alkyl group, an aryl group, or an aralkyl group. The compound represented by (S) in FIG. 10-1 is obtained by reacting, for example, 3-glycidoxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane with inorganic fine particles. Can be generated.

Hereinafter, (3) a method using the reaction between the metal hydroxyl group on the surface of the inorganic fine particles and the reactive group will be described. In addition, a metal hydroxyl group means what the hydroxyl group couple | bonded with the metal atom which comprises the inorganic type fine particle surface.
As such a method, for example, as shown in FIG. 11, the number of carbon atoms is determined by a reaction between the surface hydroxyl group of the inorganic fine particles and an epoxy group, sulfide group, oxetane group or alcoholic hydroxyl group having R. Is a method of producing composite particles having 7 or more conjugated aromatic skeletons on the surface of inorganic fine particles. Inorganic fine particles that react with an epoxy group, sulfide group, oxetane group, or alcoholic hydroxyl group in FIG. 11 are in a form in which a hydroxyl group is bonded to a metal element constituting the surface.

The present invention is also a resin composition comprising the composite particle and a resin component. The resin composition containing the composite particles of the present invention has high transparency since the dispersibility between the resin component and the composite particles is improved. Moreover, since it is a composite particle having a conjugated aromatic skeleton having 7 or more carbon atoms, it can have a high refractive index, and a cured product obtained by curing the resin composition is suitable as an optical member or the like. Can be used.
Hereinafter, the resin composition comprising the composite particles of the present invention will be described.

The content of the composite particles having a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of the inorganic fine particles in the resin composition is 0.1 to 95% by mass in 100% by mass of the resin composition. preferable. If it is less than 0.1% by mass, the refractive index of the resin composition obtained may not be sufficiently high, and if it exceeds 95% by mass, the cured product may be brittle. More preferably, it is 15 mass% or more and 90 mass% or less, More preferably, it is 20 mass% or more and 80 mass% or less.

The content of the resin component in the resin composition is preferably 5% by mass or more and 90% by mass or less in 100% by mass of the resin composition. If it is less than 5% by mass, the resulting cured product may be brittle, and if it exceeds 90% by mass, the refractive index may not be sufficiently high. More preferably, they are 10 mass% or more and 80 mass% or less, More preferably, they are 15 mass% or more and 70 mass% or less.

Although the said resin composition will not be specifically limited if the said composite particle and the resin component are included as essential, It is suitable that a polymerization initiator is further included further. The polymerization initiator is appropriately selected depending on the resin component to be used, but is preferably a cationic polymerization initiator when an epoxy compound is used as the resin component. Moreover, when it is a compound which has a radically polymerizable group, it is preferable to use a radical polymerization initiator. These polymerization initiators will be described later.

The resin component preferably contains an aromatic compound (C) having a conjugated structure composed of 7 or more carbon atoms. Thus, it can have a high refractive index by making the aromatic compound which has a conjugated structure comprised from 7 or more carbon atoms essential. Such a resin composition is particularly useful as an optical member such as a lens, a sealing material for LED, and a light extraction layer used for organic EL, which preferably has a high refractive index. In addition, since the composite particles have seven or more conjugated aromatic skeletons on the surface of the inorganic fine particles, a resin component having a similar structure (a conjugated structure composed of seven or more carbon atoms) is used. As a result, the dispersibility of the composite particles is further improved. In order to further improve the dispersibility of the composite particles, it is more preferable to use a resin component having the same skeleton as the conjugated aromatic skeleton having 7 or more carbon atoms introduced on the surface of the inorganic fine particles.

The aromatic compound (C) preferably contains a skeleton represented by the chemical formulas (1-1) to (1-8). In the case of increasing the refractive index, among these, a fluorene skeleton, a biphenyl skeleton, a carbazole skeleton, a stilbene skeleton, a naphthalene ring, an anthracene ring, and a dibenzothiophene ring are preferable. Among these, more preferably, at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is essential. As the aromatic compound having a conjugated structure composed of 7 or more carbon atoms, any compound having the above-described skeleton or ring structure can be suitably used. Moreover, as represented by the above chemical formula (1-8), a structure in which bisphenol is bonded to a fluorene skeleton (a conjugated structure composed of 25 carbon atoms) and the like are more preferable.

In the resin composition, the aromatic compound (C) is a (meth) acrylate-based compound, and is preferably heat and / or photocurable. By using a (meth) acrylate compound, the curing rate of the resin composition can be made excellent, and productivity can be improved. Moreover, the resin composition can be cured quickly and easily by being heat and / or photocurable.

It is particularly preferable that the (meth) acrylate compound has a fluorene skeleton as an essential component. When a compound having a fluorene skeleton structure as the conjugated structure is used, a cured product obtained by curing the curable resin composition of the present invention can have a refractive index of 1.60 or more. In addition, the compound in which the conjugated structure includes a fluorene skeleton structure not only has a high refractive index but also exhibits various excellent properties such as heat resistance and high transparency in the visible light region. Therefore, it can be used in various applications including optical applications such as a high refractive index lens. When the said resin composition contains the (meth) acrylate type compound which makes a fluorene skeleton essential, as content of the (meth) acrylate type compound which makes the fluorene skeleton essential in a resin composition, 100 mass% of resin components On the other hand, it is preferable that it is 20 mass% (weight%) or more. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more.

The (meth) acrylate compound having the fluorene skeleton as an essential component is represented by the following general formula (8);

(In formula, R < ¹⁰ > is the same or different and represents a hydrogen atom or a methyl group, and R < ¹¹ > is the same or different and represents a hydrogen atom, a C1-C5 alkyl group, a phenyl group, or a halogen atom. q is the same or different and is an integer of 0 to 10). More preferably, the following chemical formula (9);

Ogsol EA-0200 (Osaka Gas Chemical Co., Ltd., fluorene acrylate resin). Ogsol acrylates such as Ogsol EA-0200 are advantageous in that they have a basic structure of bisarylfluorene and have a high refractive index, low curing shrinkage, and high transparency.

The (meth) acrylate compound preferably has a biphenyl skeleton as an essential component. A compound having a conjugated structure including a biphenyl skeleton structure has an advantage that it has a high refractive index, is excellent in heat resistance, has high transparency in the visible light region, and can be used at low cost.

When the resin composition contains a (meth) acrylate compound having a biphenyl skeleton as an essential component, the content of the (meth) acrylate compound having a biphenyl skeleton as an essential component in the resin composition is 100% by mass of a resin component. On the other hand, it is preferable that it is 20 mass% (weight%) or more. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more. The (meth) acrylate having the conjugated structure preferably has two or more acrylic groups in one molecule. By having two or more, there is an advantage that the mechanical strength of the cured product can be improved. More preferably, it is 2 to 3, more preferably 2.

As the biphenyl compound, the following general formula (10);

(Wherein, R ¹² is the same or different and represents a hydrogen atom or a methyl group. S is the same or different and is an integer of 0 to 10). More preferably, the following chemical formula (11);

It is represented by

In the resin composition, the aromatic compound (C) is an epoxy compound, and is preferably heat and / or photocurable. By using an epoxy compound, the curing rate of the resin composition can be improved, and productivity can be improved. Moreover, the resin composition can be cured quickly and easily by being heat and / or photocurable.

It is particularly preferable that the epoxy compound has a fluorene skeleton as an essential component. When an epoxy compound having a fluorene skeleton as an essential component is used, a cured product obtained by curing the resin composition can have a refractive index of 1.60 or more. In addition, the epoxy-based compound essentially including the fluorene skeleton not only has a high refractive index but also exhibits various excellent properties such as heat resistance and high transparency in the visible light region. Therefore, it can be used in various applications including optical applications such as a high refractive index lens. When the said resin composition contains the epoxy-type compound which makes a fluorene skeleton essential, as content of the epoxy-type compound which makes the fluorene skeleton essential in a resin composition, it is 20 mass% with respect to 100 mass% of resin components. (% By weight) or more is preferable. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more.

Examples of the fluorene compound include the following general formulas (12-1) and (12-2);

(In formula, R <^12> is the same or different and represents a hydrogen atom or a methyl group, and R <^13> is the same or different and represents a hydrogen atom, a C1-C5 alkyl group, a phenyl group, or a halogen atom. u is the same or different and is an integer of 1 to 5, and t is the same or different and is an integer of 0 to 10). Specifically, the following chemical formula (13);

Ogsol EG-210 represented by the formula (Osaka Kaigai Co., Ltd., fluorene epoxy resin) is suitable.

The conjugated aromatic skeleton is preferably a biphenyl skeleton. The use of an epoxy-based compound that requires a biphenyl skeleton has advantages that it has a high refractive index, is excellent in heat resistance, has high transparency in the visible light region, and can be used at low cost. Less than,
Examples of the biphenyl compound include the following general formula (14);

(Wherein, R ¹⁴ are the same or different and each represents a hydrogen atom or a methyl group. V is the same or different and is an integer of 0 to 10). Specifically, the following chemical formula (15);

JER YX4000 (Japan Epoxy Resin Co., Ltd., biphenyl epoxy resin) represented by is suitable for cost reduction. In addition, as an epoxy compound having a biphenyl skeleton as an essential component, a novolak / aralkyl type glycidyl ether type epoxy obtained by further condensing a polyhydric phenol obtained by condensation reaction of bishydroxymethylbiphenyl and the like with epihalohydrin. Resins and the like are also exemplified as preferable compounds.

The aromatic compound (C) may be a thermoplastic resin. For example, an aromatic compound having a conjugated structure having 7 or more carbon atoms, and a polyester resin obtained by a polycondensation reaction between a compound having 2 or more hydroxyl groups and a carboxylic acid (anhydride) can be used.

The resin composition preferably contains a dispersant. Although it does not specifically limit as a dispersing agent contained in a resin composition, It is suitable that the dispersing agent (D) shown below is included. That is, the resin composition further includes a dispersant (D),
The dispersant (D) has the following general formula (I):
R ^a —R ^b —O— (CO—R ^c —O) _p —CO—R ^d —COOH (I)
(However, R ^a is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and a (meth) acryloyl group. R ^b is an alkylene group or an aryl group, R ^c is an alkylene group, and R ^d is at least one selected from the group consisting of an alkylene group, an aryl group, and an alkyne group. P is an integer greater than or equal to 1.) Compound (1) represented by the following general formula (II);
R ^e — [CO— (O—R ^f —CO) _n —OH] _m (II)
(However, R ^e is selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and an optionally substituted vinyl group. R ^f is an alkylene group, n is a number of 1 or more, and m is a number of 1 to 4.) and / or General formula (III);
^{R g -R h -O- (CO-} R i -O) r -H (III)
(However, R ^g is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and a (meth) acryloyl group. R ^h represents an alkylene group or an aryl group, R ⁱ represents an alkylene group, r is a number of 1 or more, and preferably includes the compound (3). . As the dispersant, it is preferable to use one or more of the compounds represented by the general formulas (I), (II), and (III). Moreover, as a dispersing agent, 1 type of the compound represented by each general formula may be used, and 2 or more types may be used together, and it is not specifically limited.

In the compound (1) represented by the above general formula (I), when R ^b is an alkylene group, for example, it is preferably a methylene group, an ethylene group or a cyclohexylene group, and when it is an aryl group, for example, phenyl It is preferably a group. R ^c preferably has a linear structure rather than a cyclic structure, and more preferably has 3 to 20 carbon atoms. R ^d is preferably an alkylene group, more preferably a linear alkylene group rather than a cyclic group, and particularly preferably an alkylene group having 2 to 6 carbon atoms. p is preferably an integer of 50 or less, and more preferably an integer of 20 or less. Moreover, it is one of the preferable forms that the said compound (1) contains at least 1 aromatic ring.

Examples of the compound (1) represented by the general formula (I) include lactone-modified carboxyl group-containing (meth) acrylates such as “Placcel FM1A” and “Placcel FM4A” manufactured by Daicel Chemical Industries, Ltd. Specific examples of the compound (1) represented by the general formula (I) include compounds represented by the following formulas (16), (17), (18) and (19).

In the compound (2) represented by the general formula (II), when R ^e is a vinyl group, for example, a methyl vinyl group is preferable. R ^f preferably has a linear structure rather than a cyclic structure, and more preferably has 3 to 20 carbon atoms. n is preferably an integer of 50 or less, more preferably an integer of 20 or less. As m, it is preferable that it is an integer of 1-4, and it is more preferable that it is an integer of 1-2.

Examples of the compound (2) represented by the general formula (II) include caprolactone-modified products of (meth) acrylic acid such as ω-carboxycaprolactone mono (meth) acrylate and ω-carboxypolycaprolactone mono (meth) acrylate. Is mentioned. Specific examples of the compound (1) represented by the general formula (II) include compounds represented by the following formulas (20), (21), (22), and (23).
_{CH 2 = C (CH 3)} -COO- (CH 2) 5 -COOH (20)
_{CH 3 -COO- (CH 2) 5} -COOH (21)

As R ⁱ of the above general formula (III), the structure of the alkylene group is preferably linear rather than cyclic, and more preferably 3 to 20 carbon atoms. Specific examples of the compound represented by the general formula (III) include “Placcel FM1” and “Placcel FM5” manufactured by Daicel Chemical Industries, Ltd., and the compound represented by the following formula (24) Can be mentioned.
_{CH 2 = C (CH 3)} -COO-CH 2 - [CO (CH 2) 5 O] g H (24)
(In the formula, g represents the average number of moles added and is an integer of 1 to 10.)

In addition to the compounds represented by the general formulas (I) to (III), as the dispersant,
—O— (CO—R ^j —O) _n ² —CO—R ^k —COOH group (in which R ^j , R ^k and n ² represent R ^c , R ^d and the same as p).
_{^{-CO- (O-R L -CO)}} n 3 -OH group (in the group, ^{R L} and ^{n 3} are respectively similar to ^{R f} and n in the general formula (II).), Or,
A polymer having —O— (CO—R ^m —O) _n ⁴ —H group (in which R ^m and n ⁴ are the same as R ⁱ and r in the general formula (III), respectively). Is mentioned. The polymer can be obtained by copolymerizing a (meth) acrylic acid ester having —O— (CO—R ^j —O) _n ² —CO—R ^k —COOH group or the like.

Among those represented by the general formulas (I) to (III), a compound in which any of the groups represented by R ^{a to} R ^m contains an aromatic ring such as an aryl group or an aralkyl group is particularly preferable. It is.
Moreover, as a more preferable thing as a compound (3) represented by the said general formula (III), following formula;

Plaxel FM-1 (manufactured by Daicel Chemical Industries, Ltd.) represented by Furthermore, as a more preferable compound (2) represented by the general formula (II), the following formula:

FM-1-Ph that can be obtained by the reaction represented by the formula (1) is a more preferred form as the dispersant (D). Thus, FM-1-Ph can be produced by synthesizing Plaxel FM-1 with a compound containing an aromatic ring and an acid anhydride structure in the same molecule. That is, a compound obtained by reacting a compound containing an aromatic ring and a lactone structure in the same molecule with Plaxel FM-1 is a preferred form as the dispersant (D).

By using such a dispersant (D), the dispersibility of the composite particles in the resin composition is improved, and a resin composition with higher transparency can be obtained. The content of the dispersant (D) is preferably (dispersant (D) / composite particles) × 100 = 0.1 to 20 (wt%). By setting the content in such a range, the dispersibility of the composite particles can be further improved. The range of the content is more preferably (dispersant (D) / composite particles) × 100 = 0.1 to 10 (wt%).

Next, the polymerization initiator that is preferably contained in the resin composition will be described.
When the resin component constituting the resin composition is a cationically polymerizable compound, a method using a cationic polymerization initiator is preferred. The cationic polymerization initiator is not particularly limited as long as it can start cationic polymerization in the curable resin composition, but a photolatent cation generator and a thermal latent cation generator are preferable.
The heat latent cation generator is also called a heat latent curing catalyst or a heat latent curing agent, and exhibits a substantial function as a curing agent when the curing temperature is reached in the resin composition. Unlike the curing agent described later, the thermal latent cation generator does not cause an increase in viscosity or gelation with time of the curable resin composition at room temperature, even if it is contained in the curable resin composition. As a function of the heat latent cation generator, an excellent curing reaction accelerating effect can be exhibited, so that a one-component resin composition (one-component optical material) excellent in handling properties can be provided. In particular, when a curable resin composition is used as an optical material, it is preferable to use a thermal latent curing agent.

When the above heat latent cation generator is used, the moisture resistance of the resulting resin composition is dramatically improved, and the excellent optical properties of the curable resin composition are maintained even in harsh usage environments. The effect which becomes what can be used suitably for a use of is acquired. Usually, if water having a high refractive index is contained in the curable resin composition or its cured product, it may cause turbidity, but when a thermal latent cation generator is used, the resulting curable resin composition has excellent moisture resistance. Therefore, such turbidity is suppressed, and it can be suitably used for optical applications such as lenses. In particular, in applications such as on-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing of lenses and deterioration of strength due to prolonged ultraviolet irradiation and high temperature exposure in summer. These phenomena are thought to be caused by the generation of oxygen radicals due to the synergistic effect of air and moisture with ultraviolet irradiation or heat ray exposure. However, the moisture resistance is improved, so that moisture absorption into the curable resin composition is prevented. Suppressed and also suppresses generation of oxygen radicals due to synergistic effects with ultraviolet irradiation or heat ray exposure, so that it can exhibit excellent heat resistance for a long time without causing yellowing or strength reduction of the curable resin composition. it can.

As the heat latent cation generator, the following average composition formula (25)
_{^{(R 15 c R 16 d R}} 17 e R 18 f Z) + w1 (AYn 5) -w1 (25)
(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 ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is the same or different and represents an organic group, c, d, e and f are 0 or a positive number, and the sum of c, d, e and f is equal to the valence of Z. Cation (R ¹⁵ _c R ¹⁶ _d R ¹⁷ _e R ¹⁸ _f Z) ^{+ w1} represents an onium salt, A represents a metal element or a metalloid which is a central atom of a halide complex, B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. Y represents a halogen element, and w is the net charge of the halide complex ion. .n ⁵ is a halide complex ion Of the number of halogen element.) It is preferably represented by the.

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 from the curable resin composition, the mold is removed from the mold and left in an air or inert gas atmosphere. It is also possible to perform heat treatment. 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. Seconds to 5 minutes.

Specific examples of the anion (AYn ⁵ ) ^-w1 of the general formula (25) 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 AYn ⁵ (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.

As specific products of the above-mentioned heat latent cation generator,
Diazonium salt type: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries)
Iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries)
Sulfonium salt type: CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (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. Among these, the Sun-Aid SI series is preferable, and Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be suitably used.

Examples of the photolatent cation generator (also referred to as photolatent curing catalyst or photocationic polymerization initiator) include metal fluoroboron complex salts and trifluoride boron complex compounds as described in, for example, US Pat. No. 3,379,653; Bis (perfluoroalkylsulfonyl) methane metal salts as described in US Pat. No. 3,586,616; aryldiazonium compounds as described in US Pat. No. 3,708,296; VIa as described in US Pat. No. 4,058,400 Aromatic onium salts of group elements; aromatic onium salts of group Va elements as described in US Pat. No. 4069055; dicarbonyl chelates of group IIIa to Va elements as described in US Pat. No. 4068091 A chain as described in US Pat. No. 4,139,655 Pyrylium salts; U.S. Pat MF as described in No. 4161478 ₆ ^- anion (where M is phosphorus, are selected from antimony and arsenic) VIb element in the form of; described in U.S. Patent No. 4,231,951 Arylsulfonium salts such as those described above; aromatic iodonium and aromatic sulfonium complex salts as described in US Pat. No. 4,256,828; R. Bis [4- (Di) as described by Watt et al. In "Journal of Polymer Science, Polymer Chemistry", Vol. 22, paragraph 1789 (1984). Ferrylsulfonio) phenyl] sulfide-bis-hexafluorometal salts (eg, phosphates, arsenates, antimonates, etc.); mixed ligand metal salts of iron compounds; silanol-aluminum complexes; . These compounds are also referred to as ultraviolet polymerization initiators. These ultraviolet polymerization initiators may be used alone or in combination of two or more.

Among the above ultraviolet polymerization initiators, arylsulfonium complex salts, aromatic iodonium complex salts of halogen-containing complex ions or aromatic sulfonium complex salts, and aromatic onium salts of group II, group V and group VI elements are preferred. Some of these include, for example, UVI-6992 (manufactured by Dow Chemical), FX-512 (manufactured by 3M), UVR-6990, UVR-6974 (manufactured by Union Carbide), and KI-85 (manufactured by Degussa). , SP-150, SP-170 (Asahi Denka Co., Ltd.) and other commercial products can be obtained.

When the resin component constituting the resin composition is a radical polymerizable compound, a method using a radical polymerization initiator is preferred.
The radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals and initiates polymerization of the curable resin composition. Specifically, 2,2′-azobis- (2-methylbutyronitrile), 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 .2′-azobis-2-methylpropionate methyl, 2,2′-azobisisobutyrate dimethyl, 2,2′azobis-2-methylvaleronitrile, 1,1′-azobis-1-cycloheptanenitrile, 1,1 Azo initiators such as' -azobis-1-phenylethane, phenylazotriphenylmethane; benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauroyl peroxide, tert-butyl peroxide, Tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1,1-bis (tert-butyl peroxide) ) -3,3,5-trimethylcyclohexane, t- butyl peroxy-2-ethylhexanoate, t- butyl peroxide initiators such as peroxy benzoate; and the like. Of these, peroxide-based initiators are particularly preferred. Specifically, t-butyl peroxybenzoate or the like is preferably used.

It is also a preferred embodiment that the radical polymerization initiator is a photo radical polymerization initiator. Examples of photo radical polymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2- Propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 Acetophenones such as hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; Be Zophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyl-diphenyl sulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4 , 6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide, (4-benzoylbenzyl) trimethylammonium chloride, etc. Benzophenones; 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy) -3 , 4-Dime Thioxanthones such as Le -9H- thioxanthone-9-Onmesokurorido. Among these, acetophenones, benzophenones, and acyl phosphine oxides are preferable. More preferred are 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one.

As a resin component contained in the said resin composition, other resin components may be included besides the aromatic compound (C) which has the conjugated structure comprised from the 7 or more carbon atom mentioned above. Moreover, organic components other than the resin component may be included. Hereinafter, other resin components and organic components other than the resin components will be described. The other resin components and organic components other than the resin components are collectively described as other organic components. The content of other organic components is preferably 0 to 50% by mass with respect to 100% by mass of the curable resin composition. More preferably, it is 0-30 mass%.
Hereinafter, other organic components will be described.

Examples of the other organic components include a curable resin, a thermoplastic resin, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, a compound having at least one epoxy group described later, ) Curable compounds such as compounds having at least one acrylic group are preferred. 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 said other organic component, an epoxy group containing compound or a (meth) acryl group containing compound from a viewpoint of a cure rate, ie, epoxy groups other than the above-mentioned epoxy compound and (meth) acrylic compound, or (meth) A compound having at least one acrylic group is preferred. By having at least one epoxy group or (meth) acryl group, it has the effect of making the curing speed sufficient, and has heat resistance comparable to inorganic glass while having workability equivalent to that of conventional thermosetting plastic materials. And exhibit excellent properties such as excellent molding and workability. Hereinafter, the compound which has at least one epoxy group which can be used suitably as an organic component of this invention is demonstrated.

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 and bisphenol S and epihalohydrin, and further adding them with bisphenols such as bisphenol A, bisphenol F and bisphenol S High molecular weight epibis type glycidyl ether type epoxy resin obtained by reaction; phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and formaldehyde, acetoaldehyde, propion Aldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, bear A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by further condensing polyhydric phenols obtained by the condensation reaction of ethylene, paraxylylene glycol dimethyl ether, dichloroparaxylylene and the like with an epihalohydrin; tetramethylbisphenol F; Aromatic crystalline epoxy resin obtained by condensation reaction of hydroquinone or the like with epihalohydrin, and further high molecular weight of aromatic crystalline epoxy resin obtained by addition reaction of bisphenols, tetramethylbisphenol F, hydroquinone or the like An alicyclic glycol or ethylene glycol hydrogenated aromatic skeleton such as the above bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, etc. , Diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, Aliphatic glycidyl ether type epoxy resin (aliphatic glycidyl ether type epoxy compound) obtained by condensation reaction of mono- and polysaccharides such as pentaerythritol and its multimers, glucose, fructose, lactose, maltose and the like and epihalohydrin; Epoxy having an epoxycyclohexane skeleton such as 4-epoxycyclohexane) methyl 3 ′, 4′-epoxycyclohexylcarboxylate Resin (epoxy compound having epoxycyclohexane skeleton); glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; condensation of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin A tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by the reaction. 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 compound having at least one epoxy group, epoxy (meth) acrylate can also be suitably used.
The epoxy (meth) acrylate is a (meth) acrylate obtained by reacting one or more epoxides with (meth) acrylic acid. Examples of the epoxide include (methyl) epichlorohydrin and hydrogenated bisphenol A. , Hydrogenated bisphenol S, hydrogenated bisphenol F, epichlorohydrin modified hydrogenated bisphenol type epoxy resin synthesized from ethylene oxide, propylene oxide modified products thereof; 3,4-epoxycyclohexylmethyl, bis- (3,4-epoxycyclohexyl) ) Cycloaliphatic epoxy resins such as adipate; Cycloaliphatic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate; (Methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, and their Epichlorohydrin-modified bisphenol-type epoxy resin synthesized from modified ethylene oxide, propylene oxide, etc .; phenol novolac-type epoxy resin; cresol novolac-type epoxy resin; various dicyclopentadiene-modified products obtained by reacting dicyclopentadiene with various phenols Epoxy products of phenol resins; aromatic epoxides such as phenyl glycidyl ether; glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol (poly) ) Glycidyl ether; (Poly) glycidyl ether of glycols modified with alkylene oxide; Trimethylolpropane, trimethylolethane, glycerin, jig (Poly) glycidyl ether of aliphatic polyhydric alcohols such as serine, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; (poly) of an alkylene oxide modified product of an aliphatic polyhydric alcohol Alkylene-type epoxides such as glycidyl ethers; glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid, itaconic acid, glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids; glycidyl (meth) acrylate, methyl Suitable are glycidyl (meth) acrylate copolymers; glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized polybutadiene, and the like.

The epoxy group-containing compound preferably has an aromatic ring in order to improve the refractive index. As the aromatic epoxy compound, a bisphenol A type epoxy resin (bisphenol A), a bisphenol F type epoxy resin (bisphenol F), an aromatic epoxy resin having a bromo substituent, or the like is preferable, and one or more of these are used. Can be used in combination. More preferably, it is a bisphenol A type epoxy resin. As the bisphenol A type epoxy resin, JER828EL (Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin) is suitable.

Other organic components may be other (meth) acrylic compounds. Examples of the monofunctional (meth) acrylate include benzyl (meth) acrylate, ethyl (meth) acrylate, methyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, dicyclo Examples include pentenyloxyethyl (meth) acrylate boronyl, (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.

Examples of the polyfunctional (meth) acrylate include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, glycerin di (meth) acrylate, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-propionate di (meth) acrylate, 1,4-butanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol hydroxypivalate, di (meth) acrylate of propylene oxide adduct of bisphenol A, 2,2'-di (hydroxypro Xylphenyl) propane di (meth) acrylate, 2,2'-di (hydroxyethoxyphenyl) propane di (meth) acrylate, bisphenol A ethylene oxide adduct di (meth) acrylate, tricyclodecane dimethylol di ( Bifunctional (meth) acrylates such as di (meth) acrylic acid adducts of (meth) acrylates and 2,2′-di (glycidyloxyphenyl) propane, and for example, pentaerythritol tri (meth) acrylate, pentaerythritol tetra ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimellitic acid tri (meth) acrylate, triallyl trimellitic acid, triallyl isocyanurate tris (2 Hydroxyethyl) tri (meth) acrylate isocyanurate, tris (hydroxypropyl) tri (meth) acrylate isocyanurate, tetramethylolmethane tri (meth) acrylate, tetra methylol methane tetra (meth) acrylate.

The (meth) acrylate compound may be a (meth) acrylate having one or more aryl groups. Examples of the (meth) acrylate having one or more aryl groups include benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypropyl (meth) acrylate, acryloyloxyethyl phthalate, cresol (meth) acrylate, paracumylphenoxy Ethylene glycol (meth) acrylate, tribromophenyl (meth) acrylate, bisphenol A di (meth) acrylate, bisphenol F di (meth) acrylate, phthalic acid di (meth) acrylate, trimethylolpropane benzoate (meth) acrylate, naphthyl ( Meth) acrylates, etc., and these ethylene oxide addition (EO-modified) products, propylene oxide addition (PO-modified) products, ethylcyclohexane addition (ECH-modified) products, etc. It is below.

The (meth) acrylate compound may be an aromatic urethane acrylate oligomer. As the aromatic urethane acrylate oligomer, trade names “Ebecry 1210” and “Ebecry 220” manufactured by Daicel Cytec Co., Ltd., trade names “Uvithanc 782”, “Uvithanc 783” manufactured by Nomura Office, and product names “Laromer LR8983” manufactured by BASF And those diluted with (meth) acrylate such as tripropylene glycol diacrylate (trade name “Ebecly 1205” manufactured by Daicel Cytec Co., Ltd.).

The other organic component may contain a solvent, and the amount of the solvent contained in the organic component is preferably 20% by mass or less with respect to 100% by mass of the organic component. When it exceeds 20 mass%, when an organic resin component (organic component which is resin) is included, there exists a possibility that a bubble may arise in a molded object. More preferably, it is 10 mass% or less as a solvent amount, More preferably, it is 5 mass% or less, Especially preferably, it is 3 mass% or less, Most preferably, it is 1 mass% or less.

In addition to the composite particles having a conjugated aromatic skeleton having 7 or more carbon atoms on the surface and the resin component, the resin composition includes the above-described polymerization initiator (curing catalyst), mold release agent, curing agent, and curing agent. Accelerators, reactive diluents, saturated compounds without unsaturated bonds, pigments, dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, polymerization inhibitors, Adhesion improvers such as inorganic and organic fillers, coupling agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, anti-settling agents Contains thickeners, anti-sagging agents, anti-coloring agents, emulsifiers, anti-slip / scratch agents, anti-skinning agents, desiccants, antifouling agents, antistatic agents, conductive agents (electrostatic aids), etc. May be.

The present invention is also a cured product obtained by curing the resin composition. The cured product obtained by curing the resin composition containing the composite particles has improved transparency, and further has a high refractive index due to having a conjugated aromatic skeleton having 7 or more carbon atoms. It will have. Such a cured product can be suitably used as an optical member, particularly as a lens having a high refractive index and a low Abbe number.
The turbidity (haze) of the cured product is preferably 20% or less. The turbidity of the cured product is more preferably 10% or less, still more preferably 5% or less, and particularly preferably 1% or less. Moreover, as transparency of hardened | cured material, it is preferable that the light transmittance of visible region (region whose wavelength is 360-780 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 2% or less, preferably 1% or less, more preferably 0.5% or less. More preferably, it is 0.2% or less.

The cured product preferably has a refractive index of 1.6 or more. By making the said hardened | cured material of a high refractive index, it can use suitably for various uses. In particular, it is useful when used for optical applications. More preferably, it is 1.61 or more as a refractive index of hardened | cured material, More preferably, it is 1.62 or more, Most preferably, it is 1.63 or more.

The cured product has high heat resistance, that is, there is no change in appearance such as generation of cracks even at high temperatures, and the rate of change in light transmittance and turbidity in the wavelength range of 360 to 780 nm is low. preferable. Specifically, when the temperature of the cured product is increased from 25 ° C. to 260 ° C., there is no change in appearance such as cracking, and the light transmittance / turbidity change rate in the wavelength range of 360 to 780 nm It is preferable that it is 20% or less. More preferably, the total light transmittance and the change rate of turbidity are 15% or less, and more preferably 10% or less. The change in light transmittance and turbidity in the wavelength range of 360 to 780 nm after standing for 500 hours at 85 ° C. and 85% humidity is preferably 20% or less. More preferably, it is 15% or less.
Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged UV irradiation and high temperature exposure in summer. The cause is considered to be the generation of oxygen radicals due to a synergistic effect with exposure to heat rays. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to synergistic effects with ultraviolet irradiation or heat ray exposure is also suppressed, so that the resin composition does not cause yellowing or strength reduction Excellent heat resistance can be exhibited for a long time.

This invention is also an optical member comprised including the hardened | cured material which hardens the said curable resin composition. The optical member is a curable material using the resin composition. The resin composition of the present invention exhibits excellent transparency and optical characteristics as described above, and the cured product obtained by curing the resin composition also exhibits similar characteristics. It can be suitably used for various applications such as applications and display device applications. Specifically, it can be more suitably used as an optical member that requires a high refractive index, such as a lens and an LED sealant.
The optical member of the present invention preferably comprises a cured product obtained by curing the resin composition with heat or light. In addition, although the optical member contains the said resin composition, it may contain the other component suitably according to the use of the optical member. Specifically, UV absorber, IR cut agent, reactive diluent, pigment, washing agent, antioxidant, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization Initiators, light stabilizers, polymerization inhibitors, antifoaming agents and the like are suitable.

As a form of the optical member, the transmittance at a wavelength of 500 nm is preferably 60% or more. When the transmittance is in such a range, an optical material having high transparency and excellent optical characteristics is obtained. The transmittance of the optical material is more preferably 80% or more, and still more preferably 85% or more. If the transmittance at a wavelength of 500 nm is less than 60%, the transmittance is insufficient for lens applications.

Specifically, the optical member is preferably used as an imaging lens for an in-vehicle camera, a PC camera, a digital camera, a mobile phone, a digital video, a surveillance camera, a PDA, a PC built-in camera, or the like. Thus, a lens using the optical member of the present invention is also one of the preferred embodiments of the present invention. Optical applications such as eyeglass lenses, filters, diffraction gratings, prisms, light guides, light beam condensing lenses and light diffusion lenses, transparent glasses such as watch glasses and cover glasses for display devices, and cover glasses; photo sensors , Photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical device adhesives, etc .; LCD, organic EL, PDP display element substrates, As an optical member for display device applications such as color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflective film high refractive index layers, antifogging films, and light extraction layers for organic EL Can also be suitably used.
When the composite particles of the present application are used for the high refractive index layer of the antireflection film, it is preferable to use dipentaerythritol hexa (meth) acrylate as the organic component.

The present invention is also an optical unit including the optical member. As described above, since the optical member of the present invention exhibits excellent transparency and optical characteristics, the optical unit including such an optical member also exhibits excellent performance. Become. Examples of the optical unit include a lens unit. Since the optical member of the present invention includes a cured product having a high refractive index, the use of this optical member can reduce the thickness of the lens and reduce the weight of the lens unit. Thus, a lens unit using the cured product is also one aspect of the present invention. Hereinafter, preferred embodiments of the lens and lens unit using the cured product of the present invention will be described in detail.

The lens using the optical member of the present invention preferably has a thickness of less than 1 mm. By setting the thickness of the lens (the maximum thickness of the region where the image is captured) to less than 1 mm, the optical path length can be shortened and the lens unit can be made smaller. The thickness of the lens is more preferably less than 800 μm, and still more preferably less than 500 μm.

In the lens unit, the number of lenses may be one, or two or more. In the case of a single lens, the Abbe number of the lens is preferably 45 or more. When there are two or more lenses, it is sufficient that the Abbe number of at least one lens is 45 or more, and the other lenses may have an Abbe number of less than 45. In the case of combining a lens having an Abbe number of 45 or more and a lens having an Abbe number of less than 45, it is more preferable to combine a lens having an Abbe number of 50 or more and a lens having an Abbe number of 40 or less. By combining a lens having an Abbe number of 50 or more and a lens having an Abbe number of 40 or less, there is an advantage that the resolution is improved and the characteristics required for the lens unit are satisfied.

Examples of the lens unit include a form including the lens. The lens preferably has a thickness of less than 1 mm and has at least one lens having an Abbe number of 50 or more. The thickness of the lens unit is preferably 50 mm or less. By setting it as such thickness, it can use suitably for various optical members, such as a camera module. More preferably, it is 30 mm or less as a thickness of a lens unit, More preferably, it is 10 mm or less.

Hereinafter, the suitable manufacturing method of the resin composition containing the said composite particle and the resin component is demonstrated.
The production method of the resin composition is not particularly limited as long as the effects of the present invention can be exhibited. For example, when it is difficult to uniformly mix the components constituting the resin composition, (1) resin It is preferable to include a step of preparing a mixture containing composite particles, a resin component, 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 the above mixture can be prepared, as long as the components constituting the curable resin composition are uniformly mixed, and any addition (blending) order and mixing method can be used. Can be used. Furthermore, the said mixture may contain the other component.
As a preparation process, it is preferable to adjust the degree of vacuum and perform the preparation at 100 ° C. or lower.
In the preparation step, the ratio of the resin component to the solvent is (composite particle component constituting the resin composition + resin component) / (composite particle component constituting the resin composition + resin component + solvent) = 10 to 90 mass. % Is preferred. More preferably, it is 15-60 mass%. Specifically, methanol, ethanol, isopropanol, butanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, acetonitrile, chloroform, toluene, xylene and the like are preferable as the solvent. More preferred are isopropanol, butanol, methyl ethyl ketone, and toluene.

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, thickening of the mixture can be effectively suppressed, 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 manufacturing method which adds a high boiling point component before degassing the solvent after mixing the component which comprises a resin composition is also one of the preferable forms of this invention.

The amount of the high boiling point component added is 0.01 to 10% by mass with respect to 100% by mass of the mixture of the resin component, the composite particle component, the solvent before degassing, the high boiling point component and other components as required. Preferably there is. More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%.
Note that the high boiling point component remains in the composition at the end of the degassing step. The proportion is preferably 0.01 to 10% by mass in 100% by mass of the mixture at the end of the degassing step. More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%.
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 resin component, curing reaction, and aggregation of the composite 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.

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 component 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 is preferably produced by the method described above. That is, the resin composition includes a step of preparing a mixture containing composite particles having a conjugated aromatic skeleton having 7 or more carbon atoms on the surface, a resin component and a solvent, and degassing the solvent from the mixture. A method for producing a resin composition comprising a deaeration step, wherein the deaeration step is performed in the presence of a high-boiling component is also a preferred embodiment of the present invention.

As a method of blending the composite particles with the resin composition, an external addition method or an internal precipitation method can be used. When using the resin composition for optical applications, when the composite particles are produced by an internal precipitation method, it is difficult to control the structure / composition of the composite particles due to a decrease in the stability of the resin composition due to the catalyst used, There is a possibility that deterioration before curing due to reaction with a resin component, residual catalyst, residual water that is difficult to remove, and the like may occur. Therefore, the external addition method is preferable when used for an optical member. The external addition method of the composite particles, specifically, the addition form of the composite particles to the resin composition and the dispersion will be described. The composite particles are preferably mixed with the resin component in a form dissolved in a powdered or liquid medium. That is, the composite particles are preferably in the form of a solution dissolved in a medium.

Examples of the medium include a solvent, a plasticizer, a monomer, and a liquid resin. As the solvent, water, organic solvents, mineral oils, vegetable oils, wax oils, silicone oils and the like can be suitably used, but the cationically polymerizable compound and / or the radically polymerizable compound used as the resin component dissolves easily. A solvent is preferred.
Examples of the solution containing the solvent and the composite particles include a form of a solvent dispersion. The content of the composite particles in the solvent dispersion is not particularly limited, but is preferably 10 to 70% by weight, more preferably 20 to 50% by weight of the entire solvent dispersion. Easy to handle in content. Although there is no limitation in particular about content of the solvent in a solvent dispersion, Preferably it is 90-30 weight% of the whole solvent dispersion, More preferably, it is 80-50 weight%.

Examples of the solvent include alcohols, ketones, aliphatic and aromatic carboxylic acid esters, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, mineral oils, There may be mentioned vegetable oil, wax oil, silicone oil and the like. Among these, a solvent in which the cationically polymerizable compound is easily dissolved is preferable, and specifically, ketones, aliphatic and aromatic carboxylic acid esters, ethers, aliphatic and aromatic hydrocarbons are preferable. .
When a curable resin is used as the resin component in the resin composition prepared as described above, the curable resin composition is prepared by adding and mixing the polymerization initiator or the curing agent described later. Can do. The polymerization initiator and the curing agent may be selected according to the type of resin component and the curing mechanism.

As a method for curing the resin composition of the present invention, various methods such as radical polymerization such as thermosetting and photocuring and cationic polymerization such as thermosetting and photocuring can be suitably used. There is a method in which the polymerization initiator and other materials as necessary are mixed to form one liquid, the mixed liquid 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. Preferably used. In such a method, it is preferable that the viscosity of the resin composition mixed with a curing catalyst or the like is not significantly increased because it is easy to handle. In the case of curing by thermosetting, the curing temperature can be appropriately set according to the resin composition to be cured, but is preferably 80 to 200 ° C. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC.

The curing method is preferably a method for producing a cured product by curing the resin composition within 5 minutes. Specifically, other materials are mixed with the curable resin composition as necessary to make one liquid, and the mixed liquid is applied to a mold that matches the shape of the cured product, and cured within 5 minutes. It is preferable to make it. By performing the curing using a mold in a short time, it is possible to make the method excellent in economic efficiency. Thus, a method for producing a cured product by curing the 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 curing time (curing time using a mold) exceeds 5 minutes, the productivity is deteriorated. More preferably, it is within 3 minutes.

In the method for curing the resin composition of the present invention, it is preferable that after curing using a mold as described above, the cured product is taken out of the mold and post-cured (baked). By performing post-cure, the cured product has sufficient hardness and can be suitably used for various applications. Moreover, in post-cure, it is excellent in handleability from the point of further curing a cured product having a certain degree of hardness. Therefore, there is an advantage that a large amount of products can be post-cured in a small area because it is not necessary to use a mold.
In the post-cure, the curing temperature and the curing time can be appropriately set according to the resin composition to be cured. For example, the curing temperature is preferably 80 to 200 ° C. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC. The curing time for the post cure is preferably 1 to 48 hours, although it depends on the curing temperature. More preferably, it is 1-10 hours, More preferably, it is 2-5 hours.

Hereinafter, the curing method of the resin composition will be further described. Various methods can be employed for curing the resin composition depending on the properties of the resin component used.
When the resin composition contains the composite particle and a resin component containing a compound having a cationic polymerizable group as an essential component, a cured product can be obtained by thermosetting using a polymerization initiator. . As the polymerization initiator, the above-described thermal latent cation generator is preferably used. In addition, as a curing method of the curable resin composition of the present invention, a curing method other than a curing method using a polymerization initiator such as a heat latent cation generator may be employed. For example, a curing agent can be used. Examples of such curing agents include methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, methylnadic acid, 3-methyl-1,2,3,6-tetrahydro. Acid anhydrides such as phthalic anhydride, 3-methyl-hexahydrophthalic anhydride, methyl-3,6 endomethylene-1,2,3,6-tetrahydrophthalic anhydride; phenol novolac resin, cresol novolac resin, bisphenol A Various phenol resins such as novolac resin, dicyclopentadiene phenol resin, phenol aralkyl resin and terpene phenol resin; obtained by condensation reaction of various phenols with various aldehydes such as hydroxybenzaldehyde, crotonaldehyde and glyoxal Price Various phenolic resins of such phenol resins; BF ₃ complex, sulfonium salts, can be used alone or in combination, such as imidazoles. Further, curing with a polyhydric phenol compound is also a preferred embodiment.

In the curing of the resin composition, a curing accelerator can be used as necessary. For example, organic phosphorus such as triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, tris (dimethoxyphenyl) phosphine One or more compounds such as compounds are preferred. As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC.
In addition, although the hardening agent and hardening accelerator mentioned above have advantages, such as accelerating the hardening reaction of a resin composition and being easy to handle, conventionally well-known hardening agents, such as such an acid anhydride and an amino compound Are known that the alicyclic acid anhydrides usually used for acid anhydride curing have a low refractive index and that amino compounds are easily yellowed. Therefore, when used for a high refractive index optical member, it is better not to use it actively unless it is essential to add a curing agent and a curing accelerator.

Since the composite particles of the present invention have a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of the inorganic fine particles, the dispersibility in the resin composition is improved, and high transparency and refractive index are achieved. It can have. Moreover, since this hardened | cured material has high transparency and refractive index, it is used suitably for various uses, such as optical uses, such as a lens unit, and an optical device use.

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

(Synthesis Example 1: Synthesis of zirconium oxide nanoparticles)
100 g of sodium hydroxide (manufactured by Kishida Chemical Co., Ltd., special grade) was added to 700 g of pure water at 40 ° C. with stirring and dissolved. Next, 495 g of neodecanoic acid (Japan Epoxy Resin Co., Ltd.) was added with stirring to prepare a sodium neodecanoate aqueous solution. The solution was brought to 80 ° C., 740 g of Zircozole ZC-20 (Daiichi Rare Elemental Chemical Co., Ltd.) was added over 20 minutes with stirring, and stirring was continued at 80 ° C. for 1 hour and a half. New zirconium neodecanoate was produced. Next, when 1270 g of tetradecane was added and stirred, a solution consisting of two phases of an oil phase composed of zirconium neodecanoate and tetradecane and an aqueous phase was obtained. The aqueous phase was separated and removed, and the oil phase portion was recovered. The oil phase part thus obtained was washed 3 times with pure water. Next, 1000 g of an oil phase and 500 g of pure water were charged into an autoclave equipped with a stirrer, and the atmosphere in the reaction vessel was replaced with nitrogen gas. Then, it heated to 175 degreeC and made it react for 3 hours. The pressure in the container during the reaction at 175 ° C. was 0.9 MPa. The solution after the reaction was taken out, and the precipitate accumulated at the bottom was collected by filtration. The precipitate was washed with acetone, dried, and then dispersed in toluene to give a cloudy solution. Next, it filtered again with the quantitative filter paper (Advantech Toyo Co., Ltd. No. 5C) as a refinement | purification process, and removed the coarse particle etc. in a deposit. Furthermore, white zirconium oxide nanoparticles were recovered by removing toluene in the filtrate under reduced pressure.

When the crystal structure of the zirconium oxide nanoparticles was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction line, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, when analyzed by an infrared absorption spectrum (FT-IR), absorption derived from C—H and absorption derived from COOH were observed. The absorption is considered to be derived from neodecanoic acid covering the zirconium oxide nanoparticles. When the mass reduction rate of the zirconium oxide nanoparticles was measured by TG-DTA (thermogravimetric-differential thermal analysis) in an air atmosphere at a rate of 10 ° C./min up to 800 ° C., the reduction rate of 19% by mass was measured. It became.

Method for synthesizing BiPh-U-Si (OEt) _{3 To} 80.16 g of toluene, 13.98 g (82.2 mmol) of paraphenylphenol and 3-isocyanatopropyltriethoxysilane (KBE-9007, Shin-Etsu Chemical Co., Ltd.) (Made) 20.34g (82.2mmol) and 0.017g of dibutyltin dilaurate (DBTDL) were added, and it heated up to 90 degreeC and heated for 5 hours. Thereby, BiPh-Si (OEt) ₃ was obtained. ^{From 1} H-NMR, it was confirmed that the reaction conversion (conversion) was 90%.

Synthesis Method of Ph-U-Si (OEt) _{3 To} 64.40 g of toluene, 7.60 g (80.8 mmol) of phenol and 3-isocyanatopropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 20.00 g (80 0.8 mmol) and 0.014 g of dibutyltin dilaurate (DBTDL) were added, and the temperature was raised to 90 ° C. and heated for 5 hours. Thereby, a Ph—U—Si (OEt) ₃ toluene solution was obtained. ^{From 1} H-NMR, it was confirmed that the reaction conversion (conversion) was 89%.

Synthesis method of Bz-U-Si (OEt) _{3 To} 67.06 g of toluene, 8.74 g (80.8 mmol) of benzyl alcohol and 20.00 g of 3-isocyanatopropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 80.8 mmol) and 0.014 g of dibutyltin dilaurate (DBTDL) were added, heated to 90 ° C. and heated for 5 hours. This obtained the Bz-U-Si (OEt) ₃ toluene solution. ^{From 1} H-NMR, it was confirmed that the reaction conversion (conversion) was 95%.

Synthesis Method of F-U-Si (OEt) ₃ 112.49 g of toluene, 28.21 g (80.8 mmol) of bisphenolfluorene, 20.00 g of 3-isocyanatopropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 80.8 mmol) and 0.024 g of dibutyltin dilaurate (DBTDL) were added, heated to 90 ° C. and heated for 5 hours. This obtained the FU-Si (OEt) ₃ toluene solution. ^{From 1} H-NMR, it was confirmed that the reaction conversion was 93%.

Synthesis method of FM-1-Ph solution To 13.52 g of toluene, 20.00 g (0.082 mmol) of Plaxel FM-1 (manufactured by Daicel Chemical Industries), 11.55 g (0.078 mol) of phthalic anhydride, triphenylphosphine 0 .4 g was added and heated at 60 ° C. for 5 hours to obtain FM-1-Ph toluene solution. It was confirmed by ¹ H-NMR that the reaction was complete.

(Synthesis Example 2: Synthesis of BiPh-U-Si (OEt) _3- treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 28.0 g of BiPh-Si (OEt) ₃ solution (solid content: 8.4 g) was added to the solution. Then, 4 g of ultrapure water was added, and the mixture was refluxed at 90 ° C. for 1 hour with stirring.
After allowing the solution after the reflux treatment to cool, n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the agglomerated particles were separated from the white turbid solution with a filter paper and vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-Si (OEt) ₃ .
When the crystal structure of the zirconium oxide nanoparticles after the treatment was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton was confirmed by H-NMR, it was confirmed that the zirconium oxide nanoparticles after the treatment were coated with two kinds of coating agents, neodecanoic acid and BiPh-Si (OEt) _3. It was confirmed. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 19% by mass.

(Synthesis Example 3: Synthesis of BiPh-U-Si (OEt) ₃ and KBM-503 treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 28.0 g of BiPh-Si (OEt) ₃ solution was added to the solution (solid content: 8.4 g). Then, 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of ultrapure water were added, and the mixture was refluxed with stirring at 90 ° C. for 1 hour.
After allowing the solution after the reflux treatment to cool, n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the aggregated particles were separated from the cloudy solution with a filter paper, and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane.
When the crystal structure of the zirconium oxide nanoparticles after the treatment was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid, BiPh-U-Si (OEt) ₃ , And it was confirmed that it was coat | covered with three types of coating agents of 3-methacryloxypropyl trimethoxysilane. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 20% by mass.

(Synthesis Example 4: Synthesis of FU-Si (OEt) _3- treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 40.4 g of a FU-Si (OEt) ₃ solution (solid content of 12.2 g) was added to the solution. 1 g), 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of ultrapure water were added, and the mixture was refluxed with stirring at 90 ° C. for 1 hour.
After allowing the solution after the reflux treatment to cool, n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the aggregated particles were separated from the cloudy solution using a filter paper, and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with FU-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the zirconium oxide nanoparticles after the treatment was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the treated zirconium oxide nanoparticles were neodecanoic acid and FU-Si (OEt) ₃ , And it was confirmed that it was coat | covered with three types of coating agents of 3-methacryloxypropyl trimethoxysilane. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 19% by mass.

(Synthesis Example 5: Synthesis of Ph-U-Si (OEt) _3- treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 23.1 g of a Ph-U-Si (OEt) ₃ solution (solid content of 6. 9 g), 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) (0.95 g) and ultrapure water (5 g) were added, and the mixture was refluxed at 90 ° C. for 1 hour with stirring.
After allowing the solution after the reflux treatment to cool, n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the aggregated particles were separated from the cloudy solution with a filter paper, and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with Ph-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the zirconium oxide nanoparticles after the treatment was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid and Ph-U-Si (OEt) ₃ . It was confirmed that it was coated with three kinds of coating agents. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 19% by mass.

(Synthesis Example 6: Synthesis of Bz-U-Si (OEt) _3- treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 24.1 g of a Bz-U-Si (OEt) ₃ solution (solid content 7. 2 g), 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of ultrapure water were added, and the mixture was refluxed with stirring at 90 ° C. for 1 hour.
After allowing the solution after the reflux treatment to cool, n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the agglomerated particles were separated from the cloudy solution with a filter paper and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with Bz-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the zirconium oxide nanoparticles after the treatment was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction lines, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid and Bz-U-Si (OEt) ₃ . It was confirmed that it was coated with three kinds of coating agents. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 20% by mass.
The zirconia particles obtained in Synthesis Examples 2 to 6 are shown in Table 2.

(Method for creating resin composition)
Resin composition for Example 1 2.5 g of the zirconium oxide particles (1) obtained in Synthesis Example 2 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), perbutyl Z (manufactured by NOF Corporation, t-butyl) After dissolving 0.1 g of peroxybenzoate) in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Example 1.

Resin composition for Example 2 2.5 g of the zirconium oxide particles (2) obtained in Synthesis Example 3 and 2.5 g of Ogsol EA-200 (Osaka Gas Chemical Co., Ltd.), Perbutyl Z (manufactured by NOF Corporation, t-butyl) Peroxybenzoate) 0.1 g was dissolved in 20.0 g of toluene, and then toluene was devolatilized by an evaporator to obtain a resin composition for Example 2.

Resin composition for Example 3 2.5 g of the zirconium oxide particles (3) obtained in Synthesis Example 4 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), perbutyl Z (manufactured by NOF Corporation, t-butyl) After dissolving 0.1 g of peroxybenzoate in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Example 3.

Resin composition for Example 4 2.5 g of the zirconium oxide particles (2) obtained in Synthesis Example 3 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), 0.05 g of FM-1 as a dispersant, After 0.1 g of perbutyl Z (manufactured by NOF Corporation, t-butyl peroxybenzoate) was dissolved in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Example 3.

Resin composition for Example 5 2.5 g of the zirconium oxide particles (2) obtained in Synthesis Example 3 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Co., Ltd.), FM-1-Ph solution 0. Example 3 After dissolving 086 g (0.06 g of solid content) and 0.1 g of perbutyl Z (manufactured by NOF Corporation, t-butyl peroxybenzoate) in 20.0 g of toluene, the toluene was devolatilized by an evaporator. A resin composition was obtained.

Resin composition for Comparative Example 1 2.5 g of the zirconium oxide particles (4) obtained in Synthesis Example 5 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), perbutyl Z (manufactured by NOF Corporation, t-butyl) After 0.1 g of peroxybenzoate) was dissolved in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Comparative Example 1.

Resin composition for Comparative Example 2 2.5 g of the zirconium oxide particles (5) obtained in Synthesis Example 6 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), perbutyl Z (manufactured by NOF Corporation, t-butyl) After dissolving 0.1 g of peroxybenzoate) in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Comparative Example 2.

After dissolving 5.0 g of the resin composition for Comparative Example 3 Ogsol EA-200 (manufactured by Osaka Gas Chemical Co., Ltd.) and 0.1 g of perbutyl Z (manufactured by NOF Corporation, t-butyl peroxybenzoate) in 20.0 g of toluene. Then, toluene was devolatilized with an evaporator to obtain a resin composition for Comparative Example 3.

Examples 1-5, Comparative Examples 1-3
The resin compositions for Examples 1 to 5 and Comparative Examples 1 and 2 were coated on a glass plate (150 mm × 70 mm × 2 mm) using a 5 mil applicator so that the film thickness was 125 μm. Then, the cured coating film was obtained by heating for 30 minutes at 150 degreeC by nitrogen atmosphere. And the transmittance | permeability of the cured coating film in wavelength 400nm was measured.

The light transmittance (light wavelength: 400 nm) in the thickness direction of an uncoated glass plate (150 mm × 70 mm × 2 mm) was used with an absorptiometer (a spectrophotometer “UV-3100” manufactured by Shimadzu Corporation). The transmittance was set to T ¹ %. Next, the light transmittance (light wavelength: 400 nm) in the thickness direction of the glass plate on which the cured coating film produced by the above method was formed was measured using an absorptiometer “UV-3100”, and the transmittance was measured. T ² %. From these values, the transmittance T was calculated by the following formula.
T = 100−T ¹ + T ²

<Measurement method of refractive index and Abbe number>
The obtained resin composition was poured into a mold adjusted to a thickness of 500 μm, then covered with a glass plate from above, and heated at 150 ° C. for 30 minutes to obtain a cured product. The refractive index of 589 nm at 20 ° C. of the cured product obtained using a refractometer (Atago Co., Ltd., DR-M2) was measured. The measurement results are shown in Table 3 below.

From Table 3, the resin composition manufactured using the composite particles of the present invention was colorless and transparent, and a cured product having a refractive index of 1.62 or more was obtained. In Comparative Example 3, since it did not contain inorganic fine particles, it was colorless and transparent and had no haze, but its refractive index was lower than that of a cured product produced using the composite particles of the present invention. It was a thing.

FIG. 1 is a schematic view showing an example of a method for surface treatment with a hydrolyzable silane compound containing a conjugated aromatic skeleton having 7 or more carbon atoms. FIG. 2 is a schematic diagram illustrating an example of a method of performing a surface treatment with a hydrolyzable silane compound including a conjugated aromatic skeleton having 7 or more carbon atoms. FIG. 3 is a schematic diagram showing an example of a method for surface treatment with a hydrolyzable silane compound containing a conjugated aromatic skeleton having 7 or more carbon atoms. FIG. 4 shows that after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a conjugated aromatic skeleton having 7 or more carbon atoms and has a reactive group. It is a schematic diagram which shows an example of the method of making the compound which has (II) react. FIG. 5 shows that after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a conjugated aromatic skeleton having 7 or more carbon atoms and has a reactive group. It is a schematic diagram which shows an example of the method of making the compound which has (II) react. FIG. 6 shows that after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a conjugated aromatic skeleton having 7 or more carbon atoms and has a reactive group. It is a schematic diagram which shows an example of the method of making the compound which has (II) react. FIG. 7 shows that after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a conjugated aromatic skeleton having 7 or more carbon atoms and has a reactive group. It is a schematic diagram which shows an example of the method of making the compound which has (II) react. FIG. 8 shows that after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a conjugated aromatic skeleton having 7 or more carbon atoms and has a reactive group. It is a schematic diagram which shows an example of the method of making the compound which has (II) react. After introducing the hydrolyzable silicon compound having the reactive group (I), the reactive group (I) and the reactive group (II) having a conjugated aromatic skeleton having 7 or more carbon atoms are added. It is a schematic diagram which shows an example of the method of making the compound which has it react. After introducing a hydrolyzable silicon compound having an epoxy group (reactive group (I)), the epoxy group and a compound having a conjugated aromatic skeleton having 7 or more carbon atoms and having an epoxy group It is a schematic diagram which shows an example of the method made to react. After introducing a hydrolyzable silicon compound having an oxetane group (reactive group (I)), the oxetane group and a compound having a conjugated aromatic skeleton having 7 or more carbon atoms and having an oxetane group It is a schematic diagram which shows an example of the method made to react. FIG. 11 is a schematic diagram showing an example of a method using a reaction between a metal hydroxyl group on the surface of inorganic fine particles and a reactive group.

Explanation of symbols

1: Inorganic fine particles 2: Organic chain

Claims (10)

A composite particle comprising a conjugated aromatic skeleton having 7 or more carbon atoms on the surface of inorganic fine particles. The conjugated aromatic skeleton essentially includes at least one structure selected from the group consisting of a fluorene skeleton, an anthracene ring, a dibenzothiophene ring, a carbazole skeleton, a stilbene skeleton, a biphenyl skeleton, and a naphthalene ring. The composite particle according to 1. The composite particle according to claim 1, wherein the inorganic fine particle is a metal oxide fine particle. The metal oxide fine particles contain at least one metal element selected from the group consisting of titanium, zirconium, zinc, lanthanum, yttrium, indium, tin and niobium. The composite particle as described. A resin composition comprising the composite particles according to claim 1 and a resin component. 6. The resin composition according to claim 5, wherein the resin component essentially comprises an aromatic compound (C) having a conjugated structure composed of 7 or more carbon atoms. The resin composition according to claim 6, wherein the aromatic compound (C) is a (meth) acrylate compound and is heat and / or photocurable. The resin composition according to claim 6, wherein the aromatic compound (C) is an epoxy compound and is heat and / or photocurable. The resin composition further includes a dispersant (D),
The dispersant (D) has the following general formula (I):
R ^a —R ^b —O— (CO—R ^c —O) _p —CO—R ^d —COOH (I)
(In the formula, R ^a is at least one selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and a (meth) acryloyl group. R ^b is an alkylene group or an aryl group, R ^c is an alkylene group, and R ^d is at least one selected from the group consisting of an alkylene group, an aryl group, and an alkyne group. (P is an integer of 1 or more)) Compound (1) represented by the following general formula (II);
R ^e — [CO— (O—R ^f —CO) _n —OH] _m (II)
(However, R ^e is selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and an optionally substituted vinyl group. R ^f is an alkylene group, n is a number of 1 or more, and m is a number of 1 to 4.) and / or General formula (III);
^{R g -R h -O- (CO-} R i -O) r -H (III)
(However, R ^g is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an aryl group, an aralkyl group, an acyl group, and a (meth) acryloyl group. R ^h represents an alkylene group or an aryl group, R ⁱ represents an alkylene group, r is a number of 1 or more, and the compound (3) is used. The resin composition according to any one of claims 5 to 8. Hardened | cured material formed by hardening the resin composition in any one of Claims 5-9.

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