JP2010037534A - Composite particle, resin composition, and its cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide composite particles, which can be excellently dispersed while keeping characteristics of inorganic fine particles, that is, can exhibit excellent transparency and high refractive index when dispersed in a dispersion medium such as a resin composition, and to provide a resin composition containing the composite particles and a resin component, and a cured product obtained by curing the resin composition. <P>SOLUTION: In the composite particles, an organic component including an aromatic skeleton and a binding structure, wherein four or more atoms are continuously coupled, to the aromatic skeleton is arranged on the surfaces of the inorganic fine particles. The resin composition comprises the composite particles and the resin component. The cured product is obtained by curing the resin composition. <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 suitable for resin compositions used for optical applications such as lenses and optical device applications, resin compositions containing the composite particles, and cured products thereof.

In recent years, resin compositions have been used as mechanical parts materials, electric / electronic parts materials, automobile parts materials, civil engineering and building materials, molding materials, etc. as so-called plastic materials, and also as materials for paints and adhesives. Under such circumstances, plastic molding materials are attracting attention from the viewpoints of light weight and workability, and are being applied 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, and it can be adapted to recent miniaturization and weight reduction, and high performance in optical characteristics is required. . However, this high required performance cannot be achieved by conventional plastic materials. For example, in plastic lenses, there has been a demand for a resin composition having excellent transparency and a high refractive index, and a cured product obtained by curing the resin composition.

One method for controlling the optical properties 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). However, in the thermosetting resin composition obtained by such a production method, when used in optical applications, coarse inorganic particles are completely eliminated and sufficiently dispersed as primary particles, and visible light is inorganic particles. There is room for improvement in making the transparency sufficient without being scattered by the light.

By the way, as a compound containing silicon and a benzene ring, a compound having an aromatic skeleton and a urethane bond produced by reacting benzyl alcohol or phenol with a silane coupling agent is disclosed (for example, Patent Document 2, (Refer nonpatent literature 1.). However, these compounds are compounds for forming a light emitting material or materials for producing polymer silica for electronic materials.

JP 2004-346288 A (page 2) Korean Patent Publication No. 2006-112966

Bing Yan, Dong-Jie Ma, “Journal of SOLID STATE CHEMISTRY”, 2006, 179, 7, pp 2059-2066

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 characteristics of inorganic fine particles, that is, excellent transparency when dispersed in a dispersion medium such as a resin composition. Composite particles that can have excellent refractive index, heat resistance, and mechanical strength, a resin composition containing the composite particles and a resin component, and a cured product obtained by curing the resin composition It is intended to provide.

The present inventor has examined inorganic fine particles suitable for inclusion in a resin composition and the like. When inorganic fine particles are contained in a resin composition and the like, the inorganic fine particles are added to the resin composition and the like. It was noted that the transparency of the resin composition and its cured product is affected by dispersibility. In order to prevent and further improve the resin composition containing inorganic fine particles and the transparency of the cured product, and further improving the bonding structure to the aromatic skeleton in which four or more atoms are linked, The present inventors have found that this can be achieved by using composite particles having an organic component containing bismuth on the surface of inorganic fine particles. Thereby, the dispersibility to the resin component which comprises a resin composition can be improved, and it can be set as the resin composition which improved transparency. Furthermore, by having an aromatic skeleton on the surface, a resin composition containing composite particles can have a high refractive index, mechanical strength, heat resistance, and the like. According to this, it is possible to obtain composite particles that can be suitably used for optical members that require high transparency and refractive index, and conceived that the above problems can be solved brilliantly. It has been reached.

That is, the present invention comprises composite particles having an organic component on the surface of an inorganic fine particle including an aromatic skeleton and a bond structure to an aromatic skeleton in which four or more atoms are linked, and the composite particles and a resin component. A resin composition and a cured product obtained by curing the resin composition.
The present invention is described in detail below.

The composite particle in the present invention has an organic component on the surface of the inorganic fine particle including an aromatic skeleton and a bonded structure to the aromatic skeleton in which four or more atoms are continuous. According to this, the inorganic fine particles and the aromatic skeleton can be in a form of being connected via a bond structure to the aromatic skeleton in which four or more atoms are linked, and for dispersing the composite particles It has been found that dispersibility in resin components and the like can be improved. Since the dispersibility of the composite particles is improved, the transparency of the composite particles (for example, a resin composition) dispersed therein can be improved. For example, when it does not have a bond structure to an aromatic skeleton, transparency can be obtained with a film-like molded product having a small film thickness, but a film-like molded product with a film thickness of about 100 μm or a thickness of about 500 μm. In the molded product, sufficient transparency could not be obtained. Therefore, by having an organic component containing a bond structure to an aromatic skeleton on the surface of the inorganic fine particles, a resin composition having excellent transparency can be obtained even in a molded product having a large thickness. Further, when a resin composition in which composite particles are dispersed is obtained, a resin composition having high transparency and high refractive index without impairing the effect of containing inorganic fine particles due to the conjugated structure of the aromatic skeleton It can be a thing. Moreover, the same effect will be acquired also in the hardened | cured material. As described above, a form in which the inorganic fine particles and the aromatic skeleton are connected via a bond structure to the aromatic skeleton in which four or more atoms are continuous is also a preferable form of the present invention. Hereinafter, the “bond structure to an aromatic skeleton in which four or more atoms are linked” is also referred to as “bond structure to an aromatic skeleton”.
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, it is preferable that the composite particles having an aromatic skeleton do not leave even when washed with an organic solvent (for example, hexane, methanol, etc.) that can dissolve the aromatic skeleton. As an example, the surface of the inorganic fine particle is a form in which a compound containing an aromatic skeleton is attached to the surface of the inorganic fine particle (it may not be chemically bonded to the atoms constituting the surface of the inorganic fine particle). A form in which the constituent element and an organic group including an aromatic skeleton are chemically bonded (covalently bonded) is preferable.
In the composite particles of the present application, the content of the “aromatic skeleton” on the surface is not particularly limited, but the composite skeleton has 100% by mass, and the aromatic skeleton has 2% by mass or more. It is preferable at the point which is excellent in the effect by (dispersibility improvement effect). 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 surface of the inorganic fine particles by washing or the like may increase. The content of “aromatic skeleton” is more preferably in the range of 3 to 20% by mass, particularly preferably in the range of 4 to 15% by mass, for the reasons described above.
The content of the aromatic skeleton that does not leave even when washed with an organic solvent is the same as the range described above. Of the aromatic skeletons on the surface, the higher the proportion of the aromatic skeleton on the surface that does not leave even after washing, the more preferable.

When the composite particles having an aromatic skeleton are in a form that does not leave even when washed with an organic solvent that can dissolve the aromatic skeleton, as one guideline, an organic solvent that can dissolve the aromatic skeleton is used. When 100 parts by mass of the organic solvent is added with 1 part by mass of composite particles and stirred for 12 hours, the aromatic skeleton remains on the surface of the inorganic fine particles. More specifically, when 1 part by mass of the composite particles is added to 100 parts by mass of the organic solvent and stirred at a temperature of 50 ° C. and a stirring speed of 100 rpm for 12 hours, the surface of the inorganic fine particles is conjugated aromatic. It is preferable that the skeleton remains. For example, it is preferable that the organic component containing an aromatic skeleton introduced 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 particle is not particularly limited as long as it has inorganic fine particles and an organic component containing an aromatic skeleton introduced into the surface of the inorganic fine particles and a bond structure to the aromatic skeleton. The component of this may be included. For example, in addition to an organic component containing an aromatic skeleton, other organic substances or other components such as inorganic substances 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, but the inorganic fine particles are preferably dispersed without agglomeration. The particle diameter of the composite particle is defined by the size of the image composed of the inorganic fine particles, and the number average particle diameter of the particle diameter is preferably 1 μm or less, more preferably 100 nm or less, and still more preferably Is 20 nm or less, and particularly preferably 15 nm or less.
The composite particles preferably have a refractive index of 1.6 or more. For example, when the resin composition includes the composite particles and the resin component, the resin generally has a refractive index of 1.4 to 1.6, and the resin component alone has a refractive index of 1.6 or more. Is difficult to form. Therefore, 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 has a refractive index that is difficult to obtain with only the resin component. be able to. 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 organic component includes an aromatic skeleton and a structure bonded to the aromatic skeleton in which four or more atoms are linked. The bond structure to the aromatic skeleton in which four or more atoms are linked is bonded to the aromatic skeleton, and the organic component is not particularly limited as long as it includes such a structure.

(Aromatic skeleton form)
The aromatic skeleton is not particularly limited as long as it includes an aromatic ring (benzene ring) structure. Since the aromatic ring has a conjugated structure, the refractive index can be increased due to the conjugated structure. For example, the aromatic ring may be in the form of a benzene ring having no substituent, or may be a structure in which aromatic ring structures are linked, such as a naphthalene ring or an anthracene ring. Moreover, the form which has a substituent may be sufficient and it is not limited at all.

Examples of the aromatic skeleton include the following chemical formulas (1-1) to (1-9);

It is preferable that it has either of the structures represented by these. That is, a benzene ring represented by the above chemical formula (1-1) (a conjugated structure composed of 6 carbon atoms), a fluorene skeleton represented by the above chemical formula (1-2) (constituted by 13 carbon atoms) Conjugated structure), anthracene ring represented by the above chemical formula (1-3) (conjugated structure constituted by 14 carbon atoms), dibenzothiophene ring represented by the above chemical formula (1-4) (12) A conjugated structure composed of carbon atoms), a carbazole skeleton represented by the above chemical formula (1-5) (a conjugated structure composed of 12 carbon atoms), the above chemical formulas (1-6-1) and (1 -6-2) stilbene skeleton (conjugated structure composed of 14 carbon atoms), biphenyl skeleton represented by the above chemical formula (1-7) (constituted by 12 carbon atoms) Role structure) preferably has any of the above formulas (conjugated structure constituted by naphthalene ring (10 carbon atoms represented by 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. 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, a biphenyl skeleton, a carbazole skeleton, a stilbene skeleton, an anthracene ring, and a dibenzothiophene ring is also included in the present invention. This is one of the preferred forms. 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 skeleton, any one having the skeleton or ring structure described above can be suitably used. As represented by the chemical formula (1-9), bisphenol is bonded to the fluorene skeleton. A structure (a conjugated structure composed of 25 carbon atoms) and the like can also be mentioned as a preferred form.

The aromatic skeleton preferably contains a benzene ring and / or a biphenyl skeleton from the viewpoint of suppressing coloring of the composite particles. For example, if the skeleton includes a fluorene skeleton or a naphthalene ring, the composite particle may be colored. However, by using a benzene ring (a conjugated structure composed of six carbon atoms) or a biphenyl skeleton, Coloring can be suppressed. In addition, using a benzene ring or a biphenyl skeleton is preferable from the viewpoint of cost reduction. For example, a compound having a fluorene skeleton or a carbazole skeleton is expensive and may increase the material cost. However, a compound containing a benzene ring or a biphenyl skeleton, particularly a benzene ring, is relatively inexpensive and keeps the production cost low. be able to.

A preferable form of the aromatic skeleton includes a form of a conjugated aromatic skeleton having 7 or more carbon atoms. As such 7 or more conjugated aromatic skeletons, those having a structure represented by the above chemical formulas (1-2) to (1-9) may be mentioned as preferred forms. With such a structure, the refractive index can be made higher due to the conjugated structure. It is a more preferable embodiment that the aromatic skeleton includes a biphenyl skeleton from the viewpoint that coloring can be suppressed and the refractive index can be further increased.

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 (c), 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 (d), 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 (e), 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 of the structures shown in the following formulas (f) and (g).

(Form of bond structure to aromatic skeleton)
The bond structure to the aromatic skeleton in which four or more atoms are linked (hereinafter, also simply referred to as “bond structure to the aromatic skeleton”) may be bonded to the aromatic skeleton. It is not limited. The bond structure to the aromatic skeleton is preferably a series of 4 to 20 atoms, more preferably a series of 4 to 10 atoms, and still more preferably 4 to 8 atoms. It is a series of atoms. When the number of connected atoms exceeds 20, the refractive index may be lowered. If the number is less than 4, the distance between the inorganic fine particles and the aromatic skeleton cannot be sufficiently separated, and the effect of improving dispersibility may not be sufficiently obtained.

Examples of the form of the bond structure to the aromatic skeleton include an alkylene group, an aryl group, and an aralkyl group in which 4 or more carbon atoms are linked. Further, as a preferred form, a form in which the terminal atom of the structure bonded to the aromatic skeleton is an oxygen atom is suitable. For example, a compound that is a source of the organic component by reacting a compound having an aromatic skeleton with a compound that includes at least a part of a structure bonded to the aromatic skeleton (for example, a compound that performs surface treatment of inorganic fine particles) When a compound containing an aromatic skeleton to which a hydroxyl group is bonded is reacted with a compound containing at least a part of the structure bonded to the aromatic skeleton, the aromatic skeleton can be easily bonded to the aromatic skeleton. A compound with a bound structure can be formed.
The bond structure to the aromatic skeleton may have a substituent. For example, a form in which a characteristic group such as a hydroxyl group, an amino group, or a carbonyl group is bonded as a side chain of an alkylene group in which four or more carbon atoms are linked may be used. Dispersibility can be further improved by the bonding structure to an aromatic skeleton containing a group having an active hydrogen such as a hydroxyl group, an amino group, or a carbonyl group. That is, the bond structure to the aromatic skeleton preferably has a hydrogen group.

The composite particle has an organic component including an aromatic skeleton and a structure bonded to an aromatic skeleton in which four or more atoms are continuous on the surface of the inorganic fine particle. A form in which four or more atoms are bonded via a bond structure to an aromatic skeleton in which the atoms are connected is preferable. As such a form, for example, MLQ (M represents a metal element constituting the surface of the inorganic fine particles. L represents a bond structure to an aromatic skeleton in which four or more atoms are linked. Q is preferably an organic group containing an aromatic skeleton). A preferable metal element M is the same as the metal element constituting the metal oxide fine particles described later. Q may be in the form of an organic group in which no substituent is bonded to the aromatic skeleton, or in the form in which a substituent is bonded to the aromatic skeleton. In addition, the organic component including the aromatic skeleton and the bond structure to the aromatic skeleton in which four or more atoms are linked is a structure in which the aromatic skeleton and the bond structure to the aromatic skeleton are connected by a chemical bond. There is no particular limitation as long as it is present. For example, when the metal element constituting the inorganic fine particle surface and the organic component are connected by a chemical bond, the atoms connected by the chemical bond with the bond structure to the aromatic skeleton bonded to the metal element are It shall be contained in the organic component. That is, in a bond form such as M-O-Si-LR (wherein M is a metal element constituting the surface of the inorganic fine particles, and L represents a bond structure to the aromatic skeleton). If present, the O-Si-LR portion is referred to as an organic component.
In addition, although the form of bonding is 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 chemically bonded. It is not a thing.

The form of the organic component bonded to the surface of the inorganic fine particle is not particularly limited as long as it includes an aromatic skeleton and a structure bonded to the aromatic skeleton. For example, the following formula (2-1) To (2-4);

(In the formula, R represents an organic group containing an aromatic skeleton. 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 And a form represented by a divalent organic group). Note that in the case of the organic component represented by the above formula (2-1), a portion excluding R (portion of —CH ₂ —CH ₂ —Si—O—) can be referred to as a bond structure to an aromatic skeleton. . Further, in the case of the organic component represented by the above formula (2-4), a portion excluding R may be a bond structure to an aromatic skeleton, and R and a siloxy bond (Si—O) portion are excluded. The structure may be a bond structure to the aromatic skeleton, and the bond structure to the aromatic skeleton may be any structure in which four or more atoms are linked.

In addition, as the form in which the bond structure L to the aromatic skeleton is bonded to R (form of RL), the following formulas (3-1) to (3-3);

(Wherein R represents a group having an aromatic skeleton) is preferred. The bond structure L to the aromatic skeleton is preferably represented by the formula (3-1). In addition, as a structure of the said organic component, the form which the structure represented by Formula (3-1)-(3-3) has couple | bonded through the siloxy bond or the siloxane bond so that it may mention later is also a preferable form. is there.

The bond structure to the aromatic skeleton is preferably bonded to the surface of the inorganic fine particle via a siloxy bond or a siloxane bond. For example, when there is a siloxy bond between an aromatic skeleton and an element constituting the surface of the inorganic fine particle, four or more atoms are present between the siloxy bond consisting of a silicon atom and an oxygen atom and the aromatic skeleton. It is preferable that there is a bond structure to a continuous aromatic skeleton. As described above, the organic component (an organic component including an aromatic skeleton and a bond structure to the aromatic skeleton) is stably present on the surface of the inorganic fine particle by bonding through a siloxy bond or a siloxane bond. In addition, by bonding through a siloxy bond or a siloxane bond, the composite particles can have a more stable form, and mechanical strength and heat resistance can be improved. Such a form can be formed by surface-treating inorganic fine particles using a silane coupling agent containing the aromatic skeleton and a structure bonded to the aromatic skeleton. More specifically, an aromatic skeleton is bonded to one end of the structure bonded to the aromatic skeleton, and the other end is formed by surface treatment using a silane coupling agent bonded with a silicon atom. Can do. As a form couple | bonded through the said siloxy bond or a siloxane bond, forms, such as MO- (Si-O) _a -LR, M- (O-Si) _b -LR, are mentioned, for example. . In the formula, M is a metal element constituting the surface of the inorganic fine particles. L represents a bond structure to the aromatic skeleton. R represents an organic group having an aromatic skeleton. a and b are the same or different and are 1 or more numbers which represent the repeating number of a structural unit. As described above, when there is a siloxy bond and / or a siloxane bond bonded to the metal element on the surface of the inorganic fine particle, it is separate from the repeating unit of the siloxy bond and / or the siloxane bond bonded to the metal element M of the inorganic fine particle. A preferred form is a form in which a bond structure to an aromatic skeleton in which four or more atoms are linked is bonded. According to this, since the distance between the metal element on the surface of the inorganic fine particles and the aromatic skeleton can be made more sufficient, the dispersibility of the composite particles can be further improved.
The form bonded through the siloxy bond or the siloxane bond may be a form in which a plurality of aromatic skeletons are connected to one metal element. For example:

(In the formula, M is a metal element constituting the surface of the inorganic fine particles. L represents a bond structure to an aromatic skeleton. R represents an organic group having an aromatic skeleton). As described above, two aromatic skeletons R and two bonded structures L to the aromatic skeleton may be bonded to one metal element M, and the form is not particularly limited.

The bond structure to the aromatic skeleton has the following general formula (a);

(Wherein R ^a represents an optionally substituted alkylene group having 1 to 10 carbon atoms) and / or the following general formula (b);

(Wherein R ^b represents an alkylene group having 1 to 10 carbon atoms which may have a substituent). Thus, it is preferable that the bond structure to the aromatic skeleton includes a structure having active hydrogen such as a hydroxyl group or a urethane bond. Further, as a more preferable form, the bond structure to the aromatic skeleton includes a urethane bond represented by the general formula (a). In the bonding structures represented by the general formulas (a) and (b), the terminal oxygen in the formula is preferably bonded to the aromatic skeleton. Such a structure can be said to be a preferable embodiment because it can be easily formed by reacting an aromatic skeleton having a hydroxyl group with a compound having at least a part of a structure bonded to the aromatic skeleton.

(Silane compound used for surface treatment)
As a method for producing the composite particles, a method in which inorganic fine particles are surface-treated with a silane compound or the like is suitable. As such a silane compound, a silane compound in which a silicon atom and an aromatic skeleton are bonded via a bond structure to the aromatic skeleton is preferable.
Examples of the silane compound in which the silicon atom and the aromatic skeleton are bonded via the bond structure to the aromatic skeleton include, for example, the following formula:
R- (L _c SiX _(4-c) ) _d
(In the formula, R represents a group having an aromatic skeleton. L is the same or different, and represents a bond structure to an aromatic skeleton in which four or more atoms are linked. X is the same or different; R ^{3 represents an} O ³ group, a hydrogen atom, a halogen atom or a hydroxyl group, R ³ is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, c is a number of 1 to 3, d represents 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 c is 1. A preferable value of d is 1 or 2, and more preferably 1.

Examples of the alkoxysilane compound include the following formula:

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

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

(Wherein R represents a group having an aromatic skeleton, 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, as R- (OH) _j , the following formula:

Or an aromatic skeleton represented by formula (1) or a compound containing a bond structure to the aromatic skeleton. Such a reaction is simple, and by performing surface treatment using an alkoxysilane compound, the inorganic fine particles after the surface treatment become stable. Among the above reaction formulas, the following formula:

A silane compound obtainable by a reaction represented by the following formula:

A silane compound obtainable by a reaction represented by the following formula:

It is more preferable that it is a silane compound which can be obtained by reaction shown by these. That is, a preferred embodiment is a silane compound obtained by reacting a compound having a biphenyl skeleton and / or a compound having a benzene ring with a silane compound having a urethane bond. Here, the group corresponding to X described above is — (OC ₂ H ₅ ), but even if it is (OCH ₃ ), substantially the same effect can be obtained.
And the following formula:

Or a silane compound that can be obtained by the reaction represented by the following formula:

It is also preferable that it is a silane compound which can be obtained by reaction shown by these. That is, a preferred embodiment is a silane compound obtained by reacting a compound having a biphenyl skeleton and / or a compound having a benzene ring with a silane compound having an epoxy group.

As described above, the composite particle of the present invention can be produced using a silane compound in which a silicon atom and an aromatic skeleton are bonded via a bonding structure to an aromatic skeleton. Among such silane compounds, it is preferable that composite particles are produced using a silane compound having an alkoxy group, that is, an alkoxysilane compound. The alkoxysilane compound exhibits high reactivity due to the alkoxy group, and can produce the composite particles of the present invention easily and with high productivity. Moreover, since the composite particle manufactured by such a method can have a structure of -Si-OM, the composite particle has a stable form and is excellent in mechanical strength and heat resistance. be able to. That is, it is one of the preferred embodiments that the organic component is derived from an alkoxysilane compound that essentially requires an aromatic skeleton and a bond structure to the aromatic skeleton.

It is also one of the preferred embodiments of the present invention that the composite particles have a structure having an essential (meth) acryl group on the surface of the inorganic fine particles. According to this, the refractive index of the composite particles can be further increased due to the double bond of the (meth) acryl group. The composite particle of the present invention has an organic component containing an aromatic skeleton and a structure bonded to four or more aromatic skeletons on the surface of the inorganic fine particles, but the steric hindrance of the introduced aromatic skeleton. Therefore, the surface of the inorganic fine particles may not be sufficiently covered. In such a case, by introducing a structure essential for the (meth) acrylic group to the surface of the inorganic fine particles, the surface of the inorganic fine particles can be sufficiently covered without causing steric hindrance or the like. In this way, by introducing an organic component essentially containing a (meth) acryl group into the surface of the inorganic fine particles, the effect of coating is further enhanced, and the dispersibility of the composite particles can be improved. Further, the refractive index due to the double bond can be improved. As a form in which the structure which essentially requires a (meth) acryl group is introduced on the surface of the inorganic fine particle, it may be contained in the organic component, or as a form different from the organic component, the surface of the inorganic fine particle May be introduced. That is, a (meth) acryl group may be present as a part of the organic component, and an organic group or the like that requires a (meth) acryl group separately from the organic component adheres to or binds to the surface of the inorganic fine particles. It may be in the form. Such composite particles can be obtained, for example, by subjecting inorganic fine particles to a surface treatment using a surface treatment agent that essentially comprises a (meth) acryl group. As a more specific example, a (meth) acryl group derived from a silane compound such as 3-methacryloxypropyltrimethoxysilane may be present independently on the surface of the inorganic fine particles. In addition, a silane compound such as 3-methacryloxypropyltrimethoxysilane and an aromatic skeleton such as BiPh-U-Si (OEt) ₃ used to produce one of the composite particles in the examples of the present application; An alkoxysilyl group with a silane compound containing a bond structure to an aromatic skeleton may be condensed and exist via a siloxy group. Specific examples of the (meth) acryl group include an acryl group, a methacryloxymethyl group, and a methacryl group.

(Surface treatment method)
The composite particle has an organic component including an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particle. As a method for making such a form, an inorganic material using a surface treatment agent is used. A method of treating the surface of the system fine particles is preferable. By using the surface treating agent, an organic component containing an aromatic skeleton and a structure bonded to the aromatic skeleton can be efficiently introduced onto the surface of the inorganic fine particles. The surface treatment agent for treating the surface of the inorganic fine particles preferably includes, for example, an aromatic skeleton and a structure bonded to an aromatic skeleton in which four or more atoms are linked. That is, the present invention is a composite particle obtained by subjecting inorganic fine particles to a surface treatment using a surface treatment agent, the surface treatment agent having an aromatic skeleton and an aromatic skeleton composed of 4 or more atoms connected to each other. It also includes a bonding structure. Thus, the inorganic fine particles surface-treated with the surface treatment agent have an organic component on the surface having an aromatic skeleton and a structure bonded to an aromatic skeleton in which four or more atoms are linked. For example, when the inorganic fine particles are contained in the resin composition, dispersibility can be improved and transparency can be improved. In addition, since it contains an aromatic skeleton, it can have a high refractive index. As a preferable form of the bond structure to the aromatic skeleton contained in the surface treatment agent, the same structure as described above can be mentioned. Among them, the following can be cited as examples of preferred forms.

The bond structure to the aromatic skeleton contained in the surface treatment agent has the following general formula (a):

(Wherein R ^a represents an optionally substituted alkylene group having 1 to 10 carbon atoms) and / or the following general formula (b);

(In the formula, R ^b represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.) Is also a preferred embodiment.

As a method of bonding an organic group containing an aromatic skeleton and a bond structure to the aromatic skeleton to the surface of the inorganic fine particle by surface-treating the inorganic fine particles, for example, an aromatic skeleton and A method of performing surface treatment by mixing a solution containing a hydrolyzable silicon compound (A) containing a bond structure to an aromatic skeleton and inorganic fine particles and stirring them is mentioned.
That is, the present invention is an inorganic fine particle subjected to surface treatment, and the inorganic fine particle has a hydrolyzable silicon compound (A) containing an aromatic skeleton and a bond structure to the aromatic skeleton as a surface. It is also an inorganic fine particle that has been treated. By subjecting the inorganic fine particles to a surface treatment, the affinity with a resin or the like is increased and the dispersibility is improved.

As a preferable form of the surface treatment agent, the above-described form of the alkoxysilane compound is preferable. That is, a form in which the hydrolyzable group of the hydrolyzable silicon compound (A) is an alkoxy group is a preferred form. When the surface treatment agent has an alkoxy group, the surface treatment can be performed efficiently, which is advantageous in terms of productivity.
The surface treatment method will be described in detail below.

With respect to the method for introducing the aromatic skeleton and the bond structure to the aromatic skeleton into the surface of the inorganic fine particles, for example, (1) hydrolyzable silicon containing the aromatic skeleton and the bond structure to the aromatic skeleton (2) surface treatment with a (silane) compound, (2) after introducing a hydrolyzable silicon compound having a reactive group (I) onto the surface of the inorganic fine particles, the reactive group (I), aromatic skeleton and aromatic After reacting with a compound having a bond structure to a group skeleton and having a reactive group (II) or introducing a hydrolyzable silicon compound having a reactive group (I) onto the surface of the inorganic fine particles, A method in which a compound containing a reactive group (II) capable of forming a bond structure to an aromatic skeleton by reaction with the reactive group (I) and an aromatic skeleton is reacted with the reactive group (I), (3) Utilizing reaction of metal hydroxyl groups and reactive groups on the surface of inorganic fine particles That method and the like are preferable. The reactive group (I) and the reactive group (II) in the method (2) are not particularly limited as long as they are groups that cause the above reaction, but preferred compounds and combinations thereof are shown in Table 1 below. Is shown. In the case of the method (3), a portion derived from the reactive group including a bond formed by a reaction between a metal hydroxyl group and a reactive group becomes a part of a structure bonded to the aromatic skeleton. Among these (1) to (3), more preferably, (1) a surface treatment is performed with a hydrolyzable silicon compound containing an aromatic skeleton and a bond structure to the aromatic skeleton. Below, the method of said (1)-(3) is explained in full detail.

For example, (A) to (E) in FIG. 1 and (H) in FIG. 2 are used for the surface treatment with the hydrolyzable silicon compound containing the above (1) aromatic skeleton and the bond structure to the aromatic skeleton. ), A method in which a hydrolyzable silicon compound represented by (K) or the like in FIG. 3 is bonded to a metal element constituting the surface of the inorganic fine particles 1. 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 (1-9) described above. 2 in FIG. 2 is an integer of 1 or more that is the same or different and represents the number of repeating structural units. M in FIG. 2 is an integer of 1 or more that is the same or different and represents the number of repeating structural units.
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, a urethane bond, 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. Hydrosilylation with a group-bonded compound and H-SiX ₃ produces a compound in which SiX ₃ and R shown by (D) in FIG. 1 are linked by an alkylene group, and this compound produces inorganic fine particles. 1 surface treatment, the surface of the inorganic fine particles 1 A composite particle having R on the surface of the inorganic fine particle; as shown in FIG. 1 (h), a vinyl group is present in SiX ₃ with respect to R-SiR ¹ R ² H. The compound shown by (E) in FIG. 1 is formed by reacting with the bound compound, and the surface of the inorganic fine particle 1 is constituted by performing surface treatment of the inorganic fine particle 1 with this compound (E). And a method of forming composite particles having R bonded to 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. Further, as shown in FIG. 3, a compound (K) is formed by reacting a compound having a thiol group bonded to R shown in (I) via an organic chain with a compound having SiX ₃ shown in (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 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 an aromatic skeleton. More preferably, the reaction is carried out with a hydrolyzable silicon compound (A) containing a hydrolyzable group bonded to a silicon atom and an aromatic skeleton. For example, as a method for introducing the organic group R containing the aromatic skeleton, 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 an aromatic skeleton. L represents an aromatic skeleton in which four or more atoms are linked. It is preferable that the bonding form is represented by the following. R may be in the form of an organic group in which no substituent is bonded to the aromatic skeleton, or in the form in which a substituent is bonded to the aromatic skeleton. The aromatic skeleton contained in R preferably has a skeleton represented by the chemical formulas (1-1) to (1-9) described above. From the viewpoint of suppressing the coloring of the composite particles, it is preferable to include a benzene ring represented by the chemical formula (1-1) and / or a biphenyl skeleton represented by the chemical formula (1-7). In the case of increasing the refractive index, the aromatic skeleton requires 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. A certain inorganic fine particle is more preferable. Among these, at least one selected from a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is more preferable.

As a more preferable method, the surface treatment is performed with a hydrolyzable silicon compound (hereinafter also referred to as “hydrolyzable silicon compound (A)”) containing the above (1) aromatic skeleton and a structure bonded to the aromatic skeleton. The following methods can be mentioned.
As the hydrolyzable silicon compound (A), the following formula:
(RL) _e- SiX _(4-e)
(In the formula, R represents a group having an aromatic skeleton. L represents a bond structure to an aromatic skeleton in which four or more atoms are linked. X is the same or different and represents an R ³ O group; R ³ is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group, and e represents a number of 1 to 3). Compounds are preferred. Thus, in the hydrolyzable silicon compound (A), a form in which R and Si are bonded via a bond structure L to the aromatic skeleton is preferable.

The hydrolyzable silicon compound (A) is preferably an alkoxysilane compound whose hydrolyzable group is an alkoxy group. That is, the surface treatment agent preferably contains an alkoxysilane compound. The alkoxy group contained in the alkoxysilane compound is highly reactive as a hydrolyzable group and can be purchased or manufactured at a lower cost than when it has other hydrolyzable groups. That is, it is one of the preferred embodiments that the organic component introduced to the surface of the inorganic fine particles is derived from an alkoxysilane compound that essentially requires an aromatic skeleton and a bond structure to the aromatic skeleton.

One preferred form of the inorganic fine particles is one obtained by surface treatment with a surface treatment agent having a radical polymerizable group. As the hydrolyzable silicon compound (B), the following general formula (4);
R ⁴ _f SiX _4-f (4)
(In the formula, R ⁴ represents an organic group having a radical polymerizable group, f 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 methacryl group, an acryl group, and a vinyl group. Thus, it is preferable that the composite particle has a structure on the surface of the inorganic fine particles, in which a radical polymerizable group is essential.

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 a C 1-20 divalent organic group which may have a substituent.)
^{_{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 C 1-20 divalent organic group 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 acryl group and a methacryl group, and the silicon compound of the general formula (4) having the organic group includes, for example, 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-acryloxypropylmethyldimethyl Toxisilane and the like can be mentioned. 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 use only 1 type or may use 2 or more types together. Examples of the radical polymerizable group-containing organic group of the general formula (7) include a 1-alkenyl group and an isoalkenyl group. Examples of the silicon compound of the general formula (4) having the organic group include 1-hexenyltrimethoxysilane, 1-hexenyltriethoxysilane, 1-octenyltrimethoxysilane, 1-decenyltrimethoxysilane, γ-trimethoxysilylpropyl vinyl ether, ω-trimethoxysilylundecanoic acid vinyl ester, 1 -Hexenylmethyldimethoxysilane, 1-hexenylmethyldiethoxysilane, etc. can be mentioned. These may use only 1 type and may use 2 or more types together.

The radical polymerizable group-containing organic group is preferably a (meth) acryl group, and the surface treating agent having the radical polymerizable group preferably has a (meth) acryl group. That is, the inorganic fine particles are preferably those that have been surface treated with a surface treating agent that essentially comprises a (meth) acrylic group. According to this, a (meth) acryl group can be introduced into the surface of the inorganic fine particles, and the refractive index can be further improved due to the double bond. For example, if it is only treated with a surface treatment agent containing an aromatic skeleton and a bond structure to four or more aromatic skeletons, steric hindrance occurs due to a bulky aromatic ring, and the surface of inorganic fine particles is sufficiently covered. However, by introducing a structure that essentially requires a (meth) acrylic group to the surface of the inorganic fine particles in this way, the coating effect is further enhanced and the dispersibility of the composite particles is improved. be able to. Further, the refractive index due to the double bond can be improved. As the surface treatment agent that requires a (meth) acryl group, a silane coupling agent having a (meth) acryl group is preferable. This corresponds to, for example, a hydrolyzable silicon compound (B) having a radical polymerizable group represented by the general formula (5). By being a silane coupling agent, it is easy to introduce onto the surface of inorganic fine particles, and by including a silane coupling agent, the structure is stable, and composite particles having excellent mechanical strength and heat resistance are produced. be able to.

The surface treatment performed with the hydrolyzable silicon compound (B) having the radical polymerizable group is a hydrolyzable silicon compound (A) having a hydrolyzable group, an aromatic skeleton, and a structure bonded to the aromatic skeleton. 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). In addition, the hydrolyzable silicon compound (the above-mentioned hydrolyzable silicon compound (7) having a radically polymerizable group, a conjugated aromatic skeleton having 7 or more carbon atoms, a bond structure to the aromatic skeleton, and a hydrolyzable silicon compound having a hydrolyzable group) It is also possible to perform the surface treatment performed by B) and the surface treatment performed by the hydrolyzable silicon compound (A) collectively.
Among such methods, as a preferred method for producing the composite particles, a method of simultaneously performing a surface treatment performed with the hydrolyzable silicon compound (A) and a surface treatment performed with the hydrolyzable silicon compound (B), Alternatively, the surface treatment is performed using the hydrolyzable silicon compound (A) and then the surface treatment is performed using the hydrolyzable silicon compound (B).

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, the method (2) for introducing the above-described aromatic skeleton and the bond structure to the aromatic skeleton to the surface of the inorganic fine particles 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 reaction contained in a compound containing the aromatic skeleton R. Sex group. That is, the method for introducing the aromatic skeleton onto the surface of the inorganic fine particles is such that after introducing the hydrolyzable silicon compound having the reactive group (I), the reactive group has an aromatic skeleton and reacts. A method of reacting a compound having a functional group (II) is also preferred. In this case, the bond structure to the aromatic skeleton may be included in the compound having the reactive group (II) and the aromatic skeleton. Further, it may be formed by reacting the reactive group (I) with the reactive group (II). In this case, the reaction between the reactive group (I) and the reactive group (II). The bond formed by is at least part of the bond structure to the aromatic skeleton.
The reactive group (I) is preferably at least one group selected from the group consisting of Si-H group, vinyl group, (meth) acryl group, isocyanate 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. Inorganic fine particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface can be produced. 4 to 10 illustrate the method (2). A composite particle having R on the surface of inorganic fine particles 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. Can be manufactured.
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 is not particularly limited as long as it is a divalent organic group containing carbon and hydrogen.

As shown in (c) of Table 1, when the reactive group (I) is a (meth) acrylic 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. Moreover, as shown in (D) of Table 1, when the reactive group (I) is a (meth) acrylic group and the reactive group (II) is a thiol, 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 acryloxypropyltrimethoxysilane with inorganic fine particles.

As shown in Table (1), when the reactive group (I) is an isocyanate 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) has an active hydrogen such as a carboxyl group, an amino group, or a hydroxyl group. When it is a group, the composite particles can be produced by the reactions 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 utilizing 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, it has a surface hydroxyl group of inorganic fine particles and a bond structure to R and an aromatic skeleton or a bond structure to an aromatic skeleton by reaction ( Or a part thereof) may be a method of producing composite particles having an aromatic skeleton on the surface of the inorganic fine particles by reaction with a compound having an epoxy group, sulfide group, oxetane group or alcoholic hydroxyl group. 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 bond formed by the reaction between the surface hydroxyl group and these reactive groups becomes at least a part of the bond structure to the aromatic skeleton. In addition, as a specific example of the method (3), for example, a method of advancing the above reaction by heating a compound having a reactive group such as an epoxy group in an organic solvent in which inorganic fine particles are dispersed is present. Is mentioned. Further, when the reactive group is an epoxy group or a sulfide group, it is more preferable that a basic catalyst such as triphenylphosphine coexists.

(Form of inorganic fine particles)
The composite particle of the present invention has an organic component containing an aromatic skeleton and a bonded structure to an aromatic skeleton in which four or more atoms are connected to the surface of the fine particle composed of an inorganic element. If it has, it will not specifically limit. 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 of the inorganic fine particles is a number average particle diameter obtained from a TEM image (transmission electron microscope observation image); E. T. T. 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 cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a cylindrical shape, a flake shape, a plate shape (for example, a hexagonal plate shape). 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 2 or more. When the refractive index of the inorganic fine particles is 2 or more, the refractive index of the resin composition containing the inorganic fine particles and the cured product thereof can be further improved. 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 organic component on the surface of a fine particle including an inorganic element, and the fine particle including an inorganic element is a metal oxide fine particle, Examples thereof include 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, and metal fine particles. 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 preferable that it is at least one kind selected. 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 for applications that require transparency. Further, since the particle size can be reduced, for example, it is more suitable in the case where the inorganic fine particles are contained in the resin composition or the like.
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, niobium and cerium. The metal oxide fine particles containing these metal elements can have a higher refractive index. Therefore, the resin composition comprising the composite particles having the aromatic skeleton on the surface of the inorganic fine particles can have a higher refractive index. For example, it is particularly preferable when used as an optical member such as a lens for a camera or an antireflection film, which is 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, niobium and / or cerium as the metal element from the viewpoint of increasing the refractive index. In the present invention, the dispersibility in the resin composition and the like can be improved by having an aromatic skeleton on the surface of the inorganic fine particles, but the effect of the present invention was 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 an aromatic skeleton on the surface of inorganic fine particles (for example, zirconium oxide) It is obvious that the effects of the present invention can be obtained in That is, the effect of the present invention can be obtained as long as it is a metal element that can have an aromatic skeleton on the surface of the inorganic fine particles. Note that the refractive index of zirconium oxide, which is one of the metal oxides, varies depending on the crystal system, but is preferable in that it has a high refractive index of about 2.0 to 2.3. In addition to being a high refractive index, it is a preferred metal oxide because it has a wide light transmission range and is excellent in chemical stability. That is, it is one of the more preferable forms that the metal oxide fine particles are fine particles of zirconium oxide.

(Resin composition)
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 an aromatic skeleton on the surface of inorganic fine particles, it can have a high refractive index, and a cured product obtained by curing the resin composition can be suitably used as an optical member or the like. it can.
Hereinafter, the resin composition comprising the composite particles of the present invention will be described.

It is preferable that content of the composite particle in the said resin composition is 0.1-99 mass% in 100 mass% of resin compositions. If it is less than 0.1% by mass, the refractive index of the resulting resin composition may not be sufficiently high, and if it exceeds 99% by mass, the cured product may become brittle. The content of the composite particles is more preferably 1% by mass or more, further preferably 10% by mass or more, and particularly preferably 30% by mass or more. Moreover, as an upper limit of content of composite particle | grains, it is preferable that it is 95 mass% or less.

As content of the resin component in the said resin composition, it is preferable that it is 99.9-1 mass% in 100 mass% of resin compositions. If it is less than 1% by mass, the resulting cured product may be brittle, and if it exceeds 99.9% by mass, the refractive index may not be sufficiently high. As content of a resin component, it is more preferable that it is 99 mass% or less, More preferably, it is 90 mass% or less, Most preferably, it is 70 mass% or less. Moreover, as content of a resin component, it is preferable that it is 5 mass% or more.

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. Further, since the composite particles have an aromatic skeleton on the surface of the inorganic fine particles, the dispersibility of the composite particles is further improved by using a resin component having an aromatic skeleton. This is thought to be because the aromatic skeleton of the aromatic compound (C) and the aromatic skeleton of the composite particles easily have a π-π stacking structure.

The aromatic compound (C) preferably contains a skeleton represented by the chemical formulas (1-2) 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 (1-9), 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. R ′ is the same or different and is a hydrogen atom or a methyl group. It is an integer). 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, 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,
As the biphenyl compound, the following general formula (14);

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

JER YX4000 represented by (Japan Epoxy Resin Co., Ltd., biphenyl epoxy resin) 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 ^c —R ^d —O— (CO—R ^e —O) _p —CO—R ^f —COOH (I)
(However, R ^c is at least one group selected from 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 ^d is an alkylene group or an aryl group, R ^e is an alkylene group, R ^f is at least one group selected from an alkylene group, an aryl group, and an alkyne group, and p is 1 or an integer of 1 or more)) (1), the following general formula (II);
_{^{R g - [CO- (O-}} R h -CO) n 1 -OH] m 1 (II)
(However, R ^g is at least one selected from 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 ^h is an alkylene group, n ¹ is a number of 1 or more, m ¹ is a number of ¹ to 4, and / or the following general formula: Formula (III);
R ^j —R ^k —O— (CO—R ^m —O) _r —H (III)
(However, R ^j is at least one group selected from 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 ^k represents an alkylene group or an aryl group, R ^m 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, 2 or more types may be used together, and it does not specifically limit.

In the compound (1) represented by the above general formula (I), when R ^d 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 ^e preferably has a linear structure rather than a cyclic structure, and more preferably has 3 to 20 carbon atoms. R ^f 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, more preferably an integer of 20 or less. Moreover, it is one of the preferable forms that 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) to (19).

In the compound (2) represented by the general formula (II), when R ^g is a vinyl group, for example, a methyl vinyl group is preferable. R ^h preferably has a linear structure rather than a cyclic structure, and more preferably has 3 to 20 carbon atoms. n ¹ is preferably an integer of 50 or less, and more preferably an integer of 20 or less. The m ^1, preferably an integer of 1 to 4, and more preferably 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) to (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] y H (24)
(In the formula, y represents the average number of added moles 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 ⁿ —O) _s —CO—R ^q —COOH group (in which R ⁿ , R ^q and s are R ^e , R ^f and p in the general formula (I), respectively) The same).
—CO— (O—R ^r —CO) _t —OH group (wherein R ^r and t are the same as R ^h and n ^{1 in the} above general formula (II)), or
A polymer having a —O— (CO—R ^s —O) _u —H group (wherein R ^s and u are the same as R ^m and r in the general formula (III), respectively) can be mentioned. It is done. The polymer can be obtained by copolymerizing a (meth) acrylic acid ester having —O— (CO—R ⁿ —O) _s —CO—R ^q —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 ^{c to} R ^s 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 g R 16 h R}} 17 i R 18 k Z) + w1 (AYn 2) -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 halogen elements. R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is the same or different and represents an organic group, g, h, i and k 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 _g R ¹⁶ _h R ¹⁷ _i R ¹⁸ _k Z) ^{+ w1} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, and B, P, As, Al, It is at least one selected from the group consisting of Ca, In, Ti, Zn, Sc, V, Cr, Mn, and Co. Y represents a halogen element, and w is the net charge of the halide complex ion. .n ² 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 ² ) ^-w1 of the average composition formula (25) include tetrafluoroborate (BF ⁴⁻ ), hexafluorophosphate (PF ⁶⁻ ), hexafluoroantimonate (SbF ⁶⁻ ), hexafluoroarsenate ^{(AsF 6-),} hexachloroantimonate (SbCl ^6-), and the like.
Furthermore, an anion represented by the general formula AYn ² (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 a photolatent curing catalyst or a photocationic polymerization initiator) include metal fluoroboron complex salts and trifluorinated boron complex compounds such as those described in 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 (t-butyl) Peroxy) -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, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, and 1-hydroxycyclohexyl phenyl ketone.

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 resin 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 resin component, an epoxy group containing compound or a (meth) acrylic group containing compound from the viewpoint of a cure rate, ie, an epoxy group 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 that of inorganic glass while having the same workability as conventional thermosetting plastic materials. And exhibit excellent properties such as excellent molding and workability. Hereinafter, a compound having at least one epoxy group that can be suitably used as the resin component of the present invention will be described.

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 condensation reaction of styrene, paraxylylene glycol dimethyl ether, dichloroparaxylylene, etc. with epihalohydrin; tetramethylbisphenol F; A high molecular weight polymer of an aromatic crystalline epoxy resin obtained by condensation reaction of hydroquinone or the like with epihalohydrin, and further by addition reaction of the above bisphenols, tetramethylbisphenol F, hydroquinone or the like Alicyclic glycols such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, etc., hydrogenated aromatic skeletons, ethylene glycol 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 Si resin (epoxy compound having epoxycyclohexane skeleton); glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; Hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin A tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by a condensation 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 resins synthesized from modified ethylene oxide, propylene oxide, etc .; phenol novolac-type epoxy resins; cresol novolac-type epoxy resins; 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 ethers of aliphatic polyhydric alcohols such as serine, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; (poly) of alkylene oxide modified products of aliphatic polyhydric alcohols Alkylene epoxides such as glycidyl ether; glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and 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 (manufactured by Japan Epoxy Resin, 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 other 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.

The resin composition includes the above-described polymerization in addition to the composite particles having the organic skeleton on the surface of the inorganic fine particles and the resin component including the aromatic skeleton and a bonded structure to the aromatic skeleton in which four or more atoms are continuous. Initiators (curing catalysts), release agents, curing agents, curing accelerators, reactive diluents, saturated compounds without unsaturated bonds, pigments, dyes, antioxidants, UV absorbers, light stabilizers, plastics Agents, non-reactive compounds, chain transfer agents, polymerization inhibitors, adhesion improvers such as inorganic and organic fillers, coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, Antifoaming agent, leveling agent, wetting / dispersing agent, anti-settling agent, thickener / anti-sagging agent, anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, desiccant, antifouling agent, electrification You may contain an inhibitor, a electrically conductive agent (electrostatic adjuvant), etc.

(Cured product)
The present invention is also a cured product obtained by molding and / or curing the above resin composition. A 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 an aromatic skeleton. 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 (A region with a wavelength of 360-780 nm, for example, wavelength 400nm) is 70% or more. The light transmittance of the cured product is more preferably 75% or more, still more preferably 80% or more, particularly preferably 85% or more, and particularly preferably 90% 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.
Although the PCT moisture absorption rate of the cured product varies depending on the curing conditions, it is preferably 2% or less, preferably 1% or less, more preferably 0.5% or less, by optimizing the curing conditions. More preferably, it is 0.2% or less.

The cured product preferably has a refractive index of 1.62 or more at a wavelength of 589 nm. 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 1.64 or more as a refractive index of hardened | cured material, More preferably, it is 1.65 or more, Most preferably, it is 1.66 or more.

The cured product has high heat resistance, i.e., there is no change in appearance such as cracking even at high temperatures, and the change rate of light transmittance and turbidity in the wavelength range of 360 to 780 nm is low. preferable. Specifically, when the cured product is heated to 260 ° C., there is no change in appearance such as generation of cracks, and the light transmittance / turbidity after heating in the wavelength range of 360 to 780 nm before heating at 260 ° C. The change rate is preferably 20% or less. More preferably, the change rate of the total light transmittance and turbidity is 15% or less, and more preferably 10% or less. Moreover, it is preferable that the change of the light transmittance and turbidity in the wavelength range of 360-780 nm after leaving for 500 hours under 85 degreeC and 85% of humidity is 20% or less. More preferably, it is 15% or less.
In particular, 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 ultraviolet 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 a synergistic effect 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.

The present invention is also an optical member including a cured product obtained by curing the 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, other components may be appropriately contained in the resin composition 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 400 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 400 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 diffusing 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, It can also be suitably used as an optical member for display device applications such as a color filter substrate, a touch panel substrate, a display protective film, a display backlight, a light guide plate, a high refractive index layer of an antireflection film, and an antifogging film. Moreover, it can use suitably also as resin for nanoimprint. 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 a resin 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 the 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.

(Method for producing resin composition)
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%.
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

In the said deaeration process, if it is the conditions which can deaerate a solvent, it will not specifically limit, However, It is preferable that they are the conditions which suppress decomposition | disassembly of a resin component, hardening reaction, and aggregation of a composite particle component excessively producing. 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. In addition, since alcohol with a boiling point of less than 100 ° C may not sufficiently prevent the mixture from thickening, an alcohol with a boiling point of 100 ° C or higher is preferable. 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 including composite particles having an organic component including an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles, a resin component, and a solvent; A degassing step of degassing the solvent from the mixture, and the method for producing a resin composition in which the degassing 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 can be easily dissolved. 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 a cationically polymerizable compound can be 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 to the resin composition prepared as described above, a curable resin composition is prepared by adding and mixing the polymerization initiator or a 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.

Moreover, when the resin composition of this invention contains a dispersing agent, the compounding method is not specifically limited, A various method can be used. For example, a method of adding particles to a mixture of a dispersant and a resin component, and post-adding the mixture to a mixture of a resin component and particles can be used. Moreover, it is one of the preferable forms that a dispersing agent mixes, after melt | dissolving in a solvent. When the dispersant is the above-described dispersant (D), the blending method is the same. When the dispersant is the dispersant (D), it is particularly preferable that the dispersant is dissolved and then mixed.

(Method for curing resin composition)
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. A method of mixing the polymerization initiator and other materials as required to form one liquid, coating the liquid mixture on a mold that matches the shape of the cured product, curing the mixture, and then removing the cured product from the mold. Preferably used. In such a method, it is preferable that the viscosity of the resin composition mixed with the curing catalyst or the like does not increase remarkably 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 form 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 particles and a resin component that essentially includes a curable resin such as cationic polymerizable or radical polymerizable, a cured product is obtained by thermosetting using a polymerization initiator. It can be. As a polymerization initiator, when using the resin component which is a compound etc. which have a cationically polymerizable group, it is preferable to use the thermal latent cation generator mentioned above. 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 a curing agent 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 novolak 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, etc. 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 particle of the present invention has an organic component having an aromatic skeleton and a bonded structure to an aromatic skeleton in which four or more atoms are continuous on the surface of the inorganic fine particles, the composite particles have a dispersibility in a resin composition or the like. It can be improved and have high transparency and refractive index. 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.

FIG. 1 is a schematic view showing an example of a method for surface treatment with a hydrolyzable silicon compound containing an aromatic skeleton and a bonded structure to an aromatic skeleton in which four or more atoms are continuous. FIG. 2 is a schematic diagram showing an example of a method for surface treatment with a hydrolyzable silicon compound containing an aromatic skeleton and a bonded structure to an aromatic skeleton in which four or more atoms are continuous. FIG. 3 is a schematic diagram showing an example of a surface treatment method using a hydrolyzable silicon compound containing an aromatic skeleton and a structure bonded to an aromatic skeleton in which four or more atoms are linked. FIG. 4 shows a bonding structure of an aromatic skeleton in which four or more atoms are linked to the reactive group (I) after introducing a hydrolyzable silicon compound having a reactive group (I). It is a schematic diagram which shows an example of the method of making it react with the compound which has and reactive group (II). FIG. 5 shows a structure in which a hydrolyzable silicon compound having a reactive group (I) is introduced, and then the reactive group (I) is bonded to an aromatic skeleton in which four or more atoms are connected to the aromatic skeleton. It is a schematic diagram which shows an example of the method of making it react with the compound which has and reactive group (II). FIG. 6 shows a structure in which a hydrolyzable silicon compound having a reactive group (I) is introduced, and then the reactive group (I) is bonded to an aromatic skeleton in which four or more atoms are linked to the aromatic skeleton. It is a schematic diagram which shows an example of the method of making it react with the compound which has and reactive group (II). FIG. 7 shows a structure in which, after introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I), an aromatic skeleton and an aromatic skeleton in which four or more atoms are linked to each other. It is a schematic diagram which shows an example of the method of making it react with the compound which has and reactive group (II). FIG. 8 shows a bond structure of an aromatic skeleton in which four or more atoms are linked to the reactive group (I) after introducing a hydrolyzable silicon compound having a reactive group (I). It is a schematic diagram which shows an example of the method of making it react with the compound which has and reactive group (II). After introducing a hydrolyzable silicon compound having a reactive group (I), the reactive group (I) has a bond structure to the aromatic skeleton in which four or more atoms are linked to the aromatic skeleton. It is a schematic diagram showing an example of a method of reacting a compound having a reactive group (II). 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.

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 (manufactured by 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 Element 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 obtain 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 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-U-Si (OEt) ₃ was obtained. ^{From 1} H-NMR, it was confirmed that the reaction conversion was 90%. BiPh-U-Si (OEt) ₃ represents the following formula:

"U" means a structure between the biphenyl skeleton and silicon. The structure of U is the same for the compounds shown below.

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 was 89%.

Synthesis Method of Bz-U-Si (OEt) ₃ 67.06 g of toluene, 8.74 g (80.8 mmol) of benzyl alcohol, 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 gave _{Bz-U-Si (OEt)} 3 in toluene. ^{From 1} H-NMR, it was confirmed that the reaction conversion (conversion) was 95%.

_{BiPh-Hyd-Si (OMe)} 3 synthetic methods toluene 80.27g para-phenylphenol (para-Phenylphenol) to 14.4 g (84.6 mmol) 3- glycidoxypropyltrimethoxysilane (KBM-403, Shin-Etsu Chemical (Manufactured by Kogyo Co., Ltd.) 20.0 g (84.6 mmol) and triphenylphosphine 0.34 g were added and heated under reflux for 5 hours. The disappearance of the raw material was confirmed by TLC to obtain BiPh-Hyd-Si (OMe) ₃ . . Here, BiPh-Hyd-Si (OMe) ₃ is represented by the following formula:

And “Hyd” means a structure between the biphenyl skeleton and silicon. The structure of Hyd is the same for the compounds shown below.

Synthesis method of Ph-Hyd-Si (OMe) ₃ 65.26 g of toluene, 7.97.4 g (84.6 mmol) of phenol and 3-glycidoxypropyltrimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 0.08 g (84.6 mmol) and 0.27 g of triphenylphosphine were added, and the mixture was heated under reflux for 5 hours. The disappearance of the raw material was confirmed by TLC to obtain Ph-Hyd-Si (OMe) ₃ .

Synthesis method of BiPh-U-Si (OMe) ₃ 308.77 g of toluene, 60.0 g (35.2 mmol) of paraphenylphenol and 3-isocyanatopropyltrimethoxysilane (Y-5187, manufactured by Momentive Performance Materials) 72.33 g (352.5 mmol) and dibutyltin dilaurate (DBTDL) 0.066 g were added, the temperature was raised to 90 ° C., and the mixture was heated for 5 hours to obtain a BiPh-U—Si (OMe) ₃ toluene solution. ^{From 1} H-NMR, it was confirmed that the reaction conversion was 92%.

(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 a BiPh-U-Si (OEt) ₃ solution was added to the solution (solid content: 8. 4 g) and 4 g of ultrapure water were added, and the mixture was refluxed at 90 ° C. with stirring for 1 hour.
The solution after the reflux treatment was allowed to cool, and then 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 then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-U-Si (OEt) ₃ .
When the crystal structure of the treated 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, 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, the zirconium oxide nanoparticles after the treatment were coated with two coating agents of neodecanoic acid and BiPh-U-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 20% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the following conditions, the results of FT-IR measurement before and after washing were the same and the weight loss in TG-DTA measurement was the same. It was confirmed that the zirconium oxide nanoparticles were composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles. Washing was performed by adding 1 part by mass of zirconium oxide nanoparticles (composite particles) to 100 parts by mass of hexane and stirring at a temperature of 50 ° C. and a stirring speed of 100 rpm for 12 hours.
Further, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton when the obtained zirconium nanoparticles (composite particles) were 100% by mass were determined by the following methods.
(1) First, an organic component derived from BiPh-U-Si (OEt) ₃ represented by the following formula (A-1) on zirconium nanoparticles obtained by ¹ H-NMR, and the following formula (B- The ratio (molar ratio) of the amount of the component resulting from neodecanoic acid represented by 1) is determined.

(2) BiPh-U-Si (OEt) ₃ is an organic unit because neodecanoic acid is bonded to zirconia as shown in the following formula (B-2) as shown in the following formula (A-2). Are respectively the following formulas (A-3) and (B-3), and the weight ratio is calculated from the respective molecular weights and the molar ratio determined in (1).

(3) Thereafter, using the weight ratio of (A-3) obtained in (2), the sum of the organic component corresponding to the formula (A-3) and the organic component corresponding to the formula (B-3) ( The aromatic skeleton content (in this case, C ₁₂ H ₉ ) contained in the formula (A-3) with respect to all organic components) is determined.
(4) Since the mass reduction rate measured by TG-DTA is the organic (total organic component) content on the zirconium nanoparticles, the mass reduction rate is multiplied by the aromatic skeleton content obtained in (3). The combined numerical value is the aromatic skeleton content of the zirconium nanoparticles (composite particles) obtained. Similarly, the content of the bond structure to the aromatic skeleton was also determined. At this time, the bond structure to the aromatic skeleton is obtained by removing the portion of the aromatic skeleton (C ₁₂ H ₉ ) from the unit represented by the formula (A-3).
Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(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 a BiPh-U-Si (OEt) ₃ solution was added to the solution (solid content: 8. 4 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.
The solution after the reflux treatment was allowed to cool, and then 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 vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the treated 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, 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. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 4: Synthesis of Ph-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 23.1 g of a Ph-U-Si (OEt) ₃ solution (solid content: 6.3 g). 9g), 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of ultrapure water were added and refluxed at 90 ° C. for 1 hour with stirring.
The solution after the reflux treatment was allowed to cool, and then 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 Ph-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the treated 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, 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 19% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 5: Synthesis of zirconium oxide nanoparticles treated with Bz-U-Si (OEt) ₃ and KBM-503)
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: 7.7 g). 2 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.
The solution after the reflux treatment was allowed to cool, and then 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 Bz-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane.
When the crystal structure of the treated 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, 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, Bz-U-Si (OEt) ₃ and It was confirmed that it was coated with three coating agents of 3-methacryloxypropyltrimethoxysilane. 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. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 6: Synthesis of BiPh-Hyd-Si (OMe) 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 27.4 g of a BiPh-Hyd-Si (OMe) ₃ solution (solid content: 8. 2g), 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.
The solution after the reflux treatment was allowed to cool, and then 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-Hyd-Si (OMe) ₃ and 3-methacryloxypropyltrimethoxysilane.
When the crystal structure of the treated 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, 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 BiPh-Hyd-Si (OMe) ₃ and It was confirmed that it was coated with three coating agents of 3-methacryloxypropyltrimethoxysilane. 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 18% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 7: Synthesis of Ph-Hyd-Si (OMe) 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 22.3 g of a Ph-Hyd-Si (OMe) ₃ solution (solid content: 6. 7 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 refluxed at 90 ° C. for 1 hour with stirring.
The solution after the reflux treatment was allowed to cool, and then 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-Hyd-Si (OMe) ₃ and 3-methacryloxypropyltrimethoxysilane.
When the crystal structure of the treated 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, 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, Ph-Hyd-Si (OMe) ₃ and It was confirmed that it was coated with three coating agents of 3-methacryloxypropyltrimethoxysilane. 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. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 8: Synthesis of KBM-103 (phenyltrimethoxysilane) -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 4.0 g of KBM-103, 3-methacryloxypropyltrimethoxysilane (Shin-Etsu) Chemical Industry Co., Ltd. KBM-503) 0.95 g and ultrapure water 5 g were added and refluxed at 90 ° C. for 1 hour with stirring.
The solution after the reflux treatment was allowed to cool, and then n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the aggregated particles were separated from the white turbid solution with a filter paper, and then vacuum dried at room temperature to prepare zirconium oxide nanoparticles treated with KBM-103.
When the crystal structure of the treated 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, 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 treated with two kinds of coating agents, neodecanoic acid and KBM-103. It was confirmed that it was coated. 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.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 4 below shows the results of measurement of the mass reduction rate determined in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.

(Synthesis Example 9: Synthesis of BiPh-U-Si (OMe) ₃ and KBM-5103-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 3.33 g of BiPh-U-Si (OMe) ₃ solution (solid content: 1.3 g) was added to the solution. 0 g), 3-acryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-5103) 1.0 g and ultrapure water 2.0 g were added, and the mixture was refluxed at 90 ° C. for 1 hour with stirring. After the refluxed solution was allowed to cool, methanol 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 dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-U-Si (OMe) ₃ and 3-acryloxypropyltrimethoxysilane.
When the crystal structure of the treated 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, 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 acrylic group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid, BiPh-U-Si (OMe) ₃ and It was confirmed that it was coated with three coating agents of 3-acryloxypropyltrimethoxysilane. 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. In addition, it was confirmed that the obtained zirconium oxide nanoparticles were composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
The obtained zirconium nanoparticles were measured for the mass reduction rate of the aromatic skeleton and the content of the bond structure to the aromatic skeleton and the aromatic skeleton in the same manner as in Synthesis Example 2. 4 shows.
About the processing agent of the zirconia nanoparticle obtained by the said synthesis examples 2-9, it shows in following Table 2 and Table 3. FIG.

(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) 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 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 (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 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 4.

Resin composition for Example 5 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 Example 5.

Resin composition for Example 6 2.5 g of the zirconium oxide particles (6) obtained in Synthesis Example 7 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 6.

Resin composition for Example 7 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), 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 with an evaporator to obtain a resin composition for Example 7.

Resin composition for Example 8 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 Co., Ltd.), FM-1-Ph solution 0. Example 7 After dissolving 071 g (solid content 0.05 g) and 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 Example 9 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), 0.1 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 9.

Resin composition for Example 10 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 Co., Ltd.), FM-1-Ph solution 0. Example 10 After dissolving 142 g (solid content: 0.10 g) and perbutyl Z (manufactured by NOF Corporation, t-butyl peroxybenzoate) in 20.0 g of toluene, the toluene was devolatilized using an evaporator. A resin composition was obtained.

1.6 g of the zirconium oxide particles (8) obtained in Synthetic Example 9 for Resin Example 11 and 0.4 g of Ogsol EA-200 (Osaka Gas Chemical Co., Ltd.), Irgacure 184 (Ciba Japan Co., Ltd., 1-hydroxy) Cyclohexylphenylketone) (0.08 g) was dissolved in toluene (2.0 g) to obtain a resin composition for Example 11.

Resin composition for Comparative Example 1 2.5 g of the zirconium oxide particles (7) obtained in Synthesis Example 8 and 2.5 g of Ogsol EA-200 (Osaka Gas Chemical Co., Ltd.), 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 1.

After dissolving 5.0 g of the resin composition for Comparative Example 2 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 2.

Examples 1-10, Comparative Examples 1-2
The resin compositions for Examples 1 to 10 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 using 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 5 below.

Example 11
The resin composition for Example 11 was coated on a glass plate (150 mm × 70 mm × 2 mm) using a bar coater so that the film thickness became 3 μm, then dried at 80 ° C. for 2 minutes, and then in a nitrogen atmosphere The film was cured by irradiating with 2000 mJ / cm ² of ultraviolet light with a high-pressure mercury lamp to obtain a cured coating film. And the transmittance | permeability of the cured coating film in wavelength 400nm and the refractive index in 550 nm were measured like Example 1-10 using the thin film measuring apparatus (FILMETRICS company make, product number: F20 thinfilm analyzer). The measurement results are shown in Table 5 below.

From Table 5, 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 1, since it is treated with an alkoxysilane that has an aromatic skeleton but does not have a bond structure to an aromatic skeleton in which four or more atoms are continuous, the resin cured film that is low in transparency and cloudy became. In Comparative Example 2, since it did not contain composite 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 inorganic fine particles of the present invention. It was a thing.

1: Inorganic fine particles 2: Organic chain

Claims (12)

A composite particle comprising an organic component including an aromatic skeleton and a bonded structure to an aromatic skeleton in which four or more atoms are continuous on an inorganic fine particle surface. The bond structure to the aromatic skeleton has the following general formula (a);

(Wherein R ^a represents an optionally substituted alkylene group having 1 to 10 carbon atoms) and / or the following general formula (b);

2. The composite particle according to claim 1, wherein R ^b represents an optionally substituted alkylene group having 1 to 10 carbon atoms. The composite particle according to claim 1 or 2, wherein the bond structure to the aromatic skeleton is bonded to the surface of the inorganic fine particle through a siloxy bond or a siloxane bond. The composite particle according to any one of claims 1 to 3, wherein the organic component is derived from an alkoxysilane compound having an aromatic skeleton and a bond structure to the aromatic skeleton as essential. The composite particle according to any one of claims 1 to 4, wherein the composite particle has a structure having a radically polymerizable group as an essential component on the surface of the inorganic fine particle. Composite particles in which inorganic fine particles are surface-treated using a surface treatment agent,
The surface treatment agent includes an organic component including an aromatic skeleton and a bond structure to the aromatic skeleton in which four or more atoms are continuous. The bond structure to the aromatic skeleton has the following formula (a):

(Wherein, R ^a represents an optionally substituted alkylene group having 1 to 10 carbon atoms) and / or the following formula (b);

The composite particle according to claim 6, wherein R ^b represents an alkylene group having 1 to 10 carbon atoms which may have a substituent. The composite particles according to claim 6 or 7, wherein the inorganic fine particles are surface-treated using a surface treatment agent essentially comprising a (meth) acryl group. A resin composition comprising the composite particles according to claim 1 and a resin component. The resin composition according to claim 9, wherein the resin component essentially comprises an aromatic compound having a conjugated structure composed of 7 or more carbon atoms. The resin composition further includes a dispersant,
The dispersant is represented by the following general formula (I);
R ^c —R ^d —O— (CO—R ^e —O) _p —CO—R ^f —COOH (I)
Wherein R ^c is at least one group selected from 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 ^d is an alkylene group or an aryl group, R ^e is an alkylene group, R ^f is at least one group selected from an alkylene group, an aryl group, and an alkyne group. Is an integer of 1 or more.) Compound (1) represented by the following general formula (II);
_{^{R g - [CO- (O-}} R h -CO) n 1 -OH] m 1 (II)
(In the formula, R ^g is at least selected from 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 ^h is an alkylene group, n ¹ is an integer of 1 or more, m ¹ is an integer of ¹ to 4, and / or the following: Formula (III):
R ^j —R ^k —O— (CO—R ^m —O) _r —H (III)
Wherein R ^j is at least one group selected from 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. Wherein R ^k represents an alkylene group or an aryl group, R ^m represents an alkylene group, r is an integer of 1 or more, and the compound (3) is essential. The resin composition according to claim 9 or 10. Hardened | cured material formed by shape | molding and / or hardening | curing the resin composition in any one of Claims 9-11.

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