JP2009062459A - Organic-inorganic composite resin composition and cured product formed by curing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic-inorganic composite resin composition, which is excellent in basic performance such as transparency, heat resistance, and humidity resistance and can be suitably applicable to various usage such as optics usage for lenses and the like, opto-device usage, display device usage, mechanical component materials, electric/electronic component materials, automobile component materials, civil engineering and building materials, molding materials and the like, and a cured product formed by curing the organic-inorganic composite resin composition. <P>SOLUTION: The organic-inorganic composite resin composition comprises an organic component and an inorganic component, and the organic component essentially includes a cationic polymerizable compound having a conjugated structure comprised of seven or more carbon atoms, while the inorganic component essentially includes an organosiloxane compound having a cationic polymerizable group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to an organic-inorganic composite resin composition and a cured product obtained by curing the organic-inorganic composite resin composition. More specifically, the present invention relates to an organic-inorganic composite resin composition useful as an optical application, an optical device application, a display device application, a machine component material, an electric / electronic component material, and the like, and a cured product obtained by curing the organic-inorganic composite resin composition.

The organic-inorganic composite resin composition is useful as, for example, a machine part material, an electric / electronic part material, an automobile part material, a civil engineering / building material, a molding material, or the like, and is also used as a material for a paint or an adhesive. is there. Furthermore, since it contains an inorganic substance, it can not only reduce the coefficient of thermal expansion, but also controls the appearance of the resin composition and its cured product by adjusting the refractive index of the inorganic substance and the resin, and is transparent. Therefore, it is particularly useful as a material for electrical / electronic component materials and optical applications. For example, digital camera modules are being miniaturized, such as being mounted on mobile phones, and cost reduction is also required. Therefore, instead of inorganic glass, plastic lenses such as PMMA / PC and polycycloolefin are being used. In recent years, needs for in-vehicle use such as in-vehicle cameras and bar code readers for home delivery companies are increasing as new applications. When applied to these applications, long-term heat resistance is required in consideration of high temperature exposure in summer. Since heat resistance superior to that of conventional plastic materials is required, studies on curable materials are progressing.

An epoxy resin encapsulant composition containing an epoxy resin having a fluorene skeleton is disclosed as a resin for encapsulating a conventional light emitting element, an element requiring transparency such as a photoelectric conversion element, or an electronic component. (For example, refer to Patent Document 1). However, there has been room for contrivance to make various properties excellent and to be applied to applications other than sealant applications.
Japanese Patent Laying-Open No. 2005-41925 (page 1-2)

The present invention has been made in view of the above situation, and has excellent basic performance such as transparency, heat resistance, moisture resistance, etc., optical use such as lenses, opto device use, display device use, mechanical component materials, To provide an organic-inorganic composite resin composition that can be suitably applied to applications such as electronic component materials, automotive parts materials, civil engineering and building materials, molding materials, and the like, and a cured product obtained by curing the organic-inorganic composite resin composition It is the purpose.

The present inventors have conducted various studies on the organic-inorganic composite resin composition, and it is preferable to use a curable resin composition having an aromatic ring (for example, an epoxy resin) in order to obtain a high refractive index. Paying attention, the epoxy resin having an aromatic structure with 7 or more carbon atoms constituting the conjugated system in the organic component is bisphenol A type epoxy due to the electron withdrawing property or steric hindrance of the aromatic ring. It has been found that the number of carbon atoms constituting the conjugated structure is lower than that of the resin.
In order to control the optical properties (Abbe number), it is effective to use a siloxane-based material. However, if a material having no functional group such as phenylsilsesquioxane is used, the cationic curability is further lowered. And found that productivity problems occur. On the other hand, by using together a siloxane-based material having a cationic polymerizable group such as an epoxy group, it was found that the cationic curability is better than the organic material alone, and the inventors have conceived that the above problems can be solved brilliantly. . Furthermore, it has also been found that it can be suitably applied to various uses such as optical applications such as lenses, opto-device applications, display device applications, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, The present invention has been achieved.

That is, the present invention is an organic-inorganic composite resin composition containing an organic component and an inorganic component, and the organic component essentially comprises a cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms, The inorganic component is an organic-inorganic composite resin composition essentially comprising an organosiloxane compound having a cationic polymerizable group. In the present specification, the organic-inorganic composite resin composition is also referred to as “curable resin composition” or “resin composition”. In the present invention, “epoxy group” means a glycidyl group and an epoxycyclohexane ring, and a compound having these groups is referred to as “epoxy resin” or “epoxy compound”.
The present invention is described in detail below.

The organic-inorganic composite resin composition of the present invention essentially comprises an organic component essentially comprising a cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms, and an organosiloxane compound having a cationically polymerizable group. An inorganic component is included. By having such a configuration, the organic-inorganic composite resin composition has a high refractive index and can produce a cured product with high productivity. In addition, the cured product of the organic-inorganic composite resin composition of the present invention can have a high refractive index of 1.57 or more (more preferably 1.60 or more). In addition, it can be set as the organic-inorganic composite resin composition which has a high refractive index by including the epoxy resin which has a conjugated structure, but this is because a conjugated structure is effective for high refractive index. The inventors have found that the cure rate is slow. The reason for the slowing of the curing rate is (1) because the aromatic ring is an electron-withdrawing group, and therefore the cation is destabilized on the epoxy ring during cationic polymerization, and (2) the steric hindrance of the bulky aromatic ring This is because of the polymerization delay due to. Moreover, when the organosiloxane compound which has a cation polymeric group was made into essential, it discovered that the said polymerization delay was improved. The mechanism of action is not clear, but in the case of an organosiloxane compound having a structure in which the cationically polymerizable group is a glycidyl group and the group is bonded to an alkyl group via oxygen, electron donation to the glycidyl ether group It is presumed that the stability of the cation on the epoxy group is improved and the curing rate is increased because the functional alkyl group is connected.

As the organic component, a cation polymerizable compound having a conjugated structure composed of 7 or more carbon atoms is essential. One preferred form of the cationic polymerizable compound is an epoxy resin, but an epoxy resin having a conjugated structure composed of 7 or more carbon atoms means a conjugated structure composed of 7 or more carbon atoms. And a cation polymerizable group described later is an epoxy group (glycidyl group, epoxycyclohexane ring). Hereinafter, the “cationic polymerizable compound having a conjugated structure composed of 7 or more carbon atoms” is also simply referred to as “cationic polymerizable compound having a conjugated structure”.
The cationically polymerizable compound having the conjugated structure has a conjugated structure composed of 7 or more carbon atoms. By having such a structure, it can be set as the organic-inorganic composite resin composition of a high refractive index, and can be used suitably for an optical use etc.
The cationically polymerizable compound having the conjugated structure means a compound having 7 or more carbon atoms in one conjugated unit. In other words, it is preferable that the number of carbons belonging to the atomic group constituting one conjugated unit is 7 or more, and at least one such conjugated structure is included.
The conjugated unit is preferably one having a conjugated double bond. More preferably, it has an aromatic ring. That is, it is more preferable that the cationic polymerizable compound has 7 or more carbon atoms constituting the conjugated structure and has an aromatic ring. By using a cationically polymerizable compound having an aromatic ring, a cationically polymerizable compound having a high refractive index can be obtained. The “conjugated unit” refers to a unit of a part related to resonance when a binding structure including the unit is shown.

The conjugated unit is preferably a conjugated system (aromatic ring) having 7 or more carbon atoms, specifically, the following chemical formula:

Fluorene, biphenyl, naphthalene, anthracene, dibenzothiophene, carbazole, and stilbene represented by the formula: Note that having in the skeleton structure means that these structures may have a substituent within a range having a resonance structure. Thus, the cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms is selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, an anthracene ring, a dibenzothiophene ring, a carbazole skeleton, and a stilbene skeleton. An organic-inorganic composite resin composition having at least one selected skeleton is also one preferred form of the present invention.
Any conjugated structure may be used as long as it has the above-described skeleton or ring structure. Among them, it is preferable to have a fluorene skeleton.

Examples of the cationic polymerizable group in the cationic polymerizable compound include a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, and an R ³ R ⁴ —C═C—O group (wherein R ³ and R ⁴ are Are the same or different and each represents a hydrogen atom or an alkyl group.), And preferably at least one selected from the group consisting of:
Specific examples of the cationic polymerizable group include three-membered rings such as a glycidyl group and an epoxycyclohexane ring: a four-membered ring such as an oxetane ring (oxetane group); a five-membered ring such as a dioxolane ring; and a 6-membered ring such as a trioxane ring. A member ring; R ³ R ⁴ —C═C—O group (wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group) is preferable. In R ³ and / or R ⁴ , the alkyl group is preferably a hydrogen atom or a methyl group. More preferably, it is a hydrogen atom. As a combination of R ³ and R ⁴ , R ³ = H, R ⁴ = CH ₃ or R ³ = H, and R ⁴ = H are preferable. More preferably, R ³ = H and R ⁴ = H.
More preferably, the cation polymerizable group is a glycidyl group, an oxetane ring, an epoxycyclohexane ring, a dioxolane ring, a trioxane ring, and an R ³ R ⁴ —C═C—O group (R ³ and R ⁴ are the same or different, Represents a hydrogen atom or an alkyl group.), More preferably a glycidyl group, an oxetane ring, or an epoxycyclohexane ring.
The cationically polymerizable compound having the conjugated structure may be any compound that has at least one cationically polymerizable group in one molecule, but preferably has two or more. 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.

The cationically polymerizable compound having the conjugated structure is not particularly limited as long as it has the conjugated structure and the cationically polymerizable group described above. And cationically polymerizable compounds having a biphenyl skeleton (also referred to as “cationic polymerizable biphenyl compounds”) are particularly preferred. The cationically polymerizable fluorene compound is usually a high refractive index resin raw material. By using these, a cured product obtained by curing the organic-inorganic composite resin composition of the present invention has a refractive index of 1.6 or more. For example, it can be suitably used as a high refractive index lens. In addition, the cationically polymerizable fluorene compound 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, and can be uniformly and uniformly dispersed in the matrix. Therefore, it can be used for various applications including optical applications. The cationically polymerizable biphenyl compound has an advantage that it has a high refractive index, excellent heat resistance, high transparency in the visible light region, and can be used at low cost.
In the “cationically polymerizable fluorene compound” and “cationically polymerizable biphenyl compound”, those having a cationically polymerizable group as an epoxy group are hereinafter referred to as “fluorene epoxy resin” and “biphenyl epoxy resin”.
Examples of the cationic polymerizable fluorene compound include the following general formulas (1) and (2):

(In formula, R < ⁵ > is the same or different and represents a hydrogen atom or a methyl group, and R < ⁶ > is the same or different and represents a hydrogen atom, a C1-C5 alkyl group, a phenyl group, or a halogen atom. m ¹ is the same or different and is an integer of 1 to 5, and n ¹ is the same or different and is an integer of 0 to 10). Specifically, the following chemical formula:

Ogsol EG-210 represented by the following formula (fluorene epoxy resin, manufactured by Osaka Treasure Co., Ltd.) is preferable.
Examples of the biphenyl resin include the following chemical formula:

JER YX4000 (Japan Epoxy Resin Co., Ltd., bisphenyl epoxy resin) represented by
When it has the said cationically polymerizable fluorene compound, it is preferable that content of a cationically polymerizable fluorene compound is 20 mass% (weight%) or more in all the cationically polymerizable compounds. If it is less than 20% by mass, the refractive index of the obtained organic-inorganic composite resin composition may not be sufficiently high. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more.
When it has the said cation polymerizable biphenyl compound, it is preferable that content of a cation polymerizable biphenyl compound is 30 mass% (weight%) or more in all the cation polymerizable compounds. If it is less than 30% by mass, the refractive index of the obtained organic-inorganic composite resin composition may not be sufficiently high. More preferably, it is 35 mass% or more, More preferably, it is 40 mass% or more.

In the organic-inorganic composite resin composition, as the organic component, a cation polymerizable compound having a conjugated structure is essential, but other organic components (also referred to as organic resin components) may be included. . The content of the cationic polymerizable compound having a conjugated structure is 10% by mass or more and 90% by mass or less in 100% by mass of the organic component (the total of the cationic polymerizable compound having a conjugated structure and the organic component). Is preferred. If it is less than 10% by mass, the refractive index of the obtained organic-inorganic composite resin composition may not be sufficiently high, and if it exceeds 90% by mass, workability may be reduced due to increase in viscosity. More preferably, they are 15 mass% or more and 80 mass% or less, More preferably, they are 20 mass% or more and 70 mass% or less. The organic component will be described later.

The organic-inorganic composite resin composition of the present invention contains an organic component and an inorganic component. By containing an inorganic component, a thermal expansion coefficient can be reduced and a mold release effect can be exhibited.
The inorganic component essentially contains an organosiloxane compound having a cationic polymerizable group. By making the organosiloxane compound having a cationic polymerizable group essential, it is possible to suppress a delay in curing speed caused by including an epoxy resin having a conjugated structure, and to maintain a preferable curing speed. In particular, the initial speed, which is important when producing a minute material such as an optical lens in a short time, can be sufficiently increased, and an optical material can be suitably produced. When the organosiloxane compound has a structure in which an electron-donating alkyl group is connected to a glycidyl ether group, the stability of the cation on the epoxy group is improved and the cation curing rate is high, so that an epoxy having a conjugated structure is used. The influence of the delay in the curing speed due to the resin being contained can be minimized, and excellent productivity can be obtained. Moreover, it can be set as the organic inorganic composite resin composition excellent in transparency by entering the said network. Further, since the crosslink density is increased, the heat resistance is increased due to an increase in the glass transition temperature.

The cationic polymerizable group is preferably the same as that described above for the organic component. That is, a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, and an R ³ R ⁴ —C═C—O group (wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom or an alkyl group) It is preferable to have at least one selected from the group consisting of:
Specific examples of the cationic polymerizable group include three-membered rings such as a glycidyl group and an epoxycyclohexane ring: a four-membered ring such as an oxetane ring (oxetane group); a five-membered ring such as a dioxolane ring; and a 6-membered ring such as a trioxane ring. A member ring; R ³ R ⁴ —C═C—O group (wherein R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group) is preferable. More preferably, a glycidyl group, an oxetane ring, an epoxycyclohexane ring, a dioxolane ring, a trioxane ring, and an R ³ R ⁴ —C═C—O group (R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group. It represents.) Thus, a glycidyl group, an epoxycyclohexane ring, an oxetane group, a dioxolane ring, a trioxane ring, and an R ³ R ⁴ —C═C—O group (R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group. It is preferably at least one selected from the group consisting of:

The organosiloxane compound has the following average composition formula:
R ¹ aR ² bYcSiOd
(In the formula, R ¹ represents at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. R ² represents an organic group containing a cationically polymerizable group. Y represents R. 'Represents at least one selected from the group consisting of an O group, a hydroxyl group, a halogen atom and a hydrogen atom, R' represents an alkyl group, and a, b, c and d are 0 ≦ a <3, 0 <b <. 3, 0 ≦ c <3, 0 <a + b + c <3, and a + b + c + 2d = 4.
The organosiloxane compound is represented by the average composition, and it is preferable that R ² which is an organic group having a cationic polymerizable group (active group) is essential.

In the organosiloxane compound, R ¹ is at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group, and these may be substituted. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, 2-ethylhexyl group, Saturated aliphatic chain hydrocarbon group (alkyl group) such as n-octyl group, lauryl group, stearyl group (group (1)): saturated fat such as cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group Aromatic cyclic hydrocarbon group (cycloalkyl group) (group (2)): A saturated aliphatic cyclic hydrocarbon group (alkyl group) part or all of the hydrogen atoms are saturated aliphatic cyclic hydrocarbon group (cycloalkyl group) ) (Group (3)); a saturated aliphatic cyclic hydrocarbon group (cycloalkyl group) part or all of the hydrogen atoms are replaced with a saturated aliphatic chain hydrocarbon group (alkyl group) Been That group ((4) group); consists of only hydrocarbon, such as - saturated aliphatic hydrocarbon group (hereinafter, unsubstituted - sometimes referred to as the hydrocarbon group (I)) is preferable.
Examples of R ¹ include aryl groups such as phenyl group, naphthyl group and anthranyl group; aralkyl groups such as benzyl group; methylphenyl group (toluyl group), dimethylphenyl group (xylylene group), diethylphenyl group, methylbenzyl A group in which part or all of the hydrogen atoms of the aryl group and aralkyl group are substituted with an aliphatic hydrocarbon group, such as a group, is preferable. These may be collectively referred to as unsubstituted hydrocarbon group (II).
Any of the above organosiloxane compounds can be suitably used as long as R ¹ is as described above.

R ¹ is more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, and 2 in terms of industrial availability. -An ethylhexyl group, a lauryl group, a stearyl group, a cyclohexyl group, a phenyl group, and a benzyl group, more preferably a methyl group, a cyclohexyl group, and a phenyl group, and particularly preferably a phenyl group. . R ¹ is preferably a phenyl group from the viewpoint of excellent compatibility with a cationically polymerizable compound having a conjugated structure, a high refractive index organic-inorganic composite resin composition, and excellent transparency. .
When there are a plurality of R ¹ groups in one molecule of the organosiloxane compound, they may be the same or different.
As a ratio of the unsubstituted hydrocarbon group (I) to the unsubstituted hydrocarbon group (II), (I) / ((I) + (II)) is preferably less than 0.5. By setting it as such a range, content of an aromatic ring in an organosiloxane compound (unsubstituted hydrocarbon group (II)) becomes sufficient, and a resin having a high refractive index can be obtained. More preferably, it is less than 0.2, More preferably, it is less than 0.1, Most preferably, it is less than 0.01.

Further, in R ¹ , a group consisting of only the hydrocarbon (unsubstituted-hydrocarbon group (I), unsubstituted-hydrocarbon group (II). Hereinafter, the generically referred to as unsubstituted-hydrocarbon group. In addition to the above, those in which part or all of the hydrogen atoms in the hydrocarbon group are substituted with a substituent other than the hydrocarbon group are also preferred, and these organosiloxane compounds having R ¹ and / or R ² are also included. Moreover, it is included in the organosiloxane compound in this invention. Examples of the hydrocarbon group substituted with such a substituent include a group in which a non-reactive substituent such as a halogen atom or an alkoxy group is substituted with a part or all of the hydrogen atoms of an unsubstituted hydrocarbon group (such as A hydrocarbon group having a non-reactive substituent is also referred to as a non-reactive group-substituted hydrocarbon group.); Hydroxyl group, amino group, thiol group, carboxylic acid group, sulfonic acid group, vinyl group, (meth) acryloyl group Reactive substituents such as polymerizable unsaturated bond groups, etc. are unsubstituted-Groups in which some or all of the hydrocarbon atoms have been substituted (reactive group substitution of hydrocarbon groups having reactive functional groups- Also referred to as a hydrocarbon group).
In the non-reactive substituent, the halogen atom is preferably a fluorine atom. As the alkoxy group, an alkyl chain constituting the alkoxy group is an alkyl group exemplified in the aliphatic hydrocarbon group (1) group in R ¹ or a cycloalkyl group also exemplified in the group (2). Some are preferred. More preferably, they are a methyl group and a cyclohexyl group.

As the R ¹ , any of the above-described unsubstituted-hydrocarbon group, non-reactive group-substituted-hydrocarbon group, and reactive group-substituted-hydrocarbon group can be preferably used. A substituted-hydrocarbon group and a non-reactive group-substituted-hydrocarbon group, more preferably an unsubstituted-hydrocarbon group. In addition, the preferable example of each hydrocarbon group is as having mentioned above.
The reactive substituent and the reactive group-substituted hydrocarbon group may be contained for the purpose of increasing the curing rate by reacting with the cationic polymerizable compound having the conjugated structure.
Further, with respect to 100% by mass of the total amount of hydrocarbon groups (R ¹ ) (including the case where R ¹ is bonded to the silicon atom at the molecular end in the organosiloxane compound), an unsubstituted hydrocarbon group and a non-reactive group The total amount of substituted-hydrocarbon groups is preferably 50% by mass or more. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.
Moreover, it is preferable that content of an unsubstituted hydrocarbon group is 50 mass% or more with respect to 100 mass% of total amounts of an unsubstituted hydrocarbon group and a non-reactive substituent-hydrocarbon group. More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.

The R ² includes at least one selected from the group consisting of a glycidyl group, an epoxycyclohexane ring, an oxetane group, a dioxolane ring, a trioxane ring, and an R ³ R ⁴ —C═C—O group. R ³ and R ⁴ are the same or different and each represents a hydrogen atom or an alkyl group. In R ³ and / or R ⁴ , the alkyl group is preferably the same as described above.
R ² is preferably a glycidyl group, an epoxycyclohexane ring, or an oxetane group, as described above. More preferably, it is a glycidyl group, an epoxycyclohexane ring, or an oxetane group, which is bonded to an electron donating group.
The content of R ² may be any as long as it has at least one cation polymerizable group in one molecule of an organosiloxane compound having a cation polymerizable group, but preferably has two or more. By having two or more, there is an advantage of improving the mechanical strength of the cured product. More preferably, it is 1 to 3, and still more preferably 2.
The content of the R ^2, also with respect to the silicon atoms of the organosiloxane compound, is preferably in a molar ratio of 0.3 or more. More preferably, it is 0.5 or more. The molar ratio is a value obtained by dividing the R ² content (mol) by the silicon atom content (mol) [R ² (mol) / Si atom (mol)].

Y is at least one selected from the group consisting of an R′O group, a hydroxyl group, a halogen atom and a hydrogen atom, and R ′ represents an alkyl group.
Y is preferably an R′O group in which R ′ is an alkyl group, a chlorine atom, a hydroxyl group, or a hydrogen atom. More preferably, R ′ is an R′O group composed of an alkyl group having 1 to 5 carbon atoms, and even more preferably, R ′ is an R′O group composed of an alkyl group having 1 carbon atom, that is, a methoxy group. .
The content of Y is preferably as small as possible. Specifically, the value of c in the average composition formula is preferably 0.5 or less. If it exceeds 0.5, the storage stability of the organic-inorganic composite resin composition may not be sufficient. More preferably, it is 0.2 or less, and further preferably 0.1 or less.

The organosiloxane compound is one represented by the average composition formula described above, terminal bonding group in the silicon atoms at the molecular ends of the organosiloxane compound is preferably a above-mentioned R ² or Y. More preferably, terminal binding group is R ^2.
Organosiloxane compounds in which part or all of the groups bonded to the silicon atom at the molecular terminal are groups or atoms other than R ² or Y are also included in the organosiloxane compounds of the present invention. The group or atom other than R ² or Y is, for example, R ¹ described above, and a more preferable embodiment is the same as R ¹ described above.
The ratio of the hydrocarbon group composed of R ¹ or R ² in the group or atomic group (terminal bonding group) bonded to the terminal silicon atom of the organosiloxane compound molecule is 50 mol% with respect to 100 mol% of the terminal bonding group. The above is preferable. More preferably, it is 80 mol% or more, More preferably, it is 90 mol% or more, Most preferably, it is 100 mol%.

In the organosiloxane compound, a, b, c, and d satisfy 0 ≦ a <3, 0 <b <3, 0 ≦ c <3, 0 <a + b + c <3, and a + b + c + 2d = 4. .
As a and b, the ratio of R ¹ and R ² is shown. As a ratio (molar ratio) between R ¹ and R ² , a / b (R ¹ / R ² ) is preferably 90/10 as a lower limit. More preferably, it is 70/30, and still more preferably 50/50. The upper limit is preferably 0/100.

The a + b + c may be greater than 0 and less than 3. Preferably, it is 0.5 or more and 2.7 or less, More preferably, it is 0.8 or more and 2.4 or less. Moreover, a + b should just be larger than 0 and less than 3. The preferable range of a + b is 0.4 or more and 2.7 or less, and more preferably 0.7 or more and 2.4 or less.
The molecular structure of the organosiloxane compound is not particularly limited, but usually a chain structure (straight or branched), a ladder structure, a network, a ring, a ring structure composed of a ladder, a cage or a particle is used. Illustrated. The molecular structure is preferably a chain, ladder, network, or basket, and more preferably a ladder, network, or basket. These ladder-like, network-like, and cage-like molecular structures are preferable because the effects are easily exhibited even when the addition amount of the organosiloxane compound is small. As described above, an organic-inorganic composite resin composition having at least one molecular structure selected from the group consisting of a ladder, a network, and a cage is also one of the preferred embodiments of the present invention. These molecular structures have the following structural formula:

(Wherein R represents an organic group). The structural formula (1) is a random structure (Random structure), the structural formula (2) is a ladder structure, and the structural formula (3) is an incomplete cage structure. ) And structural formulas (4) to (6) indicate a caged structure (Complementary condensed structures).
More preferably, the molecular structure is a ladder. In addition, when the molecular structure is ladder-like or chain-like, a material having high solubility in the resin composition and good optical transparency and mechanical properties can be obtained.
When the molecular structure is a chain structure, a preferable range of a + b + c in the average composition formula is 1.5 or more and 2.7 or less. More preferably, it is 1.8 or more and 2.4 or less, More preferably, it is 1.9 or more and 2.3 or less, Especially preferably, it is 2 or more and 2.2 or less. A preferable range of a + b is 1 or more and 2.7 or less. More preferably, it is 1.6 or more and 2.4 or less, More preferably, it is 1.8 or more and 2.2 or less, Especially preferably, it is 2 +/- 0.05.
When the molecular structure is ladder-like or cage-like, a preferable range of a + b + c in the average composition formula is 0.5 or more and 2 or less. More preferably, it is 0.8 or more and 1.6 or less, More preferably, it is 0.9 or more and 1.4 or less, Especially preferably, it is 1 or more and 1.2 or less. The preferable range of a + b is 0.4 or more and 2 or less. More preferably, it is 0.7 or more and 1.7 or less, More preferably, it is 0.8 or more and 1.2 or less, Especially preferably, it is 1 +/- 0.05.

As described above, the molecular structure of the organosiloxane compound is preferably a chain shape, a ladder shape, a net shape, or a cage shape. In this case, the a + b is preferably 1 or 2. When a + b = 1, the molecular structure is usually a two-dimensional or three-dimensional higher order structure such as a ladder shape, a cage shape, or a net shape. When a + b = 2, the molecular structure is a linear one-dimensional structure. It becomes. Thus, the form in which the organosiloxane compound is a resin composition in which a + b is 1 or 2 is also one of the preferred forms of the present invention.
The molecular structure of the organosiloxane compound is more preferably a ladder as described above. In this case, the a + b is preferably 1. That is, the organosiloxane compound is in the form of a ladder, and a resin composition in which a + b is 1 is also a preferred embodiment of the present invention.

In addition, the said average composition formula shows the average composition of the organosiloxane molecule to be used, and a, b, c and d represent the average value of the bond ratio of R ¹ , R ² , Y and O to Si, It does not specify the binding mode. Specifically, as an organosiloxane in which a ≠ 0 and b ≠ 0, when the siloxane skeleton in the molecule is formed by bonding R ¹ and R ² to an arbitrary silicon atom, R as an organic group ^The case where it consists of a silicon atom to which only 1 is bonded and a silicon atom to which only R ² is bonded, and a case where both are mixed are also included. (1) A silicon atom to which R ¹ and R ² are bonded, or (2) a silicon atom to which R ¹ is bonded and a silicon atom to which R ² is bonded are included as essential, and both R ¹ and R ² are bonded. Silicon atoms that are not present may be included. There are no limitations on the combination, ratio, position on the siloxane skeleton, etc. of these silicon atoms.

The organosiloxane compound preferably has a weight average molecular weight of 100 to 10,000. If it is less than 100, the effect of addition is small, and there is a possibility that effects such as curing acceleration effect and optical property control will not be sufficiently exerted, and there is a risk of luminescence due to heat during curing. If it exceeds 10,000, the compatibility with the organic resin component may be poor. More preferably, it is 500-5000 as said weight average molecular weight, More preferably, it is 800-2000.
Specifically, the organosiloxane compound having a cationic polymerizable group has the following chemical formula:

(Wherein n is the number of repetitions) S-501 (Arakawa Chemical Industries, Inc., glycidyl group-containing silsesquioxane) is preferred.
In the inorganic component of the present invention, an organosiloxane compound having a cationic polymerizable group is essential. “Making essential the organosiloxane compound having a cationic polymerizable group” preferably includes 10% by mass or more of the organosiloxane compound having the cationic polymerizable group in 100% by mass of the inorganic component. More preferably, it is 30 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is substantially all.
The other inorganic component is not particularly limited as long as it exhibits the effects of the present invention, but is preferably an organosiloxane compound having no cationically polymerizable group, silica, or metal oxide. Other inorganic components will be described later.

As content (addition amount) in the resin composition of the organosiloxane compound which has the said cation polymerizable group, 1-50 mass% (weight%) is preferable with respect to the total weight of an organic inorganic composite resin composition. If it is less than 1% by mass, the effect of addition is small, and there is a possibility that effects such as curing acceleration effect and optical property control will not be sufficiently exhibited. If it exceeds 50% by mass, the refractive index may not be sufficiently high. More preferably, it is 2-30 mass%, More preferably, it is 5-20 mass%.

Although it does not specifically limit as a manufacturing method of the said organosiloxane compound (The organosiloxane compound which has a cationically polymerizable group, and the organosiloxane compound which does not have a cationically polymerizable group), As long as the effect of this invention is exhibited, for example, the following Formula (I):
R ¹ _s SiX ¹ _(4-s) (I)
(In the above formula, R ¹ is the same as R ¹ described above. X ¹ is the same or different and represents a hydrolyzable group. S is 1, 2 or 3.), ):
R ² _t SiX ² _(4-t) (II)
(In the above formula, R ² is the same as R ² described above. X ² is the same or different and represents a hydrolyzable group. T is 1, 2 or 3) and (III):
R ¹ _{s ′} R ² _{t ′} SiX ³ _{(4-s′-t ′)} (III)
(In the above formula, R ¹ and R ² are the same as R ¹ and R ² described above. X ³ is the same or different and represents a hydrolyzable group. S ′ and t ′ are the same or different. 1 or 2 and s ′ + t ′ is 2 or 3.) A hydrolyzable silane compound represented by the formula (1) or 2 is preferably obtained by hydrolysis or condensation in an organic solvent alone or in combination. .
In the above formulas (I) to (III), X ¹ , X ² and X ³ may be the same or different and are preferably an R ⁷ O group, a hydroxyl group, a hydrogen atom or a halogen atom. R ⁷ represents an alkyl group. The number of carbon atoms of R ^7, 1 to 5 are preferred, 1 or 2 being more preferred. Specifically, X ¹ and X ² are preferably a methoxy group, an ethoxy group, or a chlorine atom.
In the above formulas (I) and (II), s and t are preferably the same or different and are 1, 2. In particular, trialkoxysilane compounds represented by s = 1 and t = 1 are preferable. Organosiloxane compounds obtained by hydrolyzing and condensing trialkoxysilane compounds are preferred because they are excellent in compatibility with organic resin components.
In the above (III), s ′ and t ′ are preferably 1.
When hydrolyzing and condensing the organosiloxane compound of the present invention, a silane compound other than the above formulas (I) to (III) may be used as a raw material. Thus, as a silane compound which co-hydrolyzes and condenses with said formula (I)-(III), for example, following formula (IV):
Si (X ⁴ ) ₄ (IV)
(Wherein X ⁴ represents a hydrolyzable group) is preferred.
The above X ⁴ may be the same or different, and preferred embodiments are also the same as X ¹ , X ² and X ³ .
The above formula (IV) can be suitably cohydrolyzed and condensed with the above formulas (I) to (III), but the organosiloxane compound finally obtained is represented by the above average composition formula. It is preferable to use within a range. Specifically, in the above average composition formula, it is preferable that the ratios of R ¹ and R ² are used in the above-described range. The above formulas (II) and (III) are preferably used as essential raw materials.
The organosiloxane compound obtained by hydrolytic condensation of (I) to (IV) in an organic solvent is preferably used after being purified by redissolution purification, extraction or the like.

As said other inorganic component, it is preferable that they are a metal oxide particle and the organosiloxane compound which does not have a cation polymeric group. These will be described below.
The metal oxide is preferably metal oxide nanoparticles having a refractive index of 2 or more, such as metal oxide particles such as titania, zirconia, yttria, lanthanum oxide, indium oxide, zinc oxide, and tin oxide. In particular, it is preferable for increasing the refractive index of the organic-inorganic composite resin composition and the cured product of the resin composition.
As said metal oxide particle, it is preferable that the average particle diameter of a primary particle is 100 nm or less. More preferably, it is 20 nm or less, More preferably, it is 15 nm or less. By setting it as such a range, organic-inorganic composite resin composition and hardened | cured material with transparency and high light transmittance can be obtained.
The primary particle diameter is a number average particle diameter obtained from a TEM image (observation with a transmission electron microscope); specific surface area diameter (weight average particle diameter obtained by measurement of BET surface area; powder X-ray diffraction measurement method) The average particle diameter obtained from the radius of inertia obtained by the X-ray small angle scattering method and the scattering intensity, etc. Among these, the number average particle diameter obtained from the TEM image is preferable.
The shape of the metal oxide particles is not limited to a spherical shape, and may be, for example, a thin piece such as an elliptical sphere, a cube, a rectangular parallelepiped, a pyramid, a needle, a column, a rod, a cylinder, a flake, and a (hexagon) plate A shape, a string shape or the like is preferable.

The organosiloxane compound having no cationic polymerizable group is preferably in a form that does not contain R ² in the average composition formula of the organosiloxane compound having the cationic polymerizable group described above. That is, the average composition formula:
R ¹ xYySiOz
(Wherein R ¹ represents at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. Y represents a group consisting of an R′O group, a hydroxyl group, a halogen atom, and a hydrogen atom. R ′ represents an alkyl group, and x, y, and z are numbers satisfying 0 ≦ x <3, 0 ≦ y <3, 0 <x + y <3, and x + y + 2z = 4. It is preferable that it is an organosiloxane compound represented by. In the above average composition formula, R ¹ , Y and R ′ are preferably the same as described above.
X, y and z are preferably the same as a + b, c and d, respectively.
The organosiloxane compound having no cationically polymerizable group is preferably the same as the organosiloxane compound having a cationically polymerizable group in terms of average molecular weight, molecular structure, and production method, except that it does not have cationically polymerizable properties. .
The content of the wet inorganic fine particles in 100% by mass of the other inorganic components is preferably 10 to 100% by mass. More preferably, it is 50-100 mass%, More preferably, it is 80-100 mass%.
In the organic-inorganic composite resin composition of the present invention, when increasing the refractive index, it is preferable to use the high refractive index nanoparticles, titanoxane compound, and the like as the other inorganic components. When increasing the refractive index, high refractive index nanoparticles are more preferable, and TiO ₂ is more preferable than the titanoxane compound. In addition, a titanoxane compound etc. can be mix | blended in high concentration.

The organosiloxane compound having no cationically polymerizable group preferably has an aromatic ring when increasing the refractive index. The structure of the compound may be either linear or branched, and is preferably a polysilsesquioxane having a ladder or cage structure. Specifically, silicone oligomer PPSQ-E (manufactured by Konishi Chemical Industries, PPSQ-E, number average molecular weight 850), silicone oligomer PPSQ-H (manufactured by Konishi Chemical Industries, PPSQ-H, number average molecular weight 2200), and the like. preferable. Silicone oligomer PPSQ-E is a powdered polymer silica having a benzene ring in the structure, and is in a string-like form, and thus does not aggregate in the solution and is easily dispersed.
The amount of aromatic ring in the organosiloxane compound having no cationically polymerizable group is preferably 40% by mass or more with respect to 100% by mass of silicon atom. If the amount of the aromatic ring in the organosiloxane compound having no cationically polymerizable group is less than 40% by mass, the refractive index may be sufficiently high and it may not be suitably used for optical applications. The amount of the aromatic ring is more preferably 50% by mass or more, still more preferably 100% by mass or more, and particularly preferably 200% by mass or more.

The organic component of the present invention essentially comprises a cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms. Organic components other than the cationically polymerizable compound having a conjugated structure (hereinafter referred to as “others”) May also be included.). Hereinafter, other organic components will be described.
As said other organic component, curable resin and a thermoplastic resin are preferable, for example.
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. Resins, polycarbonate resins, polyphenylene oxide, polyesters, polyimides and the like can be mentioned. As the curable compound as the other components, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and a compound having at least one epoxy group to be described later can be appropriately selected and used. That's fine.

The compound having a polymerizable unsaturated bond may be any compound having a polymerizable unsaturated bond, but one or more selected from the group consisting of a (meth) acryloyl group, a vinyl group, a fumarate group, and a maleimide group. It is preferable that it is a compound which has these groups. In the present invention, the (meth) acryloyl group means an acryloyl group and a methacryloyl group, and when it has an acryloyl group, it has a vinyl group in the acryloyl group. Does not have an acryloyl group and a vinyl group, but has an acryloyl group. The fumarate group means a group having a fumarate structure, that is, a group having a fumarate ester structure.
Examples of the compound having the (meth) acryloyl group include (poly) ester (meth) acrylate, urethane (meth) acrylate, the above-described epoxy (meth) acrylate, (poly) ether (meth) acrylate, alkyl (meth) acrylate, Examples include alkylene (meth) acrylate, (meth) acrylate having an aromatic ring, and (meth) acrylate having an alicyclic structure. Each of these can be used alone or in combination of two or more.

The other organic component is preferably an epoxy group-containing compound, that is, a compound having at least one epoxy group other than the cationic polymerizable compound having the conjugated structure described above from the viewpoint of curing speed. By having at least one epoxy group, it has the effect of making the curing speed sufficient, and has the same workability as a conventional thermosetting plastic material, while exhibiting heat resistance comparable to inorganic glass, molding, Excellent properties such as excellent workability can be exhibited. Hereinafter, a compound having at least one epoxy group that can be suitably used as the organic 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, bisphenol S, fluorene bisphenol and epihalohydrin, and these bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, etc. High molecular weight epibis type glycidyl ether type epoxy resin obtained by further addition reaction with other bisphenols; phenols such as phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol And formaldehyde, acetoaldehyde, propionaldehyde, benzaldehyde, hydroxybenzaldehyde Obtained by condensation reaction of polyhydric phenols obtained by condensation reaction of hydride, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. with epihalohydrin. Novolak aralkyl type glycidyl ether type epoxy resin; aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol and the like with epihalohydrin, and the above bisphenols and tetramethyl Aromatic crystalline epoxy tree obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc. High molecular weight polymers of the above; alicyclic glycols hydrogenated aromatic skeletons such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and its multimer, pentaerythritol and its multimer, glucose, fructose, lactose Aliphatic glycidyl ether type epoxide obtained by condensation reaction of mono / polysaccharides such as maltose and epihalohydrin Xoxy resin (aliphatic glycidyl ether type epoxy compound); (3,4-epoxycyclohexane) epoxy resin having epoxycyclohexane skeleton such as methyl 3 ′, 4′-epoxycyclohexylcarboxylate (epoxy compound having epoxycyclohexane skeleton) ); Glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; solid 3 at room temperature obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin Secondary amine-containing glycidyl ether type epoxy resin. 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;
Epichlorohydrin modified bisphenol type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, their ethylene oxide, propylene oxide modified products, etc .; phenol novolac type epoxy resin; cresol novolac type epoxy resin; Epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting pentadiene with various phenols; Epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol, aromatic epoxides such as phenyl glycidyl ether;
(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol and other glycols (poly) glycidyl ether; glycols of alkylene oxide modified products (poly) Glycidyl ether; (poly) glycidyl ether of an aliphatic polyhydric alcohol such as trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; Alkylene-type epoxides such as (poly) glycidyl ethers of alkylene oxide-modified products of aliphatic polyhydric alcohols;
Glycidyl ester of carboxylic acid such as adipic acid, sebacic acid, maleic acid, itaconic acid, glycidyl ether of polyester polyol of polyhydric alcohol and polyhydric carboxylic acid; co-polymerization of glycidyl (meth) acrylate and methylglycidyl (meth) acrylate Preferred are aliphatic epoxy resins such as glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, and epoxidized polybutadiene.

The 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 bisphenol A. As bisphenol A, specifically, the following chemical formula:

JER828EL (Japan Epoxy Resin Co., Ltd., bisphenol A epoxy resin) represented by

In addition to the cationically polymerizable compound having a conjugated structure and the organosiloxane compound having a cationically polymerizable group, which are essential components of the present invention, components that are preferably further included, preferred forms of the organic-inorganic composite resin composition, and the like are described. . Hereinafter, the inorganic component is also referred to as an organosiloxane compound.
In the said resin composition and optical material, since the thing of a high refractive index can be obtained, it is preferable to use the organic component with many amounts of unsaturated bonds. As a curable resin composition, what has an unsaturated bond amount of 40 mass% or more with respect to 100 mass% of hardened | cured bodies after hardening is preferable. Here, the amount of unsaturated bonds means carbon atoms, sulfur atoms, nitrogen atoms, boron atoms, silicon atoms, phosphorus atoms, germanium atoms, oxygen atoms, and hydrogen atoms and halogen atoms to be added. The total mass. That is, the total mass of atoms forming unsaturated bonds contained in 100% by mass of the cured product, and hydrogen atoms and halogen atoms bonded to the atoms. Specifically, when it has a —CH ₂ CH ₂ CHCl—CH═CCl—CH ₂ CH ₂ — structure, the amount of unsaturated bonds means the total mass of the CH═CCl moiety.
Moreover, when a carbon atom forms an aromatic ring, it shall represent the mass% of the aromatic ring contained in 100 mass% of hardening bodies. In this case, even if the aromatic ring has a substituent, the mass of the aromatic ring composed of carbon atoms and hydrogen atoms is not included in the mass of the unsaturated bond. You will enter the total amount calculation. In addition, when a halogen atom is bonded to the aromatic ring as a substituent, a halogen atom is also included from the above definition. In the present invention, a form in which the unsaturated bond is constituted by an aromatic ring is one of the preferred forms.

The amount of unsaturated bonds is more preferably 43% by mass or more, and still more preferably 45% by mass or more. As an upper limit, it is preferable that it is 70 mass% or less.
In the curable resin composition, the ratio (molar ratio) between the unsaturated bond of the organic component and the unsaturated bond of the inorganic component is [unsaturated bond of organic component] / [unsaturated bond of inorganic component] = 100 / It is preferable that it is 0-10 / 90. More preferably, it is 90/10 to 10/90, still more preferably 80/20 to 20/80, and particularly preferably 60/40 to 40/60. It is preferable that at least one of other organic components and other inorganic components has an unsaturated bond. In particular, it preferably has an aromatic ring.

When the unsaturated bond is derived from an aromatic ring, examples of such an aromatic ring include biphenyl, naphthalene, anthracene, dibenzothiophene, stilbene, phenyl group, fluorene skeleton, and carbazole skeleton.
In the above curable resin composition, as a method for quantifying the unsaturated bond amount of the cured product of the curable resin composition, the curable resin composition is analyzed by elemental analysis, NMR, IR, etc., and the structure and the like are clarified. Then, quantitative analysis is performed by ¹ H-NMR or the like, and carbon atoms, sulfur atoms, nitrogen atoms, boron atoms, silicon atoms, phosphorus atoms, germanium atoms, oxygen atoms, and hydrogen atoms to be added form an unsaturated bond. It can be determined by quantifying halogen atoms. In addition, as a curable resin composition, as long as the effect of this invention is exhibited, it does not specifically limit, The component which does not have an unsaturated bond may be contained.

Specifically, the amount of unsaturated bonds can be determined by the following method.
(1) A curable resin composition is cured to obtain a cured product.
(2) Elemental analysis of the cured product and / or resin composition to obtain a composition formula, presence of unsaturated bonds of the cured product by IR and NMR measurements, and functional groups that form the unsaturated bonds To identify.
(3) NMR measurement is performed using the cured body and / or resin composition whose mass has been quantified, and an external standard whose mass has been quantified.
(4) In the NMR measurement of (3) above, the amount of unsaturated bonds contained in the cured product used in the NMR measurement is calculated from the peak area of the external reference, the peak area derived from the unsaturated bond, and the mass of the external reference. calculate.
(5) From the result of (4) above, the amount of unsaturated bonds contained in 100% by mass of the cured product is determined.
In the NMR measurements (2) and (3) above, one or more optimum nuclides are selected and measured. For example, when the unsaturated bond is derived from an aromatic ring, ¹ H-NMR alone or a combination with ¹³ C-NMR is preferable, and a fluorine atom is bonded to an atom forming the unsaturated bond. In some cases, ¹⁹ F-NMR is preferred. The external standard to be used is appropriately selected according to various types, and in the case of ¹ H-NMR, TMS is generally suitable.

The curable resin composition must have an aromatic ring as an organic component, and the curable resin composition has an aromatic ring amount of 40% by mass or more with respect to 100% by mass of the cured product after curing. preferable. The curable resin composition preferably includes an organic component having an aromatic ring as another organic component.
The amount of the aromatic ring is 40% by mass or more with respect to 100% by mass of the cured product after curing. By setting it as such a range, it can be set as the curable resin composition excellent in optical characteristics, such as transparency and refractive index high enough. More preferably, it is 43 mass% or more, More preferably, it is 45 mass% or more. As an upper limit, it is preferable that it is 70 mass% or less. In addition, such an aromatic ring amount means the aromatic ring amount contained in an organic component and an inorganic component. That is, when only the organic component has an aromatic ring, it is the mass% of the aromatic ring in the organic component with respect to 100% by mass of the cured product after curing, and when the inorganic component also has an aromatic ring, the cured product after curing. It is the total mass% of the amount of aromatic rings in the organic component and the amount of aromatic rings in the inorganic component with respect to 100 mass%. When the inorganic component also has an aromatic ring, the ratio (molar ratio) of the aromatic ring of the organic component to the aromatic ring of the inorganic component is [aromatic ring of organic component] / [aromatic ring of inorganic component] = 90/10 to 10 / 90 is preferable. More preferably, it is 80 / 20-20 / 80, More preferably, it is 60 / 40-40 / 60.
The number average molecular weight of the organic component contained as an essential component in the organic resin component is preferably 150 to 10,000. If the molecular weight exceeds 10,000, the resin composition may not have sufficient transparency.

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

A preferred embodiment of the curable resin composition of the present invention is a cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms (cationic polymerizable compound having a conjugated structure) in order to increase the refractive index. As other organic components, it is preferable to contain an epoxy compound having an aromatic ring and an organosiloxane compound containing an aromatic ring regardless of the presence or absence of a cationically polymerizable group. The total mass of the aromatic ring amount in the organic component and the aromatic ring amount in the inorganic component is preferably 40% or more, and the aromatic ring amount in the organosiloxane compound is preferably 30% by mass or more. That is, a curable resin composition comprising an organic component and an inorganic component, wherein the curable resin composition essentially comprises an epoxy compound having an aromatic ring as an organic component, and an organosiloxane having an aromatic ring as the inorganic component. Curing in which the amount of aromatic rings in the organosiloxane compound with respect to 100% by mass of silicon atom is 50% by mass or more and the amount of aromatic rings is 40% by mass or more with respect to 100% by mass of the cured product after curing. A functional resin composition is also one of the preferred forms of the present invention. Moreover, as a combination of an inorganic component and an organic component, the compound mentioned above can be selected suitably and can be used. Among these combinations, a particularly preferred form is a cationically polymerizable fluorene compound. More preferred are a fluorene epoxy resin, a bisphenol A epoxy resin, and an organosiloxane compound containing a cationically polymerizable group and a phenyl group.
The organic component may contain a solvent, and the amount of the solvent contained in the organic component is preferably 20% by mass or less with respect to 100% by mass of the organic component. When it exceeds 20 mass%, when an organic resin component is included, there exists a possibility that a bubble may arise in a molded object as mentioned above. 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 of the present invention contains the organic component and the organosiloxane compound, but the lower limit is 40% by mass, more preferably the organic component, with respect to a total of 100% by mass of the organic component and the organosiloxane compound. It is preferable to contain 70% by mass and 1% by mass of an organosiloxane compound, more preferably 2% by mass, particularly preferably 5% by mass. As an upper limit, it is preferable that an organic component is 99 mass%, More preferably, it is 98 mass%, An organosiloxane compound is 60 mass%, Most preferably, it contains 30 mass%. By setting it as such content, it can be set as a highly transparent resin composition. In particular, when a thermosetting resin is used as the organic component, it is possible to overcome heat resistance that cannot be achieved with a thermoplastic resin, and it is possible to perform complicated and inexpensive processing that cannot be achieved with glass.

The resin composition preferably also includes a component having flexibility (flexible component). By including a flexible component, a resin composition having a sense of unity can be obtained. As the flexible component, both (1) a form that is a flexible component made of a compound different from the organic resin component, and (2) a form in which one of the organic resin components is a flexible component are suitable. Can be applied. Specifically, a compound having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] _m − (n is 2 or more, m is an integer of 1 or more. Preferably, n is 2 -12, m is an integer of 1-1000, more preferably, n is 3-6, m is an integer of 1-20.) For example, epoxy resin containing butylene oxide (Japan Epoxy Resin, YL -7217, epoxy equivalent 437, liquid epoxy resin (10 ° C. or higher)); polymer epoxy resin (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YL-7170, epoxy equivalent 1000, solid hydrogenated epoxy resin); fat Cyclic solid epoxy resin (EHPE-3150 manufactured by Daicel Industries, Ltd.); liquid rubber such as liquid nitrile rubber; polymer rubber such as polybutadiene; Child rubber etc. are preferred, and among these, more preferred are compounds containing a curable functional group at the terminal, side sheath, main chain skeleton, etc. Thus, the flexible component is a curable functional group. A resin composition comprising the above is also one of the preferred embodiments of the present invention, and the above-mentioned “curable functional group” refers to a “functional group that is cured by heat or light, such as an epoxy group or an oxetane group”. (Group for causing the resin composition to undergo a curing reaction) ".
As the flexible component, a compound containing a curable functional group can be suitably applied. Among the compounds containing a curable functional group, a compound containing an epoxy group is particularly preferable. Specifically, the flexible component is preferably butylene oxide.
The content of the flexible component is 40 to 99% by mass of the organic resin component and 1 to 60% by mass of the inorganic component in a total of 100% by mass of the organic resin component, the inorganic component, and the flexible component. It is preferable to contain 0.01-40 mass% of a flexible component. More preferably, it is 0.1-35 mass% as content of a flexible component, More preferably, it is 0.5-30 mass%. That is, a resin composition having a flexible component of 10% or less is preferable.
Moreover, as content of the said flexible component, 40-99 mass% of organic resin components and 1-60 mass of organosiloxane compounds in the total 100 mass% of an organic resin component, an organosiloxane compound, and a flexible component. %, And a flexible component is preferably contained in an amount of 0.01 to 40% by mass. In particular, a resin composition having a flexible component of 10% or less is suitable. More preferably, it is 0.1-5 mass% as content of a flexible component, More preferably, it is 0.5-1 mass%.
As described above, the resin composition of the present invention contains an organic component and an organosiloxane compound, and preferably contains a flexible component. That is, a form comprising a flexible material (flexible component), a cationic polymerizable fluorene compound (more preferably, a fluorene epoxy resin) and an organosiloxane compound is also one of the preferred forms of the present invention. is there.
The viscosity of the resin composition is particularly preferably 10,000 Pa · s or less, more preferably 1000 Pa · s or less, and most preferably 200 Pa · s or less.

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

In the resin composition of the present invention, a cured product having excellent transparency can be provided. However, when the transparency is improved, the performance as an optical member is improved, and the optical application, the optical device application, the display device are improved. It becomes the resin composition which can be used suitably for various uses, such as a use.

In addition to the organic components and organosiloxane compounds described above, the resin composition of the present invention includes a curing catalyst, a release agent, a curing agent, a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, and a pigment. , Dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers and organic fillers, cups Adhesion improvers such as ring agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners / sagging agents, An anti-coloring agent, an emulsifier, an anti-slip / scratch agent, an anti-skinning agent, a drying agent, an antifouling agent, an antistatic agent, a conductive agent (electrostatic aid), and the like may be contained.

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

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

The carboxylic acid ester having 8 to 36 carbon atoms is (1) carboxylic acid ester obtained from the above alcohol and carboxylic acid, and (2) carbon such as methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol, etc. Carboxylic acid ester obtained by the combination of the number 1-7 alcohol and the above carboxylic acid, (3) In the combination of the above alcohol with a carboxylic acid having 1 to 7 carbon atoms such as acetic acid, propionic acid, hexanoic acid, butanoic acid, etc. The resulting carboxylic acid ester is preferred. Among these, stearic acid methyl ester, stearic acid ethyl ester, octyl acetate and the like are preferable.
The carboxylate having 8 to 36 carbon atoms is a carboxylic acid obtained by a combination of the carboxylic acid and an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Sn. Salts and the like are preferred. Of these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.
Among the above-mentioned compounds, stearic acid compounds such as stearic acid and stearic acid esters, and alcohol compounds are more preferable, and stearic acid compounds are more preferable. Thus, the resin composition containing a stearic acid compound is also one of the preferred embodiments of the present invention.
As content of the said mold release agent, it is preferable that it is 10 mass% or less with respect to 100 mass% of resin compositions. If it exceeds 10% by mass, the resin may be difficult to cure. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

As the curing catalyst, those usually used and those conventionally known can be suitably used. For example, a photolatent curing catalyst and a thermal latent curing catalyst are suitable. Thus, the resin composition containing the photolatent curing catalyst and the thermal latent curing catalyst is also a preferred embodiment of the present invention.
The heat latent curing catalyst is also called a heat latent curing agent, a heat latent cation generator, or a cationic polymerization initiator, and exhibits a substantial function as a curing agent at the curing temperature in the resin composition. To do. Unlike the curing agent described later, the thermal latent curing catalyst does not cause an increase in viscosity or gelation with time of the resin composition at room temperature even if it is contained in the resin composition. As a function, the curing reaction can be sufficiently promoted, an excellent effect can be exhibited, and 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. Thus, a resin composition containing an organic component having an epoxy group and a thermal latent curing catalyst, the resin composition containing the organosiloxane compound represented by the above average composition formula (curable resin composition) The storage stability improving method) is also one of the preferred embodiments of the present invention. The organosiloxane compound and the organic component are as described above. As the organic component and the organosiloxane compound, those described above can be preferably used. From the viewpoint of improving the curing rate, any one of an epoxycyclohexane ring, an oxetane group, and a cationically polymerizable group bonded to an electron donating group can be used. Cationically polymerizable compounds having these are preferred, and as other organic components, alicyclic epoxy resins (epoxycyclohexane skeleton) and hydrogenated bisphenol A epoxy resins are preferred, and from the viewpoint of reducing the amount of catalyst, alicyclic Introduction of an epoxy resin is preferred.
The catalyst amount (use amount) of the thermal latent curing catalyst is preferably 0.01% by mass or more and 10% by mass or less with respect to 100% by mass of the resin composition in which the organic resin component and the inorganic component are combined. More preferably, they are 0.1 mass% or more and 5.0 mass% or less, More preferably, they are 0.2 mass% or more and 2.0 mass% or less. If the amount of the catalyst is reduced too much to be less than 0.01% by mass, curing is slow, and if it exceeds 10% by mass, there is a risk of coloring during curing or heating of the molded body.

As the above-mentioned heat latent curing catalyst, the moisture resistance of the resulting resin composition is dramatically improved, and it retains the excellent optical properties of the resin composition even in harsh usage environments, making it suitable for various applications. It can be used for. Normally, when water with a high refractive index is contained in a resin composition or its cured product, it causes turbidity, but since it can exhibit excellent moisture resistance, such turbidity is suppressed and it can be used for optical applications such as lenses. It can be used suitably. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns over yellowing and deterioration of strength due to prolonged ultraviolet irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance, moisture absorption into the resin composition is suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. Excellent heat resistance over time.

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

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

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

Specific products of the above-mentioned heat latent cation generator include diazonium salt types: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemicals)
Iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries)
Sulfonium salt type: CYRACURE series (manufactured by Union Carbide), UVI series (manufactured by General Electric), FC series (manufactured by 3M), CD series (manufactured by Satomer), optomer SP series, optomer CP series (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.

Examples of the photolatent curing catalyst (also referred to as a photolatent cation generator or a photocationic polymerization initiator) include metal fluoroboron complex salts and trifluorinated boron complex compounds as 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 ultraviolet polymerization initiators may be used alone or in combination of two or more. These ultraviolet polymerization initiators may be used alone or in combination of two or more. Of these 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 (manufactured by Asahi Denka Co., Ltd.), Sun Aid SI-60L, Sun Aid SI-80L, Sun Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like can be obtained.

As a method for curing the resin composition of the present invention, various methods such as thermosetting and photocuring can be suitably used. A method is preferably used in which the liquid mixture is coated on a mold that matches the shape of the cured product and cured, and then the cured product is removed from the mold. In such a method, it is preferable that the viscosity of the curable resin composition mixed with a curing catalyst or the like is not significantly increased because it is easy to handle.
Although it can set suitably as said hardening temperature according to the resin composition etc. to harden | cure, it is preferable that it is 80-200 degreeC. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC.

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

Hereinafter, the method for curing the resin composition of the present invention will be further described. For curing the resin composition of the present invention, a conventionally known method can be employed depending on the properties of the resin used.
The resin composition of the present invention can be made into a cured product by thermosetting using a curing catalyst. It is preferable to use the above-mentioned heat latent cation generator as the curing catalyst. In addition, as a curing method of the resin composition of the present invention, a curing method other than the curing method using a curing catalyst such as the thermal 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 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 in a high refractive index optical material, it is not actively used except when it is essential to add a curing agent and a curing accelerator, and cationic curing with a curing catalyst is preferable.

The resin composition of the present invention can obtain a cured product by the above-described curing method, and such a cured product is excellent in various optical properties. For example, the turbidity (haze) of the cured product is preferably 20% or less. Thus, the resin composition in which the turbidity of the cured product of the resin composition is 20% or less is also a preferred embodiment of the present invention. The turbidity of the cured product is more preferably 10% or less, still more preferably 5% or less, and particularly preferably 1% or less. As the transparency, the light transmittance in the visible light region (region having a wavelength of 360 to 780 nm) is preferably 75% or more. The light transmittance of the cured product is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 87% or more.
In the above cured product, a wide range of numerical values are required for the refractive index and Abbe number of the cured product depending on the optical design of the applied optical system. The light transmittance of the cured product can be measured by a method according to JIS K7361-1, the turbidity can be measured by JIS K7136, and the refractive index / Abbe number can be measured by a method according to JIS K7142.
The PCT moisture absorption of the cured product varies depending on the curing conditions, but by optimizing the curing conditions, it is preferably 2% or less, preferably 1% or less, more preferably 0.5% or less. More preferably, it is 0.2% or less.

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

The present invention is also preferably an optical material constituted by the curable resin composition. The optical material is a curable material using the resin composition, and is also simply referred to as “curable material” or “curable material for optical members”. 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. The optical material of the present invention is a curable optical material formed from the above resin composition, and is a thermo / photo curable optical material that is cured by heat or light (thermo curable optical material or photo curable optical material). It is preferable that
As a form of the optical material, the transmittance at a wavelength of 500 nm is preferably 60% or more. When the transmittance is in such a range, an optical material having high transparency and excellent optical characteristics is obtained. The transmittance of the optical material is more preferably 80% or more, and still more preferably 85% or more.
The optical material includes the resin composition, but may optionally include other components depending on the use of the optical material. 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.

The present invention is also a cured product obtained by curing the organic-inorganic composite resin composition.
As a hardened | cured material formed with the said resin composition, what is hardened | cured with the said hardening method is preferable. In the said optical member, it can be set as the high refractive index as mentioned above, and it can use for the following various uses.
Specifically, the cured product 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 a cured product is also one of the preferred embodiments of the present invention. Optical applications such as eyeglass lenses, filters, diffraction gratings, prisms, light guides, light beam condensing lenses and light diffusion lenses, transparent glasses such as watch glasses and cover glasses for display devices, and cover glasses; photo sensors , Photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical device adhesives, etc .; LCD, organic EL, PDP display element substrates, Display device applications such as color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, and antifogging films are suitable.
The shape of the cured product can be appropriately set depending on the application, and is not particularly limited. Examples of the shape of the molded product such as a deformed product, a film, a sheet, and a pellet are also included.
The cured product is preferably an optical member obtained by curing the optical material. Moreover, in the said optical use, the lens formed by hardening | curing the said optical material is also preferable. In particular, it is preferable to combine a lens or the like into a lens unit. Thus, a lens unit using the cured product is also one aspect of the present invention.

Hereinafter, the suitable manufacturing method of the organic inorganic composite resin composition of this invention is demonstrated.
The organic-inorganic composite resin composition of the present invention is not particularly limited as a production method as long as the effects of the present invention can be exhibited. For example, when uniform mixing of inorganic components and organic components is difficult, (1 Preferably, the method includes a step of preparing a mixture containing an inorganic component, an organic 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 a mixture containing the above three components can be prepared, and it is sufficient that the three components are uniformly mixed, and an arbitrary addition (mixing) order and mixing method are used. Can do. Furthermore, the said mixture may contain the other component.
As the solvent, methanol, ethanol, isopropanol, butanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, acetonitrile, chloroform, toluene, xylene, tetrahydrofuran and the like are preferable. More preferred are isopropanol, butanol, methyl ethyl ketone, and toluene.
As said preparation process, it is preferable to adjust at a pressure reduction degree and to prepare at 100 degrees C or less.
In the said preparation process, it is preferable that it is (organic component + inorganic component) / (organic component + inorganic component + solvent) = 10-90 mass% as a ratio of an organic component, an inorganic component, and a solvent. More preferably, it is 15-60 mass%.

The degassing step (2) is preferably performed in the presence of a high-boiling component. By deaeration in the presence of a high-boiling component, the inorganic component can be increased in concentration, and a highly transparent resin composition can be obtained. Moreover, the thickening of a mixture can be suppressed effectively and continuous production becomes possible. The term “in the presence of a high-boiling component” only requires a period during which the high-boiling component coexists in the deaeration process, and the coexistence period is a partial period even during the entire period of the deaeration process. However, the entire period is preferable to prevent thickening.
The method for adding the high boiling point component is not particularly limited as long as the effects of the present invention are exhibited, and may be added all at once, may be added dropwise, or may be divided additions. Among these, batch addition is preferable. Moreover, it does not specifically limit as addition time (or addition start time) of a high boiling 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 material before deaerating the solvent after mixing an inorganic component and an organic component is also one of the preferable forms of this invention.

The addition amount of the high boiling point component is 0.01 to 10% by mass with respect to 100% by mass of the mixture of the organic component, the inorganic component, the solvent before degassing, the high boiling point component and other components as required. It is preferable. More preferably, it is 0.1-5 mass%, More preferably, it is 0.5-3 mass%.
Note that the high boiling point component remains in the composition at the end of the degassing step. The proportion is preferably 0.01 to 10% by mass in 100% by mass of the mixture at the end of the degassing step. More preferably, it is 0.01-5 mass%, More preferably, it is 0.5-3 mass%.
The residual amount of the high-boiling component can be measured by gas chromatography (GC). The measurement conditions are as follows.
(GC measurement conditions)
Column: “DB-17” manufactured by GL Sciences Inc.
Carrier gas: Helium flow rate: 1.44 mL / min

The degassing step is not particularly limited as long as the solvent can be degassed, but it is preferably a condition that suppresses excessive decomposition of organic components, curing reaction, and aggregation of inorganic components. 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 material is alcohol is preferable. Among alcohols having a boiling point of 120 ° C. or higher, 2-ethyl-1-hexanol and dodecanol are more preferable, and 2-ethyl-1-hexanol is more preferable. An alcohol having a boiling point of less than 100 ° C is preferably an alcohol having a boiling point of 100 ° C or higher because the thickening of the mixture may not be sufficiently prevented. A method for producing a resin composition in which the high-boiling component is an alcohol having a boiling point of 100 ° C. or higher is also one preferred form of the present invention. Among alcohols having a boiling point of 120 ° C. or higher, alcohols having a boiling point of 150 ° C. or higher are more preferable, and alcohols having a boiling point of 190 ° C. or higher are more preferable.

The resin composition of the present invention is preferably produced by the method described above. That is, a method for producing a resin composition containing an organic component and an inorganic component, the production method comprising a step of preparing a mixture containing an inorganic component, an organic component and a solvent, and degassing the solvent from the mixture A method for producing a resin composition comprising a deaeration step, wherein the deaeration step is performed in the presence of a high-boiling component is also a preferred embodiment of the present invention.
In the said manufacturing method, although the resin composition manufactured contains an organic component and an inorganic component, the above-mentioned thing can be used suitably as an organic component and an inorganic component. Moreover, all the description regarding a resin composition, such as another component and a hardening method, can be applied suitably to the manufacturing method of the said resin composition.

The resin composition of the present invention is preferably obtained from the above production method. In this case, in the above production method, deaeration is performed in the presence of a high-boiling component, and the high-boiling component remains in the composition. Therefore, the high-boiling component is contained in the resin composition. As a preferable form of the high boiling point component, as described above, an organic component (for example, a cationic polymerizable fluorene compound (preferably fluorene epoxy resin)) which is a high boiling point alcohol and contains a high boiling point material (high boiling point alcohol); It is preferable that it is a resin composition which consists of an inorganic component. Thus, a transparent resin composition containing an alcohol, an organic component, and an inorganic component having a boiling point of 100 ° C. or higher (preferably 120 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 190 ° C. or higher). Is also one of the preferred embodiments of the present invention.

As a blending method of the inorganic component to the resin component for obtaining the resin composition, an external addition method and an internal precipitation method are preferably used. When the curable resin composition of the present invention is used for optical applications, when the inorganic component is produced by the internal precipitation method, the stability of the composition is reduced by the catalyst used, and the structure / composition of the metalloxane is controlled. There may be various effects such as difficulty, alteration before curing due to reaction with an organic component (specifically, epoxy group), residual catalyst, residual water that is difficult to remove, and the like. Therefore, when used as an optical material, the internal addition method is not preferable.
The external addition method of the said inorganic component, specifically, the addition form to the resin composition of an inorganic component, and a dispersion are demonstrated.
The form of the inorganic component is preferably mixed with the resin component in a form dissolved in a powdery or liquid medium. That is, it is preferably in the form of a solution in which the inorganic component is dissolved in the 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 preferably used, but a solvent in which a compound having an epoxy group is easily dissolved is preferable.
As a solution containing the said solvent and an inorganic component, the form of a solvent dispersion is mentioned, for example. The content of the inorganic component 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 organic solvent include alcohols, ketones, aliphatic and aromatic carboxylic esters, ethers, ether esters, aliphatic and aromatic hydrocarbons, halogenated hydrocarbons, and mineral oils. , Vegetable oil, wax oil, silicone oil and the like. Among these, a solvent in which a compound having an epoxy group is easily dissolved is preferable. Specifically, ketones, aliphatic and aromatic carboxylic acid esters, ethers, aliphatic and aromatic hydrocarbons are used. preferable.

As a method for producing an inorganic component used in the present invention, hydrolysis and condensation of a hydrolyzable silane compound essentially comprising the above formula (II) or (III) in a liquid medium containing the resin component described above. Thus, a method of obtaining an inorganic component (internal precipitation method) can also be employed. However, a method of removing the hydrolysis catalyst and mixing the resin component after hydrolyzing and condensing the alkoxide compound with a liquid solvent to obtain an inorganic component is preferable. An organic-inorganic composite is obtained by obtaining a hydrolysis condensate in a liquid medium containing a resin component, and an organic-inorganic hybrid (composite) in which an inorganic component is finely dispersed in a matrix resin. Thus, the resin composition of the present invention can be obtained. The organic-inorganic hybrid thus obtained may exhibit excellent flame retardancy.

The organic-inorganic composite resin composition of the present invention and the cured product obtained by curing the organic-inorganic composite resin composition have the above-described configuration, and have excellent basic performance such as transparency, heat resistance, and moisture resistance, and optical properties such as lenses. The present invention can be suitably applied to various uses such as uses, opto device uses, display device uses, mechanical component materials, electrical / electronic component materials, automobile component materials, civil engineering and building materials, and molding materials.

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%”.

Examples 1-5 and Comparative Examples 1-7
Add the compound shown in Table 1 and 10.0 g of toluene, mix uniformly, perform vacuum distillation at 90 ° C., cool to 50 ° C., and then cationic polymerization initiator (manufactured by Sanshin Chemical Industries, Sun Aid) SI-80L) was added so as to be 1% by mass with respect to the total weight and mixed to be uniform, and then subjected to vacuum degassing treatment.
<Curing speed test>
1 g of the blended resin composition was placed on a hot plate heated to 140 ° C., and the temperature of the resin surface was measured with a radiation thermometer. The curing speed was compared by examining the time when the exothermic temperature was maximized.

JER828EL (Japan Epoxy Resin, bisphenol A epoxy resin)
Ogsol EG (Osaka Gakkensha, fluorene epoxy resin)
JER YX4000 (Japan Epoxy Resin, Bisphenyl epoxy resin)
PPSQ-E (manufactured by Konishi Chemical Industry Co., Ltd., phenyl group-containing silsesquioxane)
S-501 (Arakawa Chemical Industries, epoxy group-containing silsesquioxane)
EP0408 (Hybrid Plastics, alicyclic epoxy group-containing cage silsesquioxane)
EP0409 (manufactured by Hybrid Plastics, epoxy group-containing cage silsesquioxane)

In the examples and comparative examples described above, a fluorene epoxy resin is used as an epoxy resin having a conjugated structure, but the mechanism for delaying the curing rate is (1) cationic polymerization because the aromatic ring is an electron-withdrawing group. This is because the cations are sometimes destabilized on the epoxy ring, and (2) the polymerization is delayed due to the steric hindrance of the bulky aromatic ring, and any epoxy resin having a conjugated structure is the same. In addition, an epoxy group-containing silsesquioxane is used as the organosiloxane compound having a cationically polymerizable group, but the mechanism for suppressing the delay in the curing rate is that an electron-donating alkyl group is connected to the glycidyl ether group. This is because the stability of the cation on the epoxy group is improved, and any epoxy resin having a conjugated structure is the same. Therefore, if the epoxy resin having a conjugated structure and the organosiloxane compound having a cationic polymerizable group are essential, it can be said that the advantageous effects of the present invention are surely exhibited. In the case where at least an organic component having a fluorene skeleton and a cation polymerizable group and a silsesquioxane as a cation polymerizable group are essential, the advantageous effects of the present invention are sufficiently obtained in the above-described examples and comparative examples. This proves the technical significance of the present invention.

Claims (7)

An organic-inorganic composite resin composition containing an organic component and an inorganic component,
The organic component essentially comprises a cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms,
The organic-inorganic composite resin composition, wherein the inorganic component essentially comprises an organosiloxane compound having a cationic polymerizable group. The organosiloxane compound has the following average composition formula:
R ¹ aR ² bYcSiOd
(In the formula, R ¹ represents at least one selected from the group consisting of an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group. R ² represents an organic group containing a cationically polymerizable group. Y represents R. 'Represents at least one selected from the group consisting of an O group, a hydroxyl group, a halogen atom and a hydrogen atom, R' represents an alkyl group, and a, b, c and d are 0 ≦ a <3, 0 <b <. 3. The organic-inorganic composite resin composition according to claim 1, wherein the organic-inorganic composite resin composition is represented by: 3, 0 ≦ c <3, 0 <a + b + c <3, and a + b + c + 2d = 4. The cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms is at least one selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, an anthracene ring, a dibenzothiophene ring, a carbazole skeleton, and a stilbene skeleton. The organic-inorganic composite resin composition according to claim 1, which has two skeletons. The cationically polymerizable compound having a conjugated structure composed of 7 or more carbon atoms has a cationically polymerizable group,
As the cationic polymerizable group, a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, and an R ³ R ⁴ —C═C—O group (wherein R ³ and R ⁴ are the same or different, The organic-inorganic composite resin composition according to claim 1, which has at least one selected from the group consisting of a hydrogen atom or an alkyl group. The organic-inorganic composite resin composition according to any one of claims 1 to 4, wherein the organosiloxane compound has at least one molecular structure selected from the group consisting of a ladder, a network, and a cage. A cured product obtained by curing the organic-inorganic composite resin composition according to claim 1. A lens comprising the cured product according to claim 6.