JP2010070640A - Hydrolyzable silicon compound, method for producing hydrolyzable silicon compound, condensate of hydrolyzable silicon compound, resin additive, inorganic surface modifier, film forming agent, and resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrolyzable silicon compound excellent in dispersibility in an organic medium, affinity for inorganic materials, and properties imparted upon surface treatment of the inorganic materials, preferably used for various applications, and forming members excellent in transparency, refractive index and so on; a condensate of the hydrolyzable silicon compound; and a method for producing the hydrolyzable silicon compound; and to provide, as use thereof, a resin additive, an inorganic surface modifier, a film forming agent, and a resin composition essentially containing the hydrolyzable silicon compound and/or a condensate of the hydrolyzable silicon compound. <P>SOLUTION: The hydrolyzable silicon compound comprises a structure having a row of a conjugated aromatic backbone, containing 7 or more carbon atoms, and 3 or more atoms. A condensate of the hydrolyzable silicon compound and a method for producing the hydrolyzable silicon compound are also disclosed. As its use, a resin additive, an inorganic surface modifier, a film forming agent essentially containing the hydrolyzable silicon compound and/or a condensate of the hydrolyzable silicon compound, as well as a resin composition essentially containing a hydrolyzable silicon compound and/or its condensate and a resin component is disclosed. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a hydrolyzable silicon compound, a method for producing the hydrolyzable silicon compound, a condensate of the hydrolyzable silicon compound, a resin additive, an inorganic surface modifier, a film forming agent, and a resin composition. More specifically, a hydrolyzable silicon compound that can be suitably used for various applications such as an optical member, a production method thereof, a condensate of the hydrolyzable silicon compound, and the hydrolyzable silicon compound and / or hydrolysis The present invention relates to a resin additive, an inorganic surface modifier, a film-forming agent, and a resin composition that essentially contain a condensate of a functional silicon compound.

Hydrolyzable silicon compounds are used in a wide range of fields as silane coupling agents, for example, hydrolyzable groups such as methoxy, ethoxy, and acetoxy groups, and organic functionalities such as amino, methacryloxy, and epoxy groups. Some have groups. A silane coupling agent having such a functional group reacts at the interface between an inorganic material such as glass, metal or mineral and an organic material such as plastic, paint or adhesive, and between different materials. It is a useful compound having a function of forming a bond or a coupling layer. By combining an inorganic material and an organic material, the physical strength, water resistance, and adhesion of the material can be improved.

Thus, hydrolyzable silicon compounds typified by silane coupling agents have the function of being able to bind inorganic materials and organic materials, so in recent years, laminates for printed circuit boards, artificial marble, plastics. It is also used in the production of inorganic / organic hybrid materials such as magnets. In these various technical fields, for example, a silane coupling agent or the like is added to the resin composition or the like. There is a need to avoid adversely affecting the properties of the formed material and product. In this regard, when a conventional silane coupling agent or the like is used, it causes a decrease in refractive index or transparency, and therefore, it can be suitably applied in the field of optical members and the like that require these characteristics. There was room for improvement in order to obtain excellent characteristics.

By the way, one of hydrolyzable silicon compounds includes silicon and a benzene ring, and in this regard, it has an aromatic skeleton and a urethane bond formed by reacting benzyl alcohol or phenol with a silane coupling agent. Compounds have been disclosed (see, for example, Patent Document 1 and Non-Patent Document 1). This compound is used as a compound for forming a light emitting material or a polymer silica for an electronic material. However, the hydrolyzable silicon compounds are industrially used in many cases as a material constituting a resin composition such as a resin additive. In these practical applications, the dispersibility in a resin, etc. The solubility was not examined.
Korean Patent Publication No. 2006-112966 Bing Yan, Dong-Jie Ma, "Journal of SOLID STATE CHEMISTRY", 2006, 179, 7, pp 2059-2066

As described above, silane coupling agents are used to bind inorganic materials to organic materials, but conventional silane coupling agents do not have sufficient characteristics for use in various applications. For example, a metal alkoxide such as silicon alkoxide is applied as a coating liquid as a polymer film or polycarbonate hard coat agent as a coating solution, and a thin film such as silica is formed by moisture curing and heating. In such a case, silicon alkoxide can be used as a metal alkoxide. However, when a film is formed using conventional silicon alkoxide, there are problems such as generation of cracks due to shrinkage, and formation of only a thin film. It was.
In addition, when used as a resin additive or a film forming agent, or when used as a material for a resin composition, the dispersibility of the hydrolyzable silicon compound is not sufficient, in terms of transparency, film uniformity, etc. Had problems.
Furthermore, when used as an inorganic surface modifier (surface treatment agent for inorganic materials), the refractive index and transparency will be reduced, and in particular, when used as an optical member or the like, sufficient properties could not be obtained. .

The present invention has been made in view of the above situation, and has excellent dispersibility in an organic medium, affinity with an inorganic material, imparting properties when an inorganic material is surface-treated, and the like. The hydrolyzable silicon compound, the condensate of the hydrolyzable silicon compound, and the above-described member can be suitably used for the above, and the member formed using the same can be made excellent in transparency, refractive index, and the like. It aims at providing the manufacturing method of a hydrolysable silicon compound. Also, as its use, to provide a resin additive, an inorganic surface modifier, a film forming agent, and a resin composition, which essentially use the hydrolyzable silicon compound and / or a condensate of the hydrolyzable silicon compound. It is intended.

The present inventor has intensively studied a hydrolyzable silicon compound suitable for use in various applications, particularly in the production of optical members and the like. As a result, the conjugated aromatic skeleton having 7 or more carbon atoms and 3 or more conjugated aromatic skeletons. By being a hydrolyzable silicon compound that requires a structure in which atoms are connected, it is possible to improve dispersibility and compatibility in organic media, surface treatment of inorganic materials, etc. It has been found that the effect can be suitably used for various applications. And by being such a compound, it can be suitably used as a film forming agent, a resin additive, a material constituting a resin composition, an inorganic surface modifier, etc. Thus, the present invention has been achieved.

That is, the present invention is a hydrolyzable silicon compound having a conjugated aromatic skeleton having 7 or more carbon atoms and a structure in which 3 or more atoms are linked.
The present invention is described in detail below.

The hydrolyzable silicon compound of the present invention essentially has a structure in which a conjugated aromatic skeleton having 7 or more carbon atoms and 3 or more atoms are linked. Such a hydrolyzable silicon compound can exhibit excellent properties in the following applications and the like. For example, since it has excellent dispersibility in an organic medium, it has excellent transparency when the hydrolyzable silicon compound of the present invention is used as a material constituting a resin composition or a resin additive. Can be. Furthermore, it can have a high refractive index due to the conjugated aromatic skeleton.
In addition, when used as a surface treatment agent (inorganic surface modifier) used for inorganic materials such as inorganic films and inorganic fine particles, it is hydrophobic and water resistant without impairing optical properties such as transparency and refractive index. Can control the refractive index. When inorganic fine particles or the like are dispersed in a resin, the dispersion stability can be increased, and the transparency of the resin can be improved.
It can also be suitably used as a film forming agent. For example, when a hydrolyzable silicon compound of the present invention and an inorganic material are used in combination to form a hybrid film of an inorganic material and an organic material, the structure is more excellent by having a structure in which three or more atoms are linked. Toughness can be imparted, and the occurrence of cracks due to shrinkage can be suppressed. As a result, it is possible to increase the thickness and improve the hard coat characteristics. Furthermore, excellent transparency and a high refractive index can be imparted, and the formed film can be suitably used as an optical member or the like.
Hereinafter, “a conjugated aromatic skeleton having 7 or more carbon atoms” is also referred to as a “conjugated aromatic skeleton”.
The “hydrolyzable silicon compound having a conjugated aromatic skeleton having 7 or more carbon atoms and a structure in which 3 or more atoms are linked” according to the present invention is also referred to as “silicon compound (A)”. A condensate containing a condensation unit derived from “silicon compound (A)” is also referred to as “condensate (A)”. That is, the condensate (A) means a condensate that essentially contains the silicon compound (A) as one of the condensing raw materials, and the condensation unit derived from the silicon compound (A) is essentially required. It means a condensate containing.

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

Examples of the conjugated aromatic skeleton include the following chemical formulas (a-1) to (a-8);

It is preferable that it has either of the structures represented by these. That is, a fluorene skeleton represented by the above chemical formula (a-1) (a conjugated structure composed of 13 carbon atoms) and an anthracene ring represented by the above chemical formula (a-2) (constructed by 14 carbon atoms) Conjugated structure), dibenzothiophene ring represented by the above chemical formula (a-3) (conjugated structure constituted by 12 carbon atoms), carbazole skeleton represented by the above chemical formula (a-4) (12) A conjugated structure composed of 14 carbon atoms), a stilbene skeleton represented by the above chemical formulas (a-5-1) and (a-5-2) (a conjugated structure composed of 14 carbon atoms), and the above chemical formula A biphenyl skeleton represented by (a-6) (a conjugated structure composed of 12 carbon atoms), a naphthalene ring represented by the above chemical formula (a-7) (constituted by 10 carbon atoms) Preferably has at least one structure chosen from the group consisting of conjugated structure) was.

In the case where the silicon compound (A) is used as a material for an optical member or as a modifier for modifying the material for an optical member, the refractive index of the optical member can be increased. The conjugated aromatic skeleton preferably includes at least one structure selected from the group consisting of a fluorene skeleton, an anthracene ring, a dibenzothiophene ring, a carbazole skeleton, a stilbene skeleton, a biphenyl skeleton, and a naphthalene ring. Among these, more preferably, at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is essential.
Any conjugated aromatic skeleton may be used as long as it has the skeleton or ring structure described above. Moreover, as represented by the above formula (a-8), a structure in which bisphenol is bonded to a fluorene skeleton (a conjugated structure composed of 25 carbon atoms) and the like are more preferable.

The conjugated aromatic skeleton preferably includes a biphenyl skeleton from the viewpoint of suppressing coloring of the member produced using the silicon compound (A). For example, the skeleton may contain a fluorene skeleton or a skeleton containing a naphthalene ring, but the use of a conjugated aromatic skeleton that is a biphenyl skeleton can suppress the coloring of the member. In addition, a compound having a fluorene skeleton or a carbazole skeleton is expensive and may increase the material cost, but a compound containing a biphenyl skeleton is relatively inexpensive, and the production cost can be kept low.

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

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

The structure in which the above three or more atoms are linked is not particularly limited as long as it is bonded to a conjugated aromatic skeleton. The structure in which 3 or more atoms are connected is preferably a structure in which 3 to 20 atoms are connected, more preferably a structure in which 3 to 10 atoms are connected, and still more preferably 3 It is a series of ~ 8 atoms. If the number of connected atoms exceeds 20, the refractive index may be lowered. When the number is less than 3, the dispersibility of the resin composition in an organic medium may be lowered.

Examples of the structure in which 3 or more atoms are linked include an alkylene group, an aryl group, and an aralkyl group in which 3 or more carbon atoms are linked. Moreover, as a preferable form, the form whose atom of the terminal of the structure where the 3 or more atom continued was an oxygen atom is mentioned. For example, when a hydrolyzable silicon compound of the present invention is formed by reacting a compound having a conjugated aromatic skeleton with a compound containing at least a part of a structure in which three or more atoms are linked, a conjugate having a hydroxyl group bonded thereto. By reacting a compound containing an aromatic skeleton with a compound containing at least a part of a structure in which three or more atoms are linked, a structure in which three or more atoms are linked to a conjugated aromatic skeleton can be easily obtained. Bound compounds can be formed.
The structure in which three or more atoms are linked may have a substituent. For example, a form in which a polar group such as a hydroxyl group, an amino group, or a carbonyl group is bonded as a side chain of an alkylene group in which 3 or more carbon atoms are linked may be used. Dispersibility in an organic medium is further enhanced by a structure containing a group having active hydrogen such as a hydroxyl group, an amino group, or a carbonyl group. That is, from the viewpoint of improving the dispersibility, the structure in which three or more atoms are connected preferably has a hydrogen group.

The structure in which three or more atoms are connected may include a silicon atom or may not include a silicon atom. For example, as a form in which the structure in which three or more atoms are linked and a conjugated aromatic skeleton are bonded, the following formulas (g-1) to (g-4);

(In formula, R ^<a> and R ^<b> are the same or different, and are an alkyl group, an aryl group, or an aralkyl group. L < ¹ >, L < ² >, L < ³ > represents a bivalent organic group. Are the same or different and each represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, wherein the portion other than R represents a structure in which 3 or more atoms are linked. The structure containing silicon atoms may be a structure in which three or more atoms are linked. Further, in the structures represented by the above formulas (g-1) to (g-4), a portion not containing silicon atoms may be a structure in which three or more atoms are connected, and a structure in which three or more atoms are connected. If it is, it will not be limited.
As a more preferable form, a conjugated aromatic skeleton and a silicon atom are connected by a structure in which three or more atoms are connected. That is, a structure in which three or more atoms not containing a silicon atom are connected is a form in which a conjugated aromatic skeleton and a silicon atom are connected.
A more preferable form of the structure in which three or more atoms are linked will be described later.

The hydrolyzable silicon compound has the following general formula (1):
(R-L-) _a Si (R ¹ _b ) X _c (1)
(In the formula, R is the same or different and represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. L represents the same or different and represents a structure in which 3 or more atoms are linked. R ¹ represents a monovalent group, X is the same or different and is an R ² O group, a hydrogen atom, a halogen atom or a hydroxyl group, R ² is the same or different and is an alkyl group, a cycloalkyl group, Represents an aryl group, an aralkyl group or an acyl group, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, and c = 4-a- b.) (hereinafter also referred to as “silicon compound (1)”).

In the above general formula (1), since one silicon atom can have two or more structures in which a conjugated aromatic skeleton and three or more atoms are linked, dispersibility in an organic medium is further improved. It can be excellent. Thereby, what was formed using the said silicon compound (1) can be made excellent in transparency. In addition, since the number of conjugated aromatic skeletons can be increased, the refractive index can be improved. From the above viewpoint, the silicon compound (1) can be preferably used as a resin additive, a resin composition, and a film forming agent. From the viewpoint of making the dispersibility and the refractive index more excellent, a in the formula (1) is preferably 2 or 3. More preferably, it is 3.
Moreover, when using as an inorganic surface modifier, it is preferable that a is 1. According to this, a large number of silicon compounds can be bonded to the inorganic material for surface modification. For example, when inorganic fine particles treated with the silicon compound (1) are used in a resin composition or the like, it is useful in that the dispersibility of the inorganic fine particles can be improved.

The hydrolyzable silicon compound has the following general formula (2);
^{_{R {-L-Si (R 1}} b) X e} d (2)
(In the formula, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. L is the same or different and represents a structure in which 3 or more atoms are linked. R ¹ represents 1 X is the same or different and each represents an R ² O group, a hydrogen atom, a halogen atom or a hydroxyl group, and R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Or an acyl group, b is an integer of 0 to 2, e is an integer of 1 to 3, e = 3-b, d is an integer of 1 or more. (Hereinafter also referred to as “silicon compound (2)”).

In the above general formula (2), two or more {-L-Si (R _b ) X _e } structures can be bonded to one conjugated aromatic skeleton, so that the hydrolyzable silicon compound The cross-linking performance is improved. According to this, since a condensate having a high molecular weight can be easily formed, for example, when this condensate is used as a film forming agent, the toughness of the film can be further increased and the mechanical strength is excellent. Even if the film thickness is increased, cracks are unlikely to occur and a film that is difficult to break can be obtained. Although d in the general formula (2) is not particularly limited, for example, 1 or 2 is preferable from the viewpoint of preventing gelation during hydrolysis condensation, and 1 is preferable. More preferred.

Below, the suitable form of the hydrolysable silicon compound of this invention and the method for producing it are demonstrated.
As the hydrolyzable silicon compound of the present invention, the following formula (h);

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

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

Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more, and the following formula (k);

(In the formula, R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. J represents an integer of 1 or more.) preferable. As R- (OH) _{j in the} above formulas (h) to (k), the following formula:

It is preferable that it is a compound which has a conjugated aromatic frame | skeleton represented by these, and a hydroxyl group. Reactions represented by the above formulas (h) to (k) are simple, and the hydrolyzable silicon compound of the present invention can be easily produced.
In particular, the structure in which three or more atoms are linked includes a structure derived from a compound having an isocyanate group as represented by the above formula (h), or a glycidyl group as represented by the above formula (i). The structure is preferably derived from a compound having That is, the hydrolyzable silicon compound of the present invention preferably has a structure in which three or more atoms shown below are linked.

The structure in which three or more atoms are linked is represented by the following general formula (3);

Wherein R ³ is the same or different and is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. R ⁴ is the same or different and may have a substituent. Represents an alkylene group of 1 to 10), and / or the following general formula (4);

(In the formula, R ⁵ is the same or different and is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. R ⁶ is the same or different and may have a substituent. Represents an alkylene group of 1 to 10.).
From the viewpoint of imparting toughness and the like, and making the mechanical strength of the member using the hydrolyzable silicon compound excellent, hydrolyzable silicon having a structure containing a urethane bond represented by the above general formula (3) Compounds are preferred. From the viewpoint of improving heat resistance, a hydrolyzable silicon compound having a structure represented by the general formula (4) is preferable.
In the structure in which three or more atoms represented by the general formulas (3) and (4) are linked, it is preferable that the terminal oxygen atom in the formula is bonded to the conjugated aromatic skeleton. is there. That is, in the general formulas (3) and (4), the terminal —O— is preferably bonded to a conjugated aromatic skeleton. Such a structure can be easily formed by reacting a conjugated aromatic skeleton having a hydroxyl group with a compound having at least a part of a structure in which three or more atoms are linked.
Hereinafter, a compound having a structure represented by the general formula (3) is also referred to as a silicon compound (3), and a compound having a structure represented by the general formula (4) is also referred to as a silicon compound (4).

The silicon compounds (3) and (4) can be produced by the following method.
That is, the present invention is a method for producing the hydrolyzable silicon compound,
The production method comprises the following formula (5):
R- (OH) _j (5)
(Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more), and the following formula (6);

(In the formula, R ⁴ is the same or different and represents an optionally substituted alkylene group having 1 to 10 carbon atoms. X is the same or different and represents an R ² O group, a hydrogen atom, a halogen atom. R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and r is an integer of 1 to 3). A compound and / or following formula (7);

(In the formula, R ⁶ is the same or different and represents an optionally substituted alkylene group having 1 to 10 carbon atoms. X is the same or different and represents an R ² O group, a hydrogen atom, a halogen atom. R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, r is an integer of 1 to 3). It is also a method for producing a hydrolyzable silicon compound including a step of reacting with a compound. According to this, the silicon compounds (3) and (4) can be easily generated.

Specific examples of preferred silicon compound (3) obtained from the compound represented by the above formula (6) include the following formula:

The silicon compound obtained by the reaction shown by is preferable. Specific examples of preferable silicon compound (4) obtained by the compound represented by the above formula (7) include the following formula:

The silicon compound obtained by the reaction shown by is preferable. That is, a preferred embodiment is a silicon compound obtained by reacting a compound having a biphenyl skeleton and a hydroxyl group with a silane compound having an isocyanate group or a silane compound having a glycidyl group.

The present invention is also a condensate (condensate (A)) containing a condensation unit derived from the hydrolyzable silicon compound. In the condensate (A), the same effect as that of the silicon compound (A) can be obtained. For example, when used in resin additives, film forming agents, resin compositions, etc., it is highly dispersible in an organic medium and can have a high refractive index due to the conjugated aromatic skeleton. It can be suitably used as a member or the like.
In the case of a condensate, since a crosslinked structure is formed, the effect of imparting toughness will be exhibited more remarkably and is particularly suitable as a film forming agent. As the form of the condensate (A), a form obtained by hydrolytic condensation between the silicon compounds (A), a form prepared by cohydrolytic condensation between the silicon compound (A) and the silicon alkoxide, the silicon compound (A) and others And the like prepared by cohydrolytic condensation with a metal alkoxide. From the viewpoint of the condensation rate, a condensate formed by cohydrolytic condensation with another metal alkoxide is a preferred form. In addition, a combination of another metal alkoxide monomer or oligomer and a condensate (oligomer or polymer) containing a silicon compound (A) having a higher degree of condensation is a preferred form.
In this specification, when the silicon compound (A) and its condensate (A) are simply described as “condensate (A) of the silicon compound (A)”, the silicon compound (A) is a single condensation. It is not limited to a product, but also means a co- (hydrolysis) condensate with other raw materials (silicon alkoxide, other metal alkoxides, etc.). The same applies to the condensates of silicon compounds (1) to (4).

The condensate (A) preferably has a weight average molecular weight of 1,000 to 1,000,000. When it is less than 1000, for example, when used as a film forming agent, there is a possibility that sufficient toughness may not be exhibited. On the other hand, if it exceeds 1,000,000, the leveling property during film formation may be deteriorated. More preferably, it is 1500-500000 as a weight average molecular weight, More preferably, it is 2000-300000.
When the condensate (A) is generated, the condensate is generated using the silicon compound (2) represented by the general formula (2) from the viewpoint that the crosslinking performance is high and the molecular weight can be easily controlled. It is preferable.

The present invention is also a film forming agent that essentially comprises the hydrolyzable silicon compound and / or the condensate of the hydrolyzable silicon compound. According to this, the toughness and heat resistance of the formed film can be made excellent. The film forming agent is a material constituting the film. For example, the film may be formed by using the silicon compound (A) alone or the condensate (A) alone, or the silicon compound (A) and the condensate. You may form a film | membrane together with (A). Since the silicon compound (A) or the condensate (A) has a high affinity at the molecular level with an inorganic material, it is preferably a film forming agent for a hybrid film used in combination with an inorganic material.
Inorganic films using only inorganic materials are prone to cracking due to shrinkage, but by using the silicon compound (A) or condensate (A) as a film forming agent, the toughness is excellent. It becomes a thing and can be set as the film | membrane which is hard to break. Therefore, hard coat characteristics and the like are improved, and a thick film can be formed. Moreover, since the silicon compound (A) and the condensate (A) have a high refractive index, a film having a refractive index close to that when PET (polyethylene terephthalate) or PC (polycarbonate) is used alone is used. it can. Thereby, it is possible to manufacture an optical film product with less glare due to reflection and less bleeding.
In particular, when a silicon compound (A) having a urethane bond such as the silicon compound (3) or a condensate thereof (A) is used, a phase with a metal alkoxide (monomer or hydrolysis condensate) such as silicon alkoxide is used. Since it is more excellent in solubility, it becomes a tough film, and the above effects become more remarkable.

The film forming agent is particularly useful for forming a high refractive index film. In order to form a high refractive index film, conventionally, a titanium alkoxide, zirconium alkoxide monomer, or a condensate of a hydrolyzable compound is applied as a coating solution, and attempts are made to form a thin film of titanium oxide or zirconium oxide by moisture curing and heating. It had been. However, for example, when oxides are formed, cracks occur due to shrinkage, and when a film is formed on a polymer film such as PET, there are problems such as cracking when bent.
In order to improve this, there is also a technique in which a silicon alkoxide containing an organic group such as R ⁷ _n Si (OR ⁸ ) _4-n is used in combination (R ⁷ is a monovalent organic group having no aromatic skeleton). R ⁸ is a hydrolyzable group, n is an integer of 1 to 3). However, since the refractive index of the organic group is low, there is a problem that the refractive index of the film is lowered. Further, even when R ⁹ (phenyl group) is used instead of R ⁷ , the problem that the refractive index of the film to be formed is not sufficiently solved. Furthermore, the effect of suppressing the generation of cracks due to shrinkage and the effect of imparting toughness were not sufficient.
When the hydrolyzable silicon compound (A) of the present invention is used, it has a conjugated aromatic skeleton and a structure in which three or more atoms are linked, thereby suppressing a decrease in refractive index and shrinking. It can be made excellent in the effect of suppressing the generation of cracks due to and the effect of imparting toughness.

As the film forming agent, any hydrolyzable silicon compound (A) of the present invention can be suitably used, and the form thereof is not particularly limited. A more preferable form as a film forming agent is the form of the silicon compounds (3) and (4) and their condensates. These compounds may be used alone or in combination. For example, the silicon compound (3) and the condensate of the silicon compound (4) may be used in combination, or may be used with each condensate.
By using the silicon compound (3) or the condensate thereof together with the silicon compound (4) or the condensate thereof, the mechanical strength (for example, toughness) and heat resistance of the film can be controlled. When the silicon compound (3) / silicon compound (4) is increased (the ratio of the silicon compound (3) is increased), the toughness is excellent and the mechanical strength is excellent. Further, when the silicon compound (3) / silicon compound (4) is reduced (the ratio of the silicon compound (3) is reduced), the heat resistance is excellent.
When the hydrolyzable silicon compound of the present invention (silicon compound (A)) is used in combination with other alkoxides (other silicon alkoxides, alkoxides of other metals, etc.), the silicon compound (A) is used as a film forming agent. Is a monomer, a condensate, another alkoxide is a monomer, a condensate, and the like. In addition, based on the form in which the hydrolyzable silicon compound prepared by cohydrolysis condensation with other alkoxide is used as a film-forming agent, and usually the alkoxide of another metal has a higher hydrolysis condensation rate. It is a preferred form to combine a monomer or oligomer of another metal alkoxide and a silicon compound (oligomer or polymer) having a higher degree of condensation.

The present invention is also a resin additive that essentially comprises a condensate that essentially contains a condensation unit derived from the hydrolyzable silicon compound (A) and / or the hydrolyzable silicon compound (A). Since such a resin additive has high dispersibility in an organic medium, it can be uniformly dispersed in the resin to obtain a high-quality resin composition. Further, even when the amount added is large, aggregation or the like does not occur, and a resin composition having high transparency can be obtained. Furthermore, since it has a conjugated aromatic skeleton, the refractive index can be controlled and the releasability can be improved without impairing the refractive index. Furthermore, since the resin additive of the present invention is a silicon compound, the effect is particularly remarkable when a silicone resin is used. Further, it is possible to improve mechanical properties and heat resistance based on a siloxane skeleton (particularly, a polysiloxane skeleton).
When used as a resin additive, the silicon compound (1) or a condensate thereof is preferable. According to this, since it can be set as the form which has one or more conjugated aromatic skeletons, it can be made more excellent in dispersibility. When using the said resin additive as a dispersing agent, it is preferable to use the said silicon compound (3) or its condensate. By including a structure having a urethane bond, phase separation or precipitation due to aggregation does not occur in an organic medium, and the dispersion stability is excellent.
When used as a resin additive, the resin can also be suitably used when a resin component used in the resin composition of the present invention described later is used. In particular, the resin component containing the aromatic compound (C) is more preferable because dispersibility is further improved.

The present invention further provides a resin composition comprising the hydrolyzable silicon compound (silicon compound (A)) and / or a condensate of the hydrolyzable silicon compound (condensate (A)) and a resin component ( Hereinafter, it is also referred to as “resin composition (A)”. According to this, the resin composition (A) has a high refractive index and transparency, and the molded product formed of the resin composition (A) has optical properties such as transparency and refractive index, and heat resistance. , Excellent toughness and the like.

The content of the silicon compound (A) and / or the condensate (A) in the resin composition (A) is preferably 0.1 to 99% by mass in 100% by mass of the resin composition (A). If it is less than 0.1% by mass, the refractive index, heat resistance and toughness of the resulting resin composition (A) may not be sufficiently increased. If it exceeds 99% by mass, the cured product may become brittle. As content of a silicon compound (A) and / or a condensate (A), it is more preferable that it is 1 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 30 mass% or more. is there.

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

The resin component preferably includes an aromatic compound (C) having a conjugated structure composed of 7 or more carbon atoms. According to this, it is possible to obtain a resin composition having a high refractive index, and it is preferable to have a high refractive index, such as a lens, an LED sealing material, and an optical extraction layer used in an organic EL. It is particularly useful as a member.
Moreover, since the silicon compound (A) has a conjugated aromatic skeleton, the dispersibility of the silicon compound (A) can be further improved, and the transparency of the resin composition (A) can be improved. Since the uniformity of the composition (A) is improved, the quality becomes higher. This is presumably because the conjugated aromatic skeleton possessed by the aromatic compound (C) and the conjugated aromatic skeleton possessed by the silicon compound (A) easily have a π-π stacking structure.

The aromatic compound (C) preferably contains a conjugated aromatic skeleton represented by the above formulas (a-1) to (a-7). When increasing the refractive index, the conjugated aromatic skeleton must have at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, a carbazole skeleton, a stilbene skeleton, a naphthalene ring, an anthracene ring, and a dibenzothiophene ring. It is preferable that More preferably, at least one structure selected from the group consisting of a fluorene skeleton, a biphenyl skeleton, and a naphthalene ring is essential. Any conjugated aromatic compound may be used as long as it has the skeleton or ring structure described above. Moreover, as represented by the above formula (a-8), a structure in which bisphenol is bonded to a fluorene skeleton (a conjugated structure composed of 25 carbon atoms) is more preferable.

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

It is particularly preferable that the (meth) acrylate compound has a fluorene skeleton as an essential component. When a compound having a fluorene skeleton having a conjugated structure is used, a cured product obtained by curing the curable resin composition can have a refractive index of 1.64 or more. In addition, the compound in which the conjugated structure includes a fluorene skeleton not only has a high refractive index but also exhibits various excellent properties such as heat resistance and high transparency in the visible light region. Thereby, it can use suitably for various uses including optical uses, such as a high refractive index lens. When the resin composition (A) contains a (meth) acrylate compound having an essential fluorene skeleton, the content of the (meth) acrylate compound having the fluorene skeleton in the resin composition (A) is essential. It is preferably 20% by mass (% by weight) or more with respect to 100% by mass of the resin component. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more.

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

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

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

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

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

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

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

It is represented by

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

It is particularly preferable that the epoxy compound has a fluorene skeleton as an essential component. When an epoxy compound having an essential fluorene skeleton is used, a cured product obtained by curing the resin composition (A) can have a refractive index of 1.64 or more. In addition, the epoxy compound having the fluorene skeleton as an essential component has not only a high refractive index, but also exhibits various excellent properties such as heat resistance and high transparency in the visible light region. Since it can be uniformly dispersed in A), it can be used in various applications including optical applications such as a high refractive index lens. When the resin composition (A) contains an epoxy compound essential for the fluorene skeleton, the content of the epoxy compound essential for the fluorene skeleton in the resin composition (A) is 100% by mass of the resin component. On the other hand, it is preferable that it is 20 mass% (weight%) or more. More preferably, it is 25 mass% or more, More preferably, it is 30 mass% or more.

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

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

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

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

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

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

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

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

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

As the heat latent cation generator, the following average composition formula (16)
_{^{(R 15 g R 16 h R}} 17 i R 18 k Z) + w1 (AYn 2) -w1 (16)
(In the formula, Z represents at least one element selected from the group consisting of S, Se, Te, P, As, Sb, Bi, O, N and a halogen element. R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ is the same or different and represents an organic group, g, h, i and k are 0 or a positive number, and the sum of g, h, i and k is equal to the valence of Z. Cation (R ¹⁵ _g R ¹⁶ _h R ¹⁷ _i R ¹⁸ _k Z) ^{+ w1} represents an onium salt, A represents a metal element or metalloid which is a central atom of a halide complex, and B, P, As, Al , Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co is at least one selected from the group consisting of Y, Y represents a halogen element, and w is the net charge of the halide complex ion. there .n ² is the halide complex ion Is the number of halogen elements in.) Is preferably represented by the.

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

Specific examples of the anion ^{(AYn 2) -w1} of the general formula (16), tetrafluoroborate ^{(BF 4-),} hexafluorophosphate ^{(PF 6-),} hexafluoroantimonate ^{(SbF 6-),} hexa Examples thereof include fluoroarsenate (AsF ⁶⁻ ) and hexachloroantimonate (SbCl ⁶⁻ ).
Furthermore, an anion represented by the general formula AYn ² (OH) ^— can also be used. Other anions include perchlorate ion (ClO ₄ ⁻ ), trifluoromethyl sulfite ion (CF ₃ SO ₃ ⁻ ), fluorosulfonate ion (FSO ₃ ⁻ ), toluenesulfonate ion, and trinitrobenzenesulfone. An acid ion etc. are mentioned.

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

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

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

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

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

The resin component contained in the resin composition (A) may contain other resin components in addition to the aromatic compound (C) having a conjugated structure composed of 7 or more carbon atoms. . Moreover, organic components other than the resin component may be included. Hereinafter, other resin components and organic components other than the resin components will be described. Such “other resin components” and “organic components other than resin components” are collectively described as other organic components. It is preferable that content of another organic component is 0-50 mass% with respect to 100 mass% of resin compositions (A). More preferably, it is 0-30 mass%.
Hereinafter, other organic components will be described.

Examples of the other resin components include a curable resin, a thermoplastic resin, a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, a compound having at least one epoxy group described later, ) Curable compounds such as compounds having at least one acrylic group are preferred. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer (AS resin), ABS resin made of acrylonitrile / butadiene / styrene, vinyl chloride resin, (meth) acrylic resin, polyamide resin, and acetal resin. , Polycarbonate resin, polyphenylene oxide, polyester, polyimide and the like.

As said other resin component, an epoxy group containing compound or a (meth) acrylic group containing compound from the viewpoint of a cure rate, ie, an epoxy group other than the above-mentioned epoxy compound and (meth) acrylic compound, or (meth) A compound having at least one acrylic group is preferred. By having at least one epoxy group or (meth) acryl group, it has the effect of making the curing speed sufficient, and has heat resistance comparable to that of inorganic glass while having the same workability as conventional thermosetting plastic materials. And exhibit excellent properties such as excellent molding and workability. Hereinafter, a compound having at least one epoxy group that can be suitably used as the resin component of the present invention will be described.

As the compound having at least one epoxy group, the following compounds are suitable. Epibis type glycidyl ether type epoxy resin obtained by condensation reaction of bisphenols such as bisphenol A, bisphenol F and bisphenol S and epihalohydrin, and further adding them with bisphenols such as bisphenol A, bisphenol F and bisphenol S High molecular weight epibis type glycidyl ether type epoxy resin obtained by reaction; phenols such as phenol, cresol, xylenol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and formaldehyde, acetoaldehyde, propion Aldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, bear A novolak-aralkyl-type glycidyl ether-type epoxy resin obtained by further condensing polyhydric phenols obtained by condensation reaction of styrene, paraxylylene glycol dimethyl ether, dichloroparaxylylene, etc. with epihalohydrin; tetramethylbisphenol F; A high molecular weight polymer of an aromatic crystalline epoxy resin obtained by condensation reaction of hydroquinone or the like with epihalohydrin, and further by addition reaction of the above bisphenols, tetramethylbisphenol F, hydroquinone or the like Alicyclic glycols such as bisphenols, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol, etc., hydrogenated aromatic skeletons, ethylene glycol Diethylene glycol, triethylene glycol, tetraethylene glycol, PEG600, propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, PPG, glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, Aliphatic glycidyl ether type epoxy resin (aliphatic glycidyl ether type epoxy compound) obtained by condensation reaction of mono- and polysaccharides such as pentaerythritol and its multimers, glucose, fructose, lactose, maltose and the like and epihalohydrin; Epoxy having an epoxycyclohexane skeleton such as 4-epoxycyclohexane) methyl 3 ', 4'-epoxycyclohexylcarboxylate Si resin (epoxy compound having epoxycyclohexane skeleton); glycidyl ester type epoxy resin obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin; Hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin A tertiary amine-containing glycidyl ether type epoxy resin solid at room temperature obtained by a condensation reaction. Among them, the aliphatic glycidyl ether type epoxy resin and the epoxy resin having an epoxycyclohexane skeleton are more preferably used for the purpose of suppressing the appearance deterioration during light irradiation.

As the compound having at least one epoxy group, epoxy (meth) acrylate can also be suitably used.
The epoxy (meth) acrylate is a (meth) acrylate obtained by reacting one or more epoxides with (meth) acrylic acid. Examples of the epoxide include (methyl) epichlorohydrin and hydrogenated bisphenol A. , Hydrogenated bisphenol S, hydrogenated bisphenol F, epichlorohydrin modified hydrogenated bisphenol type epoxy resin synthesized from ethylene oxide, propylene oxide modified products thereof; 3,4-epoxycyclohexylmethyl, bis- (3,4-epoxycyclohexyl) ) Cycloaliphatic epoxy resins such as adipate; Cycloaliphatic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate; (Methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, and their Epichlorohydrin-modified bisphenol-type epoxy resins synthesized from modified ethylene oxide, propylene oxide, etc .; phenol novolac-type epoxy resins; cresol novolac-type epoxy resins; Epoxy products of phenol resins; aromatic epoxides such as phenyl glycidyl ether; glycols such as (poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol (poly ) Glycidyl ether; (Poly) glycidyl ether of glycols modified with alkylene oxide; Trimethylolpropane, trimethylolethane, glycerin, jig (Poly) glycidyl ethers of aliphatic polyhydric alcohols such as serine, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; (poly) of alkylene oxide modified products of aliphatic polyhydric alcohols Alkylene epoxides such as glycidyl ether; glycidyl esters of carboxylic acids such as adipic acid, sebacic acid, maleic acid and itaconic acid; glycidyl ethers of polyester polyols of polyhydric alcohols and polycarboxylic acids; glycidyl (meth) acrylate, methyl Suitable are glycidyl (meth) acrylate copolymers; glycidyl esters of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, epoxidized polybutadiene, and the like.

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

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

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

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

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

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

In addition to the hydrolyzable silicon compound and the resin component, the resin composition (A) includes the above-described polymerization initiator (curing catalyst), mold release agent, curing agent, curing accelerator, reactive diluent, and unsaturated. Saturated compounds without bonds, pigments, dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, polymerization inhibitors, inorganic and organic fillers, couplings Adhesion improvers such as agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners / sagging agents, colors An anti-separation 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.

The present invention is also a cured product obtained by molding and / or curing the resin composition (A). The cured product obtained by curing the resin composition (A) containing the silicon compound (A) and / or the condensate (A) has improved transparency and further has an aromatic skeleton. , Having a high refractive index. Moreover, it becomes the thing excellent in heat resistance and toughness, and can be used suitably for various uses.
Since it is excellent in toughness, it is excellent in workability and can be finely processed. Furthermore, since it has a high refractive index and transparency, it can be used particularly suitably for optical members and the like. Such a cured product can be suitably used as an optical member, particularly as a lens having a high refractive index and a low Abbe number.
The turbidity (haze) of the cured product is preferably 20% or less. The turbidity of the cured product is more preferably 10% or less, still more preferably 5% or less, and particularly preferably 1% or less. Moreover, as transparency of hardened | cured material, it is preferable that the light transmittance of visible region (region whose wavelength is 360-780 nm) is 75% or more. The light transmittance of the cured product is more preferably 80% or more, still more preferably 85% or more, and particularly preferably 87% or more.
In the above cured product, a wide range of numerical values are required for the refractive index and Abbe number of the cured product depending on the optical design of the applied optical system. The light transmittance of the cured product can be measured by a method according to JIS K7361-1, the turbidity can be measured by JIS K7136, and the refractive index / Abbe number can be measured by a method according to JIS K7142.
Although the PCT moisture absorption rate of the cured product varies depending on the curing conditions, it is preferably 2% or less, preferably 1% or less, more preferably 0.5% or less, by optimizing the curing conditions. More preferably, it is 0.2% or less.

The cured product preferably has a refractive index of 1.50 or more at a wavelength of 589 nm. By making the said hardened | cured material of a high refractive index, it can use suitably for various uses. In particular, it is useful when used for optical applications. More preferably, it is 1.55 or more as a refractive index of hardened | cured material, More preferably, it is 1.60 or more, Most preferably, it is 1.65 or more.

The cured product has high heat resistance, i.e., there is no change in appearance such as cracking even at high temperatures, and the change rate of light transmittance and turbidity in the wavelength range of 360 to 780 nm is low. preferable. Specifically, when the cured product is heated to 260 ° C., there is no change in appearance such as generation of cracks, and the light transmittance / turbidity after heating in the wavelength range of 360 to 780 nm before heating at 260 ° C. The change rate is preferably 20% or less. More preferably, the change rate of the total light transmittance and turbidity is 15% or less, and more preferably 10% or less. Moreover, it is preferable that the change of the light transmittance and turbidity in the wavelength range of 360-780 nm after leaving for 500 hours under 85 degreeC and 85% of humidity is 20% or less. More preferably, it is 15% or less.
In particular, in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged ultraviolet irradiation and high temperature exposure in summer. The cause is considered to be the generation of oxygen radicals due to a synergistic effect with exposure to heat rays. By improving the moisture resistance, moisture absorption into the resin composition (A) is suppressed, and generation of oxygen radicals due to a synergistic effect with ultraviolet irradiation or heat ray exposure is also suppressed. Therefore, yellowing of the resin composition (A) Excellent heat resistance can be exhibited for a long time without causing a decrease in strength.

This invention is also an optical member which makes the hardened | cured material formed by hardening the said resin composition (A) essential. The resin composition (A) exhibits excellent transparency and optical characteristics as described above, and the cured product obtained by curing the resin composition (A) also exhibits similar characteristics. It can be suitably used for various applications such as applications, optical device applications, and display device applications. Specifically, it can be more suitably used as an optical member that requires a high refractive index, such as a lens and an LED sealant.
The optical member of the present invention is preferably configured to include a cured product obtained by curing the resin composition (A) with heat or light. In addition, the other component may be suitably contained in the resin composition (A) according to the use of the optical member. Specifically, UV absorbers, IR cut agents, reactive diluents, pigments, detergents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, anaerobic polymerization initiators, light stability An agent, a polymerization inhibitor, an antifoaming agent and the like are preferable.

As a form of the optical member, the transmittance at a wavelength of 400 nm is preferably 60% or more. When the transmittance is in such a range, an optical material having high transparency and excellent optical characteristics is obtained. The transmittance of the optical material is more preferably 80% or more, and still more preferably 85% or more. If the transmittance at a wavelength of 400 nm is less than 60%, the transmittance is insufficient for lens applications.

Specifically, the optical member is preferably used as an imaging lens for an in-vehicle camera, a PC camera, a digital camera, a mobile phone, a digital video, a surveillance camera, a PDA, a PC built-in camera, or the like. Thus, a lens using the optical member of the present invention is also one of the preferred embodiments of the present invention. Optical applications such as eyeglass lenses, filters, diffraction gratings, prisms, light guides, light beam condensing lenses and light diffusing lenses, transparent glasses such as watch glasses and cover glasses for display devices, and cover glasses; photo sensors , Photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical device adhesives, etc .; LCD, organic EL, PDP display element substrates, It can also be suitably used as an optical member for display device applications such as a color filter substrate, a touch panel substrate, a display protective film, a display backlight, a light guide plate, a high refractive index layer of an antireflection film, and an antifogging film.

Below, the suitable manufacturing method of the resin composition (A) containing the said silicon compound (A) and / or condensate (A) and a resin component is demonstrated.
The resin composition (A) is not particularly limited as long as the effects of the present invention can be exhibited. For example, when it is difficult to uniformly mix the components constituting the resin composition (A). (1) a step of preparing a mixture containing the silicon compound (A) and / or condensate (A) constituting the resin composition (A), a resin component, and a solvent; and (2) from the above mixture. And a degassing step of degassing the solvent.

The preparation step of (1) is not particularly limited as long as the above mixture can be prepared, and the components constituting the resin composition (A) may be uniformly mixed. Any addition (mixing) order, mixing method Can be used. Furthermore, the said mixture may contain the other component.
As a preparation process, it is preferable to adjust the degree of vacuum and perform the preparation at 100 ° C. or lower. In the preparation step, the ratio of the resin component to the solvent is (silicon compound (A) and / or condensate (A) + resin component) / (silicon compound (A) and / or condensate (A) + resin component) + Solvent) = 10 to 90% by mass is preferable. More preferably, it is 15-60 mass%. Specifically, methanol, ethanol, isopropanol, butanol, methyl ethyl ketone, acetone, methyl isobutyl ketone, acetonitrile, chloroform, toluene, xylene and the like are preferable as the solvent. More preferred are isopropanol, butanol, methyl ethyl ketone, and toluene.

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

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

The degassing step is not particularly limited as long as the solvent can be degassed, but the resin component is decomposed or cured, and the silicon compound (A) and / or the condensate (A) is excessively aggregated. It is preferable that the conditions be suppressed. Specifically, the deaeration temperature is preferably 200 ° C. or less. More preferably, it is 100 degrees C or less, More preferably, it is 80 degrees C or less. The deaeration time is preferably 72 hours or less. More preferably, it is 24 hours or less, More preferably, it is 2 hours or less. Although the normal pressure may be sufficient as the pressure in a deaeration process, it is preferable that it is 200 torr or less, and it is more preferable that it is 100 torr or less.
In the degassing step, the end of the degassing step is when the solvent content is 5% by mass or less with respect to 100% by mass of the mixture at that time. The content of the solvent at the end of the degassing step is more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

As the high boiling point component, alcohol having a boiling point of 100 ° C. or higher such as 2-ethyl-1-hexanol, dodecanol, butanol and the like is preferable. More preferred is an alcohol having a boiling point of 120 ° C. or higher (specifically, 2-ethyl-1-hexanol or dodecanol), and still more preferred is an alcohol having a boiling point of 150 ° C. or higher. Thus, the composition whose high boiling point component is alcohol is preferable. Among alcohols having a boiling point of 120 ° C. or higher, 2-ethyl-1-hexanol and dodecanol are more preferable, and 2-ethyl-1-hexanol is more preferable. An alcohol having a boiling point of less than 100 ° C is preferably an alcohol having a boiling point of 100 ° C or higher because the thickening of the mixture may not be sufficiently prevented. A method for producing the resin composition (A) in which the high-boiling component is an alcohol having a boiling point of 100 ° C. or higher is also a preferred embodiment 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 (A) is preferably produced by the method described above. That is, the resin composition (A) includes a step of preparing a mixture containing a silicon compound (A) and / or a condensate (A), a resin component, and a solvent, and degassing for degassing the solvent from the mixture. A method for producing the resin composition (A), which includes a gas step and the deaeration step is performed in the presence of a high-boiling component, is also a preferred embodiment of the present invention.

As a method of blending the silicon compound (A) and / or the condensate (A) into the resin composition (A), an external addition method or an internal precipitation method can be used. When the resin composition (A) is used for optical applications, when the silicon compound (A) and / or the condensate (A) is produced by an internal precipitation method, the resin composition (A) produced by the catalyst used is used. Deterioration of stability, difficulty in controlling the structure and composition of the silicon compound (A) and / or condensate (A), alteration before curing due to reaction with resin components, residual catalyst, residual water that is difficult to remove, etc. May occur. Therefore, the external addition method is preferable when used for an optical member. External addition method of silicon compound (A) and / or condensate (A), specifically, addition form and dispersion of silicon compound (A) and / or condensate (A) to resin composition (A) Explain the body. The form of the silicon compound (A) and / or the condensate (A) 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 silicon compound (A) and / or the condensate (A) is dissolved in a medium.

Examples of the medium include a solvent, a plasticizer, a monomer, and a liquid resin. As the solvent, water, organic solvents, mineral oils, vegetable oils, wax oils, silicone oils and the like can be suitably used, but the cationically polymerizable compound and / or the radically polymerizable compound used as the resin component can be easily dissolved. A solvent is preferred.
As a solution containing the said solvent and a silicon compound (A) and / or a condensate (A), the form of a solvent dispersion is mentioned, for example. Although there is no limitation in particular about content of the silicon compound (A) and / or condensate (A) in a solvent dispersion, Preferably it is 10 to 70 weight% of the whole solvent dispersion, More preferably, it is 20 to 50 weight% The solvent dispersion is easy to handle at this level of content. Although there is no limitation in particular about content of the solvent in a solvent dispersion, Preferably it is 90-30 weight% of the whole solvent dispersion, More preferably, it is 80-50 weight%.

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

As the curing method of the resin composition (A), various methods such as radical polymerization such as thermosetting and photocuring and cationic polymerization such as thermosetting and photocuring can be suitably used. (A) A polymerization initiator and other materials as necessary are mixed into one liquid, and the mixed liquid is applied to a mold according to the shape of the cured product and cured, and then the cured product is removed from the mold. The method of taking out is used suitably. In such a method, it is preferable that the viscosity of the resin composition (A) mixed with a curing catalyst or the like is not significantly increased because of easy handling. In the case of curing by thermosetting, the curing temperature can be appropriately set according to the resin composition (A) to be cured, but is preferably 80 to 200 ° C. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC.

The curing method is preferably a method for producing a cured product by curing the resin composition (A) within 5 minutes. Specifically, if necessary, other materials are mixed into the resin composition (A) to form one liquid, and the mixed liquid is applied to a mold that matches the shape of the cured product within 5 minutes. It is preferable to cure. By performing the curing using a mold in a short time, it is possible to make the method excellent in economic efficiency. Thus, it is a method for producing a cured product by curing the resin composition (A), and the production method is a resin for producing a cured product by curing the resin composition (A) within 5 minutes. The method for curing the composition (A) is also one of the preferred embodiments of the present invention. When the curing time (curing time using a mold) exceeds 5 minutes, the productivity is deteriorated. More preferably, it is within 3 minutes.

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

Hereinafter, the curing method of the resin composition (A) will be further described. Various methods can be employed for curing the resin composition (A) depending on the properties of the resin component used.
When the resin composition (A) contains the silicon compound (A) and / or the condensate (A) and a resin component containing a curable resin such as cationic polymerizable or radical polymerizable as an essential component, polymerization is performed. It can be set as a hardened | cured material by thermosetting using an initiator. As a polymerization initiator, when using the resin component which is a compound etc. which have a cationically polymerizable group, it is preferable to use the thermal latent cation generator mentioned above. In addition, as a hardening method of the said resin composition (A), hardening methods other than the hardening method using polymerization initiators, such as a heat latent cation generator, can also be employ | adopted. 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), a curing accelerator can be used as necessary. For example, triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, tris (dimethoxyphenyl) phosphine, etc. One type or two or more types of organic phosphorus compounds are preferred. As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC.
In addition, although the hardening | curing agent and hardening accelerator which were mentioned above have advantages, such as accelerating | stimulating the hardening reaction of a resin composition (A) and handling, it is well-known conventionally, such as such an acid anhydride and an amino compound. It is known that the curing agent or the like has a low refractive index of an alicyclic acid anhydride usually used for acid anhydride curing, and that an amino compound is easily yellowed. Therefore, when used for a high refractive index optical member, it is better not to use it actively unless it is essential to add a curing agent and a curing accelerator.

The present invention is also an inorganic surface modifier that essentially comprises the hydrolyzable silicon compound (silicon compound (A)) and / or a condensate of the hydrolyzable silicon compound (condensate (A)). According to this, the silicon compound (A) and the condensate (A) are introduced into the surface of the inorganic material. Alternatively, a part of them is introduced. Thereby, surface treatment can be performed without lowering the refractive index and transparency, and hydrophobicity, water resistance, refractive index control, and the like can be performed.
In addition, the inorganic material has a high affinity with a resin or a solution. For example, by treating the surface of the inorganic fine particles with the inorganic surface modifier of the present invention, the dispersibility of the inorganic fine particles is remarkably improved. Can be made. When an optical member is produced using a resin composition in which inorganic fine particles are dispersed in a resin or the like, transparency is improved due to excellent dispersibility, and high refraction due to the conjugated aromatic skeleton. Can have a rate.
In such a case, it becomes an inorganic material which has the said silicon compound (A) (or its part) on the surface.

Examples of the form having “on the surface” include a form attached and / or bonded to the surface. For example, an organic material (for example, hexane, methanol, or the like) that can dissolve an inorganic material having a structure in which a conjugated aromatic skeleton and a structure in which three or more atoms are connected to each other are bonded on the surface. It is preferable that it is a form which does not detach | leave after washing | cleaning. As an example, a compound containing a conjugated aromatic skeleton and a structure in which three or more atoms are connected is attached to the surface of the inorganic material (the atoms constituting the surface of the inorganic material are not chemically bonded to each other). It is preferable that the element constituting the surface of the inorganic material is chemically bonded (covalently bonded) to the structure in which three or more atoms bonded to the conjugated aromatic skeleton are connected. In the chemically bonded form, the hydrolyzable group usually reacts and bonds, so that a part of the silicon compound (A) and / or the condensate (A) is bonded to the surface of the inorganic material. It becomes a form. For example, when the composite particles are formed by surface treatment of inorganic fine particles, and the composite particles are dispersed in a resin composition or the like, the silicon compound (A) and / or the condensate thereof (from the viewpoint of imparting better dispersibility) It is more preferable to use an inorganic surface modifier that essentially requires A). An appropriate form can be selected depending on the use of the inorganic material subjected to the surface treatment. For example, from the viewpoint of redispersibility in an organic medium (when surface-treated particles are dispersed in a solvent after drying) and dispersion stability in an organic medium (no phase separation or precipitation due to aggregation), It is particularly preferable to use the silicon compound (3).

It is also a preferred form that the inorganic surface modifier is subjected to surface treatment in combination with a hydrolyzable silicon compound having a radical polymerizable group (hereinafter also referred to as “silicon compound (B)”). As the hydrolyzable silicon compound (B), the following general formula (17);
R ¹⁹ _a SiX ² _4-a (17)
(In the formula, R ¹⁹ represents an organic group having a radical polymerizable group, a represents an integer of 1 to ^3. X ² represents a hydrolyzable group). . R ¹⁹ is preferably an organic group containing at least one selected from the group consisting of a methacryl group, an acryl group, and a vinyl group. Particularly preferred is a methacrylic group and / or an acrylic group.

The surface treatment performed with the silicon compound (B) may be performed simultaneously with the surface treatment performed with the silicon compound (A), or after the surface treatment performed with the silicon compound (A) is performed, the silicon compound (B) is used. Surface treatment may be performed. The silicon compound (A) is a silicon compound having a radical polymerizable group, a conjugated aromatic skeleton having 7 or more carbon atoms, a structure in which 3 or more atoms are linked, and a hydrolyzable group. It is also possible to perform the surface treatment performed by using the silicon compound (A) and the silicon compound (B) together in a single surface treatment. As a preferable method of the surface treatment, a method of simultaneously performing a surface treatment performed with the silicon compound (A) and a surface treatment performed with the silicon compound (B), or after performing a surface treatment performed with the silicon compound (A). The surface treatment is performed using the hydrolyzable silicon compound (B).

The inorganic surface modifier is used for surface treatment of inorganic materials such as inorganic fine particles and inorganic films, and the surface of the inorganic material has a structure in which a conjugated aromatic skeleton and three or more atoms are linked. It will be a thing.

A preferable metal element M constituting the inorganic material is not particularly limited as long as it is a metal element that can be bonded to the surface of the inorganic material by surface treatment. Further, in the case of using inorganic fine particles or inorganic films subjected to surface treatment as an optical member, at least selected from the group consisting of titanium, zirconium, zinc, lanthanum, yttrium, indium, tin, niobium and cerium. One kind of metal element is preferable. Since metal oxides containing these metal elements can have a high refractive index, they can be suitably used as optical members. For example, it is particularly preferable when used as an optical member such as a lens for a camera or an antireflection film used in equipment requiring a high refractive index.

Examples of inorganic materials such as inorganic films and inorganic fine particles include metal oxides, metal oxynitrides, metal oxycarbides, metal oxysulfides, metal nitrides, metal carbides, metal sulfides, metal tellurides, and metal selenides. And metals. Among these, those having a large number of metal hydroxyl groups on the surface are preferable, specifically, at least selected from the group consisting of metal oxides, metal oxynitrides, metal oxycarbides, metal oxysulfides, and metals. One type is preferred. More preferably, it is preferably at least one selected from the group consisting of metal oxides, metal oxynitrides, metal oxycarbides, and metal oxysulfides. More preferably, it is a metal oxide.

The metal oxide may be a single oxide (an oxide composed of a kind of metal element and oxygen), a solid solution, or a complex oxide. Good. The composite oxide is in the form of an oxide containing two or more metal elements and oxygen. More preferably, it is a metal oxide containing a kind of metal element and oxygen.
The R may be in the form of an organic group in which no substituent is bonded to the conjugated aromatic skeleton, or in the form in which a substituent is bonded to the conjugated aromatic skeleton. As a more preferable bonding form of M—O—Si—LR, an atom bonded to oxygen among atoms constituting a structure in which three or more atoms are linked (L on the side not bonded to R). The terminal atom is a carbon or silicon. In addition, although the form of the bond was described here, as described above, the conjugated aromatic skeleton may be attached to the surface of the inorganic material, and is limited to a chemical bond. is not.

The structure in which three or more atoms are connected is preferably bonded to the surface of the inorganic material through a siloxy bond or a siloxane bond. For example, when there is a siloxy bond between the conjugated aromatic skeleton and the element constituting the surface of the inorganic material, three or more between the siloxy bond consisting of a silicon atom and an oxygen atom and the conjugated aromatic skeleton It is preferable that there is a structure in which the atoms are connected. In this way, by bonding through a siloxy bond or a siloxane bond, an organic component containing a structural structure in which the conjugated aromatic skeleton and three or more atoms are connected to the surface of the inorganic material (hereinafter referred to as organic component (A)). Can be present stably, and by bonding via a siloxy bond or a siloxane bond, the composite particles can have a more stable form, and can improve mechanical strength and heat resistance. . The form that binds via the siloxy bond or a siloxane bond, ^{_{e.g., M-O- (Si-O}} ) n 3 -L-R, M- (O-Si) n 4 forms such as -L-R is Can be mentioned. In the formula, M is a metal element constituting the surface of the inorganic material. L represents a structure in which three or more atoms are connected. R represents an organic group having a conjugated aromatic skeleton. n ³ and n ⁴ are the same or different and are one or more numbers representing the number of repeating structural units. Thus, when there is a siloxy bond and / or a siloxane bond bonded to the metal element on the surface of the inorganic material, separately from the repeating unit of the siloxy bond and / or the siloxane bond bonded to the metal element M on the surface of the inorganic material, A preferred form is a structure in which three or more atoms are connected. According to this, since the space between the metal element on the surface of the inorganic material and the conjugated aromatic skeleton can be made more sufficient, for example, when composite particles described later are dispersed in the resin composition Moreover, the dispersibility can be improved.
The form bonded through the siloxy bond or the siloxane bond may be a form in which a plurality of conjugated aromatic skeletons are connected to one metal element. For example:

(In the formula, M is a metal element constituting the surface of the inorganic material. L represents a structure in which three or more atoms are linked. R represents an organic group having a conjugated aromatic skeleton). As shown, a conjugated aromatic skeleton R and a structure L in which three or more atoms are connected to each other may be bonded to one metal element M, and the form is particularly limited. Not.
The case where the inorganic fine particles are surface treated using the inorganic surface modifier will be described in detail below.

By performing surface treatment of the inorganic fine particles using the inorganic surface modifier, a structure having a conjugated aromatic skeleton and a structure in which three or more atoms are linked is introduced on the surface of the inorganic fine particles. The inorganic fine particles having the structure on the surface are hereinafter referred to as composite particles.
The composite particles are not particularly limited as long as they have inorganic fine particles and the organic component (A) introduced on the surface of the inorganic fine particles, and may contain other components. For example, in addition to the organic component (A), other organic substances and other components such as inorganic materials may be attached or bonded to the surface of the inorganic fine particles.

The composite particles are preferably made of a single inorganic fine particle. That is, it is preferable that a plurality of primary particles are not aggregated due to aggregation or the like. For example, when the composite particles are observed with a transmission electron microscope, an image composed of inorganic fine particles is observed, but the inorganic fine particles are preferably dispersed without agglomeration. The particle diameter of the composite particle is defined by the size of the image composed of the inorganic fine particles, and the number average particle diameter of the particle diameter is preferably 1 μm or less, more preferably 100 nm or less, and still more preferably Is 20 nm or less, and particularly preferably 15 nm or less.
The composite particles preferably have a refractive index of 1.6 or more. For example, when the resin composition includes the composite particles and the resin component, the resin generally has a refractive index of 1.4 to 1.6, and the resin component alone has a refractive index of 1.6 or more. Is difficult to form. Therefore, by setting the refractive index of the composite particles to 1.6 or more, the refractive index of the resin composition containing the composite particles and the cured product thereof has a refractive index that is difficult to obtain with only the resin component. be able to. The refractive index of the composite particles is more preferably 1.8 or more, and further preferably 2.0 or more. Moreover, since the content of the composite particles in the resin composition can be reduced by using composite particles having a high refractive index, the transparency can be further improved.

As said inorganic type microparticles | fine-particles, it is preferable that the average particle diameter of a primary particle is 1 micrometer or less. When the average particle diameter exceeds 1 μm, sufficient transparency may not be obtained. More preferably, it is 100 nm or less, More preferably, it is 20 nm or less, Most preferably, it is 15 nm or less.

The primary particle diameter of the inorganic fine particles is a number average particle diameter obtained from a TEM image (transmission electron microscope observation image); E. T. T. The specific surface area diameter obtained by the method; the crystallite diameter obtained by the powder X-ray diffraction measurement method; Especially, the number average particle diameter obtained from a TEM image is preferable.
The shape of the inorganic fine particles is not limited to a spherical shape, and is, for example, an elliptical sphere, a cubic shape, a rectangular parallelepiped shape, a pyramid shape, a needle shape, a columnar shape, a rod shape, a cylindrical shape, a flake shape, a plate shape (for example, a hexagonal plate shape). For example, a flake shape such as a string shape or the like is preferable.
The inorganic fine particles preferably have a refractive index of 2 or more. When the refractive index of the inorganic fine particles is 2 or more, the refractive index of the resin composition containing the inorganic fine particles and the cured product thereof can be further improved. Further, since the content of the inorganic fine particles in the resin composition can be reduced, the transparency can be further improved.

Examples of a method for bonding the organic group having a structure derived from the silicon compound (A) or the condensate (A) by surface-treating the inorganic fine particles include, for example, the silicon compound (A) or the condensation The method of surface-treating by mixing the solution containing an object (A) and inorganic type microparticles | fine-particles and stirring is mentioned. By subjecting the inorganic fine particles to a surface treatment, the affinity with a resin or the like is increased and the dispersibility is improved.

The composite particles are preferably used together with a resin component as a material constituting the resin composition. That is, a resin composition that essentially includes the composite particles and the resin component is also one aspect of the present invention. As described above, the composite particles have excellent dispersibility in an organic medium, and can be a resin composition having excellent transparency. Moreover, it can be set as the resin composition which has a high refractive index resulting from a conjugated aromatic frame | skeleton and inorganic type microparticles | fine-particles.
As the resin component used together with the composite particles, the resin component described in the resin composition (A) can be preferably used. In particular, the resin component containing an aromatic compound (C) can be used more suitably. According to this, the dispersibility of the composite particles can be further improved, and the transparency of the resin composition containing the composite particles can be improved. Further, the refractive index can be increased.

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

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

Moreover, as a more preferable thing as a compound (3) represented by the said general formula (III), following formula;

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

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

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

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

The method for producing a resin composition comprising the composite particles and the resin component is not particularly limited. As a suitable manufacturing method, the same method as the resin composition (A) described above can be used. That is, a resin comprising composite particles and a resin component by using “composite particles” instead of “silicon compound (A) and / or condensate (A)” in the production method of the resin composition (A). It can be set as the suitable manufacturing method of a composition. The same applies to the curing method and the like.

The resin composition containing the composite particles can be used for various applications in the same manner as the resin composition essentially including the above-described silicon compound (A) and / or condensate (A) and a resin component. Especially, it is suitably used as an optical member. Moreover, when using the resin composition containing the said composite particle for the high refractive index layer of an antireflection film, it is preferable to use dipentaerythritol hexa (meth) acrylate as a resin component.

The hydrolyzable silicon compound of the present invention has a structure in which a conjugated aromatic skeleton and three or more atoms are linked to each other, such as a film forming agent, a resin additive, a resin composition, an inorganic surface modifier, and the like. It can be suitably used for various applications. Highly dispersible or composite particles with high dispersibility can be formed by surface treatment, so that the transparency of the member used can be made excellent, and it is also attributed to the conjugated aromatic skeleton Thus, the refractive index can be high. Because of this, it is particularly preferably used for optical applications such as lens units and optical device applications.

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

Example 1: Method for synthesizing BiPh-U-Si (OEt) _{3 To} 80.16 g of toluene, 13.98 g (82.2 mmol) of paraphenylphenol and 3-isocyanatopropyltriethoxysilane (KBE-9007, (Shin-Etsu Chemical Co., Ltd.) 20.34 g (82.2 mmol) and dibutyltin dilaurate (DBTDL) 0.017 g were added, heated to 90 ° C. and heated for 5 hours. Thereby, BiPh-U-Si (OEt) ₃ represented by the following formula (A-1) was obtained.

Identification of BiPh-U-Si (OEt) _{3 From} the reaction solution obtained by the above reaction, the solvent was distilled off to obtain a colorless transparent viscous liquid. When ¹ H-NMR (400 MHz, CDCl ₃ ) was measured for this compound, the following results were obtained.
δ 7.60-7.50 (m, 6H), 7.27-7.23 (m, 1H), 7.23-7.16 (m, 2H), 5.45-5.34 (br, 1H) ), 3.90-3.76 (q, 6H), 3.35-3.24 (q, 2H), 1.78-1.66 (m, 2H), 1.28-1.18 (t , 9H), 0.74-0.66 (m, 2H)

Comparative Example 1: Method of synthesizing Ph-U-Si (OEt) _{3 To} 64.40 g of toluene, 7.60 g (80.8 mmol) of phenol and 3-isocyanatopropyltriethoxysilane (KBE-9007, manufactured by Shin-Etsu Chemical Co., Ltd.) 20 0.000 g (80.8 mmol) and 0.014 g of dibutyltin dilaurate (DBTDL) were added, and the temperature was raised to 90 ° C. and heated for 5 hours. Thereby, a Ph—U—Si (OEt) ₃ toluene solution was obtained.

Example 2: BiPh-U-Si ( OEt) 3 of BiPh-U-Si obtained in the synthesis method in Example 1 of condensate _{(OEt) 3} in toluene 60 g, diglyme 20g, deionized water 6.98 g, octyl 0.005 g of zinc acid was placed in a flask equipped with a reflux tube, heated to reflux (83 ° C.), and stirred for 3 hours under reflux. Further, a Dean-Stark tube was connected, and the solvent was removed until the reaction solution temperature reached 138 ° C. After reaching 138 ° C, the mixture was stirred for 3 hours. The reaction solution was poured into hexane for reprecipitation to obtain 10.5 g of a white solid. The molecular weight of this white solid was 4000.

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

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

Synthesis Example 2: Synthesis of BiPh-U-Si (OEt) ₃ treated zirconium oxide nanoparticles 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 were dispersed in 87.7 g of toluene to prepare a solution. BiPh-U-Si (OEt) ₃ solution 28.0 g (solid content 8.4 g) and ultrapure water 4 g were added to the solution, and the mixture was refluxed at 90 ° C. for 1 hour with stirring.
The solution after the reflux treatment was allowed to cool, and then n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the agglomerated particles were separated from the white turbid solution with a filter paper and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-U-Si (OEt) ₃ .
When the crystal structure of the treated zirconium oxide nanoparticles was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction line, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton was confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were coated with two coating agents of neodecanoic acid and BiPh-U-Si (OEt) ₃ . It was confirmed. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 20% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the following conditions, the results of FT-IR measurement before and after washing were the same and the weight loss in TG-DTA measurement was the same. It was confirmed that the zirconium oxide nanoparticles were composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles. Washing was performed by adding 1 part of zirconium oxide nanoparticles (composite particles) to 100 parts by mass of hexane and stirring at a temperature of 50 ° C. and a stirring speed of 100 rpm for 12 hours.
In addition, the content of the conjugated aromatic skeleton and the content of a structure in which three or more atoms are connected when the obtained zirconium nanoparticles (composite particles) are 100% by mass were determined by the following method.
(1) First, an organic component derived from BiPh-U-Si (OEt) ₃ represented by the following formula (A-1) on zirconium nanoparticles obtained by ¹ H-NMR, and the following formula (B- The ratio (molar ratio) of the amount of the component resulting from neodecanoic acid represented by 1) is determined.

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

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

Synthesis Example 3: Synthesis of BiPh-U-Si (OEt) ₃ and KBM-503 treated zirconium oxide nanoparticles)
A solution was prepared by dispersing 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 in 87.7 g of toluene, and 28.0 g of a BiPh-U-Si (OEt) ₃ solution was added to the solution (solid content: 8. 4 g), 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.) and 5 g of ultrapure water were added, and the mixture was refluxed with stirring at 90 ° C. for 1 hour.
The solution after the reflux treatment was allowed to cool, and then n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the aggregated particles were separated from the cloudy solution with a filter paper and vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with BiPh-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the treated zirconium oxide nanoparticles was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction line, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid, BiPh-U-Si (OEt) ₃ , And it was confirmed that it was coat | covered with three types of coating agents of 3-methacryloxypropyl trimethoxysilane. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 20% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2.

Synthesis Example 4 Synthesis of Ph-U-Si (OEt) ₃ and KBM-503 Treated Zirconium Oxide Nanoparticles 12.3 g of the zirconium oxide nanoparticles obtained in Synthesis Example 1 were dispersed in 87.7 g of toluene to obtain a solution. Prepared, 23.1 g of Ph-U-Si (OEt) ₃ solution (solid content: 6.9 g), 0.95 g of 3-methacryloxypropyltrimethoxysilane (KBM-503, manufactured by Shin-Etsu Chemical Co., Ltd.), And 5 g of ultrapure water was added, and the mixture was refluxed with stirring at 90 ° C. for 1 hour.
The solution after the reflux treatment was allowed to cool, and then n-hexane was added to agglomerate the dispersed particles to make the solution cloudy. Next, the agglomerated particles were separated from the cloudy solution with a filter paper, and then vacuum-dried at room temperature to prepare zirconium oxide nanoparticles treated with Ph-U-Si (OEt) ₃ and 3-methacryloxypropyltrimethoxysilane. .
When the crystal structure of the treated zirconium oxide nanoparticles was confirmed with an X-ray diffractometer, diffraction lines belonging to tetragonal and monoclinic crystal structures were detected. From the intensity of the diffraction line, it was confirmed that the crystal structure was mainly composed of tetragonal crystals and slightly monoclinic crystals. Moreover, when the particle diameter of this particle | grain was measured by FE-SEM, the average particle diameter was 5 nm. Furthermore, was analyzed by infrared absorption spectrum (FT-IR), absorption and COOH absorption derived from C-H of the alkyl chain and an aromatic skeleton, can be further confirmed absorption from Si-O-C, further ¹ Since the peak derived from the aromatic skeleton and the peak derived from the double bond of the methacryl group were confirmed by H-NMR, the zirconium oxide nanoparticles after the treatment were neodecanoic acid, BiPh-U-Si (OEt) ₃ , And it was confirmed that it was coat | covered with three types of coating agents of 3-methacryloxypropyl trimethoxysilane. When the mass reduction rate of the particles when the temperature was raised to 800 ° C. in an air atmosphere by TG-DTA (thermogravimetric-differential thermal analysis), the reduction rate was 19% by mass. Moreover, although the obtained zirconium oxide nanoparticles were washed under the conditions shown in Synthesis Example 2, the FT-IR measurement results and the weight loss in TG-DTA measurement were the same before and after washing. The obtained zirconium oxide nanoparticles were confirmed to be composite particles having an aromatic skeleton and a structure bonded to the aromatic skeleton on the surface of the inorganic fine particles.
Further, for the obtained zirconium nanoparticles, the content of the aromatic skeleton and the content of the bond structure to the aromatic skeleton were determined in the same manner as in Synthesis Example 2. Table 3 below shows the results of measurement of the mass reduction rate obtained in the TG-DTA measurement and the content of the aromatic skeleton and the bond structure to the aromatic skeleton.
Measured zirconia nanoparticle treatment agent obtained in Synthesis Examples 2, 3 and 4 above, mass reduction rate obtained in TG-DTA measurement and content of conjugated aromatic skeleton and 3 or more atoms connected structure The results are shown in Table 1 below.

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

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

Resin Composition for Example 5 2.5 g of the zirconium oxide particles obtained in Synthesis Example 3 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), 0.05 g of FM-1 as a dispersant, After dissolving 0.1 g of t-butyl peroxybenzoate (manufactured by NOF Corporation) in 20.0 g of toluene, toluene was devolatilized by an evaporator to obtain a resin composition for Example 5.

Resin Composition for Example 6 2.5 g of the zirconium oxide particles obtained in Synthesis Example 3 and 2.5 g of Ogsol EA-200 (manufactured by Osaka Gas Chemical Company), 0.071 g of FM-1-Ph solution as a dispersant (solid) 0.05 g), 0.1 g of perbutyl Z (manufactured by NOF Corporation, t-butyl peroxybenzoate) was dissolved in 20.0 g of toluene, and then the toluene was devolatilized by an evaporator. Resin composition for Example 6 I got a thing.

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

Examples 3 to 6 and Comparative Example 2
The resin compositions for Examples 3 to 6 and Comparative Example 2 were applied on a glass plate (150 mm × 70 mm × 2 mm) using a 5 mil applicator so that the film thickness was 125 μm. Then, the cured coating film was obtained by heating for 30 minutes at 150 degreeC by nitrogen atmosphere. And the transmittance | permeability of the cured coating film in wavelength 400nm was measured.

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

<Measurement method of refractive index and Abbe number>
The obtained resin composition was poured into a mold adjusted to a thickness of 500 μm, then covered with a glass plate from above, and heated at 150 ° C. for 30 minutes to obtain a cured product. The refractive index of 589 nm at 20 ° C. of the cured product obtained using a refractometer (Atago Co., Ltd., DR-M2) was measured. The measurement results are shown in Table 2 below.

The resin composition containing composite particles surface-treated with the silicon compound (A) of the present invention was colorless and transparent, and a cured product having a refractive index of 1.65 or more was obtained. Moreover, the transmittance | permeability is 70% or more, and in Examples 4-6, the transmittance | permeability of 90% or more was shown. In Comparative Example 2, surface treatment is performed using an inorganic surface modifier having a conjugated structure of 6 carbon atoms (including a benzene ring), but the dispersibility of the composite particles is not sufficient, and the transmittance Was as low as 61%.

Claims (10)

A hydrolyzable silicon compound comprising a conjugated aromatic skeleton having 7 or more carbon atoms and a structure in which 3 or more atoms are linked. The hydrolyzable silicon compound has the following general formula (1):
(R-L-) _a Si (R ¹ _b ) X _c (1)
(In the formula, Rs are the same or different and each represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms. L is the same or different and represents a structure in which 3 or more atoms are linked. R ¹ represents a monovalent group, X is the same or different and is an R ² O group, a hydrogen atom, a halogen atom or a hydroxyl group, R ² is the same or different and is an alkyl group, a cycloalkyl group, Represents an aryl group, an aralkyl group or an acyl group, a is an integer of 1 to 3, b is an integer of 0 to 2, c is an integer of 1 to 3, and c = 4-a- The hydrolyzable silicon compound according to claim 1, which is represented by b). The hydrolyzable silicon compound has the following general formula (2):
^{_{R {-L-Si (R 1}} b) X e} d (2)
(Wherein, R, .L represents a group having a C 7 or more conjugated aromatic skeleton are the same or different, .R ¹ representing the continuous structure is 3 or more atoms, 1 X is the same or different and each represents an R ² O group, a hydrogen atom, a halogen atom or a hydroxyl group, and R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. Or an acyl group, b is an integer of 0 to 2, e is an integer of 1 to 3, e = 3-b, d is an integer of 2 or more. The hydrolyzable silicon compound according to claim 1. The structure in which the three or more atoms are linked has the following general formula (3):

Wherein R ³ is the same or different and is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. R ⁴ is the same or different and may have a substituent. Represents an alkylene group of 1 to 10), and / or the following general formula (4);

(In the formula, R ⁵ is the same or different and is a hydrogen atom, an alkyl group, an aryl group, an aralkyl group or an acyl group. R ⁶ is the same or different and may have a substituent. The hydrolyzable silicon compound according to claim 1, which is represented by 1 to 10 alkylene groups. The condensate of the hydrolyzable silicon compound according to claim 1. A resin additive comprising the hydrolyzable silicon compound according to any one of claims 1 to 4 and / or the condensate of the hydrolyzable silicon compound according to claim 5. An inorganic surface modifier comprising the hydrolyzable silicon compound according to any one of claims 1 to 4 and / or the condensate of the hydrolyzable silicon compound according to claim 5. A film-forming agent comprising the hydrolyzable silicon compound according to any one of claims 1 to 4 and / or the condensate of the hydrolyzable silicon compound according to claim 5. A resin composition comprising the hydrolyzable silicon compound according to any one of claims 1 to 4 and / or the condensate of the hydrolyzable silicon compound according to claim 5 and a resin component. A method for producing the hydrolyzable silicon compound according to any one of claims 1 to 4,
The production method comprises the following formula (5):
R- (OH) _j (5)
(Wherein R represents a group having a conjugated aromatic skeleton having 7 or more carbon atoms, j represents an integer of 1 or more), and the following formula (6);

(In the formula, R ⁴ is the same or different and represents an optionally substituted alkylene group having 1 to 10 carbon atoms. X is the same or different and represents an R ² O group, a hydrogen atom, a halogen atom. R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and r is an integer of 1 to 3). A compound and / or following formula (7);

(Wherein, R ⁶ are the same or different, .X that represents an alkylene group having 1 to 10 carbon atoms which may have a substituent are the same or different, R 2 ^O group, a hydrogen atom, a halogen R ² is the same or different and represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an acyl group, and r is an integer of 1 to 3). A method for producing a hydrolyzable silicon compound, comprising a step of reacting a compound.