JP2014152194A - Curable resin composition, cured product of the same, and optical material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition which can give a cured product (a molding) having a high refractive index, having high heat resistance, high adhesiveness, high chemical resistance, high thermal shock resistance and the like with good productivity, and capable of stably exhibiting high transparency and uniformity even after being exposed to a high-temperature environment, and is excellent in storage stability, and to provide a cured product and an optical material using the curable resin composition.SOLUTION: A curable resin composition contains a compound having a cation-curable cyclic ether group, a compound having a cation-curable double bond, and a boron compound. The boron compound is a compound comprising a specific Lewis acid and Lewis base.

Description

The present invention relates to a curable resin composition, a cured product thereof, and an optical material. More specifically, it contains cationically curable compounds, and can be applied to various applications such as optical materials, molding materials, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, paints and adhesive materials, etc. The present invention relates to an expected curable resin composition, and a cured product and an optical material thereof.

Among the curable resin compositions, those containing a cation curable compound can be cured as a cation curable resin composition by a cation curing reaction with a cation curing catalyst that generates cationic species by heat or light. . The cationic curing (polymerization) reaction has advantages such as no inhibition of curing by oxygen and small shrinkage at the time of curing as compared with radical polymerization reaction by vinyl group or the like, and application to various fields is expected. For example, various applications such as optical materials, molding materials, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, paints, adhesive materials, etc. are being studied. Development of a curable resin composition having excellent properties is desired.

As a conventional cationic curable resin composition, for example, an epoxy compound containing an epoxy group and having an aromatic skeleton, an aromatic monomer having a vinyl group, and a cationic curing agent are used. A cationically polymerizable resin composition for molded articles that is liquid at 25 ° C. is disclosed (see Patent Document 1). Moreover, the cationic curable resin composition containing the cationic curable compound and the cation curing catalyst which consists of a specific structure is disclosed (refer patent document 2).

JP 2008-163068 A International Publication No. 2012/060449 Pamphlet

As described above, a curable resin composition containing a cationically curable compound has been studied for use in various applications. However, since it can also exhibit transparency, it can be used in optical applications such as lenses. It is particularly useful as a material. For example, in digital camera modules, since they are mounted on mobile phones and the like, downsizing and cost reduction are also demanded, and resin lenses are being used instead of conventional inorganic glass as imaging lenses. . In the mounting process of such a member such as a lens, the solder reflow method is mainly used to reduce the cost. Therefore, when a curable resin composition is used to form an optical member such as a lens, the cured product (molded product) is exposed to a high-temperature environment such as a reflow process in addition to heat resistance that can withstand the reflow process. After that, it is required to stably exhibit high transparency.

With respect to these points, Patent Document 1 discloses a resin composition containing an epoxy compound containing an epoxy group and having an aromatic skeleton, an aromatic monomer having a vinyl group, and a cationic curing agent. and that although, cationic curing agents which are specifically disclosed, San'edo SI-45 and SI-100L (manufactured by Sanshin chemical Co., Ltd.), i.e. an anionic species SbF ₆ ^- only antimony sulfonium salt to. When such an antimony sulfonium salt is used, the molded product is colored by heat (heat at the time of curing, use environment), and as a result, there is a problem that transmittance at 400 nm which is short wavelength visible light is lowered. In addition, since the heat resistance of the molded body is not sufficient, there is room for improvement in these respects. Further, when antimony sulfonium salts are used, the curability is not sufficient and there is a problem in terms of curing speed. Even if it sees the hardening procedure described in the Example of patent document 1, it turns out that hardening (molding) requires a long time. If the curing takes a long time, the transparency of the molded product may decrease, so there is room for improvement to increase the curing speed and improve the transparency and productivity.

Patent Document 2 discloses a cation curable resin composition containing a cation curable compound and a cation curing catalyst having a specific structure. As the cation curable compound, an epoxy compound, an oxetane compound, or the like is preferable. It has been. This cationic curable resin composition is extremely useful for various applications such as optical members because it can obtain a molded article excellent in heat resistance, heat and moisture resistance, low water absorption, UV irradiation resistance and the like. However, in order to make it even more advantageous for various uses, the viscosity of the resin composition is reduced, and the storage stability of the cured product (molded product) and the handling property during production are further improved. There was room for improvement in order to achieve a higher level of heat resistance, temperature shock resistance, adhesion, etc. by further increasing the glass transition temperature.

The present invention has been made in view of the above situation, and has a high refractive index and high heat resistance, adhesiveness, chemical resistance, temperature shock resistance, etc., after being exposed to a high temperature environment. An object of the present invention is to provide a cured product (molded product) that can stably exhibit high transparency and uniformity with good productivity and to provide a curable resin composition excellent in storage stability. Another object of the present invention is to provide a cured product and an optical material using such a curable resin composition.

As a result of various studies on the cationically curable resin composition, the present inventors have found a resin composition containing a compound having a cationically curable cyclic ether group (for example, an epoxy ring) and a boron compound having a specific structure; Then, paying attention to the cured product (molded product) having excellent heat resistance, heat and humidity resistance, low water absorption, UV irradiation resistance, etc., as a component of such a resin composition, When a compound having a cation curable double bond is used in combination, the resin composition has a significantly reduced viscosity, and is excellent in storage stability (also referred to as storage stability) and handling at the time of manufacture (also referred to as handling). It has been found that the curing rate of the resin composition is improved. Since the reaction mechanism between the compound having a double bond and the compound having a cyclic ether group is greatly different, the coexisting curing reaction is not usually performed. However, the inventors of the present invention, contrary to such common technical common sense, coexisted in the presence of a specific boron compound, the reaction mechanism is unknown, but it is cured jointly and uniformly. It has been found that the reaction proceeds, and that a cured product can be obtained with high productivity while maintaining transparency and no turbidity, that is, transparency and uniformity. This cured product also has a high level of heat resistance that can withstand film formation and reflow processes at high temperatures, and has a high refractive index, as well as adhesion, chemical resistance, and temperature shock resistance (thermal shock resistance). It is also excellent). Further, it has been found that such a cured product is particularly useful for optical members (optical materials) such as lenses and sheets, and the inventors have arrived at the present invention by conceiving that the above problems can be solved brilliantly. is there.

That is, the present invention is a curable resin composition containing a compound having a cationic curable cyclic ether group, a compound having a cationic curable double bond, and a boron compound, General formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. A is an integer greater than or equal to 1, b is an integer greater than or equal to 0, and satisfy | fills a + b = 3.) The curable resin composition which is a compound which consists of the Lewis acid represented by this, and a Lewis base. It is a thing.

The present invention is also a cured product obtained by curing the curable resin composition.
The present invention is also an optical material using the curable resin composition.
The present invention is described in detail below. In addition, the form which combined each preferable form of this invention described below 2 or 3 or more is also a preferable form of this invention.

[Curable resin composition]
The curable resin composition of the present invention comprises a compound having a cationic curable cyclic ether group (also referred to as a cyclic ether compound), a compound having a cationic curable double bond (also referred to as a double bond compound), boron These compounds can be used alone or in combination of two or more. Further, if necessary, one or more other components may be further contained.

In the curable resin composition, the content of the cyclic ether compound is preferably 10% by mass or more when the total amount of the cyclic ether compound and the double bond compound is 100% by mass. Thereby, while the sclerosis | hardenability of curable resin composition increases more, the shrinkage rate at the time of hardening can be reduced more. More preferably, it is 20 mass% or more, More preferably, it is 50 mass% or more, Most preferably, it is 70 mass% or more. Moreover, it is suitable to set it as 95 mass% or less, Thereby, the viscosity reduction of curable resin composition can be implement | achieved more, and a refractive index, chemical resistance, and low water absorption are improved more. It becomes possible. More preferably, it is 90 mass% or less, More preferably, it is 80 mass% or less.

The content of the double bond compound is preferably 5% by mass or more when the total amount of the cyclic ether compound and the double bond compound is 100% by mass. As a result, the viscosity of the curable resin composition can be further reduced, and the refractive index, chemical resistance, and low water absorption can be further improved. More preferably, it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, it is suitable to set it as 90 mass% or less, Thereby, while the sclerosis | hardenability of curable resin composition increases more, the shrinkage rate at the time of hardening can be reduced more. More preferably, it is 80 mass% or less, More preferably, it is 50 mass% or less, Most preferably, it is 30 mass% or less.

The content of the boron compound is the amount of the active ingredient that does not contain a solvent or the like (the total amount of Lewis acid and Lewis base represented by the general formula (1)). It is preferable to set it as 0.01 mass part or more with respect to 100 mass parts of total amounts. Thereby, the curing rate can be further increased. More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. Moreover, it is preferable to set it as 20 mass parts or less, and this can suppress more a possibility of coloring at the time of hardening, the time of the heating of the molded object, etc. Further, for example, when reflow mounting is performed after a molded body is obtained, heat resistance of 200 ° C. or higher is necessary, which is more preferable from the viewpoint of colorlessness and transparency in that case. More preferably, it is 10 mass parts or less, More preferably, it is 5 mass parts or less.

The curable resin composition preferably has a viscosity of 100 Pa · s or less. With such a low viscosity, it is excellent in processing characteristics, for example, it is excellent for use in forming a molded body (particularly for forming a molded body of a mold), and is excellent in storage stability and handleability, and is further cured. The transparency and uniformity of the film can be further improved. In addition, it is preferable that the curable resin composition has a reduced viscosity from the viewpoint of handling such as foam removal during production, but since the viscosity of the curable resin composition of the present invention is in the above range, such handling is possible. It is also excellent in properties. More preferably, it is 50 Pa · s or less, more preferably 10 Pa · s or less, particularly preferably 5 Pa · s or less, and most preferably 3 Pa · s or less. Moreover, it is preferable that it is 0.01 Pa * s or more from viewpoints, such as a process characteristic. More preferably, it is 0.1 Pa · s or more, and further preferably 0.5 Pa · s or more.
The measurement of the viscosity can be performed on the resin composition using an E type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22 type viscometer cone plate type) under the condition of 40 ° C.

<Compound having a cationic curable cyclic ether group (cyclic ether compound)>
The cyclic ether compound is a compound having in the molecule one or more cyclic ether groups that can be cured (polymerized) by a cationic curing reaction.
The cyclic ether group means an ether group having a structure in which carbon of a cyclic hydrocarbon is substituted with oxygen. Examples include an epoxy group (also referred to as an epoxy ring), an oxetane group (also referred to as an oxetane ring), a dioxolane group, a trioxane group, and the like. Among these, an epoxy group and an oxetane group are preferable. That is, the cyclic ether compound preferably includes a compound containing an epoxy group (also referred to as an epoxy compound) and / or a compound containing an oxetane group (also referred to as an oxetane compound). Among these, it is more preferable to include at least an epoxy compound.
In addition, in this specification, an epoxy group includes an oxirane ring that is a three-membered ether. In addition to a narrowly-defined epoxy group, a group in which an oxirane ring is bonded to carbon, such as a glycidyl group, , A group containing an ether or ester bond such as a glycidyl ether group and a glycidyl ester group, an epoxycyclohexane ring, and the like.
In the present specification, compounds having one or more cyclic ether groups in the molecule and one or more unsaturated double bond groups such as vinyl groups are classified as “cyclic ether compounds”.

Below, the epoxy compound and oxetane compound which are particularly suitable as the cyclic ether compound will be specifically described.
Here, as the epoxy compound, an alicyclic epoxy compound (also referred to as an alicyclic epoxy resin), a hydrogenated epoxy compound (also referred to as an alicyclic epoxy resin), an aromatic epoxy compound (also referred to as an alicyclic epoxy resin). ), An aliphatic epoxy compound (also referred to as an alicyclic epoxy resin) is preferable, and among them, an alicyclic epoxy compound, a hydrogenated epoxy compound, and an aromatic epoxy compound are more preferable. Thus, the form in which the said cyclic ether compound contains at least 1 sort (s) selected from the group which consists of an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound, and an oxetane compound is one of the suitable forms of this invention. One. More preferably, the cyclic ether compound contains at least one selected from the group consisting of an alicyclic epoxy compound, a hydrogenated epoxy compound, and an aromatic epoxy compound.
In particular, when containing at least an alicyclic epoxy compound and / or a hydrogenated epoxy compound, the epoxy compound itself is hardly colored at the time of curing, and is not easily colored or deteriorated by light. A cured product that is more excellent can be obtained. Moreover, since the glass transition temperature of hardened | cured material is improved more when an aromatic epoxy compound is included, the hardened | cured material more excellent by heat resistance, temperature impact resistance, etc. is realizable.

-Alicyclic epoxy compounds-
Regarding the epoxy compound, the alicyclic epoxy compound is a compound having an alicyclic epoxy group. Examples of the alicyclic epoxy group include an epoxycyclohexane group (epoxycyclohexane skeleton), an epoxy group added to a cyclic aliphatic hydrocarbon directly or via a hydrocarbon (particularly an oxirane ring), and the like. In particular, the alicyclic epoxy compound is preferably a compound having an epoxycyclohexane group. Moreover, the polyfunctional alicyclic epoxy compound which has two or more alicyclic epoxy groups in a molecule | numerator is suitable at the point which can raise a hardening rate more. A compound having one alicyclic epoxy group in the molecule and an unsaturated double bond group such as a vinyl group is also preferably used as the alicyclic epoxy compound.

Examples of the epoxy compound having an epoxycyclohexane group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, epsilon-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4 ′. -Epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate and the like are preferred. Examples of the alicyclic epoxy compound other than the epoxy compound having the epoxycyclohexane group include 1,2-epoxy-4- (2-oxiranyl) cyclohexane of 2,2-bis (hydroxymethyl) -1-butanol. Examples include adducts and alicyclic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate.

-Hydrogenated epoxy compound-
The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon skeleton, and a polyfunctional glycidyl ether compound is preferred. Such a hydrogenated epoxy compound is preferably a complete or partial hydrogenated product of an aromatic epoxy compound, more preferably a hydrogenated product of an aromatic glycidyl ether compound, and still more preferably an aromatic polyfunctional compound. It is a hydrogenated product of a glycidyl ether compound. Specifically, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol S type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, and the like are preferable. More preferred are hydrogenated bisphenol A type epoxy compounds and hydrogenated bisphenol F type epoxy compounds.

-Aromatic epoxy compounds-
The aromatic epoxy compound is a compound having an aromatic ring and an epoxy group in the molecule.
Preferred examples of the aromatic epoxy compound include epoxy compounds having an aromatic ring conjugated system such as a bisphenol skeleton, a fluorene skeleton, a biphenyl skeleton, a naphthalene ring, and an anthracene ring. Among these, in order to realize a higher refractive index, a compound having a bisphenol skeleton and / or a fluorene skeleton is preferable. More preferably, it is a compound having a fluorene skeleton, whereby the refractive index can be remarkably increased and the releasability can be further enhanced. Moreover, the compound whose epoxy group is a glycidyl group in an aromatic epoxy compound is preferable, but the compound (aromatic glycidyl ether compound) which is a glycidyl ether group is more preferable. Also, it is preferable to use a brominated compound of an aromatic epoxy compound because a higher refractive index can be achieved. However, since the Abbe number slightly increases, it is preferably used as appropriate depending on the application.

Preferred examples of the aromatic epoxy compound include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, fluorene type epoxy compounds, and aromatic epoxy compounds having a bromo substituent. Of these, bisphenol A type epoxy compounds and fluorene type epoxy compounds are preferred.

Examples of the aromatic glycidyl ether compound include an epibis type glycidyl ether type epoxy resin, a high molecular weight epibis type glycidyl ether type epoxy resin, a novolak / aralkyl type glycidyl ether type epoxy resin, and the like.
Preferred examples of the epibis type glycidyl ether type epoxy resin include those obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol with epihalohydrin.
As the high molecular weight epibis type glycidyl ether type epoxy resin, for example, the above epibis type glycidyl ether type epoxy resin is further subjected to addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like. Those obtained by (1) are preferably mentioned.
Preferable specific examples of the aromatic glycidyl ether compound include bisphenol A type compounds such as 828EL, 1003, and 1007 (manufactured by Japan Epoxy Resin Co., Ltd.); oncoat EX-1020, oncoat EX-1010, Fluorene compounds such as Ogsol PG (manufactured by Osaka Gas Chemical Co., Ltd.) and the like can be mentioned. Of these, Ogsol EG-210 is preferable.

-Aliphatic epoxy compounds-
The aliphatic epoxy compound is a compound having an aliphatic epoxy group, but an aliphatic glycidyl ether type epoxy resin is particularly suitable.
Examples of the aliphatic glycidyl ether type epoxy resin include polyhydroxy compounds (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol. , Polypropylene glycol (PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose and maltose) and epihalohydrins Those obtained by a condensation reaction with are preferably mentioned. Among these, aliphatic glycidyl ether type epoxy resins having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton as the central skeleton are more preferable.

-Oxetane compounds-
The oxetane compound is a compound having an oxetane group (oxetane ring).
The oxetane compound is preferably used in combination with an alicyclic epoxy compound and / or a hydrogenated epoxy compound from the viewpoint of curing speed. Moreover, it is preferable to use the oxetane compound which does not have an aryl group or an aromatic ring from a viewpoint of light resistance improvement. On the other hand, from the viewpoint of improving the strength of the cured product, it is preferable to use a polyfunctional oxetane compound, that is, a compound having two or more oxetane rings in one molecule.

Among the oxetane compounds having no aryl group or aromatic ring, examples of the monofunctional oxetane compound include 3-methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3- Oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether and the like are preferable.

Among the oxetane compounds having no aryl group or aromatic ring, examples of the polyfunctional oxetane compound include di [1-ethyl (3-oxetanyl)] methyl ether and 3,7-bis (3-oxetanyl) -5. -Oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis ( 3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-o Cetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritoltetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether Dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether Etc. are preferred.

Specific examples of the oxetane compound include, for example, ETERNACOLL (R) EHO, ETERRNACOLL (R) OXBP, ETERRNACOLL (R) OXMA, ETERNACOLL (R) HBOX, and ETERRNACOLL (R) OXIPA (manufactured by Ube Industries, Ltd.) OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610 (above, manufactured by Toagosei Co., Ltd.) and the like are preferable.

Here, in the curable resin composition of the present invention, a molded body that is sufficiently cured can be obtained even when the cyclic ether compound includes an aromatic epoxy compound that is difficult to be cured by a conventional catalyst. Therefore, a molded article having a controlled refractive index and the like can be obtained by appropriately selecting the type of aromatic epoxy compound and the content in the composition. Moreover, since the glass transition temperature of hardened | cured material is improved more when an aromatic epoxy compound is included, the hardened | cured material more excellent by heat resistance, temperature impact resistance, etc. is realizable. That is, as the cyclic ether compound, any of a form containing only an aromatic epoxy compound (a form in which the aromatic epoxy compound is 100% by mass) and a form in which an aromatic epoxy compound and another cyclic ether compound are used in combination. Is also a preferred form of the invention. In the latter form, the other cyclic ether compound is preferably at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound.
In addition, the curable resin composition using an aromatic epoxy compound as the cyclic ether compound is suitable for applications such as a lens that particularly requires a refractive index (high refractive index).

The cyclic ether compound may also be a compound having two or more cyclic ether groups in one molecule, that is, a polyfunctional compound. Thereby, since sclerosis | hardenability is improved more and the hardened | cured material which is excellent in various characteristics can be obtained, it is suitable.
The compound having two or more cyclic ether groups in one molecule may be a compound having two or more identical cyclic ether groups, or a compound having two or more different cyclic ether groups. In particular, it is preferable to use a polyfunctional alicyclic epoxy compound, a polyfunctional hydrogenated epoxy compound, and / or a polyfunctional aromatic epoxy compound. By using these, a cured product can be obtained in a shorter time.

<Compound having a cationic curable double bond (double bond compound)>
The double bond compound is a compound having in the molecule one or more double bonds (unsaturated double bond groups) that can be cured (polymerized) by a cationic curing reaction.
The double bond that can be cured (polymerized) by the cationic curing reaction means a cationic polymerizable unsaturated bond, for example, from the group consisting of (meth) acryloyl group, vinyl group, allyl group, fumarate group and maleimide group One group of at least one selected is preferred. That is, the double bond compound is at least one selected from the group consisting of a compound having a (meth) acryloyl group, a compound having a vinyl group, a compound having an allyl group, a compound having a fumarate group, and a compound having a maleimide group. It is preferred to include seed compounds. Among these, from the viewpoint of curability, a compound having a vinyl group and / or a compound having an allyl group is preferable. Thus, the form in which the double bond compound includes a compound having a vinyl group and / or a compound having an allyl group is also a preferred form of the present invention. From the viewpoint of curability, the most preferable form is that a compound having a vinyl group is essential.

The double bond compound is also preferably a compound having an aromatic ring and / or a heterocyclic ring in the molecule from the viewpoint of increasing the refractive index of the cured product. Further, from the viewpoint of mechanical strength and chemical resistance, a compound having an aromatic ring in the molecule is particularly suitable.

The number of unsaturated double bond groups that the double bond compound has may be one or more in the molecule, but is two or more from the viewpoint of resin curability, high heat resistance, and high glass transition temperature. It is preferable. That is, the double bond compound is preferably a compound having two or more unsaturated double bond groups in the molecule.

In the present specification, for example, a compound having one or more epoxy groups in the molecule and one or more unsaturated double bond groups such as vinyl groups, such as 1,2-epoxy-4-vinylcyclohexane, Classify as “compound having epoxy group”.
In the present specification, the (meth) acryloyl group means an acryloyl group and / or a methacryloyl group. In addition, for example, in the case of having an acryloyl group, the acryloyl group contains a vinyl group. In this case, the acryloyl group does not have an acryloyl group and a vinyl group, but has a vinyl group. , Allyl group, (meth) acryloyl group, fumarate group and maleimide group. The fumarate group means a group having a fumarate structure, that is, a group having a fumarate ester structure.

-Compound having a (meth) acryloyl group-
Examples of the compound having the (meth) acryloyl group include (poly) ester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, (poly) ether (meth) acrylate, alkyl (meth) acrylate, Suitable are alkylene (meth) acrylate, (meth) acrylate having an aromatic ring, (meth) acrylate having an alicyclic structure, and the like.

The (poly) ester (meth) acrylate is a (meth) acrylate having one or more ester bonds in the main chain. For example, the following compounds are suitable.
Alicyclic modified neopentyl glycol (meth) acrylate (“R-629” or “R-644” manufactured by Nippon Kayaku Co., Ltd.), caprolactone modified 2-hydroxyethyl (meth) acrylate, ethylene oxide and / or propylene oxide modified phthalate Monofunctional (poly) ester (meth) acrylates such as acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, caprolactone-modified tetrahydrofurfuryl (meth) acrylate;
Pivalate ester neopentyl glycol di (meth) acrylate, caprolactone-modified hydroxypivalate ester neopentyl glycol di (meth) acrylate, epichlorohydrin-modified phthalic acid di (meth) acrylate; 1 mol of trimethylolpropane or glycerol Mono-, di- or tri (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to pentaerythritol or ditrimethylolpropane Mono, di, tri or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol. Monool or poly (meth) acrylate of triol obtained by adding 1 mol or more of cyclic lactone compound such as ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone to 1 mol of dipentaerythritol A mono (meth) acrylate or poly (meth) acrylate of a polyhydric alcohol such as triol, tetraol, pentaol or hexaol;

Diol components such as (poly) ethylene glycol, (poly) propylene glycol, (poly) tetramethylene glycol, (poly) butylene glycol, (poly) pentanediol, (poly) methylpentanediol, (poly) hexanediol, and malein Acid, fumaric acid, succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, het acid, hymic acid, chlorendic acid, dimer acid, alkenyl succinic acid, sebacic acid, Azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5- Potassium sulfoi Polyester polyols composed of polybasic acids such as phthalic acid, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutamic acid, trimellitic acid, pyromellitic acid ( (Meth) acrylate; polyfunctional (poly) ester such as (meth) acrylate of cyclic lactone-modified polyester diol comprising the above diol component, polybasic acid and ε-caprolactone, γ-butyrolactone, δ-valerolactone or methylvalerolactone; (Meth) acrylates and the like.

The urethane (meth) acrylate is a (meth) acrylate having one or more urethane bonds in the main chain, and is obtained, for example, by a reaction between a hydroxy compound having at least one (meth) acryloyloxy group and an isocyanate compound. The compounds obtained are preferred.

Examples of the hydroxy compound having at least one (meth) acryloyloxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxybutyl. (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylol Ethanedi (meth) acrylate, pentaerythritol tri (meth) acrylate or glycidyl (meth) acrylate- (meth) acrylic acid adduct, 2-hydroxy-3 Phenoxypropyl (meth) having various hydroxyl groups of acrylate (meth) acrylate compound or a ring-opening reaction product of a having these hydroxyl groups (meth) acrylate compound ε- caprolactone are preferred.

Examples of the isocyanate compound include p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4,4′-diphenylmethane. Aromatic diisocyanates such as diisocyanate, 3,3′-dimethyldiphenyl-4,4′-diisocyanate, 3,3′-diethyldiphenyl-4,4′-diisocyanate, naphthalene diisocyanate; isophorone diisocyanate, hexamethylene diisocyanate, 4, Aliphatic or alicyclic structures such as 4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, lysine diisocyanate Cyanates; one or more burettes of isocyanate monomers or polyisocyanates such as isocyanurates obtained by trimerization of the above diisocyanate compounds; polyisocyanates obtained by urethanization reaction of these isocyanate compounds with various polyols; It is.

As the polyol as a raw material for producing the polyisocyanate, for example, the following compounds are suitable.
(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) alkylene glycols such as tetramethylene glycol; ethylene glycol, propanediol, propylene glycol, tetramethylene glycol, pentamethylene glycol, Ethylene oxide modified products, propylene oxide modified products, butylene oxide modified products, tetrahydrofuran modified products of alkylene glycols such as hexanediol, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, dipentaerythritol, etc. , Ε-caprolactone modified product, γ-butyrolactone modified product, δ-valerolactone modified product, methyl valerolactone modified product, etc .;
Hydrocarbon polyols such as copolymers of ethylene oxide and propylene oxide, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol and hydrogenated polybutadiene glycol Aliphatic polyester polyols which are esterification reaction products of aliphatic dicarboxylic acids such as adipic acid and dimer acid and polyols such as neopentyl glycol and methylpentanediol; aromatic dicarboxylic acids such as terephthalic acid and neopentyl Aromatic polyester polyols which are esterification reaction products with polyols such as glycols; polycarbonate polyols; acrylic polyols; polytetramethylene hexaglyce Polyhydric hydroxyl compounds such as ether (hexaglycerin-modified tetrahydrofuran); mono- and polyhydric hydroxyl group-containing compounds of terminal ether groups of the above-mentioned polyhydric hydroxyl group-containing compounds; the above polyhydric hydroxyl group-containing compounds and fumaric acid, phthalic acid , Polyhydric hydroxyl group-containing compounds obtained by esterification with dicarboxylic acids such as isophthalic acid, itaconic acid, adipic acid, sebacic acid and maleic acid; esters of polyhydric hydroxyl compounds such as glycerine and fatty acid esters of animals and plants Polyhydric hydroxyl group-containing compounds such as monoglycerides obtained by exchange reaction;

The epoxy (meth) acrylate is a (meth) acrylate obtained by reacting one or more functional epoxides with (meth) acrylic acid. As the epoxide, for example, the following compounds are suitable.
Epichlorohydrin-modified hydrogenated bisphenol-type epoxy resin synthesized from (methyl) epichlorohydrin, hydrogenated bisphenol A, hydrogenated bisphenol S, hydrogenated bisphenol F, ethylene oxide, propylene oxide modified products thereof; 3,4-epoxycyclohexylmethyl Cycloaliphatic epoxy resins such as bis- (3,4-epoxycyclohexyl) adipate; cycloaliphatic epoxides such as epoxy resins containing heterocycles such as triglycidyl isocyanurate;
Epichlorohydrin-modified bisphenol-type epoxy resin synthesized from (methyl) epichlorohydrin and bisphenol A, bisphenol S, bisphenol F, their ethylene oxide, propylene oxide-modified products, etc .; phenol novolac-type epoxy resin; cresol novolac-type epoxy resin; Epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting pentadiene with various phenols; Epoxidized products of 2,2 ′, 6,6′-tetramethylbiphenol, aromatic epoxides such as phenyl glycidyl ether;
(Poly) ethylene glycol, (poly) propylene glycol, (poly) butylene glycol, (poly) tetramethylene glycol, neopentyl glycol and other glycols (poly) glycidyl ether; glycols of alkylene oxide modified products (poly) Glycidyl ether; (poly) glycidyl ether of an aliphatic polyhydric alcohol such as trimethylolpropane, trimethylolethane, glycerin, diglycerin, erythritol, pentaerythritol, sorbitol, 1,4-butanediol, 1,6-hexanediol; Alkylene-type epoxides such as (poly) glycidyl ethers of alkylene oxide-modified products of aliphatic polyhydric alcohols;
Glycidyl ester of carboxylic acid such as adipic acid, sebacic acid, maleic acid, itaconic acid, glycidyl ether of polyester polyol of polyhydric alcohol and polyhydric carboxylic acid; co-polymerization of glycidyl (meth) acrylate and methylglycidyl (meth) acrylate Glycidyl ester of higher fatty acids, epoxidized linseed oil, epoxidized soybean oil, epoxidized castor oil, aliphatic epoxy resins such as epoxidized polybutadiene;

The (poly) ether (meth) acrylate is a (meth) acrylate having one or more ether bonds in the main chain. For example, the following compounds are suitable.
Butoxyethyl (meth) acrylate, butoxytriethylene glycol (meth) acrylate, epichlorohydrin modified butyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, ethyl carbitol (meth) Acrylate, 2-methoxy (poly) ethylene glycol (meth) acrylate, methoxy (poly) propylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolypropylene glycol (meth) acrylate, phenoxyhydroxypropyl (meth) Acrylate, phenoxy (poly) ethylene glycol (meth) acrylate, polyethylene glycol mono (meth) acrylate, poly Propylene glycol mono (meth) acrylate, monofunctional (poly) ether (meth) acrylates such as polyethylene glycol / polypropylene glycol mono (meth) acrylate;
Alkylene glycol di (meth) acrylates such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, polytetramethylene glycol di (meth) acrylate; ethylene oxide and propylene oxide Copolymers, copolymers of propylene glycol and tetrahydrofuran, copolymers of ethylene glycol and tetrahydrofuran, polyisoprene glycol, hydrogenated polyisoprene glycol, polybutadiene glycol, hydrogenated polybutadiene glycol and other hydrocarbon polyols, polytetramethylene Induced from polyvalent hydroxyl compounds such as hexaglyceryl ether (hexaglycerin modified tetrahydrofuran) and (meth) acrylic acid Polyfunctional (meth) acrylates are, neopentyl glycol 1 mol to 1 mol or more of ethylene oxide, propylene oxide, di (meth) acrylate of diol obtained by adding a cyclic ether such as butylene oxide and / or tetrahydrofuran;

Di (meth) acrylates of alkylene oxide modified products of bisphenols such as bisphenol A, bisphenol F and bisphenol S; of alkylene oxide modified products of hydrogenated bisphenols such as hydrogenated bisphenol A, hydrogenated bisphenol F and hydrogenated bisphenol S Di (meth) acrylate; di (meth) acrylate of alkylene oxide modified form of trisphenols; di (meth) acrylate of alkylene oxide modified form of hydrogenated trisphenols; alkylene oxide modified form of p, p'-biphenols Di (meth) acrylate of hydrogenated biphenols, alkylene oxide modified di (meth) acrylate; di (meth) acrylate of p, p'-dihydroxybenzophenone alkylene oxide modified; trimethylolpropane Is a mono-, di- or tri (meth) acrylate of a triol obtained by adding 1 mol or more of a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of glycerin;
Mono, di, tri or tetra (meth) acrylate of triol obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of pentaerythritol or ditrimethylolpropane; Triol mono or poly (meth) acrylate triol, tetraol, pentaol, hexa obtained by adding 1 mol or more of cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide and / or tetrahydrofuran to 1 mol of pentaerythritol Monofunctional (poly) ether (meth) acrylates or polyfunctional (poly) ether (meth) acrylates of polyhydric alcohols such as all;

The alkyl (meth) acrylate or alkylene (meth) acrylate is a main chain of linear alkyl, branched alkyl, linear alkylene group or branched alkylene group, and a halogen atom and / or hydroxyl group at the side chain or terminal. (Meth) acrylate that may have, for example, the following compounds are suitable.
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, neopentyl ( (Meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl ( (Meth) acrylate, tridecyl (meth) acrylate, pentadecyl (meth) acrylate, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (Meth) acrylate, neryl (meth) acrylate, geranyl (meth) acrylate, farnesyl (meth) acrylate, hexadecyl (meth) acrylate, octadecyl (meth) acrylate, docosyl (meth) acrylate, trans-2-hexene (meth) acrylate Monofunctional (meth) acrylates such as
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,2-butylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) Acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-methyl-1,8-octanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate 1,10-decanediol di (meth) acrylate hydrocarbon diol di (meth) acrylates;

Mono (meth) acrylate, di (meth) acrylate or tri (meth) acrylate of trimethylolpropane (hereinafter, “poly” is used as a general term for polyfunctionality such as di, tri, tetra, etc.), mono (meth) of glycerin Acrylate or poly (meth) acrylate, mono (meth) acrylate or poly (meth) acrylate of pentaerythritol, mono (meth) acrylate or poly (meth) acrylate of ditrimethylolpropane, mono (meth) acrylate or poly of dipentaerythritol Mono (meth) acrylates or poly (meth) acrylates of polyhydric alcohols such as triols, tetraols, hexaols of (meth) acrylates;
Hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-chloro-2-hydroxyethyl (meth) acrylate; 2 , 3-dibromopropyl (meth) acrylate, tribromophenyl (meth) acrylate, ethylene oxide modified tribromophenyl (meth) acrylate, ethylene oxide modified tetrabromobisphenol A di (meth) acrylate and other (meth) acrylates having a bromine atom;
Trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, dodecafluoroheptyl (meth) acrylate, hexadecafluorononyl (meth) acrylate, hexa Fluorobutyl (meth) acrylate, 3-perfluorobutyl-2-hydroxypropyl (meth) acrylate, 3-perfluorohexyl-2-hydroxypropyl (meth) acrylate, 3-perfluorooctyl-2-hydroxypropyl (meth) Acrylate, 3- (perfluoro-5-methylhexyl) -2-hydroxypropyl (meth) acrylate, 3- (perfluoro-7-methyloctyl) -2-hydroxypropyl (meth) ) Acrylate, 3- (having a perfluoro-8-methyldecyl) -2-hydroxypropyl (meth) fluorine atoms, such as acrylates (meth) acrylate; and the like.

The (meth) acrylate having an aromatic ring is a (meth) acrylate having an aromatic ring in the main chain or side chain, for example, monofunctional (meth) acrylates such as phenyl (meth) acrylate and benzyl acrylate; bisphenol Diacrylates such as A diacrylate, bisphenol F diacrylate, and bisphenol S diacrylate;

The (meth) acrylate having the alicyclic structure is a (meth) acrylate having an alicyclic structure that may contain an oxygen atom or a nitrogen atom in the structural unit in the main chain or side chain. For example, cyclohexyl ( (Meth) acrylate, cyclopentyl (meth) acrylate, cycloheptyl (meth) acrylate, bicycloheptyl (meth) acrylate, isobornyl (meth) acrylate, bicyclopentyl di (meth) acrylate, tricyclodecyl (meth) acrylate, bicyclopentenyl (meth) ) Monofunctional (meth) acrylates having an alicyclic structure such as acrylate, norbornyl (meth) acrylate, bicyclooctyl (meth) acrylate, tricycloheptyl (meth) acrylate, and cholesteroid skeleton-substituted (meth) acrylate; water Di (meth) acrylates of hydrogenated bisphenols such as bisphenol A, hydrogenated bisphenol F, hydrogenated bisphenol S, di (meth) acrylates of hydrogenated trisphenols, di (meta) of hydrogenated p, p'-biphenols ) Acrylates; cyclic structures such as dicyclopentane-based di (meth) acrylates such as “Kayarad R684” (manufactured by Nippon Kayaku Co., Ltd.), tricyclodecane dimethylol di (meth) acrylate, bisphenol full orange hydroxy (meth) acrylate, etc. Polyfunctional (meth) acrylates; alicyclic acrylates having an oxygen atom and / or a nitrogen atom in the structure such as tetrahydrofurfuryl (meth) acrylate and morpholinoethyl (meth) acrylate are preferred.

Examples of the compound having the (meth) acryloyl group include poly ((meth) acrylic acid polymer and a reaction product of glycidyl (meth) acrylate, or a reaction product of a glycidyl (meth) acrylate polymer and (meth) acrylic acid). (Meth) acrylic (meth) acrylate; (meth) acrylate having an amino group such as dimethylaminoethyl (meth) acrylate; isocyanuric (meth) acrylate such as tris ((meth) acryloxyethyl) isocyanurate; hexakis [((meta ) (Acryloyloxyethyl) cyclotriphosphazene] or other phosphazene (meth) acrylate; (meth) acrylate having a polysiloxane skeleton; polybutadiene (meth) acrylate; melamine (meth) acrylate, or the like may be used. Among these compounds having (meth) acryloyl groups, compounds having 1 to 6 (meth) acryloyl groups in one molecule are preferable.

-Compound having a vinyl group-
As the compound having a vinyl group, an alkyl vinyl ether optionally substituted with a halogen atom, a hydroxyl group or an amino group (hereinafter also referred to as an alkyl vinyl ether); the other end is substituted with a halogen atom, a hydroxyl group or an amino group. An optionally substituted cycloalkyl vinyl ether (hereinafter also referred to as a cycloalkyl vinyl ether); from the group consisting of an alkyl group, a cycloalkyl group and an aromatic group, wherein the vinyl ether group is bonded to an alkylene group and may further have a substituent. Monovinyl ether, divinyl ether and polyvinyl ether having a structure in which one or more selected groups are bonded to one or more selected from the group consisting of an ether bond, a urethane bond and an ester bond Monovinyl ether, divinyl ether and Aromatic vinyl compound with a vinyl group substituted on an aromatic ring; heterocyclic vinyl compound with a vinyl group substituted on a heterocyclic ring; alkyl vinyl compound with an alkyl group substituted (excluding an allyl group); cyclic hydrocarbon And a cyclic hydrocarbon vinyl compound in which a vinyl group is substituted. Each of these can be used alone or in combination of two or more.

Examples of the alkyl vinyl ether include methyl vinyl ether, hydroxymethyl vinyl ether, chloromethyl vinyl ether, ethyl vinyl ether, 2-hydroxyethyl vinyl ether, 2-chloroethyl vinyl ether, diethylaminoethyl vinyl ether, propyl vinyl ether, 3-hydroxypropyl vinyl ether, and 2-hydroxy. Propyl vinyl ether, 3-chloropropyl vinyl ether, 3-aminopropyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether, 4-hydroxybutyl vinyl ether, isobutyl vinyl ether, 4-aminobutyl vinyl ether, pentyl vinyl ether, isopentyl vinyl ether, hexyl vinyl ether, 1,6- Hexanediol Vinyl ether, heptyl vinyl ether, 2-ethylhexyl vinyl ether, octyl vinyl ether, isooctyl vinyl ether, nonyl vinyl ether, isononyl vinyl ether, decyl vinyl ether, isodecyl vinyl ether, dodecyl vinyl ether, isododecyl vinyl ether, tridecyl vinyl ether, isotridecyl vinyl ether, pentadecyl vinyl ether , Isopentadecyl vinyl ether, hexadecyl vinyl ether, octadecyl vinyl ether, methylene glycol divinyl ether, ethylene glycol divinyl ether, propylene glycol divinyl ether, 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether, cyclohexanediol dibi Ethers, trimethylolpropane trivinyl ether, pentaerythritol tetra vinyl ether.

Examples of the cycloalkyl vinyl ether include cyclopropyl vinyl ether, 2-hydroxycyclopropyl vinyl ether, 2-chlorocyclopropyl vinyl ether, cyclopropylmethyl vinyl ether, cyclobutyl vinyl ether, 3-hydroxycyclobutyl vinyl ether, 3-chlorocyclobutyl vinyl ether, Cyclobutyl methyl vinyl ether, cyclopentyl vinyl ether, 3-hydroxycyclopentyl vinyl ether, 3-chlorocyclopentyl vinyl ether, cyclopentyl methyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-aminocyclohexyl vinyl ether, cyclohexanediol model Vinyl ether, cyclohexanedimethanol monovinyl ether, cyclohexanedimethanol divinyl ether and the like.

Among the monovinyl ether, divinyl ether and polyvinyl ether, examples of the compound having an ether bond include ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, diethylene glycol divinyl ether, triethylene glycol monovinyl ether, and triethylene glycol methyl vinyl ether. , Triethylene glycol divinyl ether, polyethylene glycol monovinyl ether, polyethylene glycol methyl vinyl ether, polyethylene glycol divinyl ether, propylene glycol methyl vinyl ether, dipropylene glycol monovinyl ether, dipropylene glycol methyl vinyl ether, dipropylene Recall divinyl ether, tripropylene glycol monomethyl ether, tripropylene glycol methyl ether, tripropylene glycol divinyl ether, polypropylene glycol monovinyl ether, polypropylene glycol methyl ether, polypropylene glycol divinyl ether,
Tetramethylene glycol methyl vinyl ether, di (tetramethylene glycol) monovinyl ether, di (tetramethylene glycol) methyl vinyl ether, di (tetramethylene glycol) divinyl ether, tri (tetramethylene glycol) monovinyl ether, tri (tetramethylene glycol) methyl vinyl ether , Tri (tetramethylene glycol) divinyl ether, poly (tetramethylene glycol) monovinyl ether, poly (tetramethylene glycol) methyl vinyl ether, poly (tetramethylene glycol) divinyl ether, 1,6-hexanediol methyl vinyl ether, di (hexamethylene) Glycol) monovinyl ether, di (hexamethylene glycol) methyl vinyl ether, di (hexa) Tylene glycol) divinyl ether, tri (hexamethylene glycol) monovinyl ether, tri (hexamethylene glycol) methyl vinyl ether, tri (hexamethylene glycol) divinyl ether, poly (hexamethylene glycol) monovinyl ether, poly (hexamethylene glycol) methyl vinyl ether Poly (hexamethylene glycol) divinyl ether and the like are suitable.

Of the monovinyl ether, divinyl ether and polyvinyl ether, the compound having a urethane bond is a monovinyl ether of (poly) alkylene glycol having at least one hydroxyl group in one molecule and at least one isocyanate in one molecule. It is preferable that it is a compound obtained by a urethanation reaction with the compound which has group.

Examples of the monovinyl ether of (poly) alkylene glycol having at least one hydroxyl group in one molecule include 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxy- 2-methylethyl vinyl ether, dipropylene glycol monovinyl ether, polypropylene glycol monovinyl ether, 4-hydroxybutyl vinyl ether, 1,6-hexanediol monovinyl ether and the like are suitable.

Examples of the compound having at least one isocyanate group in one molecule include m-isopropenyl-α, α-dimethylbenzyl isocyanate, p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene. Diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 3,3'-diethyldiphenyl-4 , 4'-diisocyanate, naphthalene diisocyanate and other aromatic isocyanates; propyl isocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate Preferred are aliphatic and alicyclic isocyanates such as silicate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate. In addition, polyisocyanates such as one or more dimers or trimers of a compound having at least one isocyanate group in one molecule may be used as a raw material for the compound having a urethane bond.

Among the monovinyl ether, divinyl ether and polyvinyl ether, the compound having a urethane bond has two or more isocyanate groups in one molecule among the compounds having at least one isocyanate group in one molecule. You may use the adduct body obtained by the urethanation reaction of a compound and various alcohols.

As the alcohols, compounds having at least one hydroxyl group in one molecule are suitable, and those having an average molecular weight of 100,000 or less are preferred.
Examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, diethylene glycol, dipropylene glycol, neopentyl glycol, 1, 3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, 2,2,4-trimethyl-1,3-pentanediol, 3- Methyl-1,5-pentanediol, dichloroneopentyl glycol, dibromoneopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethylol, 1,4-cyclohexanediol, spirogly , Tricyclodecane dimethylol, hydrogenated bisphenol A, ethylene oxide-added bisphenol A, propylene oxide-added bisphenol A, dimethylolpropionic acid, dimethylolbutanoic acid, trimethylolethane, trimethylolpropane, glycerin, 3 -One or more of methylpentane-1,3,5-triol, tris (2-hydroxyethyl) isocyanurate and the like are preferable.

As the alcohols, polyester polyols, polyether polyols, polycarbonate polyols and the like may be used.
As said polyester polyol, what is obtained by reaction of the polyol component of the above-mentioned alcohol and carboxylic acid is preferable.
As the carboxylic acid, various commonly used carboxylic acids or acid anhydrides thereof can be used. For example, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, hetic acid, highmic acid , Chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4-trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfo Of terephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, dimethyl- or diethyl ester of 5-sodium sulfoisophthalic acid, etc. Di-lower alkyl esters, Lusophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid, hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexericarboxylic acid or pyromellitic An acid or an acid anhydride thereof or an ester compound with an alcohol such as methanol or ethanol is preferable. Moreover, you may use the lactone polyol obtained by the ring-opening reaction of (epsilon) -caprolactone and the polyol component mentioned above.

As said polyether polyol, what is normally used can be used, for example, ether glycols, such as polytetramethylene glycol, propylene oxide modified polytetramethylene glycol, ethylene oxide modified polytetramethylene glycol, polypropylene glycol, polyethylene glycol, A polyether polyol obtained by ring-opening polymerization of a cyclic ether using a tri- or higher functional polyol as an initiator is preferable.

The polycarbonate polyol is preferably one obtained by a transesterification reaction between carbonate and various polyols.
Examples of the carbonate include diphenyl carbonate, bischlorophenyl carbonate, dinaphthyl carbonate, phenyl-tolyl-carbonate, phenyl-chlorophenyl-carbonate or 2-tolyl-4-tolyl-carbonate; diaryl such as dimethyl carbonate or diethyl carbonate Or a dialkyl carbonate etc. are suitable.
As the polyol as a raw material for producing the polycarbonate polyol, the alcohols, polyester polyols, polyether polyols and the like are suitable.

Among the monovinyl ether, divinyl ether, and polyvinyl ether, the compound having an ester bond is an alkylene glycol monovinyl ether having at least one hydroxyl group in one molecule and a compound having at least one carboxyl group in one molecule. What is obtained by esterification reaction with is suitable.

As the monovinyl ether of alkylene glycol having at least one hydroxyl group in one molecule, (poly) alkylene glycol monovinyl ether having at least one hydroxyl group in one molecule in the compound having a urethane bond is preferable. It is.

As the compound having at least one carboxyl group in one molecule, commonly used carboxylic acids and acid anhydrides thereof can be used. For example, formic acid, acetic acid, propionic acid, valeric acid, benzoic acid, maleic acid Acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, het acid, hymic acid, chlorendic acid, dimer acid, adipic acid, succinic acid, alkenyl succinic acid, sebacic acid, azelaic acid, 2,2,4 -Trimethyladipic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, 2-sodium sulfoterephthalic acid, 2-potassium sulfoterephthalic acid, isophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid; 5-sodium -Sulfoisophthalic acid dimethyl- or diethyl s Di-lower alkyl esters of 5-sodium-sulfoisophthalic acid, such as sodium, orthophthalic acid, 4-sulfophthalic acid, 1,10-decamethylenedicarboxylic acid, muconic acid, oxalic acid, malonic acid, glutaric acid, trimellitic acid Hexahydrophthalic acid, tetrabromophthalic acid, methylcyclohexentricarboxylic acid or pyromellitic acid, cyclohexanedicarboxylic acid or acid anhydrides thereof are preferred. Furthermore, among these carboxylic acids, a carboxylic acid obtained by a reaction between a compound having two or more carboxyl groups in one molecule and an alcohol in the compound having a urethane bond may be used.

Examples of the aromatic vinyl compound include styrene, indene, methylstyrene, styrene derivatives optionally substituted at the other end with a halogen atom, a hydroxyl group, or an alkoxy group, vinyl naphthalene, 9-vinyl-9H-fluorene, and the like. A monovinyl compound substituted with an aromatic group; a divinyl compound substituted with an aromatic group such as divinylbenzene, divinylnaphthalene and divinylfluorene;

As said heterocyclic vinyl compound, it is preferable to use 1 type, or 2 or more types of compounds etc. by which the vinyl group is substituted by cyclic compounds containing nitrogen, sulfur, or phosphorus, such as vinyl carbazole, for example.

The alkyl vinyl compound is, for example, a vinyl compound substituted with an alkyl group such as isobutene that is not classified as a compound having an allyl group, and it is preferable to use one or more of such compounds.

As the cyclic hydrocarbon vinyl compound, for example, one or more vinyl compounds having cyclic hydrocarbons such as vinylcyclohexane, vinylcyclooctane, and 3-methyl-3,4-divinylcyclohexane are preferably used.

-Compound having an allyl group-
Examples of the compound having an allyl group include compounds having a 2-propenyl group such as 1-pentene, 1-hexene, cyclohexene, 2-propen-1-ol, diaryl ether, and the like. It is preferable to use 1 type or 2 types or more.

-Compound having fumarate group-
As the compound having a fumarate group, for example, one or more of fumaric acid esters such as dimethyl fumarate and diethyl fumarate, and an esterification reaction product of fumaric acid and polyhydric alcohol are preferable. .

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

-Other double bond compounds-
As the double bond compound, the following compounds can also be used.
Monofunctional (meth) acrylamides such as N-isopropyl (meth) acrylamide; Multifunctional (meth) acrylamides such as methylenebis (meth) acrylamide; Vinyl carboxylates such as vinyl acetate and vinyl cinnamate; Styrene and divinylstyrene Styrene derivatives such as: lauryl acrylate, isodecyl acrylate, isostearyl acrylate, lauryl alcohol ethoxy acrylate, epoxy stearyl acrylate, 2- (1-methyl-4-dimethyl) butyl-5-methyl-7-dimethyloctyl acrylate, phenoxyethyl Acrylate, phenoxyethoxyethyl acrylate, phenol polyalkoxy acrylate, nonylphenoxyethyl acrylate, nonylphenol ethylene oxide modified acrelane Nonylphenol polypropylene oxide modified acrylate, butoxypolypropylene glycol acrylate, tetrahydrofurfuryl alcohol lactone modified acrylate, lactone modified 2-hydroxyethyl acrylate, 2-ethylhexyl carbitol acrylate; 2-hydroxy-3-phenoxypropyl acrylate, acrylic acid dimer, ω -Carboxy-polycaprolactone monoacrylate, tetrahydrofurfuryl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, isobornyl acrylate, dicyclopentenyloxyalkyl acrylate, dicyclopentenyl acrylate, tricyclodecanyl acrylate, tricyclo Decanyloxy Acrylates such as ethyl acrylate and isobornyloxyethyl acrylate;
Acrylamides such as acryloylmorpholine and diacetone acrylamide; N-vinylamides such as N-vinylpyrrolidone and N-vinylcaprolactam; Vinyl ethers such as hydroxybutyl vinyl ether and lauryl vinyl ether; Maleimides such as chlorophenylmaleimide, cyclohexylmaleimide and laurylmaleimide Class: ethylene glycol di (meth) acrylate, triethylene glycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, diacrylate of neopentyl glycol hydroxypivalate, diacrylate of ethylene oxide adduct of bisphenol A, bisphenol A Propylene oxide adduct diacrylate, tricyclodecane dimethylo Diacrylate, 2,2-di (glycidyloxyphenyl) propane acrylic acid adduct, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, tris (2-hydroxyethyl) isocyanate Nurate triacrylate, tris (2-hydroxyethyl) isocyanurate diacrylate, tris (hydroxypropyl) isocyanurate triacrylate, ditrimethylolpropane tetraacrylate, ditrimethylolpropane triacrylate, and the like.

<Boron compound>
The boron compound is composed of a Lewis acid (organic borane) represented by the general formula (1) and a Lewis base. Such a boron compound is preferably used as a curing catalyst. More preferably, it is used as a cationic curing catalyst. When the curable resin composition contains such a boron compound, cationic curing can be employed as a curing method, and thus, a cured product obtained as compared with a case where addition type curing such as acid anhydride curing is employed. However, it is excellent in characteristics required for optical applications such as heat resistance, chemical stability and moisture resistance. In addition, compared to the case of using a conventional cationic curing catalyst such as antimony-based sulfonium salt, coloring due to heat (heat during curing, usage environment) is reduced, and the curing rate can be increased, so that it is stable. Thus, a cured product that can exhibit high transparency and uniformity can be provided with high productivity.
Here, the cation curing catalyst is a catalyst that accelerates the cation curing reaction, and functions, for example, differently from the curing accelerator in the acid anhydride curing reaction.

In addition, the presence or absence of coloring of the hardened | cured material with the catalyst to be used can be normally confirmed also from the change of the transmittance | permeability in wavelength 400nm. That is, by measuring the 400 nm transmittance of the cured product, it is possible to evaluate the presence or absence or degree of coloring (particularly yellowness) of the cured product. In addition, by measuring the transmittance of the cured product at 600 nm, the presence or degree of haze (turbidity) of the cured product can be evaluated. When the transmittance at 400 nm is low, deterioration of the cured product due to oxidation is estimated, and when the transmittance at 600 nm is low, it is estimated that the cured product is not uniform.

R in the said General formula (1) is the same or different, and represents the hydrocarbon group which may have a substituent. Although the said hydrocarbon group is not specifically limited, It is preferable that it is a C1-C20 hydrocarbon group. The hydrocarbon group having 1 to 20 carbon atoms is not limited as long as it has 1 to 20 carbon atoms as a whole, but is preferably an alkyl group, an aryl group, or an alkenyl group. The alkyl group, aryl group, and alkenyl group may be an unsubstituted group, or may be a group in which one or more hydrogen atoms are substituted with another organic group or a halogen atom. Other organic groups in this case include an alkyl group (when the hydrocarbon group represented by R is an alkyl group, the substituted hydrocarbon group as a whole corresponds to an unsubstituted alkyl group), aryl Group, alkenyl group, alkoxy group, hydroxyl group and the like.

X in the said General formula (1) is an integer of 1-5, and is the same or different and represents the number of the fluorine atoms couple | bonded with the aromatic ring. The bonding position of the fluorine atom in the aromatic ring is not particularly limited. x is preferably 2 to 5, more preferably 3 to 5, and still more preferably 5.
Further, a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied. That is, the Lewis acid is one in which at least one aromatic ring to which a fluorine atom is bonded is bonded to a boron atom. a is more preferably 2 or more, still more preferably 3, that is, a form in which three aromatic rings to which fluorine atoms are bonded is bonded to a boron atom is further preferable.

Specific examples of the Lewis acid include tris (pentafluorophenyl) borane (TPB), bis (pentafluorophenyl) phenylborane, pentafluorophenyl-diphenylborane, and tris (4-fluorophenyl) borane. Among these, TPB is more preferable because it can improve the heat resistance, moisture and heat resistance, low water absorption, UV irradiation resistance, and the like of the molded body.
In addition, in this specification, an Example, etc., what contains TPB as a Lewis acid among the cationic curing catalysts concerning this invention may be described as a TPB type catalyst.

The Lewis base is not limited as long as it can be coordinated to the Lewis acid, that is, can form a coordinate bond with the boron atom of the Lewis acid. However, compounds having atoms with unshared electron pairs are preferred. Specifically, a compound having a nitrogen atom, a phosphorus atom or a sulfur atom is preferred. In this case, the Lewis base forms a coordinate bond by donating a non-shared electron pair possessed by a nitrogen atom, a phosphorus atom, or a sulfur atom to the boron atom of the Lewis acid. Moreover, the compound which has a nitrogen atom or a phosphorus atom is more preferable.

Preferred examples of the compound having a nitrogen atom include amines (monoamines and polyamines) and ammonia. More preferred are amines having a hindered amine structure, amines having a low boiling point, and ammonia, and still more preferred are polyamines having a hindered amine structure and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, the cured molded article can be prevented from oxidation due to the radical scavenging effect, and the resulting cured product is more excellent in heat resistance (moisture heat resistance). On the other hand, when ammonia or a low-boiling amine is used as the Lewis base, the resulting cured product is excellent in low water absorption and UV irradiation resistance. The ammonia or low boiling point amine volatilizes in the curing process, so that the salt structure derived from ammonia or the low boiling point amine in the final molded product (cured product) is reduced, so the water absorption rate of the molded product is reduced. It is speculated that it can. In particular, ammonia is preferable because of its excellent effects.

As the amine having the hindered amine structure, a nitrogen atom forming a coordinate bond with a boron atom constitutes a secondary or tertiary amine from the viewpoint of storage stability of the resin composition and curability at the time of molding. It is preferable that it is polyamine more than diamine. Specific examples of the amine having a hindered amine structure include 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine; TINUVIN770, TINUVIN765, TINUVIN144, TINUVIN123, and TINUVIN744. CHIMASSORB2020FDL (above, manufactured by BASF); Adeka Stub LA52, Adekastab LA57 (above, made by ADEKA) and the like. Among these, TINUVIN770, TINUVIN765, Adeka Stab LA52, and Adeka Stub LA57 having two or more hindered amine structures per molecule are preferable.

As the low boiling point amine, it is preferable to use an amine having a boiling point of 120 ° C. or lower, more preferably 80 ° C. or lower, still more preferably 50 ° C. or lower, still more preferably 30 ° C. or lower, particularly preferably. Is 5 ° C. or lower. Specifically, primary amines such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, ethylenediamine; secondary amines such as dimethylamine, diethylamine, dipropylamine, methylethylamine, piperidine; And tertiary amines such as trimethylamine and triethylamine.

The compound having a phosphorus atom is preferably a phosphine. Specific examples include triphenylphosphine, trimethylphosphine, tritoluylphosphine, methyldiphenylphosphine, 1,2-bis (diphenylphosphino) ethane, and diphenylphosphine.

Preferred examples of the compound having a sulfur atom include thiols and sulfides. Specific examples of thiols include methyl thiol, ethyl thiol, propyl thiol, hexyl thiol, decane thiol, and phenyl thiol. Specific examples of the sulfides include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, methoxymethylphenyl sulfide and the like.

In the boron compound, the mixing ratio of the Lewis acid and the Lewis base is not necessarily a stoichiometric ratio. That is, any one of Lewis acid and Lewis base (converted to the base point amount) may be contained in excess of the theoretical amount (equivalent). Specifically, the mixing ratio of the Lewis acid and the Lewis base in the cationic curing catalyst is the ratio of the atomic number n (b) of the atom serving as the Lewis base point to the atomic number n (a) of boron serving as the Lewis acid point. Even if it is represented by (n (b) / n (a)) and is not 1 (stoichiometric ratio), it acts suitably as a cationic curing catalyst. The ratio n (b) / n (a) in the cationic curing catalyst affects the storage stability and cationic curing characteristics (curing speed, degree of curing of the cured product, etc.) of the resin composition.
In the case where the Lewis base has two Lewis base points in the molecule, such as diamines, the ratio n is determined when the mixing molar ratio of the Lewis base to the Lewis acid constituting the cationic curing catalyst is 0.5. (B) / n (a) = 1 (stoichiometric ratio). In this way, the ratio n (b) / n (a) is calculated.

From the viewpoint of the storage stability of the curable resin composition containing the boron compound, if the Lewis acid is present in an excessive amount relative to the Lewis base, the storage stability may not be more sufficient. The ratio n (b) / n (a) is preferably 0.5 or more in order to make the resin composition more excellent in properties. For the same reason, the ratio is preferably 0.8 or more, more preferably 0.9 or more, particularly preferably 0.95 or more, and most preferably 0.99 or more.
On the other hand, from the viewpoint of cationic curing characteristics, if the Lewis base is excessively large, the low-temperature curability of the cured product may be lowered. Therefore, in order to obtain a composition having better cationic curing characteristics, n (b) / n (A) is preferably 100 or less. For the same reason, the ratio n (b) / n (a) is more preferably 20 or less, still more preferably 10 or less, and particularly preferably 5 or less.
Furthermore, from the viewpoint of cationic curing properties, a Lewis base is composed of a compound having a nitrogen atom, a sulfur atom or a phosphorus atom, and is a structure having two or more carbon substitutions (a structure having two or more carbon substitutions is a carbon atom in these atoms. The ratio n (b) / n (a) is preferably 2 or less because the acid dissociation constant is high and the steric hindrance is large. , 1.5 or less is more preferable, and 1.2 or less is still more preferable. For example, in the structure such as hindered amine, the above range is preferable.
In addition, when the Lewis base is ammonia or a low-boiling amine having a small steric hindrance, particularly ammonia, the ratio n (b) / n (a) is preferably larger than 1. More preferably, it is 1.001 or more, More preferably, it is 1.01 or more, Especially preferably, it is 1.1 or more, Most preferably, it is 1.5 or more.

The presence form of the Lewis acid and the Lewis base constituting the boron compound is not particularly limited, but it is preferable that the Lewis base is present in an electronic interaction with the Lewis acid. More preferably, at least a part of the Lewis base is coordinated to the Lewis acid, and more preferably at least a Lewis base equivalent to an equivalent amount to the Lewis acid present is coordinated to the Lewis acid. It is a form. When the abundance ratio of Lewis base to Lewis acid is equivalent or less than equivalent, that is, when the ratio n (b) / n (a) is 1 or less, almost all of the Lewis base present is coordinated to the Lewis acid. The form formed is preferable. On the other hand, in the form in which the Lewis base is contained in excess (more than equivalent), it is preferable that the Lewis base is coordinated with the Lewis acid in an equivalent amount, and the excess Lewis base is present in the vicinity of the complex.

Specific examples of the boron compound include TPB / monoalkylamine complexes, TPB / dialkylamine complexes, TPB alkylamine complexes such as TPB / trialkylamine complexes, and organic borane / amine complexes such as TPB / hindered amine complexes; TPB / NH organoborane / ammonia complex, such as ₃ complex; TPB / triarylphosphine complex, TPB / diaryl phosphine complexes, TPB / monoaryl phosphines organoborane / phosphine complexes such as complexes; TPB / organoborane / thiol complexes such as alkylthiol complex; And organic borane / sulfide complexes such as TPB / diaryl sulfide complexes and TPB / dialkyl sulfide complexes. Of these, TPB / alkylamine complexes, TPB / hindered amine complexes, TPB / NH ₃ complexes, and TPB / phosphine complexes are preferred.

<Other ingredients>
-Flexible component-
The curable resin composition preferably also includes a flexible component (flexible component). Thereby, it becomes possible to make a resin composition having a sense of unity, that is, having high toughness.
The flexible component may be a compound different from the cyclic ether compound or the double bond compound described above, or at least one of the components contained as these compounds may be a flexible component. Good.

Specifically, the flexible component is a compound having an oxyalkylene skeleton represented by (1)-[— (CH ₂ ) _n —O—] _m — (n is an integer of 2 or more and m is an integer of 1 or more. Preferably, n is 2 to 12, m is an integer of 1 to 1000, more preferably n is an integer of 3 to 6 and m is an integer of 1 to 20. An epoxy compound containing an oxybutylene group (Japan Epoxy Resin, YL-7217, epoxy equivalent 437, liquid epoxy compound (10 ° C. or higher)) is preferred. As other suitable flexible components, (2) polymer epoxy compounds (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)); 3) alicyclic solid epoxy compound (EHPE-3150 manufactured by Daicel Chemical Industries, Ltd.); (4) alicyclic liquid epoxy compound (Delcel Chemical Industries, Celoxide 2081); (5) liquid rubber such as liquid nitrile rubber, Examples thereof include polymer rubber such as polybutadiene, and fine particle rubber having a particle diameter of 100 nm or less.

Among these, a cationic curable compound containing a cationic polymerizable group at the terminal, side chain, main chain skeleton, or the like is more preferable. Examples of the cationically polymerizable group include a cyclic ether group such as an epoxy group, an oxetane group, a dioxolane group, and a trioxane group, as well as a vinyl group, a vinyl ether group, and a styryl group. Among them, a cyclic ether group is preferable. It is. An epoxy group and an oxetane group are more preferable, and an epoxy group is more preferable. That is, a compound containing an epoxy group (epoxy compound) is particularly preferable as the flexible component. Among the epoxy compounds, an epoxy compound having an oxybutylene group (— [— (CH ₂ ) ₄ —O—] _m — (m is the same as above)) is preferable.

When the curable resin composition includes a flexible component, the content thereof is 80% by mass or less with respect to 100% by mass of the total amount of the cyclic ether compound, the double bond compound, and the flexible component. Preferably it is. More preferably, it is 50 mass% or less, More preferably, it is 20 mass% or less. Moreover, 0.01 mass% or more is preferable, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.

-Release agent-
In the curable resin composition, by including the boron compound described above (preferably as a curing catalyst), an effect of improving mold releasability and an effect of reducing a release agent can be obtained. The curable resin composition is particularly suitable for a molding material. Therefore, in the curable resin composition of the present invention, the mold can be released from the mold without using the mold release agent used in the prior art, resulting in a decrease in transparency due to the inclusion of the mold release agent. Without affecting the performance of the release agent, it is possible to obtain a cured product having excellent release properties from the mold. However, you may use a mold release agent as needed. For example, in the case where a molded article such as a lens is obtained using the curable resin composition, that is, in the case where mold molding is adopted as a curing / molding method, a release agent may be included.

As the mold release agent, it is preferable to use a compound having a group that promotes rather than inhibiting the curing reaction by the boron compound.
Specifically, a compound having an alcoholic OH group and / or a carbonyl group (including a carboxyl group and an ester group) is preferable as the mold release agent, and the compatibility with the curable resin composition and the mold release effect are high. From the viewpoint, those having a hydrocarbon group having 8 or more carbon atoms are preferred. More preferably, an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, a carboxylic acid anhydride having 8 to 36 carbon atoms, and a carboxylic acid having 8 to 36 carbon atoms. It is at least one compound selected from the group consisting of salts. By containing such a release agent, it can be cured in a shorter time, and can be more easily peeled off when cured using a mold, without damaging the surface of the cured product. The appearance can be further controlled, and transparency can be further exhibited. Therefore, the curable resin composition can be made more useful for electrical / electronic component material use, optical member use, and the like.

Among the compounds mentioned as the release agent, alcohols, carboxylic acids, and carboxylic acid esters are more preferable, and carboxylic acids (particularly higher fatty acids) and carboxylic acid esters are more preferable. Carboxylic acids and carboxylic acid esters are preferred because they can sufficiently exhibit the release effect without inhibiting the cationic curing reaction. In addition, since amines may inhibit a cation hardening reaction, it is preferable not to use as a mold release agent.
The above-mentioned compound may have any structure such as linear, branched or cyclic, and is preferably branched.

The number of carbon atoms of the above compound is preferably an integer of 8 to 36, and thus exhibits excellent peelability without impairing functions such as transparency and workability of the curable resin composition. It becomes a cured product. More preferably, it is 8-20 as carbon number, More preferably, it is 10-18.

The alcohol having 8 to 36 carbon atoms is a monohydric or polyhydric alcohol and may be linear or branched. Specifically, for example, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, nonadecyl alcohol, Eicosyl alcohol, seryl alcohol, myricyl alcohol, methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, di Preferred examples include pentaerythritol and 2-phenylethanol. The alcohol is preferably an aliphatic alcohol, and more preferably octyl alcohol (octanol), lauryl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), and stearyl alcohol.

The carboxylic acid having 8 to 36 carbon atoms is a monovalent or polyvalent carboxylic acid, such as 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, and tetradecanoic acid. Preferable examples include pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, and behenic acid. Preferred are octanoic acid, lauric acid, 2-ethylhexanoic acid, and stearic acid.

Examples of the carboxylic acid ester having 8 to 36 carbon atoms include (1) carboxylic acid ester obtained from the above alcohol and the above carboxylic acid, (2) methanol, ethanol, propanol, hexanol, heptanol, glycerin, benzyl alcohol and the like. Carboxylic acid ester obtained by combining a C1-7 alcohol and the above carboxylic acid, (3) A combination of a C1-7 carboxylic acid such as acetic acid, propionic acid, butanoic acid, hexanoic acid and the above alcohol (4) a carboxylic acid ester obtained from an alcohol having 1 to 7 carbon atoms and a carboxylic acid having 1 to 7 carbon atoms, and a compound having a total carbon number of 8 to 36. Preferably mentioned. Among these, the carboxylic acid esters of (2) and (3) are preferable, and stearic acid methyl ester, stearic acid ethyl ester, acetic acid octyl ester, and the like are more preferable.
The carboxylic acid anhydride having 8 to 36 carbon atoms is an carboxylic acid anhydride having 8 to 36 carbon atoms.

As the carboxylate having 8 to 36 carbon atoms, a carboxylic acid obtained by a combination of the carboxylic acid and an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Sn. Suitable examples include salts. Among these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.

Among the above-mentioned compounds, stearic acid compounds such as stearic acid and stearic acid esters, and alcohol compounds are more preferable, and stearic acid compounds are more preferable.

When the said curable resin composition contains a mold release agent, it is preferable that it is 10 mass% or less as the content with respect to 100 mass% of the said curable resin composition. By being 10 mass% or less, fear that a curable resin composition becomes difficult to harden can be reduced more. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

-Inorganic materials-
The curable resin composition may also contain an inorganic material, and such a form is also suitable. For example, when forming a cured product using the curable resin composition, particularly when forming an optical member (optical component) such as a lens or a sheet, it is also preferable to include an inorganic material. Thus, the form in which the said curable resin composition further contains an inorganic material is also one of the suitable forms of this invention. When the curable resin composition contains an inorganic material, the strength is improved and the shrinkage rate is reduced. Therefore, the curable resin composition is excellent in molding processability, and has a low linear expansion and higher heat resistance. Further, a lens obtained by curing has a controlled Abbe number and refractive index (particularly, a silicon compound has a high Abbe number). In addition, although low viscosity can be implement | achieved in the curable resin composition of this invention, low viscosity can fully be implement | achieved also when an inorganic material is included. Therefore, it is possible to give a cured product excellent in transparency and uniformity with high productivity.

The said curable resin composition can also reduce a thermal expansion coefficient by containing an inorganic material. Furthermore, by adjusting the refractive index of the inorganic material and the resin, it is possible to control the appearance of the resin composition and its cured product (for example, a molded article such as a lens or a sheet) and to exhibit transparency. It can be particularly useful as a component material or a material in optical applications. Moreover, a mold release effect can be exhibited more by including the inorganic fine particles described later. Specifically, for example, when a thermosetting resin (particularly an epoxy compound) is included as a resin component, the resin component has an adhesive effect, and such a resin composition adheres to a mold when cured. There is a risk. However, by adding an appropriate amount of inorganic fine particles, a mold release effect is observed, and the molded body (cured product) is easily peeled off from the mold.

As the inorganic material, one or more of inorganic fine particles such as metal oxide particles, inorganic polymers such as polysiloxane compounds, and inorganic fibers such as glass cloth are preferable.
The inorganic fine particles are not particularly limited as long as they are fine particles composed of an inorganic compound such as a metal or a metal compound. Inorganic components in the inorganic fine particles include metal oxides, hydroxides, (acid) nitrides, (acid) sulfides, carbides, halides, sulfates, nitrates, (basic) carbonates, (basic) Examples include acetate. Among these, a metal oxide (metal oxide) is preferable, and silica, titanium oxide, zirconium oxide, and zinc oxide are more preferable. Although depending on the refractive index and Abbe number of the curable compound to be used, in order to obtain a molded article (cured product) having a high refractive index or a low Abbe number, usually titanium oxide, zirconium oxide or zinc oxide is preferably used. . On the other hand, silica is preferably used in order to obtain a molded article (cured product) having a low refractive index or a high Abbe number.

The inorganic fine particles also include particles that have been surface-treated for the purpose of improving the affinity of the fine particles with the resin and improving the dispersibility. The surface treatment agent is not particularly limited, and various organic compounds, inorganic compounds, organometallic compounds, and the like are used for the purpose of introducing organic chains and polymer chains on the fine particle surfaces or controlling surface charge. Examples of surface treatment agents include coupling agents such as silane coupling agents, titanate coupling agents, aluminate coupling agents, and zirconium coupling agents; metal alkoxides and (partial) hydrolysis / condensation thereof. And organometallic compounds such as metal soaps.

Examples of the inorganic polymer include polysiloxane compounds, and specific examples include polymethylsilsesquioxane and polyphenylsilsesquioxane.

Examples of the inorganic fiber include glass wool (glass fiber), rock wool, ceramic fiber, and potassium titanate fiber. Among these, glass cloth is preferable.

When the curable resin composition contains an inorganic material, it is preferable that a hydrogenated epoxy compound, an alicyclic epoxy compound and / or an aromatic epoxy compound are essential as the cyclic ether compound described above. As a result, a cured product having a higher Abbe number or a cured product having a high refractive index can be obtained, and the control of the optical characteristics becomes easier. In particular, in order to obtain a cured product having a high refractive index and low water absorption, a form in which an aromatic epoxy compound is essential is most preferable.

When the said curable resin composition contains an inorganic material, it is preferable that it is 0.01-95 mass% as the content with respect to 100 mass% of curable resin compositions. More preferably, it is 0.1-80 mass%, More preferably, it is 0.2-60 mass%, Especially preferably, it is 0.3-20 mass%, Most preferably, it is 0.5-15 mass%.

The curable resin composition may also contain carbon fibers and / or aramid fibers, and such a form is also suitable. It is light and tough by including carbon fiber, etc. while utilizing the characteristics of the resin composition of the present invention, such as fast curability (productivity), uniform curability, resin storage stability, low viscosity and heat resistance. A cured product can be obtained.

The curable resin composition may also contain conductive particles, and such a form is also suitable. The resin composition of the present invention is characterized by rapid curability (productivity), uniform curability, resin storage stability, low viscosity, heat resistance, low water absorption, and a boron compound (catalyst) having a complex structure. Due to the low corrosiveness derived from the above, by including conductive particles, a conductive cured product having excellent durability can be obtained.

The curable resin composition may also contain nanocellulose, cellulose nanofibers and / or chicken nanofibers, and such a form is also suitable. By including these, taking advantage of the characteristics of the resin composition of the present invention, such as fast curability (productivity), uniform curability, resin storage stability, low viscosity, heat resistance, and ease of refractive index control. A transparent cured product having low linear expansion, light weight, and high toughness can be obtained.

-Dye-
The curable resin composition can also contain a dye, and this form is also suitable. In addition, 1 type (s) or 2 or more types can be used as a pigment | dye.
As the dye, a dye having an absorption maximum in a wavelength region of 600 nm or more and 2000 nm or less (also referred to as a near infrared absorbing dye in the present invention) is suitable, but is not limited to a near infrared absorbing dye. What is necessary is just to select suitably the pigment | dye which has characteristic absorption in a specific wavelength in each zone | band of an ultraviolet-ray, visible light, and infrared rays according to a use purpose, and it can apply to the various uses of an optical material.

In the curable resin composition containing the pigment, the pigment is preferably dispersed or dissolved in the resin composition. More preferably, it is a form in which a pigment is dissolved and contained in the curable resin composition. That is, it is preferable that the pigment is dissolved in a resin component or a solvent constituting the curable resin composition.

As will be described later, as the near-infrared absorbing dye used for the purpose of preventing malfunction of the sensor in the imaging lens module, a dye having an absorption maximum in the wavelength region of 600 to 800 nm is suitable. More preferably, it has an absorption maximum in a wavelength region of 650 to 750 nm. It is also preferable that the dye has substantially no absorption maximum in a wavelength region of 400 nm or more and less than 600 nm.

As the near infrared absorbing dye, a dye having a π electron bond in the molecule is preferable. Such a dye having a π electron bond in the molecule is preferably a compound containing an aromatic ring. More preferably, it is a compound containing two or more aromatic rings in one molecule.
In addition, it is especially preferable that the pigment | dye which has a pi-electron bond in the said molecule | numerator is what has an absorption maximum in the suitable wavelength range mentioned above.

Examples of the dye having a π-electron bond in the molecule include, for example, phthalocyanine dyes, porphyrin dyes, cyanine dyes, quaterylene dyes, squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like. These can be used, and one or more of these can be used. Among these, a dye having neither a zwitterionic structure nor a cationic structure is preferable from the viewpoint of heat resistance and weather resistance, and a phthalocyanine dye and / or a porphyrin dye is preferable. More preferred are metal phthalocyanine complexes and / or metal porphyrin complexes.

As the phthalocyanine dye, a metal phthalocyanine complex is suitable, for example, a metal whose central metal is a metal element such as copper, zinc, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead. A phthalocyanine complex is mentioned. Among these metal elements, those having one or more of copper, vanadium, and zinc as a central metal are preferable because they are more excellent in solubility, visible light transmittance, and light resistance. The center metal is more preferably copper and zinc, and even more preferably copper. The phthalocyanine using copper is not deteriorated by light even when dispersed in any binder resin, and has very excellent light resistance.
As the porphyrin-based dye, metal porphyrin complexes such as tetraazaporphyrin are suitable.

When the said curable resin composition contains a pigment | dye, it is preferable that it is 0.0001-10 mass% with respect to 100 mass% of curable resin compositions. More preferably, it is 0.001-1 mass%.

Here, in the imaging lens module, an infrared cut filter (reflection type) in which a transparent resin sheet is used as a base material and an infrared reflection film is provided on one or both sides in order to remove (near) infrared rays in incident light that becomes noise. (Also referred to as IRCF) is known on the incident light side or the outgoing light side of the lens. However, the reflection-type IRCF needs to be improved because the spectral transmittance curve varies depending on the incident angle (depends on the incident angle).
In the reflective IRCF, the present applicant can suppress the incident angle dependency by using a resin sheet having a dye-containing layer obtained from a composition containing a near-infrared absorbing dye in a resin composition as a base material. It has already been found that a reflective IRCF can be obtained. Therefore, the resin composition is used as the curable resin composition of the present invention, that is, based on a resin sheet having a dye-containing layer obtained from a composition containing a near-infrared absorbing dye in a curable resin composition. It was confirmed that by using the material, it is possible to obtain a reflective IRCF that is suppressed in incident angle dependency and is excellent in heat resistance and the like.

That is, since the curable resin composition of the present invention has excellent heat resistance and light resistance required for IRCF for imaging lenses, a dye-containing layer obtained from the composition containing a near-infrared absorbing dye is used. The resin sheet (molded body) is useful as a base material for a reflection type IRCF in which the incidence angle dependency is suppressed. In addition, by incorporating a near-infrared absorbing dye into the lens itself obtained from the curable resin composition of the present invention, the incident angle dependency is suppressed even when the imaging lens module including the lens is equipped with a reflective IRCF. Therefore, it is preferable.
Thus, the IRCF substrate (resin sheet) used for the imaging lens module, the curable resin composition containing a near-infrared absorbing dye for lenses, and a molded body (for example, resin) obtained from the composition Sheets, lenses, etc.) are also preferred forms of the present invention.

The curable resin composition containing the near-infrared absorbing dye is not limited to the application to the IRCF substrate (resin sheet) and the lens, and various members constituting the imaging lens module such as a sealant and an adhesive. Also, it can be suitably used for other members such as a microlens above the sensor. Furthermore, it is preferably used for various applications such as LED sealing resin and LED lens resin other than the imaging lens module.

In addition to the essential components and suitable components described above, the curable resin composition may also include other curing catalysts / curing agents, curing accelerators, reactive diluents, as long as the effects of the present invention are not impaired. Saturated compounds without unsaturated bonds, pigments, dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization prohibited Adhesion improvers such as adhesives, inorganic fillers, organic fillers, coupling agents, heat stabilizers, antibacterial and antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, sedimentation Antibacterial agent, thickener / anti-sagging agent, anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, desiccant, antifouling agent, antistatic agent, conductive agent (electrostatic aid), solvent 1 type or 2 types or more, such as, may be contained.

[Preparation and curing method of curable resin composition]
The curable resin composition of the present invention can be prepared by mixing the cyclic ether compound, the double bond compound and the boron compound, and further mixing the other components as necessary. When mixing each component, if necessary, each component or mixture can be heated and mixed so as to have a uniform composition. The heating temperature is not particularly limited as long as it is not higher than the decomposition temperature of the curable resin (cyclic ether compound or double bond compound) or not higher than the reaction temperature, but preferably 140 to 20 ° C. before addition of the catalyst. More preferably, it is 120-40 degreeC.

As a method for curing the curable resin composition, various methods such as thermal curing and photocuring (curing by irradiation with active energy rays) can be suitably used. As thermosetting, it is preferable to cure at about 30 to 400 ° C., and as photocuring, it is preferable to cure at 10 to 10,000 mJ / cm ² . Curing may be performed in one stage, or may be performed in two stages such as primary curing (preliminary curing) and secondary curing (main curing). For example, when molding such as a lens is required, a demolding operation is required. However, a primary curing is performed before the demolding operation and a secondary curing is performed after the demolding operation. -A molding method is preferably employed.
Hereinafter, the case of performing the two-stage curing will be described in detail.
As a two-step curing method, as a first step corresponding to primary curing, the resin composition is photocured at 10 to 100000 mJ / cm ² or thermally cured at 80 to ²⁰⁰ ° C., and the first step It is preferable to employ a method including a second step corresponding to the secondary curing in which the cured product obtained in the step is thermally cured at a temperature exceeding 200 ° C. and not exceeding 500 ° C.

In the said 1st process, in the case of thermosetting, it is preferable to make hardening temperature into 80-200 degreeC. More preferably, it is 100 degreeC or more and 160 degrees C or less. Moreover, you may change a curing temperature in steps within the range of 80-200 degreeC.
The curing time in the thermosetting step is preferably, for example, within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.

The thermosetting step can also be performed in air or in an atmosphere of an inert gas such as nitrogen, under reduced pressure, or under pressure. For example, from the standpoint of improving productivity, etc., the resin composition is kept in the mold at a predetermined temperature and time, and then taken out of the mold and left in the atmosphere of an inert gas such as nitrogen or in a heat treatment. It is also possible to do. Moreover, you may combine photocuring (curing by active energy ray irradiation).

The first step is also preferably a curing step using a mold made of metal, ceramic, glass, resin or the like (referred to as “mold”). The curing process using a mold may be a curing process normally performed in a mold molding method such as an injection molding method, a compression molding method, a casting molding method, a sandwich molding method, etc., but the first step is If it is a hardening process using such a metal mold | die, it is excellent in various physical properties, such as abrasion resistance, a low shrinkage, a dimensional accuracy, and mold transfer property, and it can manufacture easily a transparent molded object without coloring. .

When the first step is a curing step using a mold, it is preferable to perform the demolding step after the first step and before the second step. The mold including the demolding process, that is, the cured product obtained in the first process is taken out from the mold, and the taken cured product is used for the next second process, whereby the expensive mold is effectively rotated (recycled). ) And the life of the mold can be extended, and a molded product can be obtained at low cost.
In this case, the resin composition is a one-component composition containing a curing agent and other components as necessary, and the one-component composition is filled into a mold that matches the shape of the target molded article (injection / A method in which the cured product is taken out from the mold after coating and the like is suitably used.

In the curing method, in the second step, the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is heat-cured at a temperature exceeding 200 ° C. and not more than 500 ° C. preferable. The lower limit of the curing temperature is more preferably 250 ° C. or higher, still more preferably 300 ° C. or higher, particularly preferably 330 ° C. or higher, and most preferably 350 ° C. or higher. The upper limit is more preferably 400 ° C. or lower. Further, the curing temperature may be changed stepwise within a temperature range exceeding 200 ° C. and not more than 500 ° C.
The curing time in the second step is not particularly limited as long as the curing rate of the obtained molded body is sufficient, but considering production efficiency, for example, 30 minutes to 30 hours is preferable. . More preferably, it is 1 to 10 hours.

The second step can also be performed in any atmosphere such as air or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0.5 volume% or less, Most preferably, it is 0.3 volume% or less.

The strength of the cured product obtained by the above curing method may be a strength that can be taken out of the mold and keep the shape. For example, the ratio of the shape change when extruded with a force of 9.8 × 10 ⁴ Pa or more Is preferably 10% or less. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, and still more preferably 0.01% or less.

The curable resin composition of the present invention has a high refractive index as described above, and has high heat resistance, adhesion, chemical resistance, temperature shock resistance, etc., and after being exposed to a high temperature environment. In addition, a cured product that can stably exhibit high transparency and uniformity can be provided. Thus, the hardened | cured material formed by hardening | curing the said curable resin composition is also one of this invention.

The cured product is preferably a molded body, for example, an optical material (member), a machine part material, an electric / electronic part material, an automobile part material, a civil engineering building material, a molding material, a paint or an adhesive. It is useful for various uses such as materials. Especially, it can use suitably for an optical material, an optical device member, a display device member, etc. Specific examples of such applications include spectacle lenses, imaging lenses for cameras such as (digital) cameras, mobile phone cameras, and in-vehicle cameras, lenses such as light condensing lenses, light diffusion lenses, optical sheets, LED sealing materials, optical adhesives, optical transmission bonding materials, filters, diffraction gratings, prisms, light guides, watch glasses, optical applications such as cover glasses for display devices, and cover glasses; photo Opto device applications such as sensors, photoswitches, LEDs, light emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical fiber adhesives; substrates for display elements such as LCD, organic EL, and PDP , Color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, antifogging films, etc. It chairs applications and the like.

Among these uses, an optical material is particularly suitable. Thus, the form in which the cured product is an optical material and the form in which the curable resin composition is a resin composition for an optical material are also included in preferred forms of the present invention.
The curable resin composition of the present invention is transparent and free of turbidity, that is, excellent in transparency and uniformity. However, as described above, other physical properties (for example, high heat resistance and resistance) Needless to say, it is also useful in applications where transparency and uniformity are not required because it is excellent in temperature impact, adhesiveness, and the like.

The optical material is particularly preferably a lens, an optical sheet, an LED sealing material, an optical adhesive, or a light transmission bonding material. The lens is preferably a camera lens, a light collecting lens, a light diffusion lens, and an optical pickup lens, and more preferably a camera lens. Among camera lenses, imaging lenses such as an imaging lens for a mobile phone and an imaging lens for a digital camera are preferable. Moreover, it is preferable that it is a micro optical lens.
In addition, when the said curable resin composition is a resin composition for optical materials, it may contain the other component suitably according to the use of the optical material. Specific examples of other components include UV absorbers, IR cut agents, reactive diluents, pigments, washing agents, antioxidants, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, heat transfer agents, Preferable examples include a polymerization initiator, an anaerobic polymerization initiator, a polymerization inhibitor, and an antifoaming agent.

The curable resin composition of the present invention is useful from the viewpoint of reducing the environmental load by using the above-described boron compound, as compared with the case of using an antimony cation curing catalyst, and particularly in the application of optical materials. Usefulness is high. In particular, the resin composition of the present invention is used in lenses such as imaging lenses for cameras, light condensing lenses, and light diffusion lenses, optical sheets, LED sealing materials, and optical adhesives that are expected to increase in demand worldwide. The value of using things is high. Moreover, since the molded article (cured product) obtained from the resin composition of the present invention has a low water absorption, it is preferably used in each application of a camera lens, a light condensing lens, a light diffusion lens, and an optical pickup lens. More preferred is the use of a camera lens, and among the camera lenses, an imaging lens such as an imaging lens for a mobile phone and an imaging lens for a digital camera is still more preferred. Water absorption in the molded body (cured product) causes expansion, cracking, and the like. However, in the above-described micro optical lens in which these slight changes due to water absorption tend to appear in the optical characteristics, the molded body (cured) of the present invention. Is effective.

The cured product obtained from the curable resin composition of the present invention also has high reflow heat resistance, and reduction in visible light transmittance and coloring can be suppressed. Various elements such as mobile phones, televisions, personal computers, and in-vehicle applications are in the process of adopting a solder reflow process for reasons such as simplification of manufacturing processes and cost reduction. Since the curable resin composition of the present invention or a molded product obtained from the composition suppresses deterioration of optical properties even when subjected to a solder reflow process, members of various elements that employ the solder reflow process (for example, Optical materials such as lenses, sheets, filters, adhesives, etc.). In particular, when the boron compound is a TPB catalyst, the molded article (cured product) obtained from the composition has a particularly low water absorption rate and excellent heat resistance. The resin composition is particularly useful for each optical material application described above.

The cured product preferably has a glass transition temperature (Tg) of 170 ° C. or higher. Thereby, it becomes hardened | cured material more excellent by heat resistance, temperature impact resistance, adhesiveness, etc. More preferably, it is 180 degreeC or more, More preferably, it is 190 degreeC or more, Most preferably, it is 200 degreeC or more.
The glass transition temperature of the cured product can be measured, for example, by a three-point bending test using a dynamic viscoelasticity measuring device (manufactured by TA instruments, RSA-III).

The cured product preferably has a refractive index of 1.4 to 1.65 at a wavelength of 589 nm. More preferably, it is 1.45 or more, More preferably, it is 1.47 or more, Especially preferably, it is 1.50 or more, Most preferably, it is 1.55 or more. Moreover, it is more preferable that it is 1.60 or less.
The refractive index can be measured using a refractometer (Atago Co., Ltd., DR-M2).

The cured product preferably has an Abbe number of 28 or more. Thereby, the wavelength dispersion of light can be reduced, the resolution can be improved, and the optical characteristics can be improved. More preferably, it is 30 or more. Moreover, although an upper limit is not specifically limited, Preferably it is 55 or less.
The Abbe number can be measured using a refractometer (Atago Co., Ltd., DR-M2).

Since the curable resin composition of the present invention is configured as described above, it is excellent in storage stability and handling properties, has a high refractive index, and has high heat resistance, adhesion, and chemical resistance. And a cured product (molded product) that has a high degree of transparency and uniformity even after being exposed to a high-temperature environment can be provided with high productivity. Therefore, the cured product obtained from the curable resin composition of the present invention includes optical materials, molding materials, machine parts, electrical / electronic parts, automobile parts, civil engineering and building materials, paint materials, adhesive materials, and the like. It can be suitably applied to various uses and is particularly useful as an optical material.

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%”.

Preparation Example 1: Synthesis of TPB-containing powder B According to a synthesis method described in International Publication No. 1997/031924, 255 g of Isopar E solution having a TPB (tris (pentafluorophenyl) borane) content of 7% was prepared. Water was added dropwise to this solution at 60 ° C. White crystals precipitated from the middle of the dropping. After cooling the reaction solution to room temperature, the resulting slurry was suction filtered and washed with n-heptane. The obtained cake was dried at 60 ° C. under reduced pressure, and 18.7 g of TPB / water complex (TPB-containing powder B) as white crystals was obtained. This complex had a water content of 9.2% (Karl Fischer moisture meter) and a TPB content of 90.8%. The complex after drying was subjected to ¹⁹ F-NMR analysis and GC analysis, but no peaks other than TPB were detected.
The measurement results by ¹⁹ F-NMR analysis were as follows.
¹⁹ F-NMR (CDCl ₃ ) ppm (standard substance: CFCl ₃ 0 ppm)
δ = −135.6 (6F, m)
δ = -156.5 (3F, dd)
δ = −163.5 (6F, d)

Preparation Example 2: Synthesis of Boron Compound (Cation Curing Catalyst A) 2 g of TPB-containing powder B obtained in Preparation Example 1 ((TPB pure content: 1.816 g, 3.547 mmol), (water: 0.184 g, 10. 211 mmol)), 2.1 g of γ-butyrolactone was added and mixed at room temperature for 10 minutes, then 0.778 g of ADK STAB LA57 (hindered amine, manufactured by ADEKA) was added, mixed at room temperature for 10 minutes, and further 60 The mixture was mixed at 20 ° C. for 20 minutes to obtain a uniform solution of the cationic curing catalyst A (TPB complex).

Example 1
157S-70 (a novolak type aromatic epoxy compound, epoxy equivalent: 200 to 220, manufactured by Mitsubishi Chemical Corporation) as a cyclic ether compound 70 parts, DVB-960 (divinylbenzene, manufactured by Nippon Steel Chemical Co., Ltd.) as a double bond compound 30 Part and 0.5 part of stearic acid are uniformly mixed at 80 ° C. Thereafter, the temperature was lowered to 40 ° C. 0.5 parts of dodecanol and 1 part of cationic curing catalyst A were added and mixed uniformly at 40 ° C. under reduced pressure to obtain a resin composition (1). The obtained resin composition (1) was cured by the following method to obtain a cured product.

<Curing process>
(First step)
Using two metal plates of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800), gaps at intervals of 150 μm or 1 mm were formed, and each resin composition was cast. After the primary curing at the temperature / time described in Table 1, the mold was removed.
(Second process (cure))
After curing in the first step, curing treatment was performed under the following conditions under an N ₂ atmosphere (implemented at an oxygen concentration of less than 0.1% by volume).
Conditions: 250 ° C. × 1 hour An inert gas oven (manufactured by Koyo Thermo Systems Co., Ltd., model: INL-45N1-S) was used for the test under an N ₂ atmosphere.
Temperature profile: 40 ° C x 30 minutes → Temperature rise at maximum speed (about 30 minutes) → 250 ° C x 1 hour → Temperature drop at maximum speed → 50 ° C x 30 minutes

In the following method, the viscosity and storage stability of the resin composition (1); curability (curability at the time of primary curing); glass transition temperature, refractive index, Abbe number and the cured product (after secondary curing) The transmittance was evaluated. The results are shown in Table 2.
<Viscosity>
For the resin composition (1) obtained in Example 1, the viscosity at 40 ° C. was measured.
In the storage stability evaluation test, the resin composition (1) obtained in Example 1 was allowed to stand in an environment of 40 ° C., and the viscosity (unit: Pa · s) after 8 hours was measured.
The measurement of the viscosity was performed on the resin composition using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22 viscometer cone plate type) at 40 ° C.

<Curability (curability at the time of primary curing)>
The resin composition (1) was cured under primary curing conditions. After the primary curing, the cured product taken out from the SUS plate was evaluated as “x” when the cured product was in a liquid or gel state, and “◯” when it was taken out as a solid.

<Glass transition temperature (Tg)>
The cured product (thickness 1 mm) after final curing (secondary curing) is subjected to a glass transition temperature (unit: ° C.) by a three-point bending test using a dynamic viscoelasticity measuring device (TA instruments, RSA-III). It was measured.

<Refractive index, Abbe number>
About the hardened | cured material (thickness 1mm) after final hardening (secondary hardening), the refractive index and Abbe number in wavelength 589nm were measured using the refractometer (Atago company make, DR-M2).

<Transmissivity of cured product (presence or absence of coloring)>
The transmittance of the cured product (thickness 0.15 mm) after final curing (secondary curing) was measured using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). Specifically, the transmittance at 400 nm, which is a short wavelength region of visible light, and 600 nm, which is the central region of visible light, was evaluated, and the presence or absence of coloring was evaluated.
The presence or absence of coloring (yellowishness) can be evaluated from the transmittance at a wavelength of 400 nm, and the presence or absence of haze (turbidity) can be evaluated from the transmittance at a wavelength of 600 nm.

<Heat resistance test (reflow heat resistance test)>
The cured product (thickness 0.15 mm) after final curing (secondary curing) was dried in the atmosphere at 260 ° C. for 10 minutes, and then the transmittance of the cured product at wavelengths of 400 nm and 600 nm was measured using an absorbance meter (Shimadzu Corporation). And spectrophotometer UV-3100).

Examples 2-6, Comparative Examples 1-5
Resin compositions (2) to (6) and (Ratio 1) to (Ratio 5) were produced in the same manner as in Example 1 except that the raw materials shown in Table 1 were used in the amounts shown in Table 1. . Each obtained resin composition was cured in the same manner as in Example 1. As in Example 1, the viscosity and storage stability of each resin composition; curability (curability at the time of primary curing); glass transition temperature, refractive index, Abbe number and transmission of the cured product (after secondary curing) Rate was evaluated. The results are shown in Table 2.
In addition, in the first curing step in Example 6, the adhesion of the molded product at the time of the primary curing was strong and difficult to release, so as a SUS metal plate, Die Free GA-7500 which is a fluorine-based mold release agent. (Fluorine-silicone system, manufactured by Daikin Industries, Ltd.) was sprayed on the SUS plate and wiped off, and this SUS plate was used.
In addition, as Comparative Example 1-2, a resin composition (Ratio 1) was used, and curing was performed with different primary curing conditions from Comparative Example 1, and viscosity and storage stability; curability (at the time of primary curing) Curability): The glass transition temperature, refractive index, Abbe number and transmittance of the cured product (after secondary curing) were evaluated in the same manner as in Example 1. The results are also shown in Table 2.

The symbols and abbreviations in Tables 1 and 2 are as follows.
<Table 1>
YX-8034: Hydrogenated epoxy resin, Mitsubishi Chemical Corporation CELL-2021P: Trade name “Celoxide CELL-2021P”, liquid alicyclic epoxy resin, epoxy equivalent 131, weight average molecular weight 260, Daicel Chemical Industries, Ltd. 828US: Bisphenol Type A epoxy resin (aromatic epoxy compound), Mitsubishi Chemical Corporation 1001: High molecular weight bisphenol A type epoxy resin (aromatic epoxy compound), Mitsubishi Chemical Corporation 157S-70: Novolac type aromatic epoxy resin (aromatic epoxy) compound), manufactured by Mitsubishi chemical Corporation DVB-960: divinylbenzene, manufactured by Nippon Steel chemical Co., Ltd. SI-100L: trade name "San-Aid SI-100L", antimony-based cationic curing catalyst (SbF ₆ ^- sulfonium salt), Sanshin chemical <Table 2> made by company
“S”: second “hr”: time “t”: thickness

From Tables 1 and 2, the following was confirmed.
Comparative Example 1 is an example using an antimony sulfonium salt instead of the boron compound of the present invention. In this case, the curability was inferior and a cured product was not obtained. Therefore, in Comparative Example 1-2, when the curing time in the primary curing is significantly longer than that in Comparative Example 1, although cured, at any time after the final curing (secondary curing) and after the reflow heat resistance test. Further, the transmittance of the cured product was low, and the heat resistance, heat resistance coloring property and uniformity of curing were insufficient. Further, among the cyclic ether compound, double bond compound and boron compound essential in the present invention, when the double bond compound is not included, the viscosity of the resin composition is remarkably high as shown in Comparative Examples 2 and 3, The storage stability is not sufficient, and the glass transition temperature of the resulting cured product is not sufficient. On the other hand, when the cyclic ether compound was not included, as shown in Comparative Examples 4 and 5, the curability was inferior and a cured product was not obtained.

On the other hand, the resin compositions (1) to (6) containing a cyclic ether compound, a double bond compound and a boron compound have a low viscosity and are excellent in storage stability with little increase in viscosity over time. It was. Moreover, the curability is sufficient so that it can be sufficiently cured even in the primary curing, the Tg and transmittance of the final cured product are high, the heat resistance and the heat coloring property are excellent, and the refractive index and Abbe number are also in an appropriate range. It was in. Such a mechanism of action is considered to be expressed in the same manner as long as it includes a cyclic ether compound, a double bond compound and a boron compound.

Claims (7)

A curable resin composition comprising a compound having a cationic curable cyclic ether group, a compound having a cationic curable double bond, and a boron compound,
The boron compound has the following general formula (1):

(In the formula, R is the same or different and represents a hydrocarbon group which may have a substituent. X is an integer of 1 to 5, and is the same or different and is a fluorine atom bonded to an aromatic ring. Wherein a is an integer of 1 or more, b is an integer of 0 or more, and a + b = 3 is satisfied), and a compound comprising a Lewis acid and a Lewis base. A curable resin composition. The cation-curable cyclic ether group-containing compound includes at least one selected from the group consisting of alicyclic epoxy resins, hydrogenated epoxy resins, aromatic epoxy resins, and oxetane compounds. The curable resin composition according to 1. The curable resin composition according to claim 1, wherein the boron compound is used as a curing catalyst. The curable resin composition according to claim 1, wherein the compound having a cationic curable double bond includes a compound having a vinyl group and / or a compound having an allyl group. The curable resin composition according to claim 1, wherein the curable resin composition is for an optical material. Hardened | cured material formed by hardening | curing the curable resin composition in any one of Claims 1-5. An optical material comprising the curable resin composition according to claim 1.