TWI480308B - Cationic hardening resin composition - Google Patents

Description

Cationic hardening resin composition

The present invention relates to a cationically curable resin composition. More specifically, it relates to a resin composition which contains a cationically curable compound and which can be cured by a cationic hardening reaction by a cationic hardening catalyst which generates a cationic species by heat or light.

The cation-curable resin composition is a resin composition containing a cation-curable compound and a cation-curing catalyst, and a cationic species is generated by a catalyst such as heat or light, and is cured by a cationic hardening reaction. The cation hardening (polymerization) has an advantage that it does not cause hardening by oxygen and has a small shrinkage at the time of hardening, and is expected to be used in various fields. Specifically, for example, in addition to electrical and electronic components, optical members, and molding materials, various applications such as coating materials and materials for adhesives have been studied, and it has been desired to develop cation hardenability excellent in characteristics required for each application. Resin composition.

In the case of the conventional cationically curable resin composition, for example, in order to obtain a molded article excellent in heat resistance, transparency, mold release property, and the like, a compound containing a cationically curable compound and having a boiling point of 260 ° C or less at one atmospheric pressure is used. A curable resin composition for an optical molded body of a mold and a cation-curing catalyst has been studied (for example, see Patent Document 1). Patent Document 1 discloses a case where a lanthanum cerium salt or the like is used as a cation hardening catalyst.

Further, a technique of using a boron-containing compound for hardening a resin composition has also been examined. For example, it is disclosed that tetrakis(pentafluorophenyl)borate (TEPB) is used as a photocationic polymerization initiator in a photocurable resin composition containing a photocationic polymerizable compound and a photocationic polymerization initiator. Thereby, a cured product having low moisture permeability and excellent transparency is obtained (for example, refer to Patent Document 2). Further, an amine-containing complex of boron trifluoride is used as a curable composition of a nitrogen atom-containing latent curing agent for an epoxy resin (see, for example, Patent Document 3).

The curable resin composition containing a boron-containing compound further includes a curable resin composition containing a "curable resin" and a "curing catalyst containing a Lewis acid containing trivalent boron and a nitrogen-containing molecule" (for example, refer to Patent Document 4). Patent Document 4 describes a case where the curable resin composition is cured by using an acid anhydride. In addition, a curable epoxy resin composition for encapsulating a solid element device containing an "anhydride curing agent" and a "boron-containing catalyst such as triphenylborane" (see, for example, Patent Document 5).

Patent Document 1: Japanese Laid-Open Patent Publication No. 2009-299074

Patent Document 2: Japanese Laid-Open Patent Publication No. 2005-187636

Patent Document 3: Japanese Laid-Open Patent Publication No. 62-240316

Patent Document 4: Japanese Patent Publication No. 2008-544067

Patent Document 5: Japanese Laid-Open Patent Publication No. 2003-192765

However, the cation-curable resin composition is being studied and applied to various applications, and since it can exhibit transparency, it is particularly useful as a material for optical applications such as lenses. For example, in the digital camera module, in order to reduce the size of the mobile phone and the like, and to reduce the cost, a resin lens is gradually used instead of the conventional inorganic glass as the imaging lens. In the mounting step of such a member, in order to achieve cost reduction, a solder reflow method has become mainstream. Therefore, in the case where a cationically curable resin composition is used in order to form a member such as a lens, it is required that the cured product (molded body) has heat resistance which can withstand the reflow step. Further, in the case of use as an optical material, it is also required to have heat and humidity resistance or UV radiation resistance in a use environment.

Regarding such aspects, as described above, Patent Document 1 discloses a resin composition using a lanthanum cerium salt as a cation curing catalyst. By using the bismuth salt, it can be used in the reflow method, and has achieved certain results. However, in the case of using a ruthenium salt, the formed body is colored by heat (heat during hardening, use environment), and as a result, there is a problem that the transmittance of light of 400 nm of short-wavelength visible light is lowered, and heat resistance of the molded body is obtained. Not enough yet. Further, the molded body obtained by curing the cerium-based cerium salt tends to have a relatively high water absorption rate, and when used as an optical material, there is still room for further reduction in water absorption.

On the other hand, when TEPB is used as in Patent Document 2, coloring or the like occurs due to heat in the secondary hardening or reflow step at 250 ° C, and the heat resistance of the molded body is not sufficient. Further, since the amine complex of boron trifluoride described in Patent Document 3 generates corrosive hydrofluoric acid when it comes into contact with moisture, there is no possibility of ensuring safety during work and the like. Further, as described in Patent Document 4 or Patent Document 5, when an acid anhydride is used to harden a resin composition, there is a problem that it is difficult to be hard in a short period of time as compared with hardening of a cation hardening reaction using a cationic curing catalyst. The formed body is obtained, and the heat resistance of the formed body cannot be increased to the extent that it can be used for the reflow step.

As described above, the prior art has further studied a space for providing a resin composition of a molded article having excellent properties such as heat resistance, moist heat resistance, low water absorbability, and UV radiation resistance.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a cationically curable resin composition which can obtain a molded article excellent in heat resistance, moist heat resistance, low water absorbability, UV radiation resistance, and the like, and can be used for an optical member. Shaped bodies for various purposes.

The inventors of the present invention conducted various studies on a cationically curable resin composition containing a cationic curable compound and a cationic curing catalyst as essential components, and as a result, it has been found that a compound composed of a specific Lewis acid having a boron atom and a Lewis base is used as a compound. In the cationic curing catalyst, the molded body obtained by curing the resin composition is excellent in heat resistance, moist heat resistance, low water absorption, and UV irradiation resistance. In particular, it has been found that, if the cationic hardening catalyst of the present invention is used, the transmittance of the obtained shaped body by the heat or ultraviolet light in the short-wavelength region of the visible or visible light can be suppressed as compared with the previous lanthanide cationic curing catalyst. reduce. Further, it has been found that such a molded article is extremely useful for optical applications such as lenses, and it is thought that the above problems can be completely solved, and the present invention has been completed.

In other words, the present invention relates to a cationically curable resin composition comprising a cation-curable compound and a cation-curing catalyst as essential components, wherein the cation-curing catalyst is represented by the following formula (1). Lewis acid and Lewis base,

Wherein R is the same or different and represents a hydrocarbon group which may have a substituent; x is an integer of from 1 to 5, the same or different, and represents the number of fluorine atoms bonded to the aromatic ring; a is an integer of 1 or more, and b is 0. The above integer, and satisfies a+b=3).

The present invention also relates to a molded body obtained by curing the above cationically curable resin composition.

Hereinafter, the present invention will be described in detail.

Further, a combination of two or more preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

The cationically curable resin composition (also referred to as a resin composition) of the present invention contains a cationic curable compound and a cationic curing catalyst as essential components, but may contain other components within a range that does not impair the effects of the present invention. One or two or more kinds of the components may be used.

The cation curing catalyst is composed of a Lewis acid (organoborane) represented by the above formula (1) and a Lewis base. Therefore, since cation hardening can be used as the hardening method, the cured product obtained is excellent in heat resistance, chemical stability, moisture resistance, and the like, in particular, optical use, for example, in the case of addition hardening such as curing with an acid anhydride. Those who are required to have excellent characteristics. Further, compared with the case of using a conventional cation-hardening catalyst such as a lanthanum cerium salt, color reduction due to heat (heat during curing, use environment), hygroscopicity reduction, moist heat resistance or UV irradiation resistance are obtained. A cured product excellent in durability. Further, the presence or absence of the color of the cured product based on the catalyst to be used can be generally confirmed by the change in transmittance at 400 nm. That is, by measuring the transmittance of the cured product at 400 nm, the presence or absence of the coloration of the cured product can be evaluated.

In addition, the cation hardening catalyst refers to a catalyst that promotes a cation hardening reaction, and functions differently from, for example, a hardening accelerator in an acid anhydride hardening reaction.

R in the above formula (1) is the same or different and represents a hydrocarbon group which may have a substituent. The hydrocarbon group is not particularly limited, and is preferably a hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group having 1 to 20 carbon atoms is not particularly limited as long as the total number of carbon atoms is from 1 to 20, and is preferably an alkyl group, an aryl group or an alkenyl group. The alkyl group, the aryl group and the alkenyl group may be an unsubstituted group, or may be a group in which one or two or more hydrogen atoms are substituted with another organic group or a halogen atom. The other organic group in this case may, for example, be an alkyl group (in the case where the hydrocarbon group represented by R is an alkyl group, the entire substituted hydrocarbon group corresponds to an unsubstituted alkyl group), an aryl group, an alkenyl group or an alkoxy group. Base, hydroxyl group, etc.

In the above formula (1), x is an integer of from 1 to 5, which is the same or different and represents the number of fluorine atoms bonded to the aromatic ring. The bonding position of the fluorine atom on the aromatic ring is not particularly limited. x is preferably from 2 to 5, more preferably from 3 to 5, most preferably 5.

Further, a is an integer of 1 or more, and b is an integer of 0 or more, and satisfies a+b=3. 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. More preferably, it is 2 or more, and most preferably 3, that is, a form in which three aromatic rings having a fluorine atom are bonded to a boron atom.

Specific examples of the Lewis acid include tris(pentafluorophenyl)borane (TPB), bis(pentafluorophenyl)phenylborane, pentafluorophenyl-diphenylborane, and the like. (4-fluorophenyl)borane and the like. The TPB is more preferable because it can improve heat resistance, moist heat resistance, low water absorbability, UV radiation resistance, and the like of the molded article.

Further, in the specification, the examples, and the like of the present application, the cation-curing catalyst of the present invention is described as a TPB-based catalyst in which TPB is contained as a Lewis acid.

The Lewis base is not limited as long as it can form a coordination bond with the boron atom of the Lewis acid as long as it is capable of coordinating with the Lewis acid, and it is preferably used as a Lewis base, and preferably has a non- A compound that shares the atoms of an electron pair. 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 supplying an unpaired electron pair having a nitrogen atom, a phosphorus atom, and a sulfur atom to the boron atom of the Lewis acid. Further, a compound having a nitrogen atom or a phosphorus atom is more preferred.

The compound having a nitrogen atom is preferably an amine (monoamine, polyamine), ammonia or the like. More preferred are amines having a hindered amine structure, amines having a low boiling point, ammonia, more preferably polyamines having a hindered amine structure, and ammonia. When a polyamine having a hindered amine structure is used as the Lewis base, the oxidation resistance of the cured molded body can be achieved by the radical trapping effect, and the obtained cured product is more excellent in heat resistance (humid heat resistance). On the other hand, when ammonia or a low-boiling amine is used as the Lewis base, the obtained cured product is excellent in low water absorbability and UV radiation resistance. It is presumed that since the ammonia or the low-boiling amine is volatilized in the hardening step, the salt structure derived from ammonia or a low-boiling amine in the final shaped body (hardened product) is reduced, so that the water absorption rate of the molded body can be reduced. In particular, the above effect of ammonia is excellent, and therefore it is preferable.

The amine having a hindered amine structure preferably has a nitrogen atom forming a coordinate bond with a boron atom as a secondary or tertiary amine from the viewpoint of storage stability of the resin composition and hardenability at the time of molding. More preferably, it is a polyamine of a diamine or more. As the amine having a hindered amine structure, specifically, 2,2,6,6-tetramethylpiperidine, N-methyl-2,2,6,6-tetramethylpiperidine; TINUVIN770, TINUVIN 765, TINUVIN 144, TINUVIN 123, TINUVIN 744, CHIMASSORB 2020 FDL (above, manufactured by BASF Corporation); Adekastab LA52, Adekastab LA57 (above, manufactured by ADEKA), and the like. Among them, TINUVIN770, TINUVIN765, Adekastab LA52, and Adekastab LA57 having two or more hindered amine structures in one molecule are preferable.

The amine having a low boiling point is preferably an amine having a boiling point of 120 ° C or less, more preferably 80 ° C or less, still more preferably 50 ° C or less, still more preferably 30 ° C or less, still more preferably 5 ° C or less. Specific examples thereof include a monoamine such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, and ethylenediamine; dimethylamine and diethylamine; a secondary amine such as dipropylamine, methylethylamine or piperidine; a tertiary amine such as trimethylamine or triethylamine.

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

The compound having a sulfur atom is preferably a thiol or a thioether. Specific examples of the mercaptan include methyl mercaptan, ethyl mercaptan, propanethiol, hexyl mercaptan, decyl mercaptan, and benzene mercaptan. Specific examples of the thioethers include diphenyl sulfide, dimethyl sulfide, diethyl sulfide, methylphenyl sulfide, and methoxymethylphenyl sulfide.

In the cation hardening catalyst of the present invention, the mixing ratio of the Lewis acid to the Lewis base is not necessarily a stoichiometric ratio. That is, it may contain either a Lewis acid or a Lewis base (in terms of an alkali point amount) in excess of the theoretical amount (equivalent).

That is, the mixing ratio of the Lewis acid to the Lewis base in the cation hardening catalyst is "the number of atoms n (b) of the atom which becomes the Lewis base point" with respect to "the number of atoms of boron which is the Lewis acid point n (a) The ratio (n(b)/n(a)) indicates that the cation hardening catalyst acts even if it is not 1 (metering ratio).

The ratio n(b)/n(a) in the cationic curing catalyst affects the storage stability and cationic hardening properties (hardening rate, hardening degree of the cured product, etc.) of the resin composition.

Further, when a Lewis base such as a diamine or the like has two Lewis base points in the molecule, the mixed molar ratio of the Lewis base to the Lewis acid constituting the cationic hardening catalyst is 0.5, the ratio n(b) /n(a)=1 (measurement ratio). The ratio n(b)/n(a) is calculated in this way.

From the viewpoint of the storage stability of the resin composition containing the cation-curing catalyst, if the Lewis acid is excessively excessively present in the Lewis base, the storage stability may be lowered. Therefore, in order to produce a resin excellent in storage stability The composition preferably has a ratio of n (b) / n (a) of 0.5 or more. For the same reason, the above ratio is more preferably 0.8 or more, more preferably 0.9 or more, still more preferably 0.95 or more, and still more preferably 0.99 or more.

On the other hand, in the case of the cation hardening property, when the Lewis base is excessively excessive, the low-temperature hardenability of the cured product is lowered. Therefore, in order to produce a composition having more excellent cationic hardening properties, n (b) is preferable. ) /n(a) is 100 or less. For the same reason, the ratio n(b)/n(a) is preferably 20 or less, more preferably 10 or less, and still more preferably 5 or less.

Further, from the viewpoint of cation hardening characteristics, a structure composed of a compound having a nitrogen atom, a sulfur atom or a phosphorus atom and substituted by two or more carbons (a structure substituted by two or more carbons means a structure in which two or more organic groups are bonded to each other via a carbon atom), since the acid dissociation constant is high and the steric hindrance is large, the ratio n(b)/n(a) is preferably 2 or less, more preferably 1.5 or less, more preferably 1.2 or less. For example, for the structure of the hindered amine, the above range is preferred.

Further, in the case where the Lewis base is ammonia or a low-boiling amine having a small steric hindrance, especially in the case of ammonia, the ratio n(b)/n(a) is preferably more than 1. Specifically, it is preferably 1.001 or more, more preferably 1.01 or more, still more preferably 1.1 or more, and still more preferably 1.5 or more.

Further, the form of the Lewis acid and the Lewis base constituting the cation curing catalyst is not particularly limited, and it is preferred that the Lewis base has an electronic interaction with the Lewis acid. More preferably, the form in which at least a portion of the Lewis base is coordinated to the Lewis acid is more preferably in a form in which at least an equivalent of the Lewis base and the Lewis acid are coordinated with respect to the Lewis acid present. When the ratio of the Lewis base to the Lewis acid is equivalent or less than the equivalent, that is, when the ratio n(b)/n(a) is 1 or less, it is preferably substantially the total amount of the Lewis base present. A form that is coordinated with a Lewis acid. On the other hand, in the form in which an excess (more than equivalent) of the Lewis base is contained, it is preferred that the Lewis base is coordinated with the Lewis acid equivalent, and the remaining Lewis base is present in the vicinity of the complex.

Specific examples of the cation hardening catalyst in the present invention include TPB/monoalkylamine complex, TPB/dialkylamine complex, and TPB/trialkylamine complex TPB alkyl group. Amine complex, organoborane/amine complex such as TPB/hindered amine complex; organoborane/ammonia complex such as TPB/NH ₃ complex; TPB/triarylphosphine complex, TPB/ Organoborane/phosphine complexes such as diarylphosphine complexes, TPB/monoarylphosphine complexes; organoborane/thiol complexes such as TPB/alkylthiol complexes; TPB/II An organoborane/thioether complex such as an aryl sulfide complex or a TPB/dialkyl sulfide complex. Among them, preferred are TPB/alkylamine complex, TPB/hindered amine complex, TPB/NH ₃ complex, and TPB/phosphine complex.

In the resin composition, the content of the cationic curing catalyst is preferably such that the amount of the active ingredient (solvent of the Lewis acid and the Lewis base represented by the formula (1)) is not related to the following cation. 100 parts by mass of the curable compound is set to be 0.01 to 10 parts by mass. If it is less than 0.01 part by mass, there is a possibility that the curing rate cannot be sufficiently increased. More preferably, it is 0.05 mass part or more, More preferably, it is 0.1 mass part or more. In addition, when it is more than 10 parts by mass, it may be colored at the time of curing or when the molded body is heated. For example, in the case where the molded body is obtained by reflowing the molded body, heat resistance of 200 ° C or higher is required. Therefore, from the viewpoint of colorlessness and transparency, it is preferably 10 parts by mass or less. It is more preferably 5 parts by mass or less, still more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less.

In the resin composition, the cationically curable compound (also referred to as "cationic curable resin") may be a compound which can be cured (polymerized) by a cationic curing reaction, and is preferably a compound having a cationically polymerizable group. .

The cationically polymerizable group may be a cationically curable functional group, and examples thereof include an epoxy group, an oxetane group (oxetane ring), and a dioxolane. (dioxolane) base, three Base, vinyl, vinyl ether, styryl, and the like. Among them, an epoxy group or an oxetane group is preferred. That is, the cation curable compound contains an epoxy compound and/or an oxetane compound (also referred to as an "oxetanyl group-containing compound"), and is one of preferred embodiments of the present invention. The hardening property of the above cationically polymerizable group is affected not only by the type of the base but also by the organic skeleton in which the group is bonded.

Further, the "epoxy group" in the present specification includes an oxirane ring which is an ether of a 3-membered ring, and includes an oxirane ring such as a glycidyl group in addition to the epoxy group in a narrow sense. An epoxy or ester bond-containing group such as a group bonded to carbon, a epoxidized propyl ether group or a glycidyl ester group, or an epoxycyclohexane ring.

Hereinafter, an epoxy compound and an oxetane compound will be specifically described.

The epoxy compound is preferably an alicyclic epoxy compound, a hydrogenated epoxy compound, an aromatic epoxy compound or an aliphatic epoxy compound, more preferably an alicyclic epoxy compound or a hydrogenated epoxy compound.

In the above, the cation curable compound contains at least one selected from the group consisting of an alicyclic epoxy compound, a hydrogenated epoxy compound, and an oxetane compound, and is one of preferred embodiments of the present invention.

In the above epoxy compound, the above-mentioned alicyclic epoxy compound means a compound having an alicyclic epoxy group. Examples of the alicyclic epoxy group include an epoxycyclohexyl group (epoxycyclohexane skeleton), an epoxy group directly added to a cyclic aliphatic hydrocarbon via a hydrocarbon (especially an oxirane ring). )Wait. As the alicyclic epoxy compound, a compound having an epoxycyclohexane group is preferred. Further, in terms of further improving the curing rate, a polyfunctional alicyclic epoxy compound having two or more alicyclic epoxy groups in the molecule is preferred. Further, a compound having one alicyclic epoxy group in the molecule and having an unsaturated double bond group such as a vinyl group can also be preferably used as the alicyclic epoxy compound.

As the epoxy compound having an epoxycyclohexane group, for example, 3', 4'-epoxycyclohexyl methyl ester, ε-caprolactone modified-3, preferably 3,4-epoxycyclohexanecarboxylic acid , 4-epoxycyclohexanecarboxylic acid 3',4'-epoxycyclohexylmethyl ester, bis-(3,4-epoxycyclohexyl adipate) and the like. In addition, examples of the alicyclic epoxy compound other than the epoxy compound having an epoxycyclohexane group include a 1,2-ring of 2,2-bis(hydroxymethyl)-1-butanol. An alicyclic epoxide such as an epoxy group containing a heterocyclic ring such as an oxy-4-(2-oxopentyl)cyclohexane adduct or a triglycidyl isocyanurate.

The hydrogenated epoxy compound is preferably a compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton, and is preferably a polyfunctional epoxypropyl ether compound. The hydrogenated epoxy compound is preferably a wholly or partial hydride of an aromatic epoxy compound, more preferably a hydride of an aromatic epoxidized propyl ether compound, more preferably an aromatic polyfunctional epoxy propyl ether compound. Hydride. Specifically, a hydrogenated bisphenol A type epoxy compound, a hydrogenated bisphenol S type epoxy compound, a hydrogenated bisphenol F type epoxy compound, or the like is preferable. More preferably, it is a hydrogenated bisphenol A type epoxy compound and a hydrogenated bisphenol F type epoxy compound.

The above aromatic epoxy compound means a compound having an aromatic ring and an epoxy group in the molecule. The aromatic epoxy compound is preferably an epoxy compound having an aromatic ring conjugated system such as a bisphenol skeleton, an anthracene skeleton, a biphenyl skeleton, a naphthalene ring or an anthracene ring. Among them, in order to achieve a higher refractive index, a compound having a bisphenol skeleton and/or an anthracene skeleton is preferred. More preferably, it is a compound having an anthracene skeleton, whereby the refractive index can be further remarkably increased, and the mold release property can be further improved. Further, among the aromatic epoxy compounds, a compound in which an epoxy group is a glycidyl group is preferred, and a compound in which an epoxy group is a glycidyl ether group (aromatic epoxy propyl ether compound) is more preferred. . Further, even if a higher refractive index can be achieved by using a brominated compound of an aromatic epoxy compound, it is preferable, but since the Abbe number is slightly increased, it is preferably used as appropriate depending on the use.

Examples of the aromatic epoxy compound include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a fluorene epoxy compound, and an aromatic epoxy compound having a bromine substituent. Among them, a bisphenol A type epoxy compound and a fluorene type epoxy compound are preferable.

Examples of the aromatic epoxy propyl ether compound include an epi-bis type epoxy propyl ether type epoxy resin and a high molecular weight surface-double type epoxy propyl ether type epoxy resin. , a novolac-aralkyl type epoxy propyl ether type epoxy resin, and the like.

As the above-mentioned epi-bis-epoxypropyl ether type epoxy resin, for example, a condensation reaction of a bisphenol such as bisphenol A, bisphenol F, bisphenol S or bisphenol with an epihalohydrin can be preferably exemplified. And the winner.

As the high molecular weight surface-bis-type epoxy propyl ether type epoxy resin, for example, the above-mentioned epi-bis-epoxypropyl ether type epoxy resin can be preferably further added to the above bisphenol A or bisphenol. F, bisphenol S, bisphenol and other bisphenols are added to the addition reaction.

Preferred examples of the aromatic epoxidized propyl ether compound include bisphenol A type compounds such as 828EL, 1003, and 1007 (above, manufactured by Japan Epoxy Resins Co., Ltd.); Oncoat EX-1020, Oncoat EX-1010, and OGSOL An oxime compound or the like such as EG-210, OGSOL PG (above, manufactured by Osaka Gas Chemicals Co., Ltd.), among which OGSOL EG-210 is preferred.

The above aliphatic epoxy compound means a compound having an aliphatic epoxy group. An aliphatic epoxy propyl ether type epoxy resin is preferred.

As the aliphatic epoxy propyl ether type epoxy resin, for example, a polyhydroxy compound (ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (preferably) is preferably used. PEG600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol (PPG), glycerin, diglycerin, tetraglycerol, polyglycerol, trimethylolpropane and its polymers, pentaerythritol and its polymerization Obtained by condensation reaction with epihalohydrin such as glucose, fructose, lactose, maltose, etc., and epihalohydrin. Among them, an aliphatic epoxy propylene ether type epoxy resin having a propylene glycol skeleton, an alkylene skeleton, or an alkyloxyalkyl skeleton is more preferable.

The above-mentioned oxetane compound means a compound having an oxetanyl group (oxetane ring).

From the viewpoint of the curing rate, the above oxetane compound is preferably used in combination with an alicyclic epoxy compound and/or a hydrogenated epoxy compound. Further, from the viewpoint of improving light resistance, it is preferred to use an oxetane compound which does not have an aryl group or an aromatic ring. On the other hand, from the viewpoint of enhancing the strength of the cured product, it is preferred to use a polyfunctional oxetane compound, that is, a compound having two or more oxetane rings in one molecule.

In the above oxetane compound having no aryl group or aromatic ring, as the monofunctional oxetane compound, for example, 3-methyl-3-hydroxymethyloxetane, 3- Ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, isobutoxymethyl (3-ethyl- 3-oxetanylmethyl)ether, isodecyloxyethyl (3-ethyl-3-oxetanylmethyl)ether, isodecyl (3-ethyl-3-oxo) Heterocyclic butanylmethyl)ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl)ether, ethyldiethylene glycol (3-ethyl-3-oxo) Cyclobutanemethyl)ether and the like.

In the above oxetane compound having no aryl group or aromatic ring, as the polyfunctional oxetane compound, for example, preferably bis[1-ethyl(3-oxetanyl)] Ether, 3,7-bis(3-oxetanyl)-5-oxadecane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy) Methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxocycle Butyrylmethyl)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 -oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, neopentyltetraol tetrakis(3-ethyl-3 -oxetanylmethyl)ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3- Oxetanemethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3- Oxetane ) Ether.

Specific examples of the oxetane compound include ETERNACOLL (R) EHO, ETERNACOLL (R) OXBP, ETERNACOLL (R) OXMA, ETERNACOLL (R) HBOX, and ETERNACOLL (R) OXIPA (above, Ube). Manufactured by Hyundai Co., Ltd.; OXT-101, OXT-121, OXT-211, OXT-221, OXT-212, OXT-610 (above, manufactured by Toagosei Co., Ltd.).

Among the above cationically curable compounds, an alicyclic epoxy compound or a hydrogenated epoxy compound is particularly preferred. This is equivalent to the coloring of the epoxy compound itself at the time of hardening, and it is less likely to cause coloring or deterioration by light, that is, transparency, low coloring property, and light resistance. Therefore, when the resin composition containing these is used, an optical member which is not colored and which is further excellent in light resistance can be obtained with high productivity. As described above, the cation curable compound contains at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, and is one of preferred embodiments of the present invention.

The cation-curable compound contains at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, and is preferably a content of the alicyclic epoxy compound or the hydrogenated epoxy compound. The total amount of these is 50% by mass or more based on 100% by mass of the total amount of the cationically curable compound. Thereby, the effects of using the above alicyclic epoxy compound or hydrogenated epoxy compound can be further exerted. More preferably, it is 60% by mass or more, and more preferably 70% by mass or more.

Further, in the case of the cationically curable resin composition of the present invention, even when an aromatic epoxy compound which is hard to be cured by a conventional catalyst is contained as a cationically curable compound, a sufficiently cured molded body is obtained. Therefore, a molded body obtained by controlling a refractive index or the like can be obtained by appropriately selecting the kind of the aromatic epoxy compound or the content in the composition. The form of the cationically curable compound is preferably 100% by mass of the aromatic epoxy compound and a combination of the aromatic epoxy compound and the other cationically curable compound. In the latter, a form in which at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, which is an aromatic epoxy compound and another cationically curable compound, is a more preferable form.

Further, an aromatic epoxy compound is used as the resin composition of the cationically curable compound, and is suitable for applications such as lenses requiring a refractive index (higher refractive index).

The cation-curable compound is preferably a compound having two or more cationically polymerizable groups in one molecule, that is, a polyfunctional cation-curable compound. Thereby, a cured product in which the curability is further improved and various characteristics are further improved can be obtained. In addition, the compound having two or more cationically polymerizable groups in one molecule may be a compound having two or more cationically polymerizable groups, or a compound having two or more different cationic polymerizable groups, and may be a polyfunctional compound. The cationically curable compound is preferably a polyfunctional alicyclic epoxy compound or a polyfunctional hydrogenated epoxy compound. By using these, a hardened material can be obtained in a shorter time.

It is also preferred that the above resin composition contains a flexible component (flexible component). Thereby, a resin composition having a uniform feeling, that is, a high toughness can be obtained.

The flexible component may be a compound different from the above cationically curable compound, and at least one of the cationically curable compounds may be a flexible component.

Specific examples of the flexible component include (1) a compound having an oxyalkylene group represented by -[-(CH ₂ ) _n -O-] _m - (n is 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 3 to 6, and m is an integer of 1 to 20), and for example, preferably contains an oxybutylene group. Epoxy compound (manufactured by Japan Epoxy Resins Co., Ltd., YL-7217, epoxy equivalent 437, liquid epoxy compound (10 ° C or higher)). Further, as another preferable flexible component, (2) a polymer epoxy compound (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resins Co., Ltd., YX-8040, epoxy equivalent 1000, solid hydrogenated epoxy compound)) (3) alicyclic solid epoxy compound (manufactured by Daicel Chemical Industry Co., Ltd., EHPE-3150); (4) alicyclic liquid epoxy compound (manufactured by Daicel Chemical Industry Co., Ltd., Celloxide 2081); (5) liquid A liquid rubber such as a nitrile rubber or a polymer rubber such as polybutadiene or a fine particle rubber having a particle diameter of 100 nm or less.

Among these, a cationically curable compound containing a cationically polymerizable group, such as a terminal or a side chain or a main chain skeleton, is more preferable.

Thus, as the flexible component, a cationically curable compound can be preferably used, and as the compound, an epoxy group-containing compound is preferred, and an oxybutylene group (-[-(CH ₂ ) ₄ ) is more preferred. -O-] _m - (m as above) compound.

In the case where the above-mentioned flexible component is contained, the content thereof is preferably 40% by mass or less based on 100% by mass of the total of the cationically curable compound and the flexible component. More preferably, it is 30 mass% or less, More preferably, it is 20 mass% or less. Further, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.5% by mass or more.

By using the above-mentioned catalyst in the present invention, the effect of improving the mold release property or the effect of reducing the release agent can be obtained, and the resin composition of the present invention is suitably used as a mold forming material. Therefore, in the resin composition of the present invention, the mold release agent can be released from the mold even without using the release agent used in the prior art. Therefore, it is possible to obtain a cured product which is excellent in mold release property from a mold without causing a decrease in transparency due to the release of the release agent and suppressing the influence on the performance caused by the release agent.

However, when a lens or the like is obtained by using the above resin composition, that is, when mold forming is used as a curing or molding method, a mold release agent may be contained. The mold release agent is preferably a compound having a group which does not inhibit the hardening reaction by the cation hardening catalyst and which promotes the reaction. Specifically, the release agent is preferably a compound having an alcoholic OH group and/or a carbonyl group (including a carboxyl group and an ester group), and further has a high compatibility with a cationically curable resin composition and a mold release effect. In general, it is preferably a hydrocarbon group having a carbon number of 8 or more. More preferably, it is selected from the group consisting of an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylate having 8 to 36 carbon atoms, a carboxylic acid anhydride having 8 to 36 carbon atoms, and a carboxylate having 8 to 36 carbon atoms. At least one compound of the group consisting of. By containing such a release agent, it can be hardened in a short time, and the mold can be easily peeled off when the mold is hardened, and the appearance can be controlled without causing damage to the surface of the cured product, and transparency can be exhibited. Therefore, the above resin composition can be made more useful in electrical and electronic part material applications, optical member applications, and the like.

Among the compounds exemplified as the release agent, an alcohol, a carboxylic acid or a carboxylic acid ester is more preferred, and a carboxylic acid (especially a higher fatty acid) and a carboxylic acid ester are more preferred. The carboxylic acid and the carboxylic acid ester are preferred because they can sufficiently exert a releasing effect without inhibiting the cation hardening reaction. Further, since the amine may hinder the cation hardening reaction, it is preferably not used as a release agent.

The above compound may be any of a linear, branched, or cyclic structure, and is preferably a branch.

The carbon number of the above-mentioned compound is preferably an integer of from 8 to 36, whereby the cured product exhibits excellent releasability without impairing the transparency or workability of the resin composition. The carbon number is more preferably from 8 to 20, more preferably from 10 to 18.

The above-mentioned alcohol having 8 to 36 carbon atoms is a monohydric or polyhydric alcohol, and may be a linear one or a branched one. Specific examples of the above alcohol include octanol, decyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecanol, pentadecyl alcohol, palmitol, heptadecyl alcohol, and hard. Aliphatic alcohol, nonadecanol, eicosyl alcohol, wax alcohol, beeswaxol, methylpentanol, 2-ethylbutanol, 2-ethylhexanol, 3,5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, dipentaerythritol, 2-phenylethanol, and the like. As the above alcohol, an aliphatic alcohol is preferable, and among them, octanol, lauryl alcohol, 2-ethylhexyl alcohol, and stearyl alcohol are more preferable.

The above carboxylic acid having a carbon number of 8 to 36 is a monobasic or polybasic carboxylic acid, preferably exemplified by 2-ethylhexanoic acid, octanoic acid, citric acid, citric acid, undecanoic acid, lauric acid, tridecanoic acid, and ten. Tetraic acid, pentadecanoic acid, palmitic acid, 1-yeptopentaic acid, stearic acid, nineteen acid, icosonic acid, 1-hexadecanoic acid, rosinic acid and the like. Preferred are caprylic acid, lauric acid, 2-ethylhexanoic acid, and stearic acid.

The carboxylic acid ester having 8 to 36 carbon atoms is preferably exemplified by (1) a carboxylic acid ester obtained from the above alcohol and the carboxylic acid, and (2) methanol, ethanol, propanol or hexanol. a carboxylic acid ester obtained by combining a carbon number of 1 to 7 such as heptanol, glycerin or benzyl alcohol with the above carboxylic acid, and (3) a carboxyl group having 1 to 7 carbon atoms such as acetic acid, propionic acid, butyric acid or caproic acid. a carboxylic acid ester obtained by combining an acid with the above alcohol, (4) a carboxylic acid ester obtained from a carboxylic acid having 1 to 7 carbons and a carboxylic acid having 1 to 7 carbon atoms, and a compound having a total carbon number of 8 to 36 Wait. Among these, the carboxylic acid esters of (2) and (3) are preferred, and more preferably methyl stearate, ethyl stearate or octyl acetate.

The above-mentioned carboxylic acid anhydride having a carbon number of 8 to 36 means an acid anhydride of a carboxylic acid having 8 to 36 carbon atoms.

Examples of the carboxylate having a carbon number of 8 to 36 include a carboxylic acid obtained by a combination of the above carboxylic acid and an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, and Sn. Salt and so on. Among these, zinc stearate, magnesium stearate, zinc 2-ethylhexanoate and the like are preferable.

Among the above compounds, a stearic acid-based compound such as stearic acid or stearic acid or an alcohol-based compound is more preferable, and a stearic acid-based compound is more preferable.

In the case where the above-mentioned release agent is contained, the content thereof is preferably 10% by mass or less based on 100% by mass of the resin composition. When it exceeds 10% by mass, the resin composition becomes difficult to be cured or the like. More preferably, it is 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass.

In the case of forming a lens using the above resin composition, in particular, when a lens is formed using an epoxy-based cationic curable compound, it is preferred that the resin composition contains an inorganic material. The resin composition contains a mineral material and has high strength and excellent moldability, and the lens obtained by curing has an Abbe number and a refractive index controlled (especially, a bismuth compound has a high Abbe number).

The inorganic material is preferably an inorganic fine particle such as a metal oxide particle or an inorganic polymer such as a polyoxyalkylene compound.

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. Examples of the inorganic component in the inorganic fine particles include metal oxides, hydroxides, (oxy)nitrides, (oxygen) sulfides, carbides, halides, sulfates, nitrates, and (alkaline) carbonates. , (alkaline) acetate, and the like. Among these, an oxide of a metal (metal oxide) is preferred, and more preferably cerium oxide, titanium oxide, zirconium oxide or zinc oxide. Depending on the refractive index or Abbe number of the curable compound to be used, in general, in order to obtain a molded body (cured product) having a high refractive index or a low Abbe number, titanium oxide, zirconium oxide or zinc oxide is preferably used. On the other hand, in order to obtain a molded body (hardened product) having a low refractive index or a high Abbe number, it is preferred to use cerium oxide.

The inorganic fine particles also include surface-treated particles in order to improve the affinity between the fine particles and the resin, to improve the dispersibility, and the like. The surface treatment agent is not particularly limited, and various organic compounds, inorganic compounds, organometallic compounds, and the like can be used in order to introduce an organic chain, a polymer chain, or control a surface charge on the surface of the particles. Examples of the surface treatment agent include a coupling agent such as a decane coupling agent, a titanate coupling agent, an aluminate coupling agent, and a zirconium coupling agent; a metal alkoxide and the (partial) hydrolysis-condensation thereof Metal soap; metal soap;

In addition, examples of the inorganic polymer include a polyoxymethane compound, and the like, and specific examples thereof include polymethylsilsesquioxane and polyphenylsilsesquioxane.

In the case where the resin composition contains inorganic fine particles or a polyoxyalkylene compound, the cationically curable compound is preferably in the form of a hydrogenated epoxy compound and/or an alicyclic epoxy compound. Thereby, an epoxy-based cationic hardening compound having a high Abbe number can be obtained.

The above resin composition can reduce the coefficient of thermal expansion by containing an inorganic material. Further, by combining the refractive index of the inorganic material and the resin, it is also possible to control the appearance of the resin composition and its molded body (for example, a lens, etc.) to exhibit transparency, and it can be made into an electrical and electronic part material or optical. Materials in use are especially useful. Further, the release effect can be further exhibited by the inclusion of the inorganic fine particles. Specifically, when a thermosetting resin (particularly an epoxy compound) is contained as a resin component, the resin component has a bonding effect, and when the resin composition is cured, it is followed by a mold. However, by adding an appropriate amount of inorganic fine particles, the release effect can be seen, and the molded body (cured material) can be easily peeled off from the mold.

In the case of containing the above inorganic material, the content thereof is preferably 0.01 to 95% by mass, more preferably 0.1 to 80% by mass, still more preferably 0.2 to 60% by mass, even more preferably 100% by mass based on the resin composition. 0.3 to 20% by mass, preferably 0.5 to 15% by mass.

The cation-curable resin composition of the present invention may contain a dye, particularly a pigment having a maximum absorption in a wavelength region of 600 nm or more and 2000 nm or less, as described in detail below (also referred to as a near-infrared absorbing pigment in the present invention). ), this form is also preferred.

The dye is not limited to the near-infrared absorbing dye. It is preferable to select a dye having characteristic absorption at a specific wavelength in each of ultraviolet rays, visible light, and infrared rays depending on the purpose of use, and it can be used for various uses of optical materials.

In the cationically curable resin composition containing the above dye, the pigment is preferably dispersed or dissolved in the cationically curable resin composition. More preferably, it is a form in which the pigment is dissolved and contained in the cationically curable resin composition. That is, it is preferred that the dye be dissolved in a resin component or a solvent constituting the cationically curable resin composition. The pigment may be used alone or in combination of two or more.

The near-infrared absorbing dye used to prevent malfunction of the sensor in the image pickup lens module as described below is preferably a dye having a maximum absorption in a wavelength region of 600 to 800 nm. More preferably, it has a very large absorber in the wavelength region of 650 to 750 nm. The above dyes are also preferably those having substantially no absorption in the wavelength region of 400 nm or more and less than 600 nm.

The near-infrared absorbing dye is preferably a dye having a π-electron bond in the molecule. The dye having a π-electron bond in such a molecule is preferably a compound containing an aromatic ring. More preferably, it is a compound which has two or more aromatic rings in one molecule.

Further, it is preferable that the dye having a π-electron bond in the molecule has a maximum absorption in the above-mentioned preferred wavelength region.

Examples of the dye having a π-electron bond in the molecule include a phthalocyanine dye, a porphyrin dye, a cyanine dye, a quaterrylene dye, and a squarylium dye. For the naphthalocyanine dye, the nickel complex dye, the copper ion dye, or the like, one type or two or more types may be used. The dye which does not have any of a zwitterionic structure and a cationic structure is preferable from the viewpoint of heat resistance and weather resistance, and is preferably a phthalocyanine dye and/or a porphyrin dye. More preferably, it is a metal phthalocyanine complex and/or a metal porphyrin complex.

The phthalocyanine dye is preferably a metal phthalocyanine complex, and examples thereof include metal elements such as copper, zinc, cobalt, vanadium, niobium, nickel, tin, silver, magnesium, sodium, lithium, and lead. The metal metal phthalocyanine complex of the center metal. Among these metal elements, any one of copper, vanadium, and zinc is preferably used as the center metal because of solubility, visible light transmittance, and light resistance. As the center metal, copper and zinc are more preferred, and copper is more preferred. The use of copper bismuth cyanine is not degraded by light regardless of which binder resin is dispersed, and has excellent light resistance.

The porphyrin-based dye is preferably a metalloporphyrin complex such as tetraazaporphyrin.

In the case of containing the above-mentioned dye, the content thereof is preferably 0.0001 to 10% by mass, more preferably 0.001 to 1% by mass based on 100% by mass of the resin composition.

In the imaging lens module, it is known that an infrared cut filter (also referred to as an infrared ray cut filter) is provided on the incident light side or the outgoing light side of the lens, and the infrared cut filter system is known. In order to remove (near) infrared rays in the incident light which is noise, a transparent resin sheet is used as a base material, and an infrared reflecting film is provided on one surface or both surfaces thereof. However, the reflective IRCF needs to be improved since the spectral transmittance curve differs depending on the incident angle (there is an incident angle dependency).

The present inventors have known that a reflective resin film having a pigment-containing layer (obtained from a composition in which a near-infrared absorbing pigment is incorporated into a resin composition) is used as a substrate. The reflection type IRCF obtained by the incident angle dependency is suppressed. Therefore, it has been confirmed that the resin composition is a cationically curable resin composition of the present invention, that is, a resin sheet having a dye-containing layer (which is obtained by including a near-infrared absorbing dye in a cationically curable resin composition) When the composition is obtained as a substrate, it is possible to obtain a reflection-type IRCF which is suppressed in incident angle dependency and excellent in heat resistance and the like.

In other words, the cation-curable resin composition of the present invention has a resin layer containing a pigment layer obtained by "the composition containing a near-infrared absorbing pigment" because it has excellent heat resistance and light resistance required for IRCF for an image pickup lens. A sheet (molded body) is useful as a substrate of a reflective IRCF in which incident angle dependence is suppressed.

In addition, the "lens obtained from the cation-curable resin composition of the present invention" itself contains a near-infrared absorbing dye, and the imaging lens module including the lens is suppressed in incident angle dependency even when the reflective IRCF is mounted. Therefore, it is preferred.

In other words, the cation curable resin composition containing a near-infrared absorbing dye for a substrate (resin sheet) or a lens for an image pickup lens module, and a molded body obtained from the composition (for example, a resin sheet) The use of materials, lenses, etc.) is also a preferred form of the invention.

The cationically curable resin composition containing a near-infrared absorbing pigment is not limited to the above-mentioned substrate for IRCF (resin sheet) or lens, and may be preferably used for various members constituting an image pickup lens module, such as a sealant. Other components such as the following agent, the microlens on the upper part of the sensor. Further, it can be preferably used for various applications such as an LED sealing resin other than the image pickup lens module and a lens resin for LED.

The resin composition may contain, in addition to the above-mentioned essential components or preferred components, a curing catalyst other than a cationic curing catalyst, a curing agent, a curing accelerator, and a reactive dilution, as long as the effects of the present invention are not impaired. Agent, saturated compound without unsaturated bond, pigment, dye, antioxidant, ultraviolet absorber, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization initiation Agent, polymerization inhibitor, inorganic filler, organic filler, coupling agent and other adhesion improving agent, heat stabilizer, antibacterial and antifungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wetting dispersing agent Anti-precipitation agent, tackifier-anti-sagging agent, anti-floating coloring agent, emulsifier, anti-slip agent, anti-scratch agent, anti-skinning agent, desiccant, antifouling agent, antistatic agent, conductive agent Electrostatic additives), solvents, etc.

The cationically curable resin composition of the present invention can be prepared by mixing the above cationically curable compound and a cationic curable catalyst, and mixing the above other components as necessary.

Further, when the components are mixed, each component or mixture may be heated and mixed as needed to have a uniform composition. The heating temperature is not particularly limited as long as it is at least the decomposition temperature of the curable resin or the reaction temperature, and is preferably 140 to 20 ° C, more preferably 120 to 40 ° C, before the addition of the catalyst.

The resin composition preferably has a viscosity of 10,000 Pa‧s or less. Thereby, the processing property is excellent, and it is excellent, for example, in the use for forming a molded article (especially, the use of a molded article). More preferably, it is 1000 Pa‧s or less, more preferably 200 Pa‧s or less. Further, it is preferably 0.01 Pa‧s or more, more preferably 0.1 Pa‧S or more. More preferably, it is 1 Pa‧s or more, more preferably 5 Pa‧s or more, and particularly preferably 10 Pa‧s or more.

For the measurement of the above-mentioned viscosity, the resin composition can be used under the conditions of 40 ° C and a rotation speed of D = 1 / s using an R/S Rheometer (manufactured by Brookfield, USA). In addition, when the viscosity is 20 Pa‧s or more, the measuring tool of RC25-1 is used, and when the viscosity is less than 20 Pa‧s, the fixture of RC50-1 can be used. Further, in the case where the viscosity at the rotational speed D=1/s cannot be measured, the value of the rotational speed D=5 to 100/s can be extrapolated and evaluated as the viscosity of the resin composition.

As the curing method of the above resin composition, various methods such as thermal curing or photocuring (hardening by irradiation with active energy ray) can be preferably used. As the thermosetting, it is preferably cured at about 30 to 400 ° C, and is preferably cured at 10 to 10000 mJ/cm ² as photocuring. The hardening can be carried out in one stage, or it can be carried out in two stages in the form of primary hardening (pre-hardening) and secondary hardening (formal hardening). For example, in the case where a mold is required as in the case of a lens or the like, a mold release operation is required, and it is preferable to use a hardening method and a molding method which are hardened once before the mold release operation and hardened twice after the mold release operation.

Hereinafter, the case where the two-stage hardening is performed will be described in detail.

As a two-stage hardening method, it is preferable to employ a method including the following steps: as a first step corresponding to primary hardening, photohardening the resin composition at 10 to 100,000 mJ/cm ² or at 80 to 200 ° C The step of thermosetting; and the second step of thermosetting the hardened material obtained in the first step at a temperature exceeding 200 ° C and 500 ° C or less.

In the above first step, it is preferred to set the curing temperature to 80 to 200 ° C in the case of thermal curing. More preferably, it is 100 ° C or more and 160 ° C or less. Further, the curing temperature may be changed stepwise in the range of 80 to 200 °C.

The hardening time in the above thermal hardening step is, for example, preferably 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 above thermal hardening step can also be carried out in any environment such as air or an inert gas such as nitrogen, under reduced pressure or under pressure. For example, from the viewpoint of improving productivity, the resin composition may be taken out from the mold after being held at a specific temperature and time in the mold, and left to stand in the air or in an inert gas atmosphere such as nitrogen to perform heat treatment. Further, it is also possible to combine photohardening (hardening by irradiation with active energy rays).

As the first step, it is also preferred to use a hardening step of a mold (referred to as "mold") made of metal, ceramic, glass, or resin. The hardening step using the mold may be a curing step usually performed by a mold forming method such as an injection molding method, a compression molding method, a casting molding method, or a sandwich molding method, and the first step is a curing step using the mold. Therefore, it is possible to easily produce various molded articles having excellent physical properties such as abrasion resistance, low shrinkage, dimensional accuracy, and mold transferability, and which are free from coloring and transparency.

In the case where the first step described above is a step of using a hardening step of the mold, it is preferred to carry out the demolding step after the first step and before the second step. By adopting a form including a mold release step, that is, a form in which "the cured product obtained in the first step is taken out from the mold and the removed cured product is supplied to the subsequent second step", the product can be efficiently recovered (recycled). An expensive mold and an extended life of the mold, so that the molded body can be obtained at low cost.

In this case, it is preferred to use a method in which the resin composition is a one-liquid composition containing a curing agent and other components as needed, and the one-liquid composition is filled (injected, coated, etc.). The mold conforms to the shape of the target formed body and is hardened, and thereafter the hardened material is taken out from the mold.

In the above-mentioned hardening method, in the second step, it is preferred that the cured product obtained in the first step (preferably the cured product taken out from the mold by the demolding step) is thermally hardened at more than 200 ° C and 500 ° C or lower. . The lower limit of the hardening temperature is more preferably 250 ° C or more, more preferably 300 ° C or more, particularly preferably 330 ° C or more, and most preferably 350 ° C or more. The upper limit is more preferably 400 ° C or less. Further, the curing temperature may be changed stepwise in a temperature range of more than 200 ° C and 500 ° C or less.

The curing time in the second step is not particularly limited as long as the curing rate of the obtained molded body is sufficient. However, in consideration of the production efficiency, it is preferably set to, for example, 30 minutes. ~30 hours. More preferably 1 to 10 hours.

The second step described above can also be carried out in any environment such as air or an inert gas atmosphere such as nitrogen. Among them, it is particularly preferable to carry out the above second step in an environment where the oxygen concentration is low. For example, it is preferably carried out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. It is more preferably 3% by volume or less, still more preferably 1% by volume or less, still more preferably 0.5% by volume or less, and most preferably 0.3% by volume or less.

The strength of the cured product obtained by the above-described hardening method may be any strength as long as it is taken out from the mold and maintained in shape. For example, the ratio of the shape change when extruded at a force of 9.8 × 10 ⁴ Pa or more is preferably Compressive strength below 10%. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, still more preferably 0.01% or less.

The cationically curable resin composition of the present invention can provide a molded article excellent in heat resistance, moist heat resistance, low water absorbability, and UV radiation resistance as described above. Thus, the molded body (cured product) obtained by curing the above cationically curable resin composition is also one of the inventions.

The molded article is used in various applications such as an optical material (member), a mechanical component material, an electric and electronic component material, an automobile component material, a civil engineering material, a molding material, and the like, and also as a material for a coating material or an adhesive. Among them, it can be preferably used for optical materials, optical device members, and device members. Specifically, for example, a lens for a spectacle lens, a (digital) camera, a camera for a mobile phone, an imaging lens for a camera such as an in-vehicle camera, a lens for a beam collecting lens, a lens for light diffusion, and a sealing material for an LED are preferable. Optical applications such as optical adhesives, bonding materials for optical transmission, filters, diffraction gratings, germanium, light guides, watch glass, and protective glass for display devices, etc.; optical sensors; Optical devices such as optical switches, LEDs, light-emitting elements, optical waveguides, multiplexers, demultiplexers, circuit breakers, optical splitters, and optical fiber adhesives; substrates for display components such as LCD or organic EL or PDP, and color filters The use of a display device such as a sheet substrate, a touch panel substrate, a display protective film, a display backlight device, a light guide plate, an antireflection film, and an antifogging film.

Among these applications, optical materials are particularly preferred. As described above, the form of the molded article in the form of an optical material or the form in which the cation-curable resin composition is a resin composition for an optical material is also included in the preferred embodiment of the present invention.

As the optical material, a lens, an LED sealing material, an optical adhesive, and a light transmission bonding material are particularly preferable. The lens is preferably a camera lens, a beam collecting lens, a light diffusing lens, and an optical pickup lens, and more preferably a camera lens. 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 preferable. Further, these minute optical lenses are preferred.

In the case where the resin composition is a resin composition for an optical material, other components may be appropriately contained depending on the use of the optical material. As other components, specifically, a UV absorber, an IR stopper, a reactive diluent, a pigment, a lotion, an antioxidant, a light stabilizer, a plasticizer, a non-reactive compound, and a chain transfer are preferably exemplified. Agent, thermal polymerization initiator, anaerobic polymerization initiator, polymerization inhibitor, antifoaming agent, and the like.

The cationically curable resin composition of the present invention is useful in reducing environmental load, in particular, in optical material use, by using the above-mentioned cationic curable catalyst as compared with the case of using a lanthanoid cation curing catalyst. It is more useful. In particular, the value of the resin composition of the present invention is very high for a lens for a camera, a beam condenser lens, a lens for a light diffusing lens, an LED sealing material, and an optical adhesive for an increase in demand in the world. high. Moreover, since the molded body (cured material) obtained from the resin composition of the present invention has a low water absorption rate, it is preferably used for each of a camera lens, a beam collecting lens, a light diffusing lens, and an optical pickup lens. . More preferably, it is used for a camera lens, and an image pickup lens such as an image pickup lens for a mobile phone and an image pickup lens for a digital camera is more suitable for use in a camera lens. The water absorption of the molded body (hardened material) causes expansion, cracking, and the like, but the molded body (cured material) of the present invention can be effectively used for the above-mentioned "the slight change caused by water absorption is easily expressed in optical characteristics". Tiny optical lens.

Further, the molded body (cured material) obtained from the resin composition of the present invention has high reflow heat resistance, and the visible light transmittance is reduced or the coloring is suppressed. Various components such as mobile phones, televisions, computers, and automotive applications tend to adopt solder reflow processes based on reasons such as simplification of manufacturing steps and cost reduction. The resin composition of the present invention or the molded body obtained from the composition can suppress the decrease in optical characteristics even when supplied to the solder reflow process, and thus it is used as a member (for example, a lens or a filter) of various components using a solder reflow process. Optical materials such as sheets and adhesives are very useful.

When the cation hardening catalyst used in the composition of the present invention is a TPB-based catalyst, since the molded body (cured material) obtained from the composition has a particularly low water absorption rate and excellent heat resistance, the TPB-based contact is used. The cation-curable resin composition in which the medium is a cationic curing catalyst is particularly useful for each of the above optical material applications.

Since the cationically curable resin composition of the present invention has the above configuration, it can provide a molded article excellent in heat resistance, moist heat resistance, low water absorbability, and UV radiation resistance. In particular, by using the cationic hardening catalyst of the present invention, the transmittance of the obtained molded body at 400 nm can be improved, and coloring can be reduced. Such a molded body can be preferably used for various purposes such as coating materials or adhesive materials, in addition to optical materials, mechanical parts materials, electrical and electronic parts materials, automobile parts materials, civil construction materials, molding materials, and the like, especially as Optical materials are very useful.

The invention is illustrated in more detail in the following examples, but the invention is not limited to the examples. Unless otherwise stated, "parts" means "parts by mass" and "%" means "mass%".

<Preparation of TPB complexes>

Preparation Example 1

(TPB: Synthesis of THF complex)

42.3 g of TPB (tris(pentafluorophenyl)borane) was dissolved in 60.5 g of toluene, and 7.14 g of THF (tetrahydrofuran) was added dropwise while stirring at room temperature. Thereafter, 121.1 g of n-hexane was added dropwise at room temperature. The solution was cooled in an ice bath, and after stirring for a while, white crystals were precipitated. The white crystals were filtered, washed with n-hexane and dried to give a white solid, THF: THF, 34.5 g (the content of TPB as determined by liquid chromatography was 85.05%).

[NMR data]

¹ H-NMR (CDCl ₃ ) ppm

δ=1.87(4H,m)

δ=3.63(4H,m)

¹⁹ F-NMR (CDCl ₃ ) ppm

δ=-87.7(6F,m)

δ=-80.5(3F,dd)

δ=-59.4(6F,d)

Preparation Example 2

(Preparation of TPB/hindered amine (TINUVIN770) complex)

81.1 parts of TPB: THF complex obtained in Preparation Example 1 (TPB component: 69.0 parts) and TINUVIN 770 (hindered amine, manufactured by BASF) 31.1 parts were dissolved in 88 parts of γ-butyrolactone to prepare TPB mismatch. a solution of γ-butyrolactone of (1a). n(b)/n(a) = 0.96/1 in the TPB complex (1a).

Further, a γ-butyrolactone solution of the following TPB complexes (1b) to (1e) was prepared in the same manner as above.

n(b)/n(a)

TPB complex (1b) 2.04/1

TPB complex (1c) 1.1/1

TPB complex (1d) 0.95/1

TPB complex (1e) 0.91/1

Preparation Example 3

(Preparation of TPB/Hindered Amine (Adekastab LA57) Complex) 100.0 parts of TPB:THF complex obtained in Preparation Example 1 (TPB component: 85.1 parts) and Adekastab LA57 (hindered amine, manufactured by ADEKA Co., Ltd.) 32.6 The solution was dissolved in 103 parts of γ-butyrolactone to prepare a γ-butyrolactone solution of the TPB complex (2a). Furthermore, n(b)/n(a)=0.99/1.

Further, a γ-butyrolactone solution of the TPB complexes (2b) to (2c) was prepared in the same manner as above.

n(b)/n(a)

TPB complex (2b) 1.06/1

TPB complex (2c) 1.02/1

Preparation Example 4

(Preparation of TPB/hindered amine (TINUVIN765) complex)

100.0 parts of TPB: THF complex obtained in Preparation Example 1 (TPB component: 85.1 parts) and 50.1 parts of TINUVIN 765 (hindered amine, manufactured by BASF Corporation) were dissolved in 120 parts of γ-butyrolactone to prepare a TPB mismatch. Γ-butyrolactone solution of the substance (3). Furthermore, n(b)/n(a)=1.19/1.

Preparation Example 5

(Preparation of TPB/Ammonia Complex)

130 parts of TPB:THF complex (TPB component: 110.6 parts) and 25% of NH ₃ aqueous solution (NH ₃ component: 6.5 parts) obtained in the same manner as in Preparation Example 1 were dissolved in γ-butane. In 78.2 parts of the ester, a γ-butyrolactone solution of TPB complex (4a) coordinated with NH ₃ as a Lewis base was prepared. Furthermore, n(b)/n(a)=1.77/1.

Further, the TPB‧NH ₃ component of the TPB complexes (4b) to (4f) having NH ₃ coordinated in the same manner as described above except that the amount of the 25% NH ₃ aqueous solution used was changed as follows. The γ-butyrolactone solution was prepared in a 50% manner.

The NH ₃ coordination amount in each TPB complex is as follows.

n(b)/n(a)

TPB complex (4b) 0.59/1

TPB complex (4c) 1.18/1

TPB complex (4d) 2.94/1

TPB complex (4e) 15/1

TPB complex (4f) 100/1

Preparation Example 6

(Preparation of TPB/triphenylphosphine complex)

TPB: THF complex 100 parts (TPB component: 85.1 parts) and 43 parts of triphenylphosphine were dissolved in 113.2 parts of γ-butyrolactone, and TPB/triphenyl was prepared by the same manner as in Preparation Example 1. A γ-butyrolactone solution of a phosphine complex (TPB complex (5)). The amount of triphenylphosphine coordinated in the TPB complex (5) is as follows. n(b)/n(a)=0.99/1

Preparation Example 7

(Preparation of TPB/triethylamine complex)

100 parts of TPB:THF complex obtained in Preparation Example 1 (TPB component: 85.1 parts) and 13.5 parts of triethylamine were dissolved in 99 parts of γ-butyrolactone to prepare TPB complex (6a). Γ-butyrolactone solution. Furthermore, n(b)/n(a)=0.8/1.

Further, a γ-butyrolactone solution of the TPB complex (6b) was prepared in the same manner as above. Furthermore, n(b)/n(a)=2.2/1.

<Preparation of Resin Composition and Hardened (Formed Body)>

Example 1

100 parts of Celloxide CELL-2021P (liquid alicyclic epoxy resin, epoxy equivalent 131, manufactured by Daicel Chemical Industry Co., Ltd.) as a cationically curable compound, and γ-butyrolactone of the above TPB complex (1a) 0.2 part of the solution (0.1 part of TPB/TINUVIN770 complex as a cationic curing catalyst) was uniformly mixed at 40 ° C under reduced pressure to obtain a resin composition (1). The resin composition is cured by the following method (hardening step) to obtain a cured product.

Example 2

100 parts of Celloxide CELL-2021P (liquid alicyclic epoxy resin, epoxy equivalent 131, manufactured by Daicel Chemical Industry Co., Ltd.) as a cationically curable compound, and γ-butyrolactone of the above TPB complex (4a) 0.234 parts of a solution (0.117 parts of TPB/amine complex as a cationic curing catalyst) was mixed at 40 ° C under reduced pressure to obtain a resin composition (2). The resin composition was cured by the following method to obtain a cured product.

Examples 3 to 7 and Comparative Examples 1 to 3

The resin compositions (3) to (7) were obtained in the same manner as in Example 1 except that the types and amounts of the cation-curable compound and the cation-curing catalyst constituting the resin composition were changed as shown in Tables 1 and 2. Resin composition (Comparative 1) to (Comparative 3). The resin composition was cured by the following method to obtain a cured product.

Example 8

100 parts of YX-8000 (liquid hydrogenated epoxy resin, manufactured by Mitsubishi Chemical Corporation) and 1 part of γ-butyrolactone solution of TPB complex (5) as a cation-curable compound (as a cationic hardening catalyst) TPB/triphenylphosphine complex 0.5 part) was uniformly mixed to obtain a resin composition (8). The resin composition was cured by the following method to obtain a cured product.

Examples 9 to 26 and Comparative Examples 4 to 7

Each of the resin compositions was obtained by using the cation-curable compound, the inorganic material, and the cation-curing catalyst of the types and amounts described in Tables 1 and 2. Further, when a solid epoxy resin of EHPE-3150, YX-8040, or PG-100 was mixed as a cationic curable compound, the resin was heated to 140 ° C to form a uniform composition. In the case where PMSQ-E is used as the inorganic material, the cationic hardening compound is mixed and uniformly mixed at 80 °C. When the catalyst was mixed, in the same manner as in Example 1, mixing was carried out at 40 ° C under reduced pressure to obtain a uniform composition.

The resin composition was cured by the following method to obtain a cured product.

Example 27

With respect to 100 parts of the resin composition of Example 19, 0.008 parts of TX-EX-609K (anthocyanine dye, maximum absorption wavelength 680 nm, manufactured by Nippon Shokubai Co., Ltd.) was uniformly dissolved at 40 ° C to obtain a pigment-containing resin. Composition.

Further, the resin composition was cured by the following method to obtain a cured product.

Example 28

With respect to 100 parts of the resin composition of Example 19, 0.015 parts of TX-EX-720 (anthocyanine dye, maximum absorption wavelength 715 nm, manufactured by Nippon Shokubai Co., Ltd.) was uniformly dissolved at 40 ° C to obtain a pigment-containing resin. Composition.

Further, the resin composition was cured by the following method to obtain a cured product.

Comparative Example 8

With respect to 100 parts of the resin composition of Comparative Example 6, 0.008 parts of TX-EX-609K (anthocyanine dye, maximum absorption wavelength 680 nm, manufactured by Nippon Shokubai Co., Ltd.) was uniformly dissolved at 40 ° C to obtain a pigment-containing resin. Composition.

Further, the resin composition was cured by the following method to obtain a cured product.

Comparative Example 9

With respect to 100 parts of the resin composition of Comparative Example 6, 0.015 parts of TX-EX-609K (anthraquinone-based pigment, maximum absorption wavelength of 715 nm, manufactured by Nippon Shokubai Co., Ltd.) was uniformly dissolved at 40 ° C to obtain a pigment-containing resin. Composition.

Further, the resin composition was cured by the following method to obtain a cured product.

The resin composition obtained in the above examples and comparative examples was cured by the following method to obtain a cured product (molded body).

<hardening step>

(Step 1)

Two sheets of SUS304 (manufactured by Japan Testpanel Co., Ltd., surface No. 800 finishing) were used to form a gap having a pitch of 1000 μm, and casting of each resin composition was carried out. After the hardening was performed once at the temperature/time shown in Table 1, the mold release was performed. In addition, when the adhesion of the molded article at the time of primary curing is strong and it is difficult to release the mold, DAIFREE GA-7500 (manufactured by Daikin Industries, Ltd., fluorine-polyoxygenated) is sprayed onto the SUS plate and wiped off. The SUS plate is used again.

(Step 2 (curing))

After the hardening in the first step, the curing treatment was carried out under the following conditions in an N ₂ atmosphere (as long as it was carried out at an oxygen concentration of 0.2 to 0.3% by volume unless otherwise specified).

Condition: 250 ° C × 1 hour (put the sample directly into the dryer at 250 ° C)

With respect to the resin composition or the cured product obtained in the above Examples and Comparative Examples, the transmittance, heat resistance, water absorption, heat and humidity resistance, and weather resistance of the cured product (after primary curing and after secondary curing) were measured by the following methods. (Light), storage stability, and hardenability (formability) were evaluated. The results are shown in Table 3.

<Transmittance of hardened material (with or without coloring)>

Using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100), the wavelength of 400 nm was measured at each time point after the first step (after primary curing) and after the second step (after secondary curing). Transmittance of hardened material at 500 nm.

<Heat resistance test (reflow heat resistance test)>

After curing the cured product after hardening twice in the air at 260 ° C for 10 minutes, the transmittance of the cured product at a wavelength of 400 nm and 500 nm was measured using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). .

<Water absorption test (hygroscopicity)>

The cured product after the secondary hardening was dried at 230 ° C for 1 hour in a nitrogen (N ₂ ) atmosphere to form an absolute dry state, and then the weight was measured. The mixture was allowed to stand in an environment of a temperature of 85 ° C and a relative humidity of 85% for 100 hours, and then the weight was measured. The water absorption rate was calculated based on the added weight.

<Heat and heat resistance test>

The transmittance of the cured product after the above water absorption test at wavelengths of 400 nm and 500 nm was measured using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100).

<Weathering (light) test>

The hardened material after hardening twice was used as a sample, and M6T (6 kW horizontal metal lamp weather meter) manufactured by Suga Test Machine Co., Ltd. was used for the filter: (internal) quartz / (external ) The weathering (light) test was carried out under conditions of #275 and 1 kW/m ² (300 to 400 nm), and measured at 50 ° C for 100 hours using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). The transmittance of the cured product (wavelength 400 nm, 500 nm).

<storage stability>

The resin composition (3) obtained in Example 3 and the resin composition obtained in Comparative Example 1 (Comparative 1) were allowed to stand in an environment of 40 ° C, and after a certain period of time, the viscosity was measured as follows.

The measurement of the viscosity was carried out under the conditions of a resin composition of R/S Rheometer (manufactured by Brookfield, USA) at 40 ° C and a rotation speed of D = 1 /s. In addition, when the viscosity is 20 Pa‧s or more, the measuring tool of RC25-1 is used, and when the viscosity is less than 20 Pa‧s, the fixture of RC50-1 is used. Further, in the case where the viscosity at the rotation speed D=1/s cannot be measured, the value of the rotational speed D=5 to 100/s is extrapolated, and the viscosity of the resin composition is evaluated.

The viscosity of the resin composition (3) was 0.12 Pa‧s after 0 hours (at the start of the test), and became 1.3 Pa‧S after 72 hours, and became 100 Pa‧s after 144 hours.

The resin composition (Comparative 1) was cured after 48 hours.

Further, the resin composition obtained in a part of the examples and the comparative examples (shown in Table 3) was measured for the viscosity after standing for 12 hours in an environment of 40 ° C by the same measurement method, and it was compared with the resin. The degree of change in viscosity of the composition immediately after preparation was evaluated. Specifically, the viscosity after standing at 40 ° C was evaluated as × with respect to the viscosity change immediately after preparation, and the change was less than 10 times, and it was evaluated as ○.

<Sclerosing property (formability at the time of primary hardening)>

The resin composition was cured under primary hardening conditions. After the primary hardening, the cured product having a hardness of 10 or more in which the Shore A hardness was 10 or more at the curing temperature was evaluated as ○, and the cured product having less than 10 (containing a gelled product due to poor curing) was evaluated as ×.

<Evaluation of incident angle dependence>

A cured product (secondary hardened body) having a thickness of 1 mm obtained in Examples 19, 27, and 28, and an IRCF made of glass (alternatingly evaporating 20 layers of titanium oxide/20 layers of cerium oxide on one surface) were used. The cured product and the IRCF made of glass were placed in series on the incident light source side, and the spectral transmittance measurement (transmittance spectrum measurement) was performed using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100).

For the case where the cured material and the IRCF made of glass are disposed perpendicular to the incident light (the transmittance spectrum measured in this way is also referred to as the 0° spectrum; the thickness direction of the light self-hardening material and the IRCF made of glass (vertical direction) "Measurement by incidence"), and "The case where the cured material and the IRCF made of glass are incident in such a manner that the light is incident at a direction inclined by 25° with respect to the thickness direction (vertical direction) of the cured material or the IRCF (also measured in this manner) The transmittance spectrum is referred to as a 25° spectrum).

The abbreviations in Tables 1 and 2 are as follows.

CELL-2021P: Liquid alicyclic epoxy resin "Celloxide CELL-2021P", epoxy equivalent 131, weight average molecular weight 260, manufactured by Daicel Chemical Industry Co., Ltd.

EHPE-3150: alicyclic epoxy resin, manufactured by Daicel Chemical Industry Co., Ltd.

YX-8000: liquid hydrogenated epoxy resin, weight average molecular weight 409, manufactured by Mitsubishi Chemical Corporation

YX-8034: Hydrogenated epoxy resin, manufactured by Mitsubishi Chemical Corporation

YX-8040: High molecular weight hydrogenated epoxy resin, weight average molecular weight 3831, manufactured by Mitsubishi Chemical Corporation

PG-100: Epoxy resin, manufactured by Osaka Gas Chemicals

828EL: Aromatic epoxy resin, manufactured by Mitsubishi Chemical Corporation

OXT-221: oxetane resin "ARON OXETANE OXT-221", manufactured by East Asia Synthetic Co., Ltd.

PMSQ-E: Polymethylsesquioxanes (PMSQ-E) "SR-13", manufactured by Xiaoxi Chemical Industry Co., Ltd.

SI-100L: Thermal latent cationic hardening catalyst "San-Aid SI-100L" (SbF ₆ salt), manufactured by Sanshin Chemical Industry Co., Ltd., 50% solid content

The following contents were obtained from the respective examples and comparative examples.

(about the color when it is hardened twice)

When comparing an example using an alicyclic epoxy compound as a cationically curable compound, it is known that Examples 1 and 3 using a compound containing TPB as a cationic curing catalyst (also referred to as a TPB-based catalyst), and Compared with Comparative Example 1 in which a lanthanide salt (also referred to as a lanthanide catalyst) was used, the transmittance after secondary curing was high. This situation indicates that the use of the TPB-based catalyst can further reduce the coloration at the time of secondary hardening. Further, it was found that in the TPB-based catalyst, when the hindered amine was used for the Lewis base (Example 1), the coloring reduction effect was higher than in the case of using ammonia (Example 3), and it was presumed that the hindered amine was caused by the hindered amine. It has an antioxidant effect.

On the other hand, when an example in which a hydrogenated epoxy compound is used as a cationically curable compound is used, it is found that an example of a TPB-based catalyst having a small ammonia content (Example 4) and a ruthenium-based catalyst are used. In the example (Comparative Example 2), the coloring was reduced, but the coloring reduction effect of the TPB-based catalyst having a large ammonia content (Example 5) was low. The reason is considered to be due to the amount of residual chlorine in the YX-8000.

When an example in which an aromatic epoxy compound is used as a cationically curable compound is compared, it can be confirmed that a TPB-based catalyst is used as a cationic curing catalyst (Examples 9 and 10) and a ruthenium-based catalyst is used ( In Comparative Examples 4 and 5), the coloring reduction effect was high (the transmittance at 400 nm was high), and the heat resistance (transparency) was greatly improved.

Further, in the curing of the resin composition containing the inorganic material (polyoxymethylene-based material) as in Examples 18 and 20, the cationic hardening catalyst (especially the TPB-based catalyst) of the present invention can be preferably used. . In particular, by using an inorganic material (polyoxymethylene) in combination with a TPB-based catalyst, the coloration at the time of secondary curing (increased transmittance at 400 nm) is reduced, and heat resistance (transparency) is greatly improved.

Moreover, in the case of using the TPB-based catalyst in the curing of the resin composition containing the dye (Examples 27 and 28), the heat resistance was higher than that in the case of using the ruthenium-based catalyst (Comparative Examples 8 and 9). It is suggested that a filter material having high heat resistance, productivity, and formability is formed.

(About heat resistance (reflow heat resistance))

It was found that the use of the TPB-based catalyst (Examples 17, 19) and the use of the ruthenium-based catalyst (Comparative Example 6) can achieve higher heat resistance.

(about water absorption)

In the case where an alicyclic epoxy compound is used as the cation-curable compound and a case where a hydrogenated epoxy compound is used as the cation-curable compound, it is known that a TPB-based catalyst is used as the cationic hardening catalyst. The water absorption rate can be reduced as compared with the case of using a lanthanum catalyst. The reason is considered to be that the structure of the reaction end is different. Further, it has been found that in the case of the TPB-based catalyst, the use of ammonia for the Lewis base can achieve lower water absorption. The reason is considered to be that ammonia volatilizes upon hardening.

(about heat and humidity resistance)

In the case where an alicyclic epoxy compound is used as the cation-curable compound, the case where a TPB-based catalyst is used is improved in moist heat resistance as compared with the case of using a ruthenium-based catalyst. Further, it was found that the case where a hindered amine was used in the TPB-based catalyst (Example 1) was higher in moisture heat resistance than in the case of using ammonia (Examples 2 and 3). It is presumed that the reason is the same as that of the secondary hardening, and it is the antioxidant effect of the hindered amine.

(about weather resistance (light))

It is known that the use of the TPB-based catalyst can achieve higher UV radiation resistance than in the case of using a ruthenium-based catalyst.

(about storage stability)

It is known that the use of the TPB-based catalyst can achieve higher storage stability than when the ruthenium-based catalyst is used.

(About hardenability (formability))

It was confirmed that even when an aromatic epoxy compound was used as the cationically curable compound, the TPB-based catalyst was used as the cation-curing catalyst (Example 26), and the hardenability was compared with the case of using the ruthenium-based catalyst (Comparative Example 7). Formability) is also excellent. In particular, a resin composition of a cationically curable compound which is 100% by mass of "an aromatic epoxy compound which is hardly cured in a short period of time when it is considered to be cation hardened" is also successfully cured.

(about incident angle dependence)

Examples 27 and 28 in which an absorbing dye was added to the cured product were compared with the case of using Example 19 in which no absorbing dye was added, and it was found that the long wavelength side caused by the incident angle can be reduced when the reflective IRCF is used. The difference in transmittance at the transmission end (the difference between the 0° spectrum and the 25° spectrum is small).

In the above-mentioned embodiment, the cation-curable resin composition can provide a molded article excellent in heat resistance, moist heat resistance, low water absorbability, and UV-irradiation resistance by using a specific cationic curing catalyst. The mechanism of action is identically exhibited in the cationically curable resin composition of the present invention.

Therefore, according to the results of the above-described embodiments, the present invention can be applied to all the technical scopes of the present invention and various aspects disclosed in the present specification, and an advantageous effect can be exerted.

Fig. 1 is a graph showing the results of measurement of the spectral transmittance of the cured product obtained in Example 19.

Fig. 2 is a graph showing the results of measurement of the spectral transmittance of the cured product obtained in Example 27.

Fig. 3 is a graph showing the results of measurement of the spectral transmittance of the cured product obtained in Example 28.

Claims (7)

A cationically curable resin composition comprising a cationically curable compound and a cationic curing catalyst as essential components, wherein the cationic curing catalyst is composed of a Lewis acid represented by the following general formula (1) and a Lewis base. , Wherein R is the same or different and represents a hydrocarbon group which may have a substituent; x is an integer of 1 to 5, the same or different, and represents the number of fluorine atoms bonded to the aromatic ring; a is an integer of 1 or more, and b is 0. The above-mentioned integer satisfies a+b=3); the cationically curable compound contains at least one selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound, and the cationically curable resin composition is Used in optical materials. The cationically curable resin composition according to claim 1, wherein the Lewis base is a compound having a nitrogen atom, a phosphorus atom or a sulfur atom. The cationically curable resin composition according to claim 1, wherein a mixing ratio of the Lewis acid to the Lewis base in the cationic curing catalyst is n(b)/n(a) of 0.99 or more and 5 or less. The cationically curable resin composition according to the first aspect of the invention, wherein the Lewis base is at least one selected from the group consisting of an amine having a hindered amine structure and an amine having a boiling point of 120 ° C or lower. The cationically curable resin composition of claim 1, wherein the Lewis base is ammonia. The cationically curable resin composition according to claim 1, which further comprises a near-infrared absorbing dye. A molded body obtained by curing the cationically curable resin composition according to any one of claims 1 to 6.