TW201219442A - Cation-curable resin composition - Google Patents

Abstract

The purpose of the present invention is to provide a cation-curable resin composition capable of obtaining a molded article with excellent heat resistance, moisture and heat resistance, low water absorbability, and UV-irradiation resistance and a molded body useful for a variety of applications such as in optical members, etc. The present invention provides a cation-curable resin composition with a cation-curable composition and a cation-curing catalyst as essential components thereof and wherein the cation-curing catalyst comprises a specified Lewis acid and Lewis base.

Description

201219442 6. Description of the Invention: TECHNICAL FIELD 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 curing catalyst which generates a cationic species by heat or light. [Prior Art] The cationically curable resin composition is a tree containing a cationically curable compound and a cationic curing catalyst, which is formed by a catalyst such as heat or light, and which is hardened by a cationic hardening reaction. Composition. Cationic hardening (polymerization) and radical polymerization (4) have the advantage that hardening inhibition by oxygen does not occur and shrinkage at the time of hardening is small, and it is expected to be used in various fields, for example, except for electrical and electronic components or optical members. Various applications such as coating materials and materials for coatings and adhesives have been studied in various applications, and it has been desired to develop a cationically curable resin composition having excellent properties required for each application. In the case of the conventional cationically curable resin composition, for example, in order to obtain a molded article excellent in ί ′′, 生 it 、, release property, and the like, one type of cation-curable compound contains 26 Gt or less at 1 atm. The curable resin composition for an optical molded body of a compound having a boiling point, a mold release agent, and a positive M-based ion-hardening catalyst has been prepared. 彳1 ▲ Only 4 (see, for example, Patent Document 1). Patent Document i discloses the use of a recording system with a handle and a melon as a % ion hardening catalyst. The technique of using #3 boron compounds for the hardening of resin compositions has also been explored. For example, the right 丁+t lower main 揭示 is disclosed: tetrakis(pentafluorophenyl)borate (TEPB) is used in a photocurable resin composition containing a photocationic polymerizable 201219442 compound and a photocationic polymerization initiator. As a photocationic polymerization initiator, a cured product having low moisture permeability and excellent transparency is obtained (for example, see Patent Document 2). Further, an amine compound using boron trifluoride as a curable composition containing a nitrogen atom latent curing agent for an epoxy resin has been disclosed (for example, see Patent Document 3). The curable resin composition containing a boron-containing compound further discloses 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 an acid anhydride is used to cure such a hard resin composition. Further, a curable epoxy resin composition for encapsulating a solid element device containing an "anhydride hardener" and a "boron-containing catalyst such as triphenylborane" (see, for example, Patent Document 5). Patent Document 1: Patent Document 2: Patent Document 3: Patent Document 4: Patent Document 5: [Summary of the Invention] 曰本特开2009-299074号 曰本特开2005 — 187636号曰本特开昭62 — 2403 In the case of the cation-curable resin composition, the industry is investigating that it can be applied to various applications, and since it can exhibit transparency, it is known that it is transparent to the cation-curable resin composition. It is especially useful as a material for photonic applications such as lenses. For example, in a digital camera module, in order to be mounted on a mobile phone or the like, miniaturization has been carried out, and cost reduction has been achieved. Therefore, a tree lens is used instead of the conventional inorganic glass as an imaging lens. On 4 201219442, the installation step of such a component has become the mainstream in the use of solder reflow (der ref丨0 w) in order to achieve cost reduction. Therefore, in the case where a cationically curable resin composition is used for forming 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 exposure resistance in a use environment. Regarding these parties®, as described above, Patent Document 1+ discloses a resin composition using a ruthenium salt as a cationic hardening catalyst. By using the recording system to salt, it can be used in the reflow method, etc., and has achieved certain results. However, when a recording salt is used, the formed body is colored by heat (heat during hardening, use environment), and as a result, there is a problem that the transmittance of short-wavelength visible light (10) light is lowered, and the heat resistance of the molded body is still insufficient. Further, in the case where the molded body hardened by the lanthanum lanthanum salt has a relatively high water absorption ratio, when it is used as an optical material, there is still room for research into a low water absorption. On the other hand, when τ ε ρ β 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 formed body is not sufficient. Further, since the amine complex of the trifluorochemical shed described in Patent Reading 3 produces argon-containing fluoric acid by contact with moisture, there is a fear that safety during operation and the like cannot be ensured. In the case where the acid anhydride hardens the resin composition as described in the patent document* or the patent document 5, 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 hardening catalyst. The molded body is obtained, and the heat resistance of the molded body cannot be improved to a process which can be used in the reflow step. 201219442 In this way, the prior art has further studied the space of the resin composition of the molded article having excellent heat resistance, such as resistance to moist heat, low water absorption, and uv-irradiation resistance. The present invention has been made in view of the above circumstances, and an object of the present 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, and UV-irradiation resistance, and can be used for optics. A molded body of various uses such as a member. The present inventors have conducted various studies on a cationically curable resin composition containing a cationically 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. The cation hardening catalyst is excellent in heat resistance, moist heat resistance, low water absorption = uv irradiation resistance, and the like, which is obtained by curing the resin. 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 heat or ultraviolet light in the coloring or visible light wavelength region can be suppressed as compared with the prior lanthanide cationic curing catalyst. reduce. Further, it has been found that such a molded body is extremely useful for optical applications such as lenses, and it is thought that the above problems can be completely solved to complete the present invention. In other words, the present invention relates to a cationically curable resin composition which is characterized in that a cationically curable compound and a cationic curing catalyst are required to be formed, and wherein the cationic curing catalyst is represented by the following general formula (1) The Lewis acid and Lewis base are shown, 201219442

(1) wherein R is the same or different and represents a hydrocarbon group which may have a substituent; the integer of x: 5 is the same or different, and represents the number of fluorine atoms bonded to the aromatic ring, and a is 1 or more, and u λ Λ匕 is an integer of 0 or more, and satisfies a+b = 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. The preferred embodiments of the present invention described in the following are also preferred embodiments of the present invention. The cationically curable resin composition (also referred to as a resin composition) of the present month is cationically curable. The compound and the cation-curing catalyst are essential components, and other components may be contained in the range which does not inhibit the effects of the present invention, and one or two or more kinds of these components may be used. The cation-curing catalyst is represented by the above formula (1). The Lewis acid (organoborane) and the Lewis base are shown. Thus, since cationic hardening can be employed as the hardening method, it is obtained by, for example, addition hardening such as acid needle hardening. The cured product is excellent in heat resistance, chemical stability, moisture resistance, etc., and is particularly excellent in characteristics required for optical use: it is obtained by comparison with the case of using a conventional cationic hardening catalyst such as a sulfonium salt. Heat (heat at the time of hardening, use environment), color reduction, hygroscopicity, heat resistance, or yttrium resistance, etc., are excellent in durability and hardened material. Furthermore, the color of the cured product based on the catalyst used is colored. The presence or absence of 201219442 degree 'is usually also confirmed by the change of Φ1 in the transmission of 400 _. That is, the transmittance of 曰 and b in Yang (10) can be evaluated for the presence or absence of hardened material. Further, the cation hardening catalyst means that the hardening accelerator in the cation hardening reaction and the acid squeezing reaction, for example, are different from each other in the above formula (1), and represent a group which may have a substituent. The above hydrocarbon group is not particularly limited to a hydrocarbon group having preferably a carbon number of U. The hydrocarbon group having a carbon number of 20 is preferably an alkyl group or an aryl group as long as the number of carbon atoms in the whole is [~20] The alkyl group, the aryl group, and the alkenyl group may be an unsubstituted group, or may be a group in which one or more hydrogen atoms are substituted by another organic group or a γ atom. Examples of the group include an alkyl group (in the case where the hydrocarbon group represented by R is an alkyl group, the entire hydrocarbon group after substitution corresponds to an unsubstituted alkyl group), an aryl group, a dilute group, an alkoxy group, a hydroxyl group, and the like. X in the formula (1) is an integer of 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 2~ 5' is more preferably 3 to 5, and most preferably 'a is an integer of 1 or more' b is an integer of 0 or more, and satisfies & + b = 3. That is, at least one of the above Lewis acids is bonded with fluorine. The atomic aromatic ring is bonded to the 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. As the Lewis acid 'specifically, for example, it is preferably three (five gas 201219442 phenyl) borane (TPB), bis(pentafluorophenyl)phenylborane, pentafluorophenyl diphenylborane Tris(4-fluorophenyl)borane and the like. Further, it is more preferable because it can improve the heat resistance, the heat and humidity resistance, the low water absorbability, the υ 照射 irradiance, and the like of the molded article. Further, in the specification, the examples, and the like of the present application, the cation-hardening catalyst of the present invention is characterized in that cerium is used as a Lewis acid as a τρΒ-based catalyst. The Lewis base may be infinitely arbitrarily formed as long as it is capable of coordinating with the Lewis acid, and may be used as a Lewis base. Preferably, the Lewis base is used as a Lewis base. A compound that shares the atoms of an electron pair. Specifically, a compound having a nitrogen atom '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 amide), ammonia or the like. More preferably, it is an amine having a hindered amine structure, a low boiling amine, ammonia, more preferably a polyamine having a hindered amine structure, 4. When the polyamine having a hindered amine structure is used as the Lewis test, 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, if ammonia or a low-boiling amine is used as the above-mentioned Lewis test, the cured product obtained is excellent in low water absorption and ultraviolet radiation resistance. It is presumed that since the ammonia or the low-boiling amine is volatilized in the hardening step, the structure of the salt derived from ammonia 201219442 or the low-boiling amine in the final shaped body (hardened product) is reduced, so that the water absorption of the formed 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, it can be exemplified by: 2,2,6,6-tetradecyl brigade, N-mercapto-2,2,6,6-tetramethyl 0 bottom bite; TINUVIN770 , TINUVIN 765, TINUVIN 144, TINUVIN 123, TINUVIN 744, CHIMASSO RB 2020 FDL (above, manufactured by BASF Corporation); Adekastab LA52, Adekastab LA57 (above, manufactured by ADEKA Corporation), and the like. Among them, TINUVIN770 'TINUVIN765, Adekastab LA52, Adekastab LA57® having two or more hindered amine structures in one molecule is preferable as the above-mentioned low-boiling amine, and it is preferred to use an amine having a boiling point of 120 ° C or less, more preferably 80. Below °C, more preferably 50 ° C or less, more preferably 30 ° C or less, and particularly preferably 5 ° C or less. Specific examples thereof include a monoamine such as monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, and ethylenediamine; dinonylamine, 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, triterpene phenylphosphine, decyl diphenylphosphine, 1,2-bis(diphenylphosphino)ethane, and diphenyl. Phosphine and the like. The compound having a sulfur atom is preferably a thiol or a thioether. Specific examples of the mercaptan include mercapto mercaptan, ethyl mercaptan, 10 201219442 as a sulfur iso group, monoethyl sulfide, methyl propanethiol, hexyl mercaptan, antimony mercaptan, and benzene sulfur. Alcohol, etc. Examples thereof include diphenyl sulfide, diinylthiosulfonyl phenyl sulfide, and methoxymethylphenyl sulfide. In the cationic hardening catalyst of the present invention, the mixing ratio of the Lewis acid to the Lewis test is not necessarily a stoichiometric ratio. That is, the Lewis acid and the Lewis base (in terms of the amount of alkali points) may be used in excess of the theoretical amount (equivalent), that is, the mixing ratio of the Lewis acid to the Lewis test in the 'cation hardening catalyst is "to become the Lewis base point. The ratio of the atomic number of atoms n ( b )" to "the number of atoms of boron which is the Lewis acid point n(a)j (n(b) means that the cation hardening touch is exhibited even if it is not 1 (metering ratio) The role of the medium. n(b) /n(a) in the cationic hardening catalyst affects the storage stability and cationic hardening properties of the resin composition (hardening rate, hardening degree of hardened material, etc.). For example, when a diamine or the like has two Lewis base points in the molecule, the ratio of the @@斯斯 test to the cation-hardening catalyst = the acid-hardening catalyst is 〇5, the ratio η.) / ): "measuring ratio.) Calculate the ratio n (b) /n (a) in this way. From the viewpoint of the storage stability of the resin composition having a cationic hardening catalyst, δ, if the Lewis acid is relative to the Lewis base If there is too much excess, there will be a situation in which the preservation stability is lowered. It is preferable that the resin composition which is more excellent in storage stability is preferably 比(1)/n(a) is 〇5 or more. For the same reason, the above ratio is more preferably 0.8 or more, more preferably 0.9 or more, more preferably 〇. In particular, in the case of the cation hardening property, if the base of the Lewis 201219442 is excessively excessive, the low-temperature hardenability of the cured product is lowered, so that the composition for further improving the cation hardening property is obtained. Preferably, η ((8) / n(a) is 1 〇〇 or less. For the same reason, n(b) /η(& is more preferably 20 or less, more preferably 1 〇 or less, and particularly preferably 5 Further, in view of the cation hardening property, a structure composed of a compound having a nitrogen atom, a sulfur atom or a filling atom and substituted by 2 carbons (a structure in which two or more carbons are substituted) 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(1)8(a) is preferably 2 or less, more preferably K5. Hereinafter, it is more preferably 1> or less. For example, for the structure of a hindered amine In general, in the case where the Lewis base is ammonia or a low-boiling amine having a small steric hindrance, 'in particular in the case of ammonia' is more than n(b). Specifically, it is preferably LOO! or more, more preferably $1 G1 or more, more preferably M or more, and still more preferably 1.5 or more. Further, the Lewis acid and the Lewis base which constitute the cationic curing catalyst are not particularly limited. Preferably, the Lewis base is present in a state in which the Lewis acid is in an electronic interaction. More preferably, the Lewis base is in a form of coordination with the Lewis acid, more preferably at least relative to The Lewis acid is equivalent to the equivalent Lewis base and the Lewis acid coordination: sad. When the ratio of the Lewis base to the Lewis acid is equivalent or less than 隋^, that is, when the ratio n(b) / n(a) is 1 or less, the approximate amount of the Lewis base present is The form of Lewis acid coordination. On the other hand, in the form of an excess (more than equivalent) containing Lewis base 12 201219442, it is preferred that the Lewis test is coordinated with the Lewis acid equivalent, and the remaining Lewis is present in the vicinity of the complex. Specific examples of the cationic hardening catalyst in the present invention include: TPB/single-base amine complex, τρΒ/di-cavity amine complex, τρΒ/trialkylamine complex #ΤΡΒ丝amine Complexes, τρΒ/hindered amine complexes, etc. (4) amine complexes; 职/ΝΗ3 complexes, etc., organic/ammonia complexes, ruthenium/triarylphosphine complexes, τρΒ/diarylphosphines Organic (tetra)/thiol complex such as complex compound, argon/monoarylphosphine complex, organoborane, phosphine complex; τρΒ/alkylthiol complex; τρΒ/diaryl sulfide An organoborane a ether complex such as a substance, a hydrazine/dialkyl sulfide complex or the like. Wherein ' is preferably a ruthenium/homoxylamine complex, a τρΒ/hindered amine complex, a ruthenium/iridium 3 complex, and a ruthenium/phosphine complex. In the resin composition, the content of the cation hardening catalyst is preferably such that the amount of the active ingredient (solvent of the Lewis acid represented by the formula (1) and the Lewis test) is not related to the following cationic curing property. The compound (10) parts by mass is set to be O.HW parts. If the quality is not reached (4), then it is impossible to further improve the hardening speed (U) 5 ft or more. More preferably (more than or equal to the mass of the denier). In the case of heating, for example, after the molded body is obtained, the molded body 20 is reflowed (the heat resistance of TC or higher is required, and therefore, the heat is required, and the transparency is preferably set to 丨. It is more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and particularly preferably 2 parts by mass or less. ·,,,, in the above resin composition, a cationic hardening compound (also referred to as 13 201219442 " The cation-curable resin σ / is a compound which can be hardened (polymerized) by a cation hardening reaction, and a compound having a cationically polymerizable group is also known as a cationic polymerizable group. The σ r group may be a cation-hardening group, and examples thereof include w / lactyl-oxetane (oxetane ring), - oxalate: / 〇1 pentane (di〇x〇lane), triterpene, B a vinyl group, a vinyl group, preferably an epoxy group or an oxetanyl group. That is, the sulfonate compound contains epoxidized oxime and/or Oxygen heterocyclics, "(also known as "oxyxetane" "H is a preferred embodiment of the invention - the hardening characteristics of the upper::: subpolymerizable group are not only affected by the type of the base Also, the effect of the organic skeleton formed by the combination of the mysterious base. In addition, in the present specification, the phrase "the « « 甲 甲 包含 包含 包含 包含 包含 oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi oxi The secret of the epoxy group, in addition to the narrow epoxy group, also includes (a) urethane hydroxy-heterocyclic (tetra) ring-bonded fluorene group, ring-crossing group and glycidyl ester-based soil, etc. 3 (four) or 0 The base of the oxime bond or the epoxycyclohexane ring is specifically described as the upper core... human acetophenane compound. The epoxide compound, the aromatic "di-"epoxy compound, and the gas are more preferably 彳, An aliphatic epoxy compound, ',, an anthracene oxygen compound, a hydrogenated epoxy compound. Thus, the above cationic hardening compound Oxygen compound 'Hydrogenation 惫#人& Select a alicyclic ring chain from the group consisting of a milk compound and an oxetane compound, at least one of the group, you can + 4 丄 still form the species It is also a preferred embodiment of the present invention. 14 201219442 The above epoxy compound means that the right g β 〜 ', 丨 ° 咏 咏 环氧 epoxy compound is a compound having 舳 % of an epoxy group. List: epoxy production ρ its f ”, a clothing type oxy group, such as clothing gas% hexyl (epoxycyclohexane guanidine, ancient secret 々 into k lumber) directly or via hydrocarbon plus true p 4 (especially, an oxirane ring), etc. As a known % epoxy compound, it is preferably an epoxycyclohexane group. Further, it is possible to further improve the hardness of the hardening molecule, and in terms of the rate of valence, it is preferably a polycyclic epoxidized epoxidation of the compound oxime oxy group, and has an alicyclic type in the sub-group. The saturated crepe is octadecyloxy and has a vinyl group or the like. j" is preferably used as an alicyclic epoxidation in combination with the above-mentioned oxo compound having an epoxycyclohexane group of 3 4 - fluorene #, for example, preferably, oxocyclohexanecarboxylic acid 3, 4, Epoxy 33⁄4 e | # 改质一^ Clothing % hexyl methyl ester, ε ~ caprolactone, epoxy cyclohexane carboxylic acid 3,, 4, an epoxy w at double ~ clothing hexyl methyl ester, hexane Acid (3,4-epoxycyclohexyl ester) and the like. Further, as the production of an alkyl group & X, as the above-mentioned alicyclic epoxy compound having an epoxycyclohexyloxy compound: a sputum sputum, for example, can be listed as a double bis (transyl) group.卜 醇 之 u u 环氧 环氧 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环 环. As the hydrogenated epoxy compound, a compound having a direct or indirect y, a saturated aliphatic cyclic hydrocarbon skeleton, and a % oxypropyl ether group which is more than #1 β β is preferably bonded. :::! ! Epoxy propyl mystery compound. Such a hydrogenated epoxidized aromatic epoxide: a wholly or partial hydride of the % oxygen compound is more preferably a hydride of a cyclocarbon: a hydride of a compound, more preferably a vapor of an aromatic polyfunctional compound. Specifically, it is preferred to vaporize the bismuth 15 201219442 epoxy compound, hydrogenated double s epoxy compound, and the like. More preferably, it is a chlorine compound & a hydrogenated double-aged F type powder F-type epoxy compound. The epoxy compound and the hydrogenated double aromatic epoxy compound are compounds of the formula. As the aromatic: the medium-sized scented ring and the epoxy have a double-aged skeleton and a second skeleton, and for example, a common compound epoxy compound or the like can be preferably used: an aromatic ring such as wood, f ring or onion ring. For compounds with a double-aged skeleton and "=higher refractive index, compared to the skeleton, borrow & "mouth." More preferably, it is a compound having an anthracene epoxy group as a glycidyl group, and a compound of a core: a compound, preferably a group ether group (aromatic/, more preferably an epoxy group, is a solvent for the use of the epoxy group). Even if it is borrowed, it is better, but it is suitable for use because it has a higher refracting degree. Therefore, it is preferably used as the above-mentioned aromatic epoxidized "epoxy compound, double". 】 epoxidation: a double-object'-having a substituent of an aromatic epoxidized compound, a bismuth octadecyl epoxy compound, and (iv) an epoxy compound. Among them, 'preferably = the above: scent epoxy The propyl compound, for example, can be listed (叩--ΡΟepoxypropyl ether type epoxy tree month..., table-dual type epoxy propyl singer type epoxy resin, Pan light varnish two knives amount oxypropyl ether) A type of epoxy resin, etc., and a quaternary alkyl type ring as the above-mentioned surface-bis-type epoxy propyl type epoxy resin, for example, can be exemplified by bisphenol A, bisphenol F, bisphenol s, and Obtained by condensation reaction of bisphenols such as bisphenol with epihalohydrin. As the above high molecular weight one-type epoxy propyl ether epoxy resin For example, it is preferable to add the above-mentioned table-bis-epoxypropyl ether type epoxy oxime to the above-mentioned double-aged a, biguanide f, double s, and double age. A preferred example of the aromatic epoxy propyl ether compound is bisphenol A type compound such as 828EL, 1〇03, 1007 (above, manufactured by Japan Ep〇xy Co., Ltd.); 〇neoat Εχ—1〇2〇, 〇nc〇at Εχ—1010, OGSOL EG- 210, OGSOL PG (above, 0saka Gas

An oxime compound or the like is manufactured by Chemicals Co., Ltd., and preferably 〇gS〇l EG - 2 1 0 〇 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 (PEG 600)) is preferably exemplified. , propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol (PP(J), glycerin, diglycerin, tetraglycerol, polyglycerol, trihydroxydecyl propane and its polymers, pentaerythritol and its multimers A compound obtained by a condensation reaction of an epihalohydrin such as a glucose, a fructose, a lactose or a maltose, etc. with an epihalohydrin, etc. Among them, a propylene glycol skeleton and an alkylene skeleton are more preferably contained in the central skeleton. An aliphatic epoxy propyl ether type epoxy resin or the like which is an oxygen-extended base skeleton. The above-mentioned oxetane compound means a compound having an oxetanyl group 17 201219442 (oxetane ring). The oxetane compound is preferably used in combination with an alicyclic epoxy compound and/or a hydrogenated epoxy compound from the viewpoint of the tempering speed. Further, from the viewpoint of improving light resistance, it is preferred. Λ佶田τ目女〇好环氧The heterocyclic butyl is converted into (10)/without a square group or a fragrant heart. On the other hand, from the viewpoint of enhancing the strong yield of the cured product, it is preferably an etched field - and preferably a multi-s An oxetane compound, i.e., a compound having two or more oxetane rings. The above oxetane having no aryl or aromatic ring condensed into an early functional oxetane compound For example, preferably 3-methyl-3-(trans)f-based oxetane, 3-indene, 3-ethyl-3-(2-ethylhexyl), very 'methyloxetanyloxy Base) oxetane, isoxyl-diethyl-ethyl-3-oxetanyl methyl), hetero-obtained B/3-oxacyclobutanemethyl)ether, different Acetylene (ethyl-3-pentapylbutanyl, yl) ether, 2-ethylhexyl (i)-:yl-3-oxecyclobutanylmethyl)-, ethyldiethylene glycol ethyl A 3-oxetanylmethyl)ether or the like. In the case of an oxetane compound having an aryl group or an aromatic ring, as a poly(oxetane compound), for example, di-ethyl(3-oxetanyl)methyl ether is preferred. , 3,7 -5-oxazolidine, i,2-bis[(3-acetamidine), bis-[(3~ethyl-3-oxetan) ] Propane, ethylene glycol bis(3-ethyl-3-oxecyclobutane == ring oxime diyl dimethylene (3-ethyl + oxastyrene alkyl methyl) (4) propyl propyl tris(3-ethyl + oxa 18 201219442 cyclobutanylmethyl) shout, bis (3-ethyl-3 oxacyclobutanyl methoxy) butadiene, ... double (3 —Ethyl-3-oxetanylmethoxy)hexanol, pentaerythritol tris(3~ethyl_3_oxetanylmethyl)anthracene, pentaerythritol IV (3 -ethyloxetanylmethyl) linkage, polyethylene glycol bis(3-ethyl-3~oxetanyl)ether, dipentaerythritol hexa(3-ethyl-ethyl) 3-oxetanylmethyl)ether, dipentaerythritol penta(3-ethyl-3-oxetandinyl fluorenyl)ether, dipentaerythritol tetrakis(3_ethyl one) 3 - oxygen As the oxetane compound, as the above-mentioned oxequid compound, specifically, for example, ETERNACOLL (R) EHO, ETERNACOLL (R) 〇χβρ. ETERNACOLL (R) ΟΧΜΑ, ETERNACOLL (R) ΗΒ〇χ, ETErnACOLL(r) ΟΧΙΡΑ (The above 'Ube Industries Co., Ltd. manufactures Hirose-ΗΠ, 0ΧΤ-121, 〇χτ-211, 〇χτ_22ι 〇χτ—212, ΟΧΤ—6 10 (above, manufactured by East Asia Synthetic Co., Ltd.) Among the above cationically curable compounds, an alicyclic epoxidized person or a hydrogenated epoxy compound is particularly preferred. This is equivalent to the coloring of the epoxidized person itself when hardening occurs. Η The coloring or deterioration caused by light is generated, that is, transparent When the resin composition containing the material is prepared, the optical member having no coloring and excellent light resistance is obtained with high productivity. Thus, the above cationic curing compound is selected. The open state of at least one of the group consisting of the free alicyclic epoxy compound and the hydrogenated epoxy compound is also one of the preferred embodiments of the present invention. The composition comprises a form selected from the group consisting of an alicyclic epoxy compound and a hydrogenated epoxy compound to a quinone species. 19 201219442 bis == oxygen compound or hydrogenated epoxy compound content, more than (10) mass. (5): The total amount of the upper sclerosing compound is alicyclic epoxidized, whereby the effect of using the above-mentioned more preferably 60% by mass of the coating oxygen compound can be further exerted. More preferably, it is 70% by mass or more. ” = ionic hardening resin composition, and ionic hardening compound is produced by cutting 忭 忭 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳 阳The type or composition of the curable compound, which will be the shaped body of the control. The form of the cation cation and the epoxide and the epoxy compound are 1% by mass. (4) The form in which the scented scented epoxy compound and other cation-curable persons are used in combination is preferable. In the latter case, 匕 = mouth oxygen compound and ^ oxygen (iv) free alicyclic ring state is a better form. At least one of the groups of the composition of the substance uses an aromatic epoxy compound as a cation hardening property.匕Required refractive index (the above-mentioned cation-curable compound such as a lens having a higher refractive index is preferably a compound of the above cationically polymerizable group, that is, a compound having two or more compounds, thereby obtaining a hardening property and further hardening ☆ hardening A hardened product with excellent properties. Further, as a compound having a more polymerizable group of π, it may be: a compound having more than one of the same cationic polymerizabilities 20 201219442, or may be issued as 1, and has 2 More than one compound of different cationic polymerizable groups, as a multi-guana Afc, it is a cation-hardening compound, especially a polyfunctional alicyclic epoxy compound, and more S-deuterated epoxy compounds. The cured product can be obtained in a shorter period of time by using the above 4. The above resin composition preferably also contains a pliable component (flexible thief-forming blade), thereby making it possible to have a uniform feeling, that is, a high toughness. The resin component may be a compound different from the above cationically curable compound, or at least one of the cationically curable compounds may be a flexible component. The flexible component is specifically (1) a compound having an oxyalkylene group represented by [1(CH2)n-〇-]m- (n is 2 or more 'm is 1 or more) Preferably, η is 2 to 12, m is an integer of 1 to 1000, more preferably 11 is 3 to 6, and the claw is an integer, and for example, an epoxy compound containing an oxybutylene group is preferred ("pan" Made by the company, YL-7217, epoxy equivalent (1), liquid epoxy compound O〇t or more)) 〇, as other preferred flexible components, preferably (2) high molecular epoxy compounds (such as hydrogenation double Phenol (made by japanEp〇xy heart sins, YX_8〇4〇, epoxy equivalent 1〇〇〇, solid hydrogenated epoxy compound)); (3) alicyclic solid epoxy compound (Daice® Chemical Industry △ Division, EHPE _ 3150 ) ; ( 4 ) alicyclic liquid epoxy compound (Daicel Chemical Industry Co., Ltd., Cell〇xide 2〇81 wide (5) liquid nitrile rubber liquid rubber, polymer rubber such as polybutadiene , fine particle rubber having a particle diameter of 1 〇〇 nm or less, etc. 21 201219442 =, more preferably terminal or side chain or main chain skeleton polymerizability The cation-curable compound may be preferably used as the above-mentioned flexible cleavage, and a cationic macrochemical compound may be preferably used as the compound. Preferably, the compound having an oxybutylene group (" (called hi-Uh)) has a content of the above-mentioned cationic hardening compound and a flexible component when 3 has the above flexible component. The total amount of enamel is 4.% by mass or less, more preferably 3% by mass or less, more preferably 2. 篁/0 or less. Further, preferably 〇〇1% by mass or more, more preferably quality % above 'better than 0.5 quality. /〇 above. 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. The resin composition of the present invention is suitably used as a mold forming material. Since the resin composition of the present invention can be released from the mold even if the release agent used in the prior art is not used. Therefore, it is possible to obtain a cured product which is excellent in mold release property from the mold because it does not cause a decrease in transparency due to the release of the release agent and suppresses 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, P; when a mold is formed as a curing or molding method, a release agent may be contained. The release agent is preferably a release agent which not only does not inhibit the hardening reaction caused by the cationic curing catalyst but also promotes the reaction, and specifically has an alcoholic hydrazine. The compound having a fluorenyl group and/or a carbonyl group (containing a carboxyl group and an ester group) has a carbon number of 8 or more in terms of compatibility with a cation hardening 22 201219442 resin composition and a high mold release effect. Hydrocarbon based. More preferably, it is selected from the group consisting of an alcohol having a carbon number of 8 to 36, a carboxylic acid having a carbon number of 8 to 36, a carboxylate having a carbon number of 8 to 36, a carboxylic acid anhydride having a carbon number of 8 to 36, and a carboxylate having a carbon number of 8 to 36. At least one compound of the group consisting of. By containing such a releasing 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 vinegar is more preferred, and a carboxy hydrazine (especially a higher fatty acid) and a carboxylic acid vinegar are more preferred. The carboxylic acid and the citric acid S are preferred because they can sufficiently exert the releasing effect without hindering the cation hardening reaction. Therefore, since the H amine is preferred to hinder the cationic hardening reaction, it is preferably not used as a releasing agent. The above compound may be a linear, branched or cyclic structure, and is preferably a branch. The carbon number of the material is an integer of 8 to 36, whereby the cured product exhibits excellent peeling properties without the function of transparency or workability of the composition. The carbon number is preferably from 8 to 20, more preferably from 10 to 18. The alcohol having an inverse number of 8 to 36 is a mono- or polyhydric alcohol, and may be a linear one or a branched one. As AW ^ ^ direct bond list: octyl alcohol, preferably tetraol, pentadecyl alcohol, undecyl alcohol, lauryl yeast, tridecyl alcohol, deca alcohol, decyl alcohol, maytanol, dimethyl glycol , T T Tetyl., 2__ethylbutanol, 2-ethylhexyl 23 201219442 alcohol, 3,5-dimethyl-b-hexanol, 2,2,4-trimethyl-pentanol, Dixin = alcohol, 2-phenylethanol, and the like. The above alcohol is preferably an aliphatic alcohol, and more preferably octanol, lauryl alcohol, 2-ethylhexyl alcohol or stearyl alcohol. The above-mentioned slow acid having a carbon number of 8 to 36 is a monovalent or polybasic acid. Preferably listed are: 2-ethylhexanoic acid, octanoic acid, citric acid, citric acid, deca-acid, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, hexadecanoic acid, stearic acid , octadecanoic acid, icosonic acid, i-hexadecanic acid, rosinic acid, etc. Preferably, octanoic acid, lauric acid, 2-ethylhexanoic acid, stearic acid, as the above carbon number is 8 to 36 (four) g Preferably, (1) a carboxylic acid vinegar obtained from a sulphuric acid and the above carboxylic acid, and (7) an alcohol having a carbon number of an indanol, an ethanol, a propanol, a hexanol, a heptanol, a glycerol or a hexanol a carboxylic acid obtained by combining the above-mentioned carboxylic acid with a combination of the above-mentioned carboxylic acid, (3) a combination of a carboxylic acid of a miscible fish having a specific carbon number of 1 to 7 of acetic acid, propionic acid, butyric acid or caproic acid and the above alcohol; The acid ester, (4) a certain acid ester obtained from an alcohol having 1 to 7 carbon atoms and a decanoic acid having 1 to 7 carbon atoms, and a compound having a carbon number of 8 to 36, etc., among these, preferably (1) and (a)) m 'better than hard fat Acid vinegar, hard vinegar acid vinegar, acetic acid vinegar, etc. 36 carboxylic anhydride refers to the above carbon number of 8 to 36, the above carbon number is the acid of the acid, and the amine: the above carbon number is 8 Examples of the acid salt of the hexa-36 acid group include a few acid salts obtained from the above-mentioned several acids f, :, Mg, Ca, Mn'Fe, c〇, NiCu, and ZnSn ^, etc. Among them, hard fat is preferred. Acidic acid, zinc 2-ethylhexanoate, etc. The stearic acid is preferably stearic acid such as stearic acid and stearic acid 24 201219442 compound, alcohol compound, more preferably stearic acid compound When the above-mentioned release agent is contained, the content of the resin composition is preferably 10% by mass based on 1% by mass of the resin composition. "In view of the above, the resin composition becomes difficult to harden, etc., and more than 10% of the mass is more than 10%. Good for. -1~2%%. 佳$好为°·1~5 mass When a lens is formed using the above resin composition, when a straight dioxygen cation hardening compound forms a lens, the second is a resin composition It contains a form of an inorganic material. The above resin composition dreams of containing an inorganic material, and the strength is high, and the forming processability is excellent. The hard ::: lens becomes an Abbe number and the refractive index is controlled (especially the Shi Xi compound becomes south As the inorganic material, an inorganic fine particle such as a metal oxide particle or an inorganic polymer such as a polyoxyalkylene compound is preferable. The inorganic fine particle 'is inorganic as a metal or a metal compound. The compound may be composed of (4), and there is no (four) limit = = inorganic component, which can be exemplified by metal oxides, oxychlorides, ruthenium, sulphate, (oxygen) sulfides, carbides, teeth a compound, barium sulfate, preferably: gold: anatase) carbonate, (test) acetate, etc. These are metal oxides (metal oxides), more preferably cerium oxide, titanium oxide, oxidized wheat ,child From the ritual enthalpy, the radiance or the Abbe number: the sclerosing compound used for overnight ' 'in order to obtain a higher refractive index or a lower Abbe number hardened material, preferably using titanium oxide, oxidizing or oxidizing Zinc. In order to obtain a lower refractive index or a lower Abe number, it is preferable to use a dioxane. (Hard 25 201219442 As the inorganic fine particles, in order to improve the affinity of the fine particles with the resin, and to improve the dispersibility, etc., The surface-treated particles are also not particularly limited, and various organic compounds 'inorganic compounds, organic metal 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 matrix coupling agent; a metal alkoxide and the (partial) Z. Further, as the inorganic polymer, examples of the inorganic polymer include a polymethyl sesquivalent compound; and (p) Ethylsusesquioxane), polyphenylsilsesquioxane, etc. In the above resin composition, in the case of containing inorganic fine particles or compounds, as a cationic hardening compound, the epoxy compound and/or the alicyclic ring are burned. Oxygen = 2 This can be made into a shape with a high Abbe number. The number of shells... is a cationic hardening compound. The above resin composition is obtained by containing an inorganic material. The inorganic material fish tree reduces the thermal expansion coefficient, the refractive index of the resin, the resin composition and the molded body thereof (for example, the transparency can also be controlled, so that it can be made into a crucible, and the material in the performance is particularly useful. Electricity: The material of the part or the optical use step exerts the release effect. Specifically, μ is made of inorganic fine particles, which is an epoxy compound, as a tree stalk; for example, a thermosetting resin (especially in the case of a knife, resin) The composition has a effect of 26 201219442, and (4) the resin composition is entangled in the mold at the time of hardening. However, by adding an appropriate amount of inorganic fine particles, the mold release effect can be seen, and the molded body (cured material) can be easily peeled off from the mold. The content of the inorganic material containing λ is preferably from 0. 01% to 95% by mass, more preferably from 1.00 to 8% by mass, more preferably from 0.2% by mass based on 1% by mass of the resin composition. 60% by mass, particularly preferably 〇3 to 2% by mass, most 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 6 〇〇 nm or more and 2 Å or less, as described in detail below (also referred to as a dye in the present invention). The near-infrared absorbing pigment) is also preferred. The dye is not limited to the near-infrared absorbing dye. It is preferable to select a dye having a characteristic absorption of 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 colorant 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. As the near-infrared absorbing dye used to prevent malfunction of the sensor in the image pickup lens module, it is preferable that the dye has a maximum absorption in the wavelength region of 6 (10) to (10). More preferably, it has a very large absorber in the wavelength region of 65 〇 to 75 〇 nm. The above-mentioned pigment is also preferably not substantially absorbed in the region of the wavelength of less than 600 nm on the 27 201219442. The near-infrared absorbing dye is preferably a dye having a redundant electron bond in the molecule. The dye having 7 turns of an electron bond in such a molecule is preferably a compound containing an aromatic ring. More preferably, it is a compound which contains two or more aromatic rings in one molecule. Further, it is preferable that the dye having a ruthenium electron bond in the above molecule has a large absorption in the above 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 jquaterrylene dye, a squary Uum pigment, and naphthalene. The naphthalene (cyanine) dye, the nickel complex dye, and the copper ion dye may be used alone or in combination of two or more kinds. The dye having no zwitterionic structure or cationic structure is preferred in terms of heat resistance, time: preferably, phthalocyanine pigment and porphyrin color... more preferably metal sapphire Complex and/or metal. Bu Lin complex. The ugly cyanine dye is preferably a metal-brown cyanine complex, and is exemplified by a metal such as copper, #, Μ, 鉄, nickel, tin, silver, magnesium, sodium, or misalignment. Metallic ugly green complex. Among these, it is preferable to use copper, hunger, and zinc as the middle one. The reason is that solubility, light transmission, and light resistance are more ":: ~ metal" It is preferably copper and zinc, more preferably copper. It is copper-based, and: it is excellent in light resistance caused by light in the adhesive resin. In the case of the above-mentioned pigment, the content of the above-mentioned pigment is preferably 0 0001 to 10% by mass, more preferably 〇 〇 10 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 In the image pickup lens module, it is known that an infrared cut filter (also referred to as an infrared ray cut filter) is also provided on the incident light side or the outgoing light side of the lens. The cut-off filter is formed by disposing a transparent resin sheet as a base material and providing an infrared reflecting film on one or both sides thereof in order to remove (near) infrared rays in the incident light of the noise. However, the reflective IRCF is transmitted by the light transmission. Rate curve varies depending on the angle of incidence In the reflective IRCF, a resin sheet having a pigment-containing layer (a composition in which a near-infrared absorbing pigment is pushed into a resin composition) is known. As the substrate, the reflection type IRCF in which the incident angle dependency is suppressed can be obtained. 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. Sheet (formed body)' is a reflection type that is suppressed in incidence angle dependency. 29 201219442 IRCF substrate is very useful. 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. That is, a 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 by 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 effect of the present invention is 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, poly-δ inhibitor, inorganic filler, organic filler, coupling agent and other adhesion improver, heat stabilizer, anti-bacterial and anti-fungal agent, flame retardant, matting agent, antifoaming agent, leveling agent, wet dispersion Agent, anti-sinking agent, viscosity-increasing agent - anti-sagging agent, anti-30 201219442 floating coloring agent, emulsifier, anti-slip agent, anti-scratch agent, anti-skinning agent, desiccant, anti-fouling agent, antistatic agent, Conductive agent (electrostatic aid), solvent, etc. The cationically curable resin composition of the present invention can be prepared by mixing the above cationic hardening compound and a cationic curable catalyst, and mixing the above other components as necessary. Further, when the components are mixed, the components or the 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 hardening resin or the reaction temperature, and is preferably 140 to 20 ° C, more preferably 12 to 40 ° C before the addition of the catalyst. (The resin composition is preferably a viscosity of 1 0000 Pa·s or less. Therefore, the processing property is excellent, and it is more excellent, for example, in the use of a molded article (especially, the use of a molded article). 1000 Pa.s or less, more preferably 200 Pa.S or less. Further, preferably 0.01 Pa.s or more, more preferably 0,1 Pa.S or more, more preferably 1 Pa.s or more, more preferably 5 Above Pa.s, it is preferably 10 Pa. S or more. For the measurement of the above viscosity, R〆$ Rhe〇meter (manufactured by Br〇〇kfield, USA) can be used for the resin composition, and the rotation speed D is 4 generations. Under the condition of =l/S. In addition, when the viscosity is 2〇pas or more, the measuring tool of RC25-1 is used, and when the viscosity is less than 2〇pa · s, the fixture of RC50-1 can be used. For the viscosity at which the rotational speed cannot be measured, the value of the rotational speed D=5 to 1 〇〇/s is extrapolated, and the viscosity of the resin composition is evaluated. As the curing method of the resin composition, heat can be preferably used. Hard 31 201219442 Method: Made as: Hard (: live: hardening caused by raw energy ray irradiation), etc., preferably 30~40 (hardened under rc, as light '^good for 1G~1G_w/one hardened 4 can be &quot; MW into the shape when forming, for example, need to mold the mold as a lens, etc. It is preferable to use a hardening and a forming method which are hardened 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. The method comprising the following steps: as the phase of the phase-hardening of the 1st person, the step of the hardening of the resin composition, or the step of thermally hardening the resin composition at 8G to .c; C. The second step of thermosetting the hardened material obtained in the i-th step to a temperature equal to or lower than the second step. In the first step, it is preferably in the case of thermal hardening. The curing temperature is set to 80 to 20 (TC. More preferably 1 Torr (rc or more, 16 Å or less. Further, the curing temperature may be changed stepwise within the range of 8 〇 2 to 2 (10). Hardening time in the hardening step, for example, preferably within (7) minutes, more preferably Within 5 minutes, it is more preferably within 3 minutes. Further, preferably 10 seconds or more, more preferably 3 seconds or more. The above thermal curing step can also be carried out under air or in an inert gas atmosphere or under reduced pressure. For example, in terms of improving productivity, the resin composition can be taken at a specific temperature and time in the model (4), taken out from the model, and in the air or nitrogen. It is allowed to stand in an inert gas atmosphere and heat-treated. In addition, it can be combined with photohardening (hardening caused by the radiation of the activity 32 201219442). As the above! The step is also preferably a hardening step using a model such as a metal resin (j, breaking, and raw (% is a mold).) The hardening step, 〇|LW using a die casting method, a sandwich evaluation report The mold forming method, the forming method, and the pouring forming method 4 are usually carried out, and the hardening step of the mouth im 1 4 is required to be the first step to harden the wear resistance by using the hardening of the mold. , low shrinkage, can be used in the first step and before the second step. The mold release step can be efficiently recovered (recycled) by the form 1 of the mold release step, "the hard 2 obtained in the first step is taken out from the mold" and the removed cured product is supplied to the subsequent step 2 step. The expensive mold and the long life of the mold are extended, so that the molded body can be obtained at low cost. In this case, it is preferred to use a method in which the above resin composition is made into a hardener and other components as needed. Sputum The product is filled (injected, coated, etc.) into a mold conforming to the shape of the target molded body and hardened, and then the cured product is taken out from the mold. In the above hardening method, the second Preferably, the hardened material obtained in the above-mentioned second step (preferably the hardened material taken out from the mold by the demolding step) is thermally hardened at more than 2001, 500X: or less. The lower limit of the hardening temperature is preferably 250. Above °C, more preferably 3〇〇. (: Above, especially good is 330X: Above 'best is 350°C or more. The upper limit is better 40〇. (3 or less. Also, the hardening temperature can be exceeded In the temperature range of 200 ° C and 500 ° C or less, the stage 33 201219442 changes sexually. Regarding the hardening time in the above 2+ ^ , A step, it is only necessary to set the hardening rate of the obtained tantalum shaped body to be ☆ The time of the brothers can be no particular limitation. If the manufacturing efficiency is taken into consideration, Zhao is better as a dice. Hours are set to, for example, 3° minutes to 30 hours. - Environment ~ Step: Also in the air Or an inert gas environment such as nitrogen &lt;Brothers, and medium, especially in the environment with low oxygen concentration. The second step above. For example, the brothers are going to carry out the atmosphere under the atmosphere. Further, (4) the inertia of the 1G body (4) or less is preferably 3% by volume or less, more preferably the following, and particularly preferably 0.5% by volume a, more preferably 1% by volume, and most preferably 〇3% by volume or less. The intensity of the hardened material obtained by the above-mentioned hardening method 0 A ,, the σ mold is taken out and the shape of the shape is produced to the strength of 98 χ 1 Λ 4 ρ u. For example, it is preferably extruded at a force of 9.8×10 Pa or more. The shape ^. The generalized ratio is a compressive strength of 10 〇 / 〇 or less. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, still more preferably 0 _ 0 1% or less. The cationically curable resin group m of the present invention is as described above. In the case of the molded article having excellent heat resistance, moist heat resistance, low water absorbability, ', ^. LL 7 uv irradiation property, etc., the cation hardenability is improved, and the cured product is cured. The obtained molded body (cured material) is also one of the inventions. The above-mentioned molded body is, in addition to, for example, an optical material, a mechanical component material, an electro-oxidic electronic component material, an automobile part, and a bamboo, civil engineering. In addition to materials, molding materials, etc., it is also used as a material for coatings. Among them, it can be used particularly for optical materials, 7-leaf equipment components, equipment components, etc. For example, a light lens, a lens (a number of 34, 201219442), a camera for a mobile phone, an image camera such as a camera for a mobile phone, a lens for a photon lens, a lens for light diffusion, a sealing material for LED, and optical Using adhesive, light Optical applications such as transparent glass or protective glass for bonding materials, filters, diffraction gratings, prisms, light guides, watch glass, and protective glass for display devices; optical sensors, optical switches, LEDs, and light-emitting components , optical waveguides, combiners, splitters, circuit breakers, optical splitters, optical fiber adhesives, etc.; Lcd or organic EL or PDP and other substrates for display, color filter substrates, touch The use of a display panel substrate, a display protective film, a display backlight device, a light guide plate, an anti-reflection film, an anti-fog film, etc., etc. Among these applications, an optical material is particularly preferable. Thus, the above-mentioned molded body is an optical material. The form of the cation-curable resin composition or the resin composition for an optical material is also included in the preferred embodiment of the present invention. The optical material is preferably a lens, an LED sealing material, or an optical adhesive. The bonding material for light transmission. 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. In the lens, an imaging lens such as an imaging lens for a mobile phone and a digital phase imaging lens is preferable. X is preferably such a micro optical lens. Further, in the case where the resin composition is a resin composition for an optical material. In other cases, other components may be appropriately contained depending on the use of the optical material. As other components, a uv absorber, a ruthenium blocking agent, a reactive diluent, a pigment, a lotion, and an antioxidant may be preferably used. , light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, 35 201219442 anaerobic polymerization initiator, polymerization inhibitor, antifoaming agent, etc. The cationically curable resin composition of the present invention The use of the above-mentioned cationic curable catalyst is more versatile than the case of using a lanthanoid cation-curing catalyst, and is particularly useful for optical materials. In particular, the lens for a camera, a beam condenser lens, a lens for light diffusion, a lens for a light diffusion lens, an optical adhesive, and an optical adhesive for use in the world, which are expected to have a high demand in the world, are used. The value is very high. The molded body (hardened product) obtained by the resin composition of the present invention is preferably used for a camera lens, a beam collecting lens, a light diffusing lens, and an optical pickup lens because of a low water absorption rate. use. 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 a camera lens for a digital camera in a camera lens is a better use of a molded body (cured material), which causes swelling, cracking, and the like, but the present invention The formed body (cured material) can be effectively formed by the above-mentioned resin composition of the present invention by the above-mentioned microscopic "microscopic love" of water absorption and the optical lens. Body (higher heat resistance of hardened reflow soldering) Reduced visible light transmittance: In the case of simplification of the manufacturing process, cost reduction, etc., the second reflow process is used. The resin composition of the solder shape I or the low P obtained from the composition is supplied to the solder reflow process, and the optical characteristics of the lens, the gloss sheet, and the components of the various components of the soldering process are suppressed (for example, Optical materials such as sheets and adhesives are very useful. 36 201219442 When the cationic hardening catalyst used in the composition of the present invention is a ruthenium catalyst, due to the composition Since the obtained molded body (cured material) has a particularly low water absorption rate and is excellent in heat resistance, a cation-curable resin composition in which a τρΒ-based catalyst is used as a cation-curing catalyst is particularly useful for each of the above optical material applications. Since the cation-curable resin composition has the above-described configuration, it can provide a molded article excellent in heat resistance, moist heat resistance, low water absorbability, and radiation resistance, etc. In particular, by using the cationic hardening in the present invention. The catalyst can improve the transmittance of the obtained molded body at 400 nm and reduce the coloration. The molded body is other than optical materials, mechanical parts materials, electrical and electronic parts materials, automobile parts materials, civil construction materials, molding materials, and the like. It can also be preferably used in various applications such as materials for coatings or adhesives, especially useful as optical materials. [Embodiment] The following disclosure examples illustrate the invention in more detail, but the invention is not limited to For example, "parts" means "parts by mass" and "%" means "mass%" unless otherwise specified. &lt;Preparation of TPB complex&gt; Preparation Example 1 (TPB: synthesis of THF complex) TPB (tris(pentafluorophenyl)borane) 42 3 g was dissolved in toluene (9) $ g, and then At room temperature, THF (tetrahydrofuran) was added dropwise while stirring, and then, 121 g of 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. Filtered white knots 37 201219442 After washing and drying, a white solid of ΤρΒ : THF complex 34.5 g (the content of TPB by liquid chromatography was 85.05%) was obtained. [NMR data] 'H-NMR (CDC13) pprn δ = 1.87 ( 4Η, m) δ = 3.63 ( 4H} m) 19F-NMR (CDCI3) ppm δ = - 87.7 ( 6F, m) δ = - 80.5 ( 3F , dd) δ = - 59.4 (6F, d ) Preparation 2 (Preparation of TPB/hindered amine (TINUVIN770) complex) TPB obtained in Preparation Example 1 : THF complex 8 1.1 parts (TPB component: 69.0 parts), TINUVIN77(R) (hindered amine, manufactured by BASF Corporation) 3 1 · 1 part of a solution of 7-butyrolactone of TPB complex (ia) was prepared from 88 parts of γ-butyrolactone. n(b) / n(a) = 0.96 / 1 in the TPB complex (la). Further, the following butyl lactone solution of TPB complexes (lb) to (le) was prepared in the same manner as above. n ( b ) / η ( a ) TPB complex (lb ) 2.04/ 1 TpB complex (lc) 1.1/ 1 TPB complex (w ) 0.95/ 1 TPB complex (le) 〇_91/ 1 38 201219442 Preparation Example 3 (Preparation of TPB/Hindered Amine (Adekastab LA57) Complex) The tpb:THF complex oxime fraction obtained in Preparation Example 1 (tpb component .85.1 parts) and Adekastab LA57 ( The hindered amine, manufactured by ADEKA Co., Ltd., was dissolved in 1 〇 3 parts of γ-butyrolactone to prepare a γ-butyrolactone solution of the τρΒ complex (2a). Furthermore, n(b)/n(a) = 〇 99 / 1. Further, a r-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 4 (Preparation of TPB/hindered amine (TINUVIN765) complex) Preparation Example 1 TPB obtained in the THF: 100.0 parts of THF complex (TPB component: 85.1 parts) and TINUVIN 765 (hindered amine, manufactured by BASF) 5 0.1 part dissolved in 120 parts of r-butyrolactone to prepare TPB complex (3 a solution of r-butyrolactone. Furthermore, n(b) /n(a) = 1.19/1. Preparation Example 5 (Preparation of TPB/Ammonia complex) TPB obtained by the same procedure as in Preparation Example 1 : 130 parts of THF complex (TPB component: 110.6 parts) and 26 parts of 25% aqueous NH3 solution (NH3) Ingredients: 6.5 parts) Dissolved in 78.2 parts of 7-butyrolactone to prepare a TPB complex (4a) coordinated with NH3 as a Lewis base, r-buty 39 201219442 Xi's solution. Furthermore, n(b) /n(a) = 1, 77/1. In addition, the TPB.NH3 component of the TPB mismatch (4b) to (4f) coordinated with NH3 is 50 ❶/, except that the amount of the 25% leg 3 aqueous solution used is changed and the same as described above. The indole lactone solution is made by the method of sputum. ^ The NH3 coordination amount in each TPB complex is as follows. n ( b) /η ( a) TPB complex (4b) 0 59/1 TPB complex (4c) 1.18/1 TPB complex (4d) 2.94/1 TPB complex (4e) I?〆 i TPB complex (4f) loo/i Preparation Example 6 (Preparation of TPB / bis-phosphoryl complex) TPB obtained by the same manner as in Preparation Example 1 : THF mismatched bruise (TPB component) .85.1 parts) and 43 parts of triphenylphosphine were dissolved in r dibutylene - 113.2 parts to prepare a r-butyrolactone solution of TPB/triphenylphosphine complex (τρΒ complex (5)). The coordination amount of the triphenylphosphine in the τρΒ complex (5) is as follows. n (b) /n ") = 〇99/1 Preparation Example 7 (Preparation of TPB / diethylamine complex) TPB: THF complex ι 〇〇 obtained in Preparation Example 1 (τρΒ component : 85.i part) and 13 parts of triethylamine dissolved in 99 parts of butyrolactone 'preparation of TPB complex f 6a) γ butyl + ^ ^ n river. Milk V &amp; aj γ - Butyrolactone solution. Further, n 201219442 (b ) / η ( a) = 0.8 / 1 帛 The r-butyrolactone solution of the TpB complex (6b) was prepared in the same manner as above. , n(b) eight (1) = 2 &quot;&lt;Preparation of Resin Composition and Cured Product (Formed Body)&gt; Example 1 celi0xide CELL — 2〇21P (liquid alicyclic epoxy resin, epoxy equivalent ΐ3ι, —Μ 4 as a cationic hardening compound was charged.匕 工业 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 TP TP TP TP TP TP TP The mixture was uniformly mixed under reduced pressure to obtain a resin composition (1). The resin composition was cured by the following method (hardening step) to obtain a cured product. Example 2 Cell 〇xide CELL-2021P was introduced as a cationic hardening compound. (liquid alicyclic epoxy resin, epoxy equivalent 丨3ι, manufactured by Ducei Chemical Industry Co., Ltd.) 1 GG part, and the above TPB complex (0.24 parts of r _butyrolactone solution of 4 ( (as a cationic hardening catalyst) The τΡΒ/amine complex 0.11 7 parts) was mixed at 401 and reduced under reduced pressure to obtain a resin composition (2). The resin composition was cured by the following method to obtain a cured product. ~7, Comparative Example 1~3 In addition to the composition of the tree The resin composition (3) to (7) and the resin composition 201219442 were obtained in the same manner as in Example 1 except that the types and amounts of the cationically curable compound and the cationic curing catalyst of the composition were changed as shown in Tables L to 2. (Comparative 1) to (Comparative 3) The cured resin composition was cured by the following method to obtain a cured product. Example 8 Incorporation of γχ as a cationic hardening compound _ 8〇〇〇 (liquid hydrogenated epoxy resin) 'Mitsubishi Chemical Co., Ltd.' 1 part, and TPB complex (5) 7 - 1 part of butyl vinegar solution (Tpb / triphenylphosphine complex 0.5 part as cationic hardening catalyst), evenly mixed The resin composition (8) was obtained. The resin composition was cured by the following method to obtain a cured product. Examples 9 to 2 6. Comparative Examples 4 to 7 Using the types and amounts of cationic hardening described in Tables 1 and 2 Compound, inorganic material, and cationic hardening catalyst, each resin composition is obtained. Further, when a solid epoxy resin of EHPE-3150, YX-8〇4, or PG-100 is mixed as a cationic hardening compound, Heat to 14 (rc, form A uniform composition. When PMSQ-E is used as the inorganic material, the cationic hardening compound is mixed and uniformly mixed at 8 〇t. When the catalyst is mixed, it is the same as in Example 1 at 40 ° C under reduced pressure. The mixture was mixed so as to have a uniform composition. The resin composition was cured to obtain a cured product by the following method. Example 27 1 part of the resin composition of Example 19, at 4 (rc τ χ ~ EX — 609 Κ (酞 青 色素 色素 , 最大 最大 最大 〇 〇 〇 〇 〇 〇 。 。 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Further, the resin composition was cured by the following method to obtain a cured product. 42 201219442 Example 28 Relative to the resin composition of Example 19, χ , χ EX EX EX 于 40 40 40 40 EX EX EX EX EX EX 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 One to five parts were uniformly dissolved to obtain a pigment-containing resin composition 0, and 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, 0.018 parts of TX-EX-609K (anthocyanine dye, maximum absorption wavelength 680 nm, manufactured by Sakamoto Catalyst Co., Ltd.) was uniformly distributed at 40 °C. Dissolved 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 Relative to 100 parts of the resin composition of Comparative Example 6, it was 40. (: A resin-containing resin composition was obtained by uniformly dissolving 0.015 parts of TX-EX-609K (anthocyanine dye, maximum absorption wavelength 715 nm, manufactured by Nippon Shokubai Co., Ltd.). Further, the resin was obtained by the following method. The composition was hardened 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). &lt;hardening step&gt; (1st step) Using a metal plate of 2 pieces of SUS304 (manufactured by Test本Testpanel Co., Ltd., surface finish), a gap of 10 0 0 // m is formed, and each resin is used. Casting of the composition. After the hardening was performed once at the temperature/time shown in Table 1, the mold release was performed. In addition, the formation of the product at the time of the hardening of the \ 生 43 201219442 Strong and difficult to demould, DAIFREE GA — 7500 (made by Daikin Industries, fluorine-polyoxygen) sprayed onto the sus board Wipe off again and use the SUS plate. (Second Step (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). Conditions: 250 ° C X 1 hour (the sample was directly placed in a 25 crc dryer) For the resin composition or cured product obtained in the above Examples and Comparative Examples, the cured product was obtained by the following method (after the hardening and 2 times) The transmittance, heat resistance, water absorbability, moist heat resistance, weather resistance (light), storage stability, and hardenability (formability) after curing were evaluated. The results are shown in Table 3. &lt;Transmittance of cured product (with or without coloring)&gt; After the first step (after primary curing) and after the second step (2 times) using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer uv-3100) At each time point after hardening, the transmittance of the cured product at a wavelength of 4 〇〇 nm and 5 〇〇 nm was measured. &lt;Heat resistance test (reflow heat resistance test)&gt; The cured product after the second hardening was dried in the air at 260 ° C for 10 minutes, and then an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV) was used. 3 1 00 ) The transmittance of the cured product at wavelengths of 400 nm and 500 nm was measured. &lt;Water absorption test (hygroscopicity)&gt; The cured product after the secondary hardening was subjected to a dry state in a nitrogen (n2) atmosphere at 230 44 201219442 c dry coal for 1 hour, and then the weight was measured. After standing at a temperature of 85 C and a relative humidity of 85% for 1 hour, the weight was measured. The water absorption rate was calculated based on the added weight. <Heat-and-moisture resistance test> The transmittance of the cured product after the water absorption test at a wavelength of 4 〇〇 nm and 500 nm was measured using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). &lt;Weather resistance (light) test>, the cured product after hardening for 2 persons was a sample, and M6T (6 kW horizontal metal tube weathering machine (metaling) manufactured by a testing machine company was used.

Weather meter )), performing the financial (light) test on the filter: (internal) quartz / (external) # 275, kW / m (3GG 4GG nm), and using an absorbance meter (manufactured by Shimadzu Corporation) , Spectroscopic domain Μ - 31 〇 (〇 measured at 5 (TC· transmittance of cured product after 1 hr (wavelength 400 nm '500 nm) ° &lt;preservation stability&gt; The obtained resin composition (3) and the resin composition obtained in the comparative work were allowed to stand in an environment of υ94 ,, and after a certain period of time, the viscosity was measured as follows. The above viscosity was measured for the resin composition. Use R/s Rheometer (Br〇〇kfield, USA 劁Α ★ . J, at 4 (TC, rotation speed D = 1/s). Also, when the degree is 20 Pa.s or more, use Rc25 -1 measuring fixture, the viscosity is less than 20Pa, 1々, as the spoon recognizes Pa.s when 'use RC50-1's fixture. Also, the viscosity can not be measured for the rotation speed D=丨/ s 45 201219442 as resin The composition was evaluated by extrapolating the viscosity of the rotational speed d=5 to 100/s. The viscosity of the resin composition (3) after the hour (after the start of the test) was 〇·12 pa.s, and after 72 hours, it became 1 3 pa s, and after that it became 100 pa.s. Resin composition (Comparative 1 After curing for 48 hours, the resin composition obtained in a part of the examples and the comparative examples (shown in Table 3) was measured by the same measurement method, and allowed to stand in the environment for 12 hours. The viscosity after the evaluation is compared with the degree of change of the viscosity of the resin composition immediately after preparation. Specifically, it will be 4 〇 &lt; 3 (: the viscosity after standing is changed with respect to the viscosity immediately after preparation) When the ratio is less than or equal to 1 and the change is less than 1 〇, the evaluation is 〇. &lt;Curability (formability at the primary curing)&gt; The resin composition is cured under the primary curing condition. A hardened material having a hardness of 1 〇 or more at a hardening temperature and having a hardness of 1 〇 or more is evaluated as X (a gelled substance caused by poor hardening), and is evaluated as X. Evaluation of angular dependence &gt; Thickness obtained by Examples 19, 27, and 28 was used. 1 mm hardened material (second hardened body) and glass IRCF (alternatively vapor-deposited 20 layers of oxidized zirconia / ruthenium dioxide 2 〇 layer on one surface), and arranged hardened materials in series on the incident light source side, The glass-made IRCF was measured for spectral transmittance (transmittance spectrum measurement) using an absorbance meter (manufactured by Shimadzu Corporation, spectrophotometer UV-3100). 46 201219442 For the case where the hardened material and the glass IRCF are arranged perpendicular to the incident light (the transmittance spectrum measured in this way is also referred to as 〇. spectrum; in the thickness direction of the light self-hardening material and the glass IRCF ( "Vertical direction" is measured by the method of "incident"), and "the light is incident from the direction of the hardened object, the thickness of the ircf and the direction of the vertical direction (vertical direction) by 25, and the IRCF of the glass is formed (4). ) 彳 彳 = transmittance spectrum measured in this way is also called 47 201219442 [Table l] cation hardening compound (resin) (parts) Inorganic material (parts) alicyclic epoxy resin hydrogenated epoxy resin aromatic ring Oxygen oxetane inorganic polymer CE3JL-2Q21P EHPE-3150 YX-800C YX-8Q34 YX-804C PG-100 828EL OXT-22I PMSQ-E Example 1 100 - - - - - - - - Example 2 100 - - - - - - - - Example 3 100 - - - - - - - - Example 4 - 75 - 25 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - 100 - - - - - - Example 7 - - 100 - - - - - - Example 8 - - 100 - - - - - - Example 9 20 20 - 40 - 20 - I - Example 10 20 10 - 40 - 20 10 - Example 11 - - - 30 - 50 20 - Example 12 - - 100 - - - - - - Example 13 - 100 - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - Example 17 20 - - 80 - - - - - Example 18 20 - 80 - - - 5 Example 19 20 - - 80 - - - - - - Example 20 23 - - 23 - - - - 54 Example 21 10 - 40 - 30 - - 20 - Example 22 100 - - - - - - - Example 23 100 Example 24 100 - - - - - - - - Example 25 100 Implementation Example 26 - - - - - - 100 - - Example 27 20 - - 80 - - - - - Example 28 20 - - 80 - - - - - - Comparative Example 1 100 - - - - - - - - Comparative Example 2 - 75 - 25 - - - - Comparative Example 3 - 100 - - - - - - Comparative Example 4 20 20 - 40 - 20 - - - Comparative Example 5 20 10 - 40 - 20 10 - Comparative Example 6 20 - - 80 — - - - — Comparative Example 7 — - - - - One 100 - - Comparative Example 8 20 - - 80 - - - - - Comparative Example 9 20 - - 80 - — - - - 48 201219442

&lt;N s if® | ί \ want s | TPB complex | I (6b) | 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 i 1 1 °·10 - -1 1 1 1 1 1 1 1 1 1 1 1 1 (6a) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1·10 1 1 1 1 1 1 1 1 1 1 1 1 1 1 /-v «η Vw- 1 1 1 1 1 1 1 «Λ 1 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (4f) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 10101 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (4e) 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 010 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (4d) | 1 1 1 0.090 1 1 1 ! 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 丨(8)j 1 1 1 1 | 0.442 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (4b) I 1 1 1 1 0.434 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 t 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 | (4a) 1 丨〇 Old 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 5 1 1 1 1 1 1 L〇i?J 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1(5)" 1 1 1 1 1 1 1 1 1 1 1 0-30 1 1 1 1 1 1 1 1 1 1 1 0-5Q 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1(8); 1 1 1 1 1 1 1 1 Bu_25 1 1 1 1 1 1 1 1 0-25 | 1 0-25 1 1 Q-^ J | 0.30 1 1 1 1 1 1 1 1 1 1 1 0-15 1 I 1 1 1 1 1 1 1 1 1 (^a) | 1 1 1 1 1 W1 © 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 1 1 1 丨(5)| 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 〇·^ 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 〇d)| 1 1 1 1 1 1 1 1 1 1 1 1 1 0-50 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (8)1 1 1 1 1 1 1 1 ! 1 1 0-50 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (lb) I 1 1 1 1 1 1 0.50 1 1 ! 1 1 1 1 1 1 1 1 1 1 1 1 1 1 (la); o 1 i 1 1 1 1 1 〇·^〇1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 13⁄4 ion hardening catalyst (salt salt solids (parts)) | lanthanide | I SI-100L I 1 1 1 1 1 1 1 1 1 0.05 I «Λ d •Λ 0.25 1 0.25 I 0.25 I 0.25 I 0.25 1 0.25 1 I Example i | I Lean Example 2 I 1 Example 3 II Example 4 II Example 5 1 I Example 6 I 1 Example 7 1 1 Example 8 1 I Example 9 II Example 丨〇 I Embodiment 1丨1 1 Embodiment II2 II Example 13 II Example 14 II Example 15 1 I Example 16 II Example 丨 7 1 I Example 丨 8 1 I Example 丨 9 II Real Example 20 J 1 Example 21 I | Example 22 I | Example 23 I | Lean Example 24 I | Example 25 I | Example 26 I | Example 27 I | Example 28 I | Comparative Example | Example 2 I | Comparative Example 3 I | Comparative Example 4 I | Comparative Example 5 1 | Comparative Example 6 I | Comparative Example 7 1 | Comparative Example 8 I | Comparative Example 9 1 201219442 1 Curability 1 Formability at the 1st hardening 1 〇- 〇〇〇〇〇〇〇〇X 〇X 〇〇〇1 1 X 1 1 Storage stability | Viscosity change 1 1 1 1 〇〇〇〇X 〇〇〇1 〇〇〇〇〇〇〇1 1 〇1 1 1 Transmittance (°/. II Metal tube test (light resistance) | 1 500 nm I 1 87.9 I 1 1_8ZA_ 1 1 1 1 1 1 1 1 . 85-4 . I 1 1 1 J | 400 nm | 1 71.4 I 1 1_ill_1 1 1 1 1 1 1. 1 1 1 1 1 1 1 1 1_63^_1 1 1 1 ! I Transmittance (%) | | After water absorption test (heat and humidity resistance) | | 500 nm 1_9〇4._ 1 1___1 | 88.6 1 | 66.6 1 1 1 1 1 1 1 1 1 1 1 1 1 1 I 1 1 | 88.9 | 1_6U__I 1 1 1 1 ί 1 400 nm | 1_ΏΑ_1 1____1 1____1 1_^_I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1__^_1 00 K 1 1 1 1 1 1 1 Water absorption rate (%) 1_2^5_I 1 P 1 1 1 1 1 1 1 1 1 1 1 9 1 1 1 I 1 1 1 1 ! 1 1 Ι_3·Π_I ON 'β 1 1 1 1 1 1 1 1 Transmission abundance (%) I 1 After reflow heat test | 1 500 nm 1 1 1 1 i 1 1 1 1 1 1 1 1 1 1 1 έ 1 91.6 1 1—91.8 1 1 1 1 1 1 1 1 00 00 1 89.5 I 1 1 1 1 1 1-79-9 1 I 1 77·3 1 1 76.7 1 1 400 nm 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 丨83.4 1 丨85.7 1 00 1 1 1 1 1 1 1 L 53.3 1 丨牴2 I 1 1 1 1 1 1 1 18.2 1 I Transmittance (%) | | 1 after hardening 1 1 500 nm 1 91·0 1 1 1 892 1 1 ^9.6 1 1 883 1 1- 87.8 1 | 90.0 1 | 88.8 | L"8-_2...1 丨队4 | | 88.9 | 1 1 89.4 I | 88.9 | 1 9»·6 1 1 91.7 1 1 91.8 I 1 92·2 1 υ.〇_ · 2—" 1 1 1 1 1 1-J8·4- 1 1st order 1 1 | 89.8 | 1 56·2 1 1 72·2 1 | 88.6 I 00 1 86.2 I 1 1 83.7 I 1 82.6 1 | 400 nm LJt-9 丨1 1 79.8 IL^i·2 1 s〇v£&gt; 1 76.5 II 74.9 | 1 83.8 1 1 81.6 1 丨7 | 1 847 1 丨71-2 1 1 1 72.1 | L.71.2 1 1 7〇·9 1 i 1 86.1 1 | 88.2 1 1 89·2 1 1 85.2 I 1 1 1 1 1 1 53·9 1 1 48·5 1 00 oo ON • ri (N 1 656 1 1 56.2 1 丨47.5 1 1 | 28.8 1 1 23.4 1 | After hardening | | 500 nm 1 91.0 1 1 92·4 1 1 91-2 1 丨88.7 | | 88.9 | 丨91.2 1 1 91.2 | ljl.7 1 1-89.1 1 丨88.7 1 1 89.6 I 1 | 89.8 1 1 89.6 | 1 896 1 \ 91-9 1 1 91.8 1 | 92.0 | 1 92.3 I 1 91.2 | 1 91.4 I 1 1 90.9 1 1 丨88.7 1 1 896 1 1 91.4 1 | 92.9 1 | 90.9 1 卜 | 88.9 IL^j_| 1 88.9 1 1 Diaphragm 3 1 1 89.3 1 | 400 run | 89.9 1 | 88.8 1 | 89.8 1 丨83.3 1 1 85·〇1 L_g6AJ 11 1 丨87.3 1 1 86.5 1 1 88·3 1 丨幻_4 | 1 1 88.5 I | 88.2 1 1 90.1 1 1 90 .4 1 丨like 1 | 90.9 1 1 89.7 | | 89.9 1 1 1 »9.3 1 1 1 562 1 1 49.0 1 1 91-9 | 丨85.7 | 1 88.6 1 1team 2 1 ss 1 99 1 1 Hardening conditions | l40eCx2min | | 140eCx2min | | l40eCx2min | 1 140eCx2min | | 14〇eC^2min | | 140e〇2 min j 1 14〇t&gt;2 min j 1 170eCx2min | 1 150e〇2min | 1 150·〇2πώι 1 | 150.010 min | | 15〇t&gt;2 min | | 150e〇2min | | 150e〇2min | 丨150e〇2min | 1 150*02 min | j 140〇C x2 min | 1 140*Cx2min | | M0e〇2min | 160.02 min | | 15〇X&gt;l〇min | 140*C χ2 min | 140*C χ2 min j 140*C χ2 min | | 140ec *2 min | | 160eCx2min | 1 140.02 min | j 140eCx2min | :140*02 Min | 140·〇2 min | 140〇C χ2 min | 150*C x2 min | 150e〇2min | 140*02 min | 160X^2 min | 140e〇2 min | 14〇e〇2min | | 1 1 实 绝 W 2 | | Example 3 1 1 Example 4 1 I Example 5 1 | Example 6 | 1 贲 Example 7 1 | Example 8 | | Example 9 | 1 Example 丨〇 1 1 Implementation Example 1 | |Example 丨2 | |Example 丨3 | |Example 14 I |Example丨5 1 1Example 16 1 |Example丨7 1 1 Example 1 8 1 I Example 19 1 1 Example 20 1 1 Example 21 I 1 Real Example 22 I | Example 23 1 | Example 24 | | Example 25 | | Example 26 | 27 | |Example 28 | |Comparative Example 1 | |Comparative Example 2 | |Comparative Example 3 1 |Comparative Example 4 |Comparative Example 5 1 |Comparative Example 6 1 |Comparative Example 7 |1Comparative Example 8 1 1Comparative Example 9 1 201219442 The abbreviations in Tables 1 to 2 are as follows.

CELL-2021P: Liquid alicyclic epoxy resin “ceU〇xide CELL —2021P”, epoxy equivalent 131, weight average molecular weight 26〇, manufactured by Daicel Chemical Industry Co., Ltd. EHPE — 3150: alicyclic epoxy resin, Daicel Chemical Industrial company manufacturing YX-8000: liquid hydrogenated epoxy resin weight average molecular weight 4〇9, manufactured by Mitsubishi Chemical Corporation YX 8〇34 'weathered 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-1: 苐 epoxy resin, 828EL manufactured by Osaka Gas Chemicals Co., Ltd.: aromatic epoxy resin, OXT 221 manufactured by Mitsubishi Chemical Corporation. Oxeane resin "ARON OXETANE OXT — 221』, East Asia Synthetic Co., Ltd. manufactures PMSQ-E. Polymethylsesquioxanes (PMSQ-£) "SR-13", manufactured by Xiaoxi Chemical Industry Co., Ltd. SI-1〇〇L: Thermal latent cationic hardening catalyst San-Aid SI — i〇〇L』 (SbF6 salt, manufactured by Sanshin Chemical Industry Co., Ltd., 50% solid content) The following contents were obtained from the respective examples and comparative examples. Coloring when changing) When comparing the case of using a ruthenium-type epoxy compound as a cationic hardening compound, it is known that a compound containing TPB as a cationic hardening contact agent is also used (also known as TPB-based catalyst). In Examples ι and 3, the transmittance after secondary hardening was higher than that in the comparative example using the salt-separating salt (also referred to as recorded catalyst). This condition indicates that the use of the TPB-based catalyst can be further reduced. In the case of secondary hardening, it was found that the hindered amine was used for the Lewis test in the lanthanide catalyst (in the case of Example υ and ❹ ammonia (Example 3), the color reduction effect was higher, It is presumed that the reason is the antioxidant effect of the hindered amine. The other side of the product, using a hydrogenated epoxy compound as a cationic hardening compound, is known as an example of using a catalyst having a low ammonia content ( In the example 4), the coloring can be reduced as compared with the case of the (10)-based catalyst (Comparative Example 2). However, the color reduction effect of the τρΒ-based catalyst having a large ammonia content (Example 5) is low. Think that the reason is It is affected by the amount of residual gas in γχ-8000. If a comparison is made between the case of using an aromatic epoxy compound as a cationically curable compound, it can be confirmed that a ruthenium-based catalyst is used as a cationic hardening catalyst (Example 9, 1G) Compared with the case of using a catalyst (Comparative Examples 4 and 5), the color reduction effect is higher (the transmittance at 4 〇〇 nm is higher), and the heat resistance (transparency) is greatly improved. In the curing of the resin composition containing the inorganic material (polyoxymethylene-based material) as in Examples 18 and 20, the cationic curing catalyst (especially the TPB-based catalyst) of the present invention can be preferably used. In particular, by using an inorganic material (polyoxygen-based oxygen) and a TPB-based catalyst in combination, the reduction in the second-time hardening (increased transmittance at 400 nm) is reduced, and the heat resistance (through the moon) is greatly increased. Heading. 52 201219442 ...H匕T , 1 The case of using the scorpion-based catalyst (Embodiment 7, 28) is higher in heat resistance than the case of using the system catalyst (Comparative Examples 8 and 9). It suggests a filter material that is more economical, productive, and formable. (Heat resistance (reflow heat resistance)) It is known that the use of a ruthenium-based catalyst (Example ΐ7, Μ) is higher in heat resistance than in the case of using a catalyst (Comparative Example 6). . (About water absorption) It is known that the case where an alicyclic epoxy compound is used as the cationically curable compound and the case where a hydrogenated epoxy compound is used as the cationically curable compound are all used as a cationic hardening agent. The case of the catalyst can reduce the water absorption rate as compared with the case of using the 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 ruthenium catalyst, the use of ammonia for the Lewis test can achieve lower water absorption. The reason for this is that ammonia volatilizes when hardened. (Heat-to-moisture resistance) In the case of using an alicyclic epoxy compound as a cation-curable compound, the case of using a ruthenium-based catalyst is improved as compared with the case of (10) a catalyst. Further, it was found that a hindered amine was used in the ruthenium-based catalyst (Example υ is higher in moisture heat resistance than in the case of using ammonia (Examples 2 and 3). It is presumed that the cause and the coloration at the time of secondary hardening The same is due to the antioxidant effect of the hindered amine. (About weathering (light)) It is known that the use of lanthanide catalysts is comparable to the use of recorded catalysts. (About storage stability) It is better than the knowledge of Qian Qing Qian (4) to achieve high storage stability. Phase (on hardenability (formability)) It is known that even if a compound of a scented epoxy compound is used as a cationic hardening compound When the TPB-based catalyst was used as the cation-curing catalyst (Example 26), the curability (formability) was superior to that of the case of using the ruthenium-based catalyst (Comparative Example 7). In particular, (10)% by mass was used. The "aromatic epoxy compound which is hardly cured in a short time at the time of cation hardening" is also successfully cured as a resin composition of a cationically curable compound. (About incident angle dependence) In Examples 27 and 28 in which an absorbing dye was added, compared with the case of using Example 19 in which an absorbing dye was not added, it was found that the transmission end of the long wavelength side caused by the incident angle can be reduced when the reflective IRCF is used. The difference in transmittance (〇. The difference between the spectrum and the spectrum of 25 is small). In the above embodiment, as the cationically curable resin composition, heat resistance, moist heat resistance, and heat resistance can be provided by using a specific cationic curing catalyst. It is considered that such a mechanism of action is excellent in the composition of the cation-curable resin composition of the present invention, and is excellent in all of the techniques of the present invention. The present invention can be applied to the various aspects disclosed in the specification, and the advantageous effects can be exerted. [Simplified description of the drawings] 54 201219442 Fig. 1 shows the spectroscopic light of the hardened material 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 measurement results of spectral transmittance chart Example 28 In medium-butoxy another user kg of the obtained cured product of. DESCRIPTION Main reference numerals without a 55

Claims (1)

201219442 VII. Patent application scope: 1. A cationic hardening resin composition comprising a cationic hard chelating compound and a cationic hardening catalyst as essential components, wherein the cationic hardening catalyst is composed of the following formula (1) ) The road shown ^ is composed of 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, and a is an integer of 1 or more, 1? The cationically curable resin composition of the above-mentioned item of the invention, wherein the cationically curable compound contains an epoxy compound and/or 3. The cationically curable resin composition as claimed in claim 2 or 2 wherein the Lewis base is a compound having a nitrogen atom, a phosphorus atom or a sulfur atom. 4. The cationically curable resin composition of any one of claims 1 to 3, wherein the cationically curable resin composition is used for an optical material. 5. A molded article obtained by curing the cationically curable resin composition according to any one of claims 1 to 4. 56