JP2011241380A - Resin composition for cured molded article, and the cured molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for a cured molded article, which can obtain the cured molded article having high water absorption properties and exhibiting a stable performance even under a harsh usage environment; and to provide the cured molded article useful for many purposes of an optical element and the like.SOLUTION: The resin composition comprises a fusible inorganic compound, a curable organic compound and a curing agent, wherein the curable organic compound comprises a compound having an oxetane ring.

Description

The present invention relates to a resin composition for a cured molded body and a cured molded body. More specifically, for example, a cured molded body resin composition applied to various uses such as optical members, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, and cured molded body resin compositions are cured. It is related with the hardening molding obtained by making it.

A cured molded body is a cured product obtained by curing and molding (molding) a resin composition by heating or light irradiation, and is used for various applications such as optical members, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials. However, various developments have been made on the curable resin composition forming the same. For example, a resin composition containing an inorganic substance can not only reduce the coefficient of thermal expansion, but also control the appearance of the resin composition and its cured product by matching the refractive index of the inorganic substance and the resin. Since transparency can also be expressed, it is particularly useful as a material for obtaining a cured molded body for use in electric / electronic parts and optical members. In these applications, for example, a digital camera module is mounted on a mobile phone, and the size of the cured product has been reduced, and cost reduction is also required. Therefore, acrylic resin (PMMA) is used instead of inorganic glass. The adoption of plastic lenses using thermoplastic resins such as polycarbonate (PC) and polycycloolefin is progressing. In recent years, the application to in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.) that can be used outdoors has been studied. In addition, resistance to the external environment such as dust and cleaning liquid, that is, high level heat resistance, wear resistance, light resistance, and the like are required. However, a cured product using a thermoplastic resin does not have sufficient performance, and scratches and wear occur due to dust and cleaning liquid. Therefore, a hard coat film or a cover glass (inorganic glass) may be provided on the upper layer. It is necessary and very expensive. In addition, the optical member used for a sensor having physical contact, such as a touch panel, also needs strength.

On the other hand, technologies related to cured products using thermosetting resins have been studied, and various cured products obtained by curing highly reactive epoxy compounds have been developed. However, since the epoxy compound has the property of being excellent in adhesiveness and adhesion, the releasability is not sufficient, and for example, it cannot be suitably applied to a technique of obtaining a molded body using a mold. Therefore, a technique for obtaining a molded body having high dimensional accuracy and excellent mold transferability by using a mold release agent has been developed. For example, an organic resin, an alcohol having 8 to 36 carbon atoms, a carboxylic acid, a carboxylic acid ester, and A transparent organic resin composition containing at least one compound selected from the group consisting of carboxylates is disclosed (see Patent Document 1, etc.).

Further, as a technique for improving and improving the heat resistance and mechanical properties of a cured product, a resin composition is disclosed in which an epoxy group-containing compound is essential as an organic resin component and an organosiloxane compound is essential as an inorganic component. (See Patent Document 2 etc.). In Patent Document 2, when a polysiloxane compound having a functional group is used, the viscosity increases with time even at room temperature, and the epoxy compound has a high curing reactivity. Although gelation occurs, it is described that if an organosiloxane compound having a low-reactivity organic group as a functional group is used, it is possible to achieve suppression of thickening and gelation while improving heat resistance and mechanical properties. Yes.

In general, a siloxane resin is excellent in transparency and light resistance, but has a problem that the hardness of a cured product is low. As a resin composition capable of solving such a problem, a carboxyl group-containing polymer having a specific organic group is known. A siloxane resin composition containing a siloxane, an epoxy compound and / or an oxetane compound, and a curing agent is disclosed (see Patent Document 3, etc.). In Patent Document 3, a cured product having high transparency and hardness is obtained by using such a siloxane resin composition, and such a resin composition is a one-part curable resin composition having excellent workability. It is described that it can be used.

JP 2008-088249 A (second page, etc.) JP 2008-133442 A (2nd, 4th to 5th pages, etc.) JP 2009-079219 (pages 1-4)

As described above, various curable resin compositions have been studied. For example, as disclosed in Patent Documents 1 and 2, the resin composition is excellent in transparency and durability and extremely useful for various applications including optical applications. Technology related to products and their cured products has been developed.
By the way, the deterioration of the cured molded body also occurs due to moisture absorption in addition to the above-described factors. If the cured molded body has high water absorption, not only the mechanical properties are deteriorated due to moisture absorption, but also the refractive index and shape of the molded body easily change. For this reason, it is desirable to suppress the water absorption of the molded body as much as possible, especially in optical applications where a material with little change in optical characteristics with time is required. However, a resin composition comprising a conventional organic component and inorganic component can be obtained. In order to obtain a cured molded article with lower water absorption, which can be suitably used for an optical member or the like that exhibits a relatively high water absorption property and exhibits excellent stability against environmental changes. There was room for ingenuity.

The present invention has been made in view of the above situation, and has a low water absorption and a resin composition for a cured molded body capable of obtaining a cured molded body that exhibits stable performance even in a harsh usage environment, and An object of the present invention is to provide a cured molded body useful for various uses such as an optical member.

The present inventors paid attention to a resin composition for a cured molded body containing a condensable inorganic compound, a curable organic compound, and a curing agent when variously examining the resin composition for a cured molded body having a low water absorption. And while examining the kind of the curable organic compound that can be suitably used, it is obtained that the curable organic compound contains a compound having an oxetane ring as compared with the case where the compound having an oxetane ring is not included. It has been found that the water absorption rate of the cured molded body is significantly reduced. In general, a compound having an oxetane ring in a polymerization reaction has a slow initiation reaction, but once the growth reaction starts, the polymerization proceeds at a high speed and becomes a polymer having a large molecular weight. Usually, when the resin composition for a cured molded body is cured (polymerized), side reactions and termination reactions occur at the same time, and these reactions generate a hydroxyl group. However, a curable organic containing a compound having an oxetane ring. By using a compound, the growth reaction is prioritized and side reactions and termination reactions are suppressed, so the number of hydroxyl groups in the cured molded body can be suppressed, and as a result, the water absorption rate of the cured molded body is reduced. Guessed. Thus, this inventor is obtained by using the curable organic compound containing the compound which has an oxetane ring in the resin composition for hardening molded objects containing a condensable inorganic compound, a curable organic compound, and a hardening | curing agent. It has been found that the water absorption of the cured molded body can be sufficiently suppressed, and further, such a cured molded body can stably exhibit excellent optical properties and mechanical properties even in harsh usage environments. The present inventors have arrived at the present invention by conceiving that the above-mentioned problems can be solved brilliantly.

That is, the present invention is a resin composition for a cured molded article comprising a condensable inorganic compound, a curable organic compound, and a curing agent, wherein the curable organic compound includes a compound having an oxetane ring. It is a resin composition for moldings.
The present invention is described in detail below.

The resin composition for a cured molded article of the present invention contains a condensable inorganic compound, a curable organic compound and a curing agent, but may contain other components as long as these are essential components. Each component can be used alone or in combination of two or more.

The curable organic compound contained in the resin composition for cured molded bodies includes a compound having an oxetane ring.
When the curable organic compound contains a compound having an oxetane ring (oxetane compound), water absorption of the resulting cured molded article can be sufficiently suppressed.
The compound having an oxetane ring is not particularly limited as long as it has one or more oxetane rings in one molecule. However, in terms of improving the refractive index while maintaining the curing rate, aryl in the molecule. It is preferable to use an oxetane compound having a group or an aromatic ring. In addition, when an oxetane compound having an aryl group or an aromatic ring is used, compared to using an oxetane compound having no aryl group or aromatic ring (that is, an oxetane compound having neither an aryl group nor an aromatic ring). Thus, the cured product has excellent heat resistance. This is thought to be because an oxetane compound having an aryl group or aromatic ring has a phenyl skeleton, whereas an oxetane compound having no aryl group or aromatic ring is composed of only an aliphatic chain. Furthermore, among the oxetane compounds having an aryl group or an aromatic ring, when a compound in which a phenyl group is bonded to the meta position is used, the cured product tends to have excellent oxidation resistance. This is because the phenyl group is bonded to the meta position, so that compatibility with epoxy compounds and condensable inorganic compounds is improved, and a uniform resin composition is obtained. Therefore, it is considered that various characteristics such as oxidation deterioration resistance and heat resistance are excellent.
On the other hand, from the viewpoint of improving light resistance, it is preferable to use an oxetane compound having no aryl group or aromatic ring. On the other hand, from the viewpoint of improving the strength of the cured product, it is preferable to use a polyfunctional oxetane compound, that is, a compound having two or more oxetane rings in one molecule. Moreover, the water absorption rate of a hardening molded object can be further reduced by using what has little content rates of polar parts, such as ester group, in a structure.

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

Among the oxetane compounds having an aryl group or an aromatic ring, examples of monofunctional oxetane compounds include 3-methyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, and dicyclopentadiene. (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, and the like are preferable.

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

Among the oxetane compounds having an aryl group or an aromatic ring, examples of the polyfunctional oxetane compound include phenol novolac oxetane, dioxetane compound having biphenyl skeleton (manufactured by Ube Industries, ETERNACOLL (R) OXBP), and phenyl skeleton. Preferred are dioxetane compounds (Ube Industries, Ltd., ETERNACOLL (R) OXTP, ETERNCOLL (R) OXIPA), isophthalic acid-bis [(3-ethyloxetane-3-yl) methyl], dioxetane compounds having a fluorene skeleton, and the like.

As long as the said curable organic compound contains the compound which has the said oxetane ring, it may contain the other curable organic compound.
Here, the curable organic compound means an organic compound having a curable functional group. The curable functional group refers to a functional group that undergoes a curing reaction by heat or light (a group that causes the resin composition to undergo a curing reaction). Examples of the curable functional group include the ring-opening polymerizable group such as the oxetane ring and the epoxy group described above, an acryl group, and a vinyl group.
Among the compounds having such a curable functional group, the curable organic compound preferably includes a compound having an epoxy group (epoxy compound) in addition to the compound having the oxetane ring. As described above, the compound having an oxetane ring has a slow initiation reaction in the polymerization reaction (curing reaction), but once the growth reaction starts, the polymerization (curing) proceeds at a high speed and becomes a polymer having a large molecular weight. On the other hand, a compound having an epoxy group generally has a fast initiation reaction but a slow growth reaction, and only an oligomer having a molecular weight of about several thousand can be obtained. Therefore, by using a compound having an oxetane ring and a compound having an epoxy group in combination, it is possible to achieve both high molecular weight and improvement in the initiation reaction rate, and a sufficiently large molecular weight polymer (cured molded article) in a short time. ) Can be obtained. As a result, it is possible to obtain a cured molded article that is excellent in flexibility, releasability, and moldability (molding) in a short time.
Thus, it is one of the preferred embodiments of the present invention that the curable organic compound of the present invention further contains a compound having an epoxy group.
The epoxy group includes an oxirane ring that is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to an epoxy group in a narrow sense.

As the compound having an epoxy group, an alicyclic epoxy compound, a hydrogenated epoxy compound, an aliphatic epoxy compound, and an aromatic epoxy compound are preferable, and among them, a compound containing an alicyclic epoxy compound is preferable.
The alicyclic epoxy compound is a compound having an alicyclic epoxy group, and the epoxy compound itself is hardly colored at the time of curing, and is not easily colored or deteriorated by light. That is, since it is excellent in transparency, low colorability, and light resistance, a cured molded body that is excellent in light resistance without coloration can be obtained with high productivity by using a resin composition containing such an epoxy compound. . Moreover, since such an epoxy compound is more excellent in releasability and curability when used in combination with a cationic curing catalyst, it is also preferable in that the curing rate can be increased.
Thus, it is one of the suitable embodiment of this invention that the compound which has an epoxy group of this invention contains an alicyclic epoxy compound.

Examples of the alicyclic epoxy group include an epoxycyclohexane group (epoxycyclohexane skeleton), an epoxy group added to a cyclic aliphatic hydrocarbon directly or via a hydrocarbon, and the like. Among these, a compound having an epoxycyclohexane group is preferable. Moreover, the polyfunctional alicyclic epoxy compound which has two or more alicyclic epoxy groups in a molecule | numerator is suitable at the point which can raise a hardening rate more. A compound having one alicyclic epoxy group in the molecule and an unsaturated double bond group such as a vinyl group is also preferably used. Further, from the viewpoint of lowering the water absorption rate of the cured molded body, it is preferable to use an epoxy compound having a small polar site such as an ester group in the structure.

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

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

The said aliphatic epoxy compound is a compound which has an aliphatic epoxy group, and an aliphatic glycidyl ether type epoxy resin is suitable.
Examples of the aliphatic glycidyl ether type epoxy resin include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol (PEG 600), propylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, polypropylene glycol ( PPG), glycerol, diglycerol, tetraglycerol, polyglycerol, trimethylolpropane and multimers thereof, pentaerythritol and multimers thereof, mono / polysaccharides such as glucose, fructose, lactose, maltose, etc., and epihalohydrin Preferred are those obtained, those having a propylene glycol skeleton, an alkylene skeleton, an oxyalkylene skeleton, etc. A. Among these, aliphatic glycidyl ether type epoxy resins having a propylene glycol skeleton, an alkylene skeleton, and an oxyalkylene skeleton as the central skeleton are preferable.

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

As the aromatic epoxy compound, for example, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a fluorene type epoxy compound, an aromatic epoxy compound having a bromo substituent, and the like are preferable. A fluorene epoxy compound is preferred. Specifically, bisphenol A type epoxy compound (Japan Epoxy Resin Co., Ltd., 828EL, 1003 or 1007), bisphenol F type epoxy compound, fluorene type epoxy compound (Osaka Gas Chemical Co., Ltd., ONCOAT EX-1020 or OGSOL EG-) 210), a fluorene-based epoxy compound (Osaka Gas Chemical Co., Ltd., ONCOAT EX-1010 or OGSOL PG) and the like are preferably used. More preferred are bisphenol A type epoxy compounds and fluorene type epoxy compounds (Ossol EG-210, manufactured by Osaka Gas Chemical Company).

As the aromatic epoxy compound, an aromatic glycidyl ether compound is also suitable, but as the aromatic glycidyl ether compound, for example, an epibis type glycidyl ether type epoxy resin, a high molecular weight epibis type glycidyl ether type epoxy resin, A novolak aralkyl type glycidyl ether type epoxy resin may be mentioned.
As said epibis type glycidyl ether type epoxy resin, what is obtained by condensation reaction of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and epihalohydrin, for example is suitable.
The high molecular weight epibis type glycidyl ether type epoxy resin can be obtained, for example, by subjecting the epibis type glycidyl ether type epoxy resin to an addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, and fluorene bisphenol. Are preferred.

Examples of the novolak aralkyl type glycidyl ether type epoxy resin include phenols, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and other phenols, formaldehyde, acetoaldehyde, propion Polyhydric phenols obtained by condensation reaction of aldehyde, benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc., and epihalohydrin What is obtained by performing a condensation reaction is suitable.

Examples of the aromatic epoxy compound further include, for example, an aromatic crystalline epoxy resin obtained by condensation reaction of tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, and the like with epihalohydrin, and the bisphenols and tetramethyl. High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of biphenol, tetramethylbisphenol F, hydroquinone, naphthalene diol, etc .; obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin The glycidyl ester type epoxy resin etc. which can be used can also be used.

As the epoxy compound, a tertiary amine-containing glycidyl ether type epoxy resin which is obtained by condensation reaction of hydantoin, cyanuric acid, melamine, benzoguanamine and epihalohydrin at room temperature can also be used.

The compound having an epoxy group may be a compound having one or more epoxy groups in one molecule, but a compound having two or more epoxy groups in total, that is, a polyfunctional compound is preferably essential. . As a result, the curing reactivity is further increased, and the resin composition is excellent in curability and curing speed, so that a cured molded body can be obtained in a shorter time.

In the resin composition for a cured molded body, the content of the compound having an oxetane ring is preferably 1% by mass or more and 97% by mass or less with respect to 100% by mass of the total amount of the curable organic compound. Thereby, the effect by using an oxetane compound can be exhibited more. More preferably, they are 10 mass% or more and 97 mass% or less, More preferably, they are 30 mass% or more and 90 mass% or less.

In the form in which the curable organic compound further includes a compound having an epoxy group, the content of the compound having an epoxy group is 1% by mass or more and 95% by mass with respect to 100% by mass of the total amount of the curable organic compound. % Or less is preferable. Thereby, the effect by using an epoxy compound can be exhibited more. More preferably, it is 3.5 mass% or more and 90 mass% or less, More preferably, it is 10 mass% or more and 70 mass% or less.
The ratio of the mass of the epoxy compound and the mass of the oxetane compound is preferably 1/27 to 27/3. That is, in the present invention, the ratio of the content mass of the compound having an epoxy group to the content mass of the compound having an oxetane ring is 1/27 to 27/3, which is one preferred embodiment of the present invention. . As a result, the water absorption of the resulting cured molded body is sufficiently suppressed, and the cured molded body is excellent in flexibility, releasability, and molding (molding) properties. More preferably, it is 3/27 to 21/9, and further preferably 9/21 to 21/9.

As content of the said sclerosing | hardenable organic compound, 1 mass% or more and 50 mass% with respect to 100 mass% of the said resin composition for hardening molded objects (total amount of a condensable inorganic compound, a curable organic compound, and a hardening | curing agent). It is preferable that it is less than. That is, the content of the curable organic compound of the present invention is 1% by mass or more with respect to 100% by mass of the resin composition for a cured molded body (total amount of the condensable inorganic compound, the curable organic compound, and the curing agent), It is one of the preferred embodiments of the present invention that it is less than 50% by mass. Thereby, coloring at the time of hardening can be reduced, transparency can be improved, and the intensity | strength and surface hardness of a hardening molded object can fully be raised. Moreover, the viscosity of the resin composition can be made suitable for molding. More preferably, it is 10 mass% or more and less than 50 mass%, More preferably, it is 20 mass% or more and less than 60 mass%.

The resin composition for a cured molded article of the present invention also contains a condensable inorganic compound. The condensable inorganic compound means an inorganic compound having a condensable group. A condensable group refers to a functional group that condenses with heat. Such a condensable inorganic compound is a compound having a condensable group and having a metalloxane bond (M-O-M bond, M represents a silicon or metal atom) (polymetalloxane compound). Preferably it is. Specific examples of the condensable group include, for example, a M-O-R group (R represents an alkyl group, an aryl group or an aralkyl group), a M-OH group, a M-X group (X is a halogen atom). Represents an atom), and MH groups are preferred. Among these condensable groups, an M—O—R group or an M—OH group is particularly preferable from the viewpoint of curing reactivity.

The compound having a metalloxane bond is not particularly limited, but an atom represented by M is Si, Mg, Al, Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Sr, It may contain one or more of Zr, Nb, Mo, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, Ta, W, Ir, Tl, Pb, Bi, and Ra. preferable. More preferably, M includes one or more of Si, Al, Ti, Zn, Zr, Sn, Ba, and Ra, and more preferably Si, Ti, Zn, and Zr. Of these, one or more are included. It is particularly preferable to include a compound in which M is Si, that is, a polysiloxane compound, from the viewpoint of stability of the compound and ease of production.
When the compound having a metalloxane bond includes a polysiloxane compound, the content of the siloxane bond is preferably 30% by mass or more with respect to 100% by mass of the total amount of all metalloxane bonds. More preferably, it is 50 mass% or more, More preferably, it is 80 mass% or more.

In the M-O-R group, R represents an alkyl group, an aryl group, or an aralkyl group, and may have two or more of these. Moreover, it is suitable that carbon number is 1-20. More preferably, it is 1-8, More preferably, it is 1-3.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and 2-ethyl. Chain alkyl group such as xyl group, n-octyl group, lauryl group, stearyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group; one of hydrogen atoms of chain alkyl group A group in which part or all are substituted with a cycloalkyl group; a group in which some or all of the hydrogen atoms of a cycloalkyl group are substituted with a chain alkyl group, and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group and the like, and a group in which part or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylphenyl group (toluyl group), Dimethylphenyl group (xylylene group), diethylphenyl group, etc.).
Examples of the aralkyl group include a benzyl group and the like, and a group in which some or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylbenzyl group).

Among the R, an alkyl group (that is, a form in which the RO group is an alkoxy group) is preferable, and an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group is particularly preferable. is there. This makes it possible to further reduce shrinkage in the thermosetting process. A methyl group or an ethyl group is more preferable, and an ethyl group is most preferable because the reaction can be easily controlled.
R may have a substituent. Further, it may be a chain (linear or branched) structure or a cyclic structure.
The halogen atom represented by X is not particularly limited, but a fluorine atom is particularly preferred.

Although it does not specifically limit as a molecular structure of the said polymetalloxane compound, Usually, a chain structure (straight chain shape, branched shape), a ladder-like structure, a cyclic structure, a cage | basket shape, and a particulate form are illustrated. Among these, from the viewpoint of high solubility in a resin component such as a compound having a ring-opening polymerizable group, a chain shape, a ladder shape, and a cage shape are preferable. Further, from the viewpoint of obtaining a cured molded body having high solubility and higher optical transparency and mechanical properties, a chain shape and a ladder shape are more preferable, and a ladder shape is particularly preferable. In particular, when a ladder-shaped polymetalloxane compound is used, the release property, controllability of optical properties (transparency, Abbe number, refractive index, etc.), machine, etc. can be added with a small amount compared to the case of using other structures. The characteristic can be further improved. That is, (1) the cured molded body can be easily released from the molding die after curing (excellent mold release properties), (2) transparency, Abbe number and refractive index of the curable resin composition Can be strictly controlled (excellent controllability), (3) the transparency, Abbe number and refractive index of the cured molded product can be strictly controlled (excellent controllability), (4) Addition effects such as excellent mechanical properties (high modulus of elasticity and high breaking strength) of the cured molded body can be exhibited.
The polymetalloxane compound may be liquid at room temperature or may be solid.

As a weight average molecular weight of the said polymetalloxane compound, 300 or more are preferable and it is preferable that it is 100,000 or less. If it is less than 300, the storage stability of the resin composition containing the polymetalloxane compound may not be sufficient, and the releasability, controllability of optical properties, and mechanical properties may not be further improved. There is. If it exceeds 100,000, there is a possibility that the compatibility with a resin component such as a compound having a ring-opening polymerizable group cannot be made more sufficient. More preferably, it is 500 or more, More preferably, it is 1000 or more, More preferably, it is 50,000 or less, More preferably, it is 10,000 or less.
The said weight average molecular weight can be calculated | required as a molecular weight of polystyrene conversion of a gel permeation chromatography (GPC), for example.

In the form in which the polymetalloxane compound includes a polysiloxane compound, the polysiloxane compound is particularly preferably a structural unit having a silicon atom bonded to three silicon atoms by a siloxane bond (Si—O—Si bond), that is, silyl. A compound mainly containing a sesquioxane unit and containing a condensable group in the molecule (this compound is referred to as “silsesquioxane having a condensable group”, simply “silsesquioxane”, or “polysyl Also referred to as “sesquioxane”). Such a polysiloxane compound is, for example, the following average composition formula (1):
R ¹ xYySiOz (1)
(R ¹ represents an alkyl group, an aryl group, or an aralkyl group. Y represents a condensed group or a condensed atom, and is bonded to Si to form the condensable group. X, y, and z are , Represents the average value of the bonding ratio of R ¹ , Y and O to Si, respectively, 0 <x <2, 0 <y <2, 1 <z <2, 0 <(x + y) <2, and x + y + 2z = 4) is particularly preferred. By using such silsesquioxane, the heat resistance and mechanical properties are improved and improved, and the increase in viscosity of the resin composition with time is suppressed. Therefore, the resin composition for a cured molded body can be made into a one-pack type resin composition (one-part curable resin composition) that is excellent in handling properties, and more efficiently and simply with excellent physical properties. It becomes possible to obtain a cured molded body having the same.

In the average composition formula (1), R ¹ represents an alkyl group, an aryl group, or an aralkyl group, and these carbon numbers are preferably 1-20. More preferably, it is 1-8, More preferably, it is 1-3. Of the alkyl group, aryl group, and aralkyl group, an alkyl group is preferable, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. A chain alkyl group such as a group, pentyl group, hexyl group, 2-ethylhexyl group, n-octyl group, lauryl group, stearyl group; cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group, etc. An alkyl group; a group in which some or all of the hydrogen atoms of the chain alkyl group are substituted with a cycloalkyl group; a group in which some or all of the hydrogen atoms of the cycloalkyl group are substituted with chain alkyl groups; Etc. Of these, alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an isopropyl group are preferable from the viewpoint of further increasing the surface hardness. More preferably, it is a methyl group. In view of increasing the refractive index, an aralkyl group is preferable, and a phenyl group is particularly preferable.
R ¹ may have a substituent, but is particularly preferably a group having no substituent.
In the present specification, the “alkyl group” includes not only a linear or branched alkyl group but also a cyclic alkyl group (cycloalkyl group).

The polysiloxane compound may be replaced with one having a group that forms a bond with an organic resin component (such as a compound having a curable functional group) instead of R ¹ . For example, in the average composition formula (1), a compound having a curable functional group may be used in place of R ¹ . However, it is preferable not to use such a compound from the viewpoint of the stability of the organic resin component.

Y represents a condensed group or a condensed atom, and is bonded to Si to form the condensable group. Therefore, Y is preferably at least one selected from the group consisting of an OR group (R represents an alkyl group, an aryl group or an aralkyl group), a hydroxyl group, a halogen atom (X) and a hydrogen atom. is there. Suitable forms of R and X are as described above.

X, y and z in the above average composition formula (1) satisfy 0 <x <2, 0 <y <2, 1 <z <2, 0 <(x + y) <2 and x + y + 2z = 4 It is.
The above y represents the average value of the bonding ratio of Y to Si, and is a number exceeding 0 and less than 2. However, if y is 2 or more, there is a possibility that bubbles are generated in the molded body due to the condensation of Y. . Preferably it is less than 1, more preferably less than 0.5, particularly preferably less than 0.3. Moreover, it is preferable that it is a value larger than 0.001. If it is less than 0.001, the effect of improving the hardness due to the condensation of the condensable inorganic compound in the thermosetting step will be small, and the compatibility with the epoxy resin will be small. More preferred is a value greater than 0.01, even more preferred is a value greater than 0.05, and particularly preferred is a value greater than 0.08.

The z may be a number greater than 1 and less than 2. Preferably it is greater than 1.2 and less than 1.8, more preferably greater than 1.35 and less than 1.65.
The x + y may be a number greater than 0 and less than 2. Preferably it is more than 0.4 and less than 1.6, more preferably more than 0.7 and less than 1.3.
The x is preferably set as appropriate so that y and x + y satisfy the above-described preferable ranges.

In the resin composition for a cured molded body, the content of the condensable inorganic compound is 100% by mass with respect to 100% by mass of the resin composition for a cured molded body (total amount of the condensable inorganic compound, the curable organic compound and the curing agent). 50 mass% or more and less than 99 mass%. That is, the content of the condensable inorganic compound of the present invention is 50% by mass or more with respect to 100% by mass of the resin composition for a cured molded body (total amount of the condensable inorganic compound, the curable organic compound, and the curing agent), It is one of the preferred embodiments of the present invention that it is less than 99% by mass. Thereby, coloring at the time of hardening can be reduced, transparency can be improved, and the strength and surface hardness of the cured molded body can be sufficiently increased. Moreover, the viscosity of the resin composition can be made suitable for molding. More preferably, they are 50 mass% or more and less than 90 mass%, More preferably, they are 60 mass% or more and less than 80 mass%.

The condensable inorganic compound (preferably polysilsesquioxane) may also contain other metals and inorganic elements as components from the viewpoint of controlling optical properties. Examples of the metal element include alkaline earth metal elements such as Be, Mg, Ca, Sr, Ba, and Ra; lanthanoid metal elements such as La and Ce; actinoid metal elements such as Ac; IIIa such as Sc and Y Group metal elements; Group IVa metal elements such as Ti, Zr and Hf; Group Va metal elements such as V, Nb and Ta; Group VIa metal elements such as Cr, Mo and W; Group VIIa metals such as Mn, Tc and Re Element; Group VIII metal element such as Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt; Group Ib metal element such as Cu, Ag, Au; Group IIb metal element such as Zn, Cd, Hg; Group IIIb metal elements such as Al, Ga, In, and Tl; Group IVb metal elements such as Ge, Sn, and Pb; Group Vb metal elements such as Sb and Bi; Group VIb metal elements such as Se and Te One of these It may be present together of two or more. These can be appropriately selected depending on the electrical characteristics, optical characteristics, magnetic characteristics and the like of the composition. For example, Ti, Zr, In, Zn, La, Al, etc. are preferable when it is desired to obtain a resin composition having a high refractive index among optical properties.

What is necessary is just to select suitably as a hardening | curing agent in the said resin composition for hardening molded objects according to the hardening reaction of a resin composition. For example, when heat curing is performed, a commonly used curing agent such as acid anhydride, phenol, or amine can be used in addition to the heat latent cationic curing catalyst. Among these, it is particularly preferable to use a heat latent cationic curing catalyst. Moreover, when hardening by active energy ray irradiation, a photoinitiator can be used as a hardening | curing agent, and it is suitable to use a photolatent cationic curing catalyst especially. These curing agents can be used alone or in combination of two or more.
In addition, as a manufacturing method of a hardening molded object, the thermosetting process by specific temperature and / or the hardening process by active energy ray irradiation (1st process) which are mentioned later, and the thermosetting process at high temperature (2nd process) When the method including these is adopted, the curing agent may be appropriately selected according to the curing reaction in the first step.

Thus, in the present invention, it is preferable to use a cationic curing catalyst such as a heat latent cationic curing catalyst or a photolatent cationic curing catalyst, but this allows the curing reaction to proceed suitably in a short time, Since the matrix (cured product) can be formed quickly, the production efficiency can be improved. In addition, in the case where a method for producing a cured molded body including a curing step at a specific temperature (first step) and a curing step at a high temperature (second step) as described below is employed, a condensable inorganic material is used in the first step. It is possible to sufficiently suppress the progress of the curing reaction of the compound. Furthermore, a cured molded body having excellent heat resistance and high releasability can be obtained, and the cured molded body composition can stably exist as a one-component composition (one-component property) excellent in handling properties. That is, by using a cation curing catalyst, the effects of the present invention can be more fully exhibited. Especially, when using the said resin composition for an optical member use, it is especially suitable to use a heat | fever latent cationic curing catalyst at least.

The thermal latent cationic curing catalyst is also called a thermal acid generator, a thermal latent curing agent, a thermal latent cation generator, or a cationic polymerization initiator. When the curing temperature is reached in the resin composition, the thermal latent cationic curing catalyst is substantially used as a curing agent. It demonstrates a typical function. By using a heat-latent cationic curing catalyst, a compound containing a cationic species is excited by heating to cause a thermal decomposition reaction and heat curing proceeds, but a heat-latent cationic curing catalyst is generally used as a curing agent. Unlike acid anhydrides, amines, phenolic resins, etc., which are contained in the resin composition, the resin composition does not increase in viscosity over time at normal temperature or cause gelation. As an action of the heat latent cationic curing catalyst, the curing reaction can be sufficiently promoted to exert an excellent effect, and a one-component resin composition (one-component material) having superior handling properties can be provided. .

In addition, by using a heat-latent cationic curing catalyst, the moisture resistance and heat resistance of the cured molded product obtained from the resulting resin composition are dramatically improved, and the excellent optical properties of the resin composition even in harsh usage environments It retains its characteristics and can be suitably used for various applications. Normally, when water having a low refractive index is contained in the resin composition or its cured product, it causes turbidity.However, when a heat-latent cationic curing catalyst is used, excellent moisture resistance can be exhibited, and thus such turbidity is exhibited. It is suppressed and can be suitably used for optical applications such as lenses. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged UV irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance and heat resistance, moisture absorption and oxidative degradation of the resin composition are suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. It can exhibit excellent durability and optical characteristics over a long period of time without causing any damage.

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

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

Specific products of the above-mentioned heat-latent cationic curing catalyst include, for example, diazonium salt types such as AMERICURE series (American Can), ULTRASET series (Adeka), and WPAG series (Wako Pure Chemical Industries). Iodonium such as UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), Photoinitiator 2074 (manufactured by Rhone-Poulenc), WPI series (manufactured by Wako Pure Chemical Industries, Ltd.) Salt type: CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Satomer), Optomer SP series Optomer CP series (Adeka) ), Sun Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San Apro), etc. It is done.

As the photopolymerization initiator, it is preferable to use a photolatent cationic curing catalyst as described above. The photolatent cationic curing catalyst is also called a photocationic polymerization initiator, and exhibits a substantial function as a curing agent when irradiated with light. By using a photolatent cationic curing catalyst, a compound containing a cationic species is excited by light, a photodecomposition reaction occurs, and photocuring proceeds. Similar to the heat-latent cationic curing catalyst, the photo-latent cationic curing catalyst is different from acid anhydrides, amines, phenol resins, etc. that are generally used as curing agents. Even if it is included, it does not cause the viscosity increase or gelation of the resin composition over time at normal temperature, and as a function of the photolatent cationic curing catalyst, it fully accelerates the curing reaction and exhibits an excellent effect Therefore, it is possible to provide a one-component resin composition (one-component material) that is superior in handling properties.
Also, by using a photolatent cationic curing catalyst, the moisture resistance and heat resistance of the cured molded product obtained from the resulting resin composition are dramatically improved, and the excellent optical properties of the resin composition even in harsh usage environments It retains its characteristics and can be suitably used for various applications. Normally, when water having a low refractive index is contained in a resin composition or its cured product, it causes turbidity.However, when a photolatent cationic curing catalyst is used, excellent moisture resistance can be exhibited. It is suppressed and can be suitably used for optical applications such as lenses. Especially in applications such as in-vehicle cameras and bar code readers for home delivery companies, there are concerns about yellowing and deterioration of strength due to prolonged UV irradiation and high temperature exposure in summer. It is thought that the generation of oxygen radicals is caused by the synergistic effect of exposure to heat rays. By improving moisture resistance and heat resistance, moisture absorption and oxidative degradation of the resin composition are suppressed, and generation of oxygen radicals due to the synergistic effect of ultraviolet irradiation or heat ray exposure is also suppressed. It can exhibit excellent durability and optical characteristics over a long period of time without causing any damage.

Examples of the photolatent cationic curing catalyst include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) Phenyl] sulfide bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methyl) Ethyl) benzene] -Fe- hexafluorophosphate, diaryliodonium hexafluoroantimonate and the like. These can be easily obtained from the market. For example, SP-150, SP-170 (manufactured by Asahi Denka); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide) CD-1012 (manufactured by Sartomer) and the like are suitable. Among these, it is preferable to use an onium salt. Moreover, as an onium salt, it is preferable to use at least 1 sort (s) among a triarylsulfonium salt and a diaryl iodonium salt.

In the curing by the active energy ray irradiation, it is preferable to use a photosensitizer in addition to the photopolymerization initiator. Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethyl). Amines such as amino) ethyl, 4-dimethylaminobenzoic acid (n-butoxy) ethyl, 2-dimethylhexyl 4-dimethylaminobenzoate, and the like are preferable.

The compounding amount of the photosensitizer is 0.1 to 20% by mass with respect to 100% by mass of the resin composition for a cured molded body (total amount of a condensable inorganic compound, a curable organic compound and a curing agent). It is preferable. If it is less than 0.1% by mass, the photopolymerization may not proceed more efficiently, and if it exceeds 20% by mass, the ultraviolet ray may be prevented from being transmitted to the inside, and the curing may not be sufficient. . More preferably, it is 0.5-10 mass%.

The content of the cation curing catalyst is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the curable organic compound as a solid equivalent amount as an amount of the active ingredient not containing a solvent or the like. It is. If it is less than 0.01 part by weight, the curing rate cannot be increased sufficiently, and there is a possibility that the effect of being able to be cured sufficiently in a short time and being moldable cannot be fully exhibited. More preferably, it is 0.1 weight part or more, More preferably, it is 0.2 weight part or more. On the other hand, if the amount exceeds 10 parts by weight, there is a risk of coloring during curing or heating of the molded article. For example, when the molded body is reflow-mounted after the molded body is obtained, heat resistance of 200 ° C. or higher is necessary, and therefore it is preferably 10 parts by weight or less from the viewpoint of colorlessness and transparency. . More preferably, it is 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.

When the cationic curing catalyst as described above is used, the following excellent effects can be obtained as compared with the case where an acid anhydride curing agent is used. That is, since no ester bond is generated, a cured product having low water absorption and excellent temporal stability can be obtained. In addition, since it can be used in a one-component system, there are advantages such as no need for mixing before use, long pot life, good productivity and handling, and non-uniform mixing, curing unevenness, and foaming. Furthermore, since the curing speed is high, it is advantageous for molding and the productivity is good. Furthermore, the molded product obtained is excellent in light resistance, weather resistance, and hydrolysis resistance. Moreover, a molded object becomes the thing excellent in heat resistance. In particular, a molded article having excellent heat resistance and coloring resistance during reflow can be obtained.

In the case of using a commonly used curing agent such as an acid anhydride, phenol, or amine as the curing agent, those usually used may be used as these curing agents. For example, as the acid anhydride-based curing agent, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthal, acid anhydride, methylhexahydrophthalic anhydride, nadic acid anhydride, Methyl nadic acid anhydride, het acid anhydride, hymic acid anhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydro anhydride Alicyclic carboxylic acid anhydrides such as phthalic acid-maleic anhydride adduct, chlorendic acid, methylendomethylenetetrahydrophthalic anhydride; dodecenyl succinic anhydride, polyazelineic anhydride, polysebacic anhydride, polydodecanedioic anhydride Aliphatic carboxylic acid anhydrides such as phthalic anhydride, trime Tsu DOO anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol trimellitic anhydride, aromatic carboxylic acid anhydrides such as biphenyltetracarboxylic acid anhydride.

Examples of the phenolic curing agent include bisphenol A, tetrabromobisphenol A, bisphenol F, bisphenol S, 4,4′-biphenylphenol, 2,2′-methylene-bis (4-methyl-6-tert- Butylphenol), 2,2'-methylene-bis (4-ethyl-6-tert-butylphenol), 4,4'-butylene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenol), trishydroxyphenylmethane, pyrogallol, phenols having a diisopropylidene skeleton; phenols having a fluorene skeleton such as 1,1-di-4-hydroxyphenylfluorene Class of phenolic polybutadiene Novolac resins made from various phenols such as phenolic compounds, phenols, cresols, ethylphenols, butylphenols, octylphenols, bisphenol A, brominated bisphenol A, bisphenol F, bisphenol S, naphthols, etc .: phenol novolac containing xylylene skeleton Various novolak resins such as resins, dicyclopentadiene skeleton-containing phenol novolak resins, and fluorene skeleton-containing phenol novolak resins are exemplified.

Among the commonly used curing agents such as acid anhydrides, phenols or amines, acid anhydrides are preferred, more preferably methyltetrahydrophthalic anhydride, tetrahydrophthalic anhydride, methylhexahydro. Phthalic anhydride and hexahydrophthalic anhydride are preferable, and methylhexahydrophthalic anhydride and hexahydrophthalic anhydride are more preferable.

In the case of using a commonly used curing agent such as acid anhydride, phenol or amine, the content of the curing agent is a resin composition for a cured molded body (condensable inorganic compound, curable organic compound and curing). The total amount of the agent is preferably 25 to 70% by mass with respect to 100% by mass. More preferably, it is 35-60 mass%. Moreover, it is preferable that the mixing ratio of the said curable organic compound and these hardening | curing agents mixes a hardening | curing agent in the ratio of 0.5-1.6 equivalent with respect to 1 chemical equivalent of a curable organic compound. More preferably, the mixing is performed at a ratio of 0.7 to 1.4 equivalents, more preferably 0.9 to 1.2 equivalents.

When a commonly used curing agent such as acid anhydride, phenol or amine is used, it is preferable to use a curing accelerator in combination. Examples of the curing accelerator include organic base acid salts or aromatic compounds having tertiary nitrogen, and organic base acid salts include organic onium salts such as organic phosphonium salts and organic ammonium salts and tertiary nitrogen. Examples thereof include acid salts of organic bases. Examples of organic phosphonium salts include phosphonium bromides having four phenyl rings such as tetraphenyl phosphonium bromide and triphenyl phosphine / toluene bromide. Examples of organic ammonium salts include tetraoctyl ammonium bromide, tetra Examples include tetra (C1-C8) alkylammonium bromides such as butylammonium bromide and tetraethylammonium bromide. Examples of acid salts of organic bases having tertiary nitrogen include alicyclic bases having tertiary nitrogen in the ring. Examples include acid salts and organic acid salts of various imidazoles.

Examples of the organic acid salt of an alicyclic base having tertiary nitrogen in the ring include 1,8-diazabicyclo (5,4,0) undecene-7 phenol salt, 1,8-diazabicyclo (5,4). , 0) Salts of diaza compounds such as octylate of undecene-7 and phenols, the following polyvalent carboxylic acids, or phosphinic acids.
Examples of the organic acid salts of the various imidazoles include salts of imidazoles with organic acids such as polycarboxylic acids. Examples of imidazoles include 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, and 1-benzyl. Examples include 2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, and the like. Preferable imidazoles include, for example, the same imidazoles as the phenyl group-substituted imidazoles in the aromatic compound having the following tertiary nitrogen.

Examples of the polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and naphthalenedicarboxylic acid, and aliphatic polyvalent carboxylic acids such as maleic acid and oxalic acid. Examples of preferred polyvalent carboxylic acids include aromatic polyvalent carboxylic acids such as terephthalic acid, trimellitic acid, and pyromellitic acid. Examples of preferable salts of imidazoles with organic acids such as polyvalent carboxylic acids include polyvalent carboxylates of imidazoles having a substituent at the 1-position. More preferred is, for example, trimellitic acid salt of 1-benzyl-2-phenylimidazole.

Examples of the aromatic compound having tertiary nitrogen include phenyl group-substituted imidazoles and tertiary amino group-substituted phenols. Examples of phenyl group-substituted imidazoles include 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, Examples include 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl-2-phenyl-3,5-dicyanoethoxymethylimidazole, and the like. Preferable examples include imidazoles having an aromatic substituent at the 1-position, and more preferable examples include 1-benzyl-2-phenylimidazole. Examples of tertiary amino group-substituted phenols include phenols having 1 to 3 di (C1-C4) alkylamino (C1-C4) alkyl groups such as 2,4,6-tri (dimethylaminomethyl) -phenol. Is mentioned.

Among the above-mentioned curing accelerators, particularly preferred curing accelerators include, for example, phenol salts of 1,8-diazabicyclo (5,4,0) undecene-7, 1,8-diazabicyclo (5,4,0) undecene-7, and the like. Octyrate, 2,4,6-tri (dimethylaminomethyl) -phenol, tetrabutylammonium bromide, tetraethylammonium bromide, 1-benzyl-2-phenylimidazole, trimellitic acid salt of 1-benzyl-2-phenylimidazole Tetraphenylphosphonium bromide and triphenylphosphine-toluene bromide.
The said hardening accelerator can be used 1 type or in combination of 2 or more types. The amount of the curing accelerator used is preferably 0.01 to 5% by mass with respect to 100% by mass of the resin composition for a cured molded body (total amount of the condensable inorganic compound, curable organic compound and curing agent). More preferably, it is 0.03 to 3% by mass.

The resin composition for a cured molded body preferably includes a flexible component (flexible component), which makes it possible to obtain a resin composition with a sense of unity. Moreover, the hardness of resin improves by including a flexible component.
The flexible component may be a compound different from the curable organic compound, and at least one of the curable organic compounds may be a flexible component.

Specifically, the flexible component is a compound having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] _m — (n is 2 or more, and m is an integer of 1 or more. Preferably, n is 2 to 12, m is an integer of 1 to 1000, and more preferably, n is 3 to 6 and m is an integer of 1 to 20.), for example, (1) An epoxy compound containing an oxybutylene group (Japan Epoxy Resin, YL-7217, epoxy equivalent 437, liquid epoxy compound (10 ° C. or higher)) is preferred. As other suitable flexible components, (2) polymer epoxy compounds (for example, hydrogenated bisphenol (manufactured by Japan Epoxy Resin, YL-7170, epoxy equivalent 1000, solid hydrogenated epoxy compound)); 3) alicyclic solid epoxy compound (EHPE-3150 manufactured by Daicel Chemical Industries, Ltd.); (4) alicyclic liquid epoxy compound (Delcel Chemical Industries, Celoxide 2081); (5) liquid rubber such as liquid nitrile rubber, Polymer rubber such as polybutadiene, fine particle rubber having a particle size of 100 nm or less, and the like are preferable.

Among these, more preferred are compounds containing a curable functional group as described above at the terminal, side chain, main chain skeleton or the like.
As described above, a compound containing a curable functional group can be suitably used as the flexible component, but the compound is preferably a compound containing an epoxy group, and more preferably oxybutylene. A compound having a group (— [— (CH ₂ ) ₄ —O—] _m — (m is the same as above)).

The content of the flexible component is preferably 40% by mass or less with respect to 100% by mass of the total amount of the curable organic compound and the flexible component. More preferably, it is 30 mass% or less, Most preferably, it is 20 mass% or less. Moreover, 0.01 mass% or more is preferable, More preferably, it is 0.1 mass% or more, More preferably, it is 0.5 mass% or more.

The resin composition for a cured molded body preferably contains a release agent. As the mold release agent, a normal mold release agent can be suitably used, but an alcohol having 8 to 36 carbon atoms, a carboxylic acid having 8 to 36 carbon atoms, a carboxylic acid ester having 8 to 36 carbon atoms, and 8 carbon atoms. It is preferably at least one compound selected from the group consisting of a carboxylic acid salt having ˜36 and a carboxylic acid anhydride having 8 to 36 carbon atoms. By including such a mold release agent, the mold can be easily peeled off when cured using a mold, and the appearance is controlled without damaging the surface of the cured product, thereby expressing transparency. Therefore, it is possible to obtain a cured molded body having more excellent transparency, surface appearance, dimensional accuracy, mold transferability, etc., and further useful curing for electrical / electronic component material use, optical member use, etc. It becomes a molded body.

Among these compounds, more preferred are alcohols, carboxylic acids, and carboxylic acid esters, and even more preferred are carboxylic acids (particularly higher fatty acids) because the release effect can be sufficiently exhibited without inhibiting the cationic curing reaction. ) And carboxylic acid esters. In addition, since amines may inhibit a cation curing reaction, when accompanying a cation curing reaction, it is preferable not to use as a mold release agent.
The above-mentioned compound may have any structure such as linear, branched or cyclic, and is preferably branched.
The number of carbon atoms of the compound is preferably an integer of 8 to 36, and thereby, a cured product exhibiting excellent peelability without impairing functions such as transparency and workability of the resin composition; Become. More preferably, it is 8-20 as carbon number, More preferably, it is 10-18.

The alcohol having 8 to 36 carbon atoms is a monovalent or polyhydric alcohol, and may be linear or branched. Specifically, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl Alcohol, ceryl alcohol, myricyl alcohol, methylpentyl alcohol, 2-ethylbutyl alcohol, 2-ethylhexyl alcohol, 3.5-dimethyl-1-hexanol, 2,2,4-trimethyl-1-pentanol, dipentaerythritol 2-phenylethanol and the like are preferred. The alcohol is preferably an aliphatic alcohol, and more preferably octyl alcohol (octanol), lauryl alcohol, 2-ethylhexyl alcohol (2-ethylhexanol), and stearyl alcohol.

The carboxylic acid having 8 to 36 carbon atoms is a monovalent or polyvalent carboxylic acid, and includes 2-ethylhexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, and tetradecanoic acid. Pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like are suitable. Preferred are octanoic acid, lauric acid, 2-ethylhexanoic acid, and stearic acid.

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

The carboxylate having 8 to 36 carbon atoms is a carboxylic acid obtained by a combination of the carboxylic acid and an amine, Na, K, Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn, or Sn. Salts and the like are preferred. Among these, Zn stearate, Mg stearate, Zn 2-ethylhexanoate and the like are preferable.
Examples of the carboxylic acid anhydride having 8 to 36 carbon atoms include the carboxylic acid anhydrides having 8 to 36 carbon atoms described above.

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

As content of the said mold release agent, it is 10 mass% or less with respect to 100 mass% of said resin compositions for hardening molded objects (total amount of a condensable inorganic compound, a curable organic compound, and a hardening | curing agent). preferable. If it exceeds 10% by mass, the resin composition for cured molded bodies may be difficult to cure. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

In addition to the above-described essential components and suitable components, the cured molded body resin composition is saturated without inorganic fine particles, reactive diluents, and unsaturated bonds as long as the effects of the present invention are not impaired. Compound, Pigment, Dye, Radical scavenger, Antioxidant, UV absorber, Light stabilizer, Plasticizer, Non-reactive compound, Chain transfer agent, Thermal polymerization initiator, Anaerobic polymerization initiator, Polymerization inhibitor, Inorganic filling Adhesion improvers such as adhesives, organic fillers, coupling agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, anti-settling agents, Contains anti-sticking agent, anti-sagging agent, anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, drying agent, antifouling agent, antistatic agent, conductive agent (electrostatic aid), etc. Good.

Among the above, it is preferable to contain at least one selected from the group consisting of an ultraviolet absorber, a radical scavenger and an antioxidant. Thereby, the heat-and-moisture resistance and heat resistance (heat-resistant discoloration property) of the hardening molded object obtained using the said resin composition can be made further excellent. More preferably, it contains at least one of a radical scavenger and an antioxidant, and more preferably contains both a radical scavenger and an antioxidant. A preferable content of these additives is 0.01 to 1% by mass with respect to 100% by mass of the resin composition (total amount of the condensable inorganic compound, the curable organic compound, and the curing agent).

As the ultraviolet absorber, for example, Tinuvin 384-2 (manufactured by BASF Japan Ltd.) is suitable.
As the radical scavenger, for example, IRGANOX 1010 (manufactured by BASF Japan) is suitable.
As the antioxidant, for example, ADK STAB PEP36 (manufactured by ADEKA) is suitable.

The resin composition for a cured molded body preferably has a viscosity of 10,000 Pa · s or less. Thereby, it becomes more excellent in processing characteristics, and a cured molded body having further excellent dimensional accuracy and mold transferability can be obtained. More preferably, it is 1000 Pa.s or less, More preferably, it is 200 Pa.s or less. Moreover, it is preferable that it is 0.01 Pa.s or more. More preferably, it is 0.1 Pa · s or more, further preferably 1 Pa · s or more, and particularly preferably 5 Pa · s or more.
The viscosity can be measured, for example, at a measurement temperature of 40 ° C. using an R / S rheometer manufactured by Brookfield.

The present invention is also a cured molded body obtained by curing the resin composition for cured molded body.
The cured molded body is low in water absorption due to being obtained from the above-described resin composition for cured molded body, and can exhibit stable performance even in a severe use environment.

Below, the method to manufacture a hardening molding from the said resin composition for hardening moldings is demonstrated.
Although it does not specifically limit as a manufacturing method of a hardening molded object, The hardening process (1st process) by the thermosetting process and / or active energy ray irradiation in specific temperature, The thermosetting process (2nd process) at high temperature, It is preferable to employ a method including: As a result, it is possible to easily produce a cured cured product that is excellent in heat resistance, wear resistance, and mold releasability, has a small shrinkage rate, and has no coloration.

In the method for producing the cured molded body, as a first step, a process of thermally curing a resin composition for cured molded body (also simply referred to as “resin composition”) at 80 to 200 ° C., a resin composition for cured molded body A step of curing by irradiation with active energy rays, or a step of thermosetting the resin composition for cured molded bodies at 80 to 200 ° C. and curing by irradiation of active energy rays, the first step And a second step of thermally curing the cured product obtained in step 200 to 200 ° C. or less. In addition, as long as the effect of the manufacturing method of the said hardening molded object is not impaired, the other process performed at a normal shaping | molding (molding) process may further be included.

In the said 1st process, when making it thermoset, it is suitable for hardening temperature to be 80-200 degreeC. If it is less than 80 ° C., the resin composition for a cured molded body cannot be sufficiently cured, and an organic resin matrix having a small shrinkage rate cannot be produced. Therefore, there is a possibility that curing shrinkage will increase in the subsequent second-stage thermosetting process. When the temperature exceeds 200 ° C., the curing reaction due to the condensation reaction of the condensable inorganic compound becomes conspicuous, so the curing shrinkage due to the condensable inorganic compound increases, and foaming occurs due to vaporization of water or alcohol by-produced by the condensation reaction. Thus, there is a possibility that the curing reaction cannot be performed, and there is a possibility that a cured molded body having high strength and surface hardness and high appearance cannot be obtained. Furthermore, the mold release property is not sufficient, and there is a possibility that a cured molded article excellent in dimensional accuracy and mold transferability cannot be obtained. Preferably it is 100 degreeC or more, Preferably it is 160 degreeC or less.

What is necessary is just to set suitably the hardening time in the said thermosetting process according to the kind etc. of hardening agent to be used. For example, when a cationic curing catalyst is used as a curing agent, that is, when curing is performed by a cationic curing reaction, the curing reaction can be sufficiently performed even if the curing time is short. This is suitable because the reaction of the condensable inorganic compound hardly occurs in the process. Moreover, it is suitable also in the point which can improve manufacturing efficiency. Furthermore, the cationic curing catalyst is an organic resin component having excellent heat resistance in that no ester is produced. For example, the curing time is preferably within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer. Moreover, when using normally used hardening | curing agents, such as an acid anhydride type, a phenol type, and an amine type, in order to fully harden | cure, it is suitable for hardening time to be 15 minutes-48 hours. More preferably, it is 30 minutes to 36 hours.

The thermosetting step can also be performed in air and / or under an inert gas atmosphere such as nitrogen under reduced pressure or under pressure. Moreover, you may change a curing temperature in steps within the range of 80-200 degreeC of curing temperature. For example, from the viewpoint of improving productivity, etc., the resin composition for a cured molded body is held in a mold at a predetermined temperature and time, and then taken out from the mold and statically placed in an air and / or an inert gas atmosphere such as nitrogen. It is also possible to place and heat-treat. Moreover, you may combine hardening by active energy ray irradiation.

In the said 1st process, when making it harden | cure by active energy ray irradiation, what is necessary is just to be able to produce | generate active species, such as a radical and a cation, as an active energy ray. For example, ionizing radiation such as ultraviolet rays, visible rays, electron beams, α rays, β rays, and γ rays, microwaves, high frequencies, infrared rays, laser beams, etc. are suitable, taking into consideration the absorption wavelength of the compound that generates radically active species. And may be selected as appropriate. Among these, ultraviolet rays or visible rays having a wavelength of 180 to 500 nm are preferable because they can be easily handled. Among these wavelength ranges, light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is particularly effective for curing.
In addition, the hardening process by the said active energy ray irradiation can be performed in air and / or an inert gas under any atmosphere under reduced pressure or under pressure.

Examples of the light generation source of ultraviolet light or visible light having a wavelength of 180 to 500 nm include, for example, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a chemical lamp, a black light lamp, a mercury-xenon lamp, an excimer lamp, Short arc lamps, helium / cadmium lasers, argon lasers, excimer lasers, sunlight and the like are suitable.

What is necessary is just to set suitably the irradiation time of the said active energy ray irradiation, ie, the hardening time in the hardening process by an active energy ray, according to the kind, irradiation amount, etc. of an active energy ray. For example, the irradiation time of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is preferably 0.1 microseconds to 30 minutes, and more preferably 0.1 milliseconds to 1 minute.

As described above, the first step includes one or more steps of a step of thermally curing the resin composition for a cured molded body at 80 to 200 ° C. and a step of curing by irradiation with active energy rays. It is preferable to perform at least the step of thermosetting the resin composition for a cured molded body at 80 to 200 ° C. Thereby, the target shape can be obtained more easily in the first step, the shape can be maintained more easily in the second step, and the molded body by gas that can be generated by condensation of the condensable inorganic compound in the second step. The foaming inside can be prevented more sufficiently.

The first step is also preferably a curing step using a mold made of metal, ceramic, glass, resin or the like (referred to as “mold”). The curing process using a mold may be a curing process normally performed by a mold molding method such as an injection molding method, a compression molding method, a casting molding method, or a sandwich molding method. If it is a hardening process using such a mold, it is excellent in various physical properties such as wear resistance, low shrinkage, dimensional accuracy and mold transferability, and easily produces a transparent cured molded body without coloring. It is possible to more fully demonstrate the effect of being able to.

When the first step is a curing step using a mold, it is preferable to perform the demolding step after the first step and before the second step. The mold including the demolding process, that is, the cured product obtained in the first process is taken out from the mold, and the taken cured product is used for the next second process, whereby the expensive mold is effectively rotated (recycled). ) And the life of the mold can be extended, so that a cured molded body can be obtained at low cost.
In this case, the resin composition for a cured molded body is a one-part composition containing a curing agent and other components as required, and the one-part composition is placed in a mold that matches the shape of the target cured molded body. Is preferably used by filling (injection / coating, etc.) and curing, and then removing the cured product from the mold.

In the above manufacturing method, the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is used for the second step, but in the cured product in the second step. In order to prevent foaming, it is preferable that the pencil hardness of the cured product obtained in the first step is 9B or more. More preferably, it is 6B or more, More preferably, it is 2B or more, Most preferably, it is F or more.
The pencil hardness can be measured using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) in accordance with JIS-K5600-5-4 (established in 1999) with a load of 1000 g.

In the manufacturing method, in the second step, the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is heat-cured at a temperature exceeding 200 ° C. and not more than 500 ° C. Become. When the heat curing temperature in the second step is 200 ° C. or less, the polysiloxane compound does not sufficiently undergo a curing reaction, and therefore, a high level of surface hardness required for outdoor use or the like, that is, curing with excellent wear resistance. There is a possibility that a molded body cannot be obtained. Further, a large amount of unreacted epoxy compound or oxetane compound remains, and there is a possibility that sufficient durability and water absorption cannot be obtained. Moreover, when it exceeds 500 degreeC, there exists a possibility that the coloring and hardness by decomposition | disassembly of an organic resin component may fall. Preferably it is 250 degreeC or more, More preferably, it is 300 degreeC or more, Especially preferably, it is 330 degreeC or more, Most preferably, it is 350 degreeC or more. Moreover, Preferably, it is 400 degrees C or less.

The curing time in the second step is not particularly limited as long as the curing rate of the resulting cured molded body is sufficient, but considering production efficiency, for example, it is preferably set to 30 minutes to 30 hours. is there. More preferably, it is 1 to 10 hours.

The second step can also be performed in any atmosphere of air and / or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration from the viewpoint of effectively performing a curing reaction of the polysiloxane compound and further improving transparency and surface hardness (abrasion resistance). . For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0.5 volume% or less, Most preferably, it is 0.3 volume% or less. Further, the curing temperature may be changed stepwise within a temperature range exceeding 200 ° C. and not more than 500 ° C.

According to the manufacturing method described above (hereinafter also referred to as the curing method (1)), the heat resistance and the wear resistance are excellent, the shrinkage rate is small, and the releasability, low colorability and transparency are excellent. It is possible to obtain a cured molded body that can sufficiently exhibit mechanical characteristics and optical characteristics, and in particular, it is possible to obtain a cured molded body that has high hardness and extremely high wear resistance.
As described above, the curing method (1) is particularly suitable for the production of a cured molded body having excellent wear resistance, but the method for producing a cured molded body of the present invention is not limited thereto, and is required for a cured molded body. Appropriate methods and conditions can be selected as appropriate according to the characteristics.

For example, when obtaining a cured molded article excellent in heat resistance, more specifically, a cured molded article excellent in heat discoloration resistance in which discoloration due to heat or reduction in transmittance is suppressed, a curing method (2 ) Is preferred.
That is, a method in which the maximum heating temperature in the curing step is 150 to 250 ° C. is suitable.
The curing step in the curing method (2) may consist of one step or two steps, but preferably comprises two steps as follows.
(First step)
The step of thermosetting the resin composition for cured molded bodies at 80 to 150 ° C., the step of curing the resin composition for cured molded bodies by irradiation with active energy rays, and the resin composition for cured molded bodies at 80 to 150 ° C. Any of the steps of thermosetting and curing by irradiation with active energy rays.
(Second step)
A step of thermally curing the cured product obtained in the first step at a temperature exceeding 150 ° C. and not exceeding 250 ° C.

The first step is a curing step using a mold. The cured product obtained in the first step is preferably removed from the mold after the completion of the first step, and used for the second step.
Other suitable forms in the first step and the second step are the same as those described above for the curing method (1).

As described above, the curing method (2) is an excellent curing method particularly for obtaining a cured molded body having excellent heat resistance (heat discoloration). In order to further improve the heat resistance, it is preferable to use a resin composition containing at least one selected from the group consisting of an ultraviolet absorber, a radical scavenger and an antioxidant. preferable. Among these, those containing at least one of a radical scavenger and an antioxidant are more preferred, and those containing both a radical scavenger and an antioxidant are preferred. A preferable content of these additives is 0.01 to 1% by mass with respect to 100% by mass of the resin composition (total amount of the condensable inorganic compound, the curable organic compound, and the curing agent).

The cured molded body obtained by the manufacturing method described above is excellent in heat resistance and wear resistance, has a small shrinkage ratio, is excellent in releasability, low colorability and transparency, and has mechanical characteristics and optical characteristics. It can be fully demonstrated. In addition, the cured molded body is low in water absorption due to being obtained from the above-described resin composition for cured molded body, and can exhibit stable performance even in a severe use environment. Such a cured molded body is preferably a mold molded body, but may be in the form of a film, a sheet, a pellet or the like.

Since the cured molded article has excellent characteristics, for example, optical members, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, and other materials for paints and adhesives. It is useful for various uses such as. Especially, it can use suitably for an optical member, an optical device member, a display device member, etc. Specific examples of such applications include eyeglass lenses, (digital) cameras, imaging lenses for cameras such as mobile phones, vehicle cameras, surveillance cameras, and lenses such as light beam condensing lenses and light diffusion lenses. Applications: Transparent sheets such as watch glass and cover glass for display devices; Various optical applications such as filters, diffraction gratings, prisms, light guides; photosensors, photoswitches, LEDs, light emitting elements, optical waveguides, multiplexing Opto device applications such as optical devices, duplexers, disconnectors, optical splitters, optical fiber adhesives; LCD, organic EL and PDP display element substrates, color filter substrates, touch panel substrates, display protective films, display backs Applications for display devices such as lights, light guide plates, antireflection films, and antifogging films; applications with physical contact such as touch panels It is suitable.

Among these uses, an optical member is particularly suitable. The optical member is particularly preferably a lens. The lens is preferably a camera lens, a light beam condensing lens, and a light diffusion lens, and more preferably a camera lens. Among camera lenses, imaging lenses such as an imaging lens for a mobile phone and an imaging lens for a digital camera are preferable. Moreover, it is preferable that it is a micro optical lens.
In addition, when the said hardening molded object is an optical member, the said resin composition for hardening molded objects may contain the other component suitably according to the use of the optical member. Specifically, UV absorber, IR cut agent, reactive diluent, pigment, washing agent, antioxidant, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization Initiators, light stabilizers, polymerization inhibitors, antifoaming agents and the like are suitable.

Since the resin composition for a cured molded body of the present invention has the above-described configuration, it is possible to obtain a cured molded body having low water absorption and exhibiting stable performance even in a severe use environment. . The cured molded body obtained by curing the resin composition for a cured molded body of the present invention can be suitably used as an optical member having very little change in refractive index and shape.

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

Production Example 1 (resin composition (1))
9 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Aron oxetane OXT221 (manufactured by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 2 (resin composition (2))
9 g of Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Alonoxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 3 (resin composition (3))
3 g of Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 27 g of Aron Oxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 4 (resin composition (4))
3 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 27 g of Alonoxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 5 (resin composition (5))
15 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 15 g of Aron Oxetane OXT221 (manufactured by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 6 (resin composition (6))
21 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 9 g of Aron oxetane OXT221 (manufactured by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 7 (resin composition (7))
15 g of Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 15 g of Alonoxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 8 (resin composition (8))
10 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 10 g of Celoxide 2081 (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), and 10 g of Aron Oxetane OXT221 (produced by Toa Gosei Co., Ltd.) 70 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industry Co., Ltd., polymethylsilsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 9 (resin composition (9))
6 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 14 g of Aron oxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethyl) 80 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 10 (resin composition (10))
9 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Alonoxetane OXT212 (produced by Toagosei Co., Ltd., oxetane resin), PMSQ-E (SR-13) (produced by Konishi Chemical Industries, polymethyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 11 (resin composition (11))
9 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of EHO (Ube Industries, Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, Ltd., polymethylsilsesqui) 70 g of oxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 12 (resin composition (12))
9 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of ETENACOL OXIPA (manufactured by Ube Industries, Ltd., oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethylsil) 70 g of sesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Production Example 13 (resin composition (13))
21 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 9 g of ETENACOL OXIPA (produced by Ube Industries, Ltd., oxetane resin), PMSQ-E (SR-13) (produced by Konishi Chemical Industries, polymethylsil) 70 g of sesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.5 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Production Example 14 (resin composition (14))
15 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, alicyclic epoxy resin), 15 g of ETENACOL OXIPA (manufactured by Ube Industries, Oxetane resin), PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, polymethylsil 70 g of sesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.5 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Production Example 15 (resin composition (15))
9 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of Aron Oxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMPSQ-E (SR-3321) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of phenylsilsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.2 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Production Example 16 (resin composition (16))
15 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 15 g of Aron oxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), PMPSQ-E (SR-3321) (manufactured by Konishi Chemical Industries, polymethyl) 70 g of phenylsilsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.2 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Production Example 17 (resin composition (17))
9 g of Celoxide 2021P (produced by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 21 g of ETENACOL OXIPA (produced by Ube Industries, Ltd., oxetane resin), PMPSQ-E (SR-3321) (produced by Konishi Chemical Industries, polymethylphenyl) 70 g of silsesquioxane) and 0.5 g of stearic acid were added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.2 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Comparative Production Example 1 (Comparative Resin Composition (1))
30 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 70 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, Ltd., polymethylsilsesquioxane), and 0.5 g of stearic acid are added. And mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Comparative Production Example 2 (Comparative Resin Composition (2))
30 g of Celoxide 2081 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 70 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, Ltd., polymethylsilsesquioxane), and 0.5 g of stearic acid are added. And mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Comparative Production Example 3 (Comparative Resin Composition (3))
20 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 80 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industries, Ltd., polymethylsilsesquioxane), and 0.5 g of stearic acid are added. And mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Comparative Production Example 4 (Comparative Resin Composition (4))
30 g of Aron oxetane OXT221 (manufactured by Toa Gosei Co., Ltd., oxetane resin), 70 g of PMSQ-E (SR-13) (manufactured by Konishi Chemical Industry Co., Ltd., polymethylsilsesquioxane), 0.5 g of stearic acid were added, and 80 ° C. Until uniform. After cooling to 40 ° C., a mixture of SI-60L (manufactured by Sanshin Chemical Industry Co., Ltd.) (0.2 g) and propylene glycol monomethyl ether acetate (PGMEA) (0.5 g) was added and mixed under reduced pressure until uniform.

Comparative Production Example 5 (Comparative Resin Composition (5))
30 g of Celoxide 2021P (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), 70 g of PMPSQ-E (SR-3321) (manufactured by Konishi Chemical Industries, Ltd., polymethylphenylsilsesquioxane), and 0.5 g of stearic acid Added and mixed at 80 ° C. until uniform. After cooling to 40 ° C., a mixture of 0.2 g of SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) and 0.5 g of propylene glycol monomethyl ether acetate (PGMEA) was added and mixed under reduced pressure until uniform.

Example 1
(First step)
The resin composition (1) obtained in Production Example 1 was sandwiched between two metal plates of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800) having a 1 mm gap, and cast-molded. After being cured by heating at 140 ° C. for 2 minutes, the mold was removed.
(Second step)
The cured body after the first step was heated from room temperature to 330 ° C. (15 ° C./min) under N ₂ atmosphere (unless otherwise specified, carried out at an oxygen concentration of 0.2 to 0.3% by volume). Then, after heat treatment at 330 ° C. for 1 hour, the temperature was lowered to 50 ° C. (10 ° C./min).

Examples 2-17, Comparative Examples 1-5
Instead of the resin composition (1) obtained in Production Example 1, the resin compositions (2) to (17) and Comparative resin compositions (1) to (1) obtained in Production Examples 2 to 17 and Comparative Production Examples 1 to 5 ( A curing treatment was performed in the same manner as in Example 1 except that 5) was used.

About the hardening molded object obtained in Examples 1-17 and Comparative Examples 1-5, according to the following measuring method, the moldability, the surface hardness, the water absorption rate, the transmittance | permeability, heat-and-moisture resistance, and heat resistance were evaluated. Table 1 shows the results of evaluation of moldability, water absorption, transmittance, wet heat resistance and heat resistance.
In addition, the hardened | cured body obtained at the 1st process was used for evaluation of a moldability, and the hardened | cured body obtained at the 2nd process was used for the other evaluation.

<Moldability>
The cured body was released without cracking (with a sense of unity): A, cracked in the cured body, but released: B, insufficiently cured or hard brittle and no cured body was obtained: x.

<Surface hardness>
It measured based on JIS-K5600-5-4 (1999 establishment) using the pencil scratch hardness tester (made by Yasuda Seiki Seisakusho). The load was 1000 g. About Example 1, 2, 4-14 from which the hardening molded object was obtained, and Comparative Examples 1-3, all showed hardness 7H or more. About Examples 15-17 and the comparative example 5, all showed hardness H or more.

<Water absorption rate>
About 2 g of the cured product was placed in a hot air dryer at 50 ° C., dried for 24 hours, and then weighed. After being immersed in 200 g of pure water at 25 ° C. for 24 hours, moisture on the surface was wiped off and the weight was measured. The water absorption was calculated from the increased weight.

<Transmissivity>
The transmittance of the cured product at a wavelength of 400 nm was measured using an absorptiometer (manufactured by Shimadzu Corporation, spectrophotometer UV-3100).

<Heat and heat resistance>
The cured body was held in a thermo-hygrostat (manufactured by ESPEC Co., Ltd., environmental tester SH-221, test condition: 85 ° C. and 85% RH) for 500 hours, and a wet heat test was performed. The transmittance of the cured product at a wavelength of 400 nm after the wet heat test was measured, and the reduction rate of the transmittance (400 nm) by the wet heat test was calculated.

<Heat resistance>
The cured body was kept in an oven at 120 ° C. or 150 ° C. for 72 hours in an air atmosphere. The transmittance of the cured product at a wavelength of 400 nm after the heat resistance test was measured, and the decrease rate of the transmittance (400 nm) by the wet heat test was calculated.

Examples 18-22, Comparative Examples 6-17
Various additives of 0.1 to 0.5% based on the weight of the resin composition were added to the resin composition (1) and the comparative resin composition (1) obtained in Production Example 1 and Comparative Production Example 1. After producing the cured product in the same manner as shown in Example 1, the heat and moisture resistance was evaluated. The results are shown in Table 2.
As additives, the following were used.
Ultraviolet absorber: Tinuvin 384-2, Tinuvin 1130, Tinuvin P, Tinuvin 329, Tinuvin 477 (all manufactured by BASF Japan)
Radical scavenger: IRGANOX1010 (manufactured by BASF Japan)
Antioxidant: L-ascorbic acid (manufactured by Wako Pure Chemical Industries), SUMILIZER GS, SUMILIZER GP (manufactured by Sumitomo Chemical Co., Ltd.), ADK STAB PEP36 (manufactured by ADEKA)

Examples 23-26, Comparative Examples 18-21
Various additives of 0.05 to 0.5% are added to the resin composition (13) and the comparative resin composition (1) obtained in Production Example 13 and Comparative Production Example 1 with respect to the weight of the resin composition. Alternatively, a cured product was prepared by the same step as shown in (First step) of Example 1 and the following second step without adding an additive. About the obtained hardening body, heat resistance evaluation was performed. The results are shown in Table 3. As additives, IRGANOX 1010 (radical scavenger, manufactured by BASF Japan) and ADK STAB PEP36 (antioxidant, manufactured by ADEKA) were used.
(Second step)
The cured body after the first step was heated from room temperature to 180 ° C. (15 ° C./min) under N ₂ atmosphere (unless otherwise specified, carried out at an oxygen concentration of 0.2 to 0.3% by volume). Then, after heat treatment at 180 ° C. for 1 hour, the temperature was lowered to 50 ° C. (10 ° C./min), and the cured product was taken out.

The following was found from the above Examples and Comparative Examples.
Among the resin compositions (1) to (17) used in Examples 1 to 17, cured molded bodies could be obtained from resin compositions other than the resin composition (3). Moreover, in all Examples and Comparative Examples where cured molded bodies were obtained, sufficient surface hardness and transmittance were obtained, and it was found that all cured molded bodies were excellent in wear resistance and transparency. .

Comparative Examples 1-3, 5 and 5 are examples in which only an epoxy compound was used as the curable organic compound, but in each Example in which a part of these epoxy compounds was replaced with an oxetane compound, the water absorption rate was significantly reduced. I understood that. Further, for example, from Example 4, there is a tendency that the water absorption rate further decreases as the content of the oxetane compound increases. However, as in Comparative Example 4, when only the oxetane compound is used as the curable organic compound (epoxy) When no compound was included), the onset of the curing reaction was slow, and a cured molded body could not be obtained under the curing conditions described above. This shows that it is suitable to use together an oxetane compound and an epoxy compound having a fast initiation reaction as the curable organic compound.
Also, when using an epoxy compound (ceroxide 2081) with a smaller proportion of polar sites in the structure as in Comparative Example 2 or when increasing the content of the condensable inorganic compound as in Comparative Example 3, Although there is a tendency for the water absorption rate to decrease, in these cases as well, for example, as in Examples 2 and 9, it is possible to further reduce the water absorption rate by using an oxetane compound as the curable organic compound. I understand that.

In Comparative Examples 1 to 3, which do not use an oxetane compound, the transmittance was significantly reduced after the wet heat test, whereas in each Example in which the oxetane compound was used in combination, the transmittance was sufficiently reduced by the wet heat test. It turns out that it is suppressed. From this, it was found that by using an oxetane compound in combination as the curable organic compound, it is possible to impart wet heat resistance to the resulting cured molded article. Moreover, in each Example, also in the heat test of 120 degreeC and 150 degreeC, the heat resistance improvement was seen by changing the epoxy resin of the comparative example 1 into an oxetane resin. Furthermore, in Examples 12 to 14 where OXIPA was selected as the oxetane resin, it was found that the heat resistance could be remarkably improved as compared with the case where other oxetane resins were used. This is considered to result from OXIPA having a phenyl group and a structure in which the phenyl group is bonded to the meta position. Moreover, it turned out that high heat resistance is shown, so that the content rate of OXIPA is high.

Moreover, as shown in Table 2, the cured molded bodies obtained by adding various additives to the comparative resin composition (1) of Comparative Example 1 all have reduced transmittance reduction due to the moist heat test, and are resistant to moist heat. Was found to have improved. In the cured molded body obtained by adding various additives to the resin composition (1) of Example 1 in which an oxetane compound is used in combination as a curable organic compound, the heat and humidity resistance is further improved, and even after the wet heat test. Almost no change in transmittance was observed. From these things, it turned out that the wet heat resistance of a hardening molded object can be improved by adding a ultraviolet absorber, a radical scavenger, or antioxidant.
Moreover, as shown in Table 3, the cured product obtained by adding an additive to the comparative resin composition (1) of Comparative Example 1 (the cured product of Comparative Examples 19 to 21) has a decrease in transmittance due to the heat resistance test. It was found that the heat resistance was improved as the amount of the additive was increased. In the cured product obtained by adding an additive to the resin composition (13) of Example 13 in which an oxetane compound is used in combination as the curable organic compound (cured product of Examples 24-26), the heat resistance is further improved. The transmittance was hardly changed even after the heat test. By combining several kinds of additives, the heat resistance of the cured product containing an oxetane ring structure could be further improved.

Claims (7)

A resin composition for a cured molded body comprising a condensable inorganic compound, a curable organic compound, and a curing agent,
The curable organic compound contains a compound having an oxetane ring. The said curable organic compound contains the compound which has an epoxy group further, The resin composition for hardening molded objects of Claim 1 characterized by the above-mentioned. The resin composition for a cured molded article according to claim 2, wherein the compound having an epoxy group contains an alicyclic epoxy compound. The ratio of the content mass of the compound having an epoxy group and the content mass of a compound having an oxetane ring in the resin composition for a cured molded body is 1/27 to 27/3, The resin composition for cured molded bodies according to 1. The said condensable inorganic compound is 50 mass% or more and less than 99 mass% with respect to 100 mass% of the total amount of the resin composition for hardening molded objects, The any one of Claims 1-4 characterized by the above-mentioned. A resin composition for a cured molded body. The said curable organic compound is 1 mass% or more and less than 50 mass% with respect to 100 mass% of the total amount of the resin composition for cured moldings, The one in any one of Claims 1-5 characterized by the above-mentioned. A resin composition for a cured molded body. A cured molded body obtained by curing the resin composition for a cured molded body according to claim 1.