JP2009256586A - Curable resin composition for molded articles, molded article, and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide: a curable resin composition for molded articles capable of producing a molded article excellent in fundamental performances such as heat resistance and having satisfactory optical characteristics such as transparency, and of making excellent the mold-release property of the molded article when the molded article is taken out of a mold; a molded article produced by molding the curable resin composition; and a production method thereof. <P>SOLUTION: This curable resin composition for molded articles is a curable resin composition for molded articles containing an epoxy resin and further containing as an essential component, a silicon compound having a polyoxyalkylene chain and/or an aryl group. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a curable resin composition for molded bodies, a molded body formed by molding the same, and a method for producing the same. More specifically, the present invention relates to a curable resin composition for molded bodies useful as optical applications, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, and the like, and a molded body formed by molding the same, and a method for producing the same. .

Thermosetting resin compositions are useful as, for example, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, molding materials, etc., and also used as materials for paints and adhesives It is. Furthermore, since transparency can be expressed, it is particularly useful as a material for electrical / electronic component materials and optical applications. For example, since digital camera modules are mounted on mobile phones and the like, and miniaturization advances and cost reduction is also required, instead of the conventionally used inorganic glass, polymethyl methacrylate, polycarbonate, poly Adoption of plastic lenses such as cycloolefin is progressing. In recent years, as a new application of this plastic material, there is an increasing need for in-vehicle use such as an in-vehicle camera and a bar code reader for home delivery companies. When applied to these applications, taking into account high temperature exposure in summer, etc., long-term heat resistance, that is, heat resistance superior to conventional plastic materials, is required. Consideration is progressing. There is also a need for plastic materials that can withstand the solder reflow process.

Regarding materials used for conventional electrical / electronic component materials and optical applications, a thermosetting resin containing an alicyclic epoxy resin is dissolved and mixed in an organic solvent in which inorganic particles having a particle size of 70 nm or less are dispersed, Next, a method for producing a thermosetting resin composition is disclosed in which an organic solvent is removed from this product, and then a curing agent is added and mixed (see, for example, Patent Document 1).
However, in a thermosetting resin composition obtained by such a production method, sufficient transparency that can be used for optical applications cannot be obtained. For this reason, it is required that the coarse inorganic particles are completely disappeared and sufficiently dispersed as primary particles, thereby making the transparency sufficient without scattering visible light by the inorganic particles. Specifically, the above document discloses a resin composed of a dispersion in which dry silica is dispersed in a solvent and an alicyclic epoxy. However, such a resin composition has flexibility, fracture resistance, There was room for improvement to sufficiently improve the optical properties such as transparency after making the viscosity suppressing effect and preventing mixing of impurities during mixing of the bead mill appropriate. Further, when such a resin composition is molded using a mold or the like, it has been desired to improve the releasability when the cured product is taken out from the mold and to produce a molded body with high productivity. .

Furthermore, an epoxy resin molded body molded by curing a composition comprising at least an epoxy resin and inorganic oxide particles, wherein inorganic oxide particles having an average particle size of 50 nm or less are dispersed in the molded body. There is disclosed an epoxy resin molded body characterized by the above (for example, see Patent Document 2). Here, an example including wet silica and an epoxy resin is disclosed, and bisphenol A (Abbe number 34.1) is used as the epoxy resin. However, in such a case, it is necessary to suppress the thickening at the time of solvent degassing while making the silica concentration sufficient, and there is room for improvement for improving the material strength and transparency. And it has been desired to improve the releasability when taking out the cured product from the mold and to produce a molded body with high productivity.
Therefore, conventionally, it has basic performance such as heat resistance, improves optical characteristics such as transparency, and in terms of productivity, it has a releasability when taking out the cured product from the mold. It can be said that an improved material that can be suitably applied to various optical members has not been found. Since transparency and releasability are in a contradictory relationship, when one is increased, the other is decreased, so there is room for improvement. If a molded body exhibits excellent characteristics and can improve the productivity of such a molded body, its usefulness as an industrial product will be greatly increased. Therefore, there is a need for such a curable resin composition for molded bodies. It was about to be done.
JP 2004-346288 A (pages 2, 13 etc.) Japanese Patent Application Laid-Open No. 2004-250521 (Pages 2, 7, etc.)

The present invention has been made in view of the above-mentioned present situation, and is excellent in basic performance such as heat resistance and sufficient optical properties such as transparency, and at the time of molding, it is separated from the mold. It is an object of the present invention to provide a curable resin composition for molded bodies that can be excellent in moldability, a molded body formed by molding the molded resin composition, and a method for producing the molded body.

The present inventors have made various studies on a curable resin composition for molded bodies containing an epoxy resin excellent in basic performance such as heat resistance, and the curable resin composition for molded bodies further contains a silicon compound as an essential component. As a result, it was first found that the mold can be excellent in releasability when taken out from the mold during molding, and the molded body can be produced with high productivity. Further, it has been found that if a silicon compound which is compatible with other components in the resin composition and does not cause turbidity is used, transparency suitable for electric / electronic component materials and optical applications can be exhibited. Among such silicon compounds, it has been found that those that exhibit effects such as transparency are limited. That is, it has been found that by using a silicon compound having a specific organic group, the releasability and transparency as a material in the above applications can be made sufficiently excellent. When a silicon compound having a polyoxyalkylene chain and / or an aryl group is contained in a curable resin composition for molded bodies, the basic performance such as heat resistance and the releasability when taking out from the mold during molding are sufficiently good. In addition, it is possible to obtain a molded article that has excellent optical properties such as Abbe number and refractive index and is excellent in transparency and can be suitably used for the above-mentioned applications. And in such a curable resin composition for molded bodies, it is possible to remarkably improve the release action by using a compound having a specific boiling point and / or a release agent in combination. Moreover, if the curable resin composition for molded bodies of the present invention further contains a thermal latent curing catalyst, the effects of the present invention can be exhibited remarkably, and the above problems can be solved brilliantly. The present invention has been reached.

That is, the present invention is a curable resin composition for molded bodies containing an epoxy resin, wherein the curable resin composition for molded bodies further comprises a silicon compound having a polyoxyalkylene chain and / or an aryl group. It is a curable resin composition for molded bodies contained as:
Here, the thermosetting resin means a resin that can be cured by heat, and does not specify a curing method. Therefore, both thermosetting and photocuring can be used for curing the curable resin composition for molded bodies of the present invention. What is known as a thermosetting resin can be used suitably as curable resin which the curable resin composition for molded objects of this invention contains.
This invention is also a molded object formed by shape | molding the said curable resin composition for molded objects.
The present invention is also a molded article containing a silicon compound having a polyoxyalkylene chain and / or an aryl group and / or a compound having a boiling point of 260 ° C. or less under 1 atmosphere.
The present invention is a method for producing a molded body from a curable resin composition for molded bodies containing an epoxy resin, wherein the production method further comprises a silicon compound having a polyoxyalkylene chain and / or an aryl group. It is also a method for producing a molded body including a step of molding a curable resin composition for molded bodies contained as a component.
In the present specification, “further containing” a compound or the like does not mean a process procedure, for example, to distinguish it from an epoxy resin contained in a conventional curable resin composition for molded bodies. , Means "contains another component". “Containing a compound or the like as an essential component” or “making it an essential component” means containing the above compound or the like so as to achieve the effects of the present invention.
The present invention is described in detail below.

The curable resin composition for molded bodies of the present invention further contains a silicon compound having a polyoxyalkylene chain and / or an aryl group as an essential component.
By further containing such a compound as an essential component, the release property when the cured product is taken out from the mold is sufficient, and the silicon compound is another component in the curable resin composition for molded bodies. Therefore, the turbid resin composition for molded body and the molded body can exhibit optical properties such as transparency.

The reason why the releasability at the time of mold molding is improved by including a silicon compound having a polyoxyalkylene chain and / or an aryl group is considered as follows. The silicon compound is also used as a mold release agent and is excellent in mold release properties, so that the mold release properties when taking out the cured product from the mold can be made sufficient. In general, the silicon compound is inferior in compatibility with the curable resin, but in the present invention, it is not a mere silicon compound and has a specific organic group such as a polyoxyalkylene chain and / or an aryl group. By using a specific silicon compound, the compatibility between the silicon compound and the other components in the curable resin composition for molded bodies is improved, and turbidity is less likely to occur. As a result, it is possible to achieve both releasability when taking out from the mold and optical properties such as transparency, and since the surface of the molded body is not damaged, a highly transparent molded body is continuously produced. This makes it particularly useful as a material in electrical / electronic component materials and optical applications. In addition, even if it is cured in a short time, the releasability can be sufficiently expressed, and from this, an imaging lens for a digital camera, a pickup lens, etc. for which curing is completed in a short time to perform fine processing This is particularly suitable for use in micro optical systems. Furthermore, since the mold releasability of the molded body is improved, the amount of the release agent used can be reduced.

That is, when a silicon compound having a polyoxyalkylene chain and / or an aryl group is contained in a curable resin composition for molded bodies, transparency before and after curing is sufficient as a material for electrical / electronic component materials and optical applications. In addition, the releasability when taken out from the mold is sufficiently excellent. On the other hand, when the resin composition contains a silicon compound having no other polyoxyalkylene chain or aryl group and having an organic group other than that, for example, a silicon compound having a methyl group or an epoxy group, the mold release performance Although it is exhibited, the transparency of the resin composition before curing becomes inferior, and it cannot be used for the above-mentioned purposes substantially.
There are three types of silicon compounds in the present invention: those having a polyoxyalkylene chain, those having an aryl group, and those having both of these. From the common sense of technology, it is not easy to imagine that these exert common effects.

The silicon compound having a polyoxyalkylene chain and / or an aryl group may be bonded to at least one silicon constituting the silicon compound. By including such a silicon compound in the resin composition, it is possible to make both the releasability when taking out from the mold and the optical characteristics such as transparency excellent as described above.

The polyoxyalkylene chain is usually formed in a chain form by adding two or more oxyalkylene groups, but may be formed by one oxyalkylene group. In a chain formed by adding two or more oxyalkylene groups, it is formed by one or more oxyalkylene groups, and when formed by two or more oxyalkylene groups, The addition form is not particularly limited. For example, two or more oxyalkylene groups may be any addition form such as random addition, block addition, and alternate addition, but block addition is preferable. .

The average number of added moles of the oxyalkylene group in the silicon compound is preferably 2 to 100. This is because the effect of the present invention is remarkably easily exhibited in the above range. More preferably, it is 3-60. More preferably, it is 5-10. The average added mole number means an average value of the number of moles of the oxyalkylene group added in 1 mole of the polyoxyalkylene chain of the silicon compound.

In the silicon compound, the polyoxyalkylene chain preferably has an oxyethylene group. As a result, the transparency of the silicon compound is improved and the effects are sufficiently exhibited.
In the oxyalkylene group, the amount of oxyethylene group in 100 mol% of all oxyalkylene groups is preferably 50 to 100 mol%. When the amount of the oxyethylene group is 50 mol% or more, the effect of the present invention is more easily exhibited. Therefore, the amount of the oxyethylene group is more preferably 60 mol% or more, further preferably 70 mol% or more, and most preferably 90 mol% or more.
Moreover, the form in which the silicon compound having the polyoxyalkylene chain has a polyoxyethylene chain is particularly preferable.

The aryl group preferably has 6 to 20 carbon atoms. This is because the effect of the present invention is remarkably easily exhibited in the above range. More preferably, it is C6-C14, More preferably, it is C6-C10. Specifically, phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl A group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are suitable, and one of these may be used, or two or more may be used. More preferably, it is a phenyl group.
In the following, possible forms and preferred forms of the molecular structure of the silicon compound having the polyoxyalkylene chain and / or aryl group will be described in detail.

The silicon compound having a polyoxyalkylene chain and / or an aryl group may be, for example, one having one silicon atom (also referred to as a monomer in the present specification) and having two or more silicon atoms. Although it may be a thing (it is also called a polymer in this specification), it is preferable that it is a polymer.
The ratio of the total content of polyoxyalkylene chains and aryl groups in the polymer to the number of silicon atoms in the polymer is preferably 1/10 to 1/2. More preferably, it is 1/8 to 1/3, and still more preferably 1/6 to 1/4. Moreover, it is preferable that the said total content is 1-20 per polymer molecule. More preferably, it is 1-15, More preferably, it is 2-10.
Among these, a mode in which the silicon compound is a polysiloxane compound (also referred to as polysiloxane in the present specification) is preferable. That is, it is a preferred embodiment of the present invention that the release agent contains a polysiloxane compound as an essential component.

The polysiloxane compound is a polysiloxane compound having two or more silicon atoms having a siloxane bond and having a polyoxyalkylene chain and / or an aryl group bonded to at least one silicon atom constituting the siloxane bond. Good. The polysiloxane compound is usually liquid at 50 ° C.
A preferred form of the polysiloxane compound is a form of polysiloxane having a structural unit composed of a disubstituted siloxane. In other words, a polysiloxane compound having a disubstituted siloxane unit as a structural unit is preferable. That is, it is a preferred embodiment in the curable resin composition for molded articles of the present invention that the silicon compound is a polysiloxane compound having a structural unit derived from disubstituted siloxane.
The above-mentioned disubstituted siloxane unit means that two of the four bonds of silicon atom are bonded to oxygen forming siloxane, and the remaining two are a polyoxyalkylene chain, an aryl group or other organic group (functional group). ). The “disubstituted siloxane” or “disubstituted siloxane unit” is also referred to as “bifunctional siloxane” or “bifunctional siloxane unit”.
In addition, the smallest polysiloxane compound is a dimer, for example, following formula (1);

(In the formula, A is an arbitrary group, but at least one A represents a polyoxyalkylene chain or an aryl group.)
It is represented by

(Polysiloxane compound structure and raw materials)
Examples of the structure of the polysiloxane compound include a chain shape, a ladder shape, a cage shape, and a particle shape. Examples of the chain include those having no branch and those having a branch.
The polysiloxane compound having the above structure has two or more silicon atoms having a siloxane bond as described above, and a polyoxyalkylene chain and / or an aryl group is bonded to at least one silicon atom constituting the siloxane bond. Any polysiloxane compound having the above structure is preferably produced by, for example, the following method.
Chained;
・ Non-branched linear dialkoxysilane (main chain) hydrolysis / condensate, or dialkoxysilane (main chain) and monoalkoxysilane (terminal) hydrolysis / condensate / branched as required Co-hydrolyzed condensate of linear dialkoxysilane (main chain) with trialkoxysilane and / or tetraalkoxysilane. Add monoalkoxysilane before or during cohydrolysis as needed.
Ladder form: hydrolysis / condensation product of trialkoxysilane (main chain).
Cage-like: Hydrolyzed / condensed product of trialkoxysilane (main chain).
Particle form: Hydrolyzed / condensed product containing tetraalkoxysilane and / or trialkoxysilane as essential components, preferably as a main component.
Especially, the form whose molecular structure is chain shape is preferable. More preferably, it is a form that is linear without branching.
In any case, it is preferable that the polysiloxane compound having the above structure is produced by using an alkoxysilane having a silicon atom to which a polyoxyalkylene chain and / or an aryl group are bonded. The alkoxysilane is at least one selected from the group consisting of monoalkoxysilane, dialkoxysilane and trialkoxysilane.

As described above, the polysiloxane compound preferably has a disubstituted siloxane unit in the molecule. In other words, the polysiloxane compound preferably has a disubstituted siloxane unit. Among them, the number of disubstituted siloxane units is the number of all silicon atoms. When 100 is 100%, a form of 60% or more is preferable. This is because the effect of the present invention is likely to be exhibited remarkably if it is 60% or more. Preferably, it is 80% or more, more preferably 90% or more. The upper limit is, for example, preferably 100%, that is, essentially all silicon atoms constitute a disubstituted siloxane unit.

The position of the polyoxyalkylene chain and / or aryl group in the polysiloxane compound is such that the polyoxyalkylene chain and / or aryl group is bonded to the terminal silicon atom in the polysiloxane compound, or the non-terminal in the polysiloxane compound. Any of those bonded to silicon atoms are suitable.

Specific examples of the polysiloxane compound include, for example, KF-56, HIVAC-F-4 (both are silicone oils in which part of the side chain of the polysiloxane is a phenyl group, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), KF -6004 (modified silicone oil introduced with an organic group having a polyoxyethylene chain and a polyoxypropylene chain at both ends, trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), these may be used alone or in two kinds You may use the above together.

As the monomer, any polyoxyalkylene chain and / or aryl group bonded to one silicon constituting the silicon compound may be used. For example, two polyoxyalkylene chains and / or aryl groups or polyoxyalkylene A di-substituted product in which one chain or aryl group and one other substituent are bonded to each other, or three polyoxyalkylene chains and / or aryl groups, two polyoxyalkylene chains and / or aryl groups and other substitutions A tri-substituted product in which one group or any one of a polyoxyalkylene chain or an aryl group and two other substituents are bonded is preferable. The silicon compound having a polyoxyalkylene chain is preferably a disubstituted product such as dialkoxysilane or a trisubstituted product such as trialkoxysilane.
Furthermore, the total content of the polyoxyalkylene chain and the aryl group in the silicon compound is preferably 1 to 4 per monomer (per silicon atom). More preferably, it is 2-4, More preferably, it is 3 or 4.
Specifically, phenyltrimethoxysilane and / or phenylmethyldiethoxysilane are particularly suitable.

The silicon compound having a polyoxyalkylene chain and / or an aryl group preferably has a weight average molecular weight of 500 or more and 100,000 or less. When the weight average molecular weight of the silicon compound is in such a range, the compatibility of the silicon compound with the curable resin composition is excellent, and the molded product obtained is likely to have excellent transparency, and the molded product is Since the bleed property in the manufacturing process is also good, the release property is likely to be excellent, and thereby, the effect of the present invention that makes the release property excellent at the time of molding processing is more prominently exhibited. Because it becomes. The weight average molecular weight of the silicon compound is more preferably 1000 to 90,000, and still more preferably 1500 to 80,000.
In addition, as a measuring method of the weight average molecular weight of the said silicon compound, the following method can be used, for example.

<Measurement method of weight average molecular weight>
The weight average molecular weight of the release agent can be measured using, for example, gel permeation chromatography. The measurement is preferably performed under the following conditions using HLC-8220GPC (gel permeation chromatography, trade name, manufactured by Tosoh Corporation).
(Measurement conditions for weight average molecular weight)
Column: “TSK-GEL SUPER HZM-N 6.0 * 150” x 4 manufactured by Tosoh Corporation Eluent: Tetrahydrofuran Flow rate: 0.6 mL / min Temperature: 40 ° C.
Calibration curve: Prepared using polystyrene standard sample (manufactured by Tosoh Corporation).

The other substituents other than the polyoxyalkylene chain and the aryl group in the silicon compound are organic groups bonded to silicon of the silicon compound and may be any non-hydrolyzable as long as they do not interfere with the effects of the present invention. Groups are preferred. Examples of the non-hydrolyzable group include alkyl groups such as a methyl group, an ethyl group, and a propyl group, and an epoxy group. These may be used alone or in combination of two or more. Of these, a methyl group is preferred.

As content of the silicon compound which has the said polyoxyalkylene chain and / or an aryl group, it is 0.01 mass% or more and 10 mass% or less with respect to 100 mass% of curable resin compositions for molded objects of this invention. Preferably there is. If the content of the silicon compound is less than 0.01% by mass, the above-described effects may be insufficient. If the content exceeds 10% by mass, the resin may be difficult to cure. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%. When the content of the silicon compound is 5% by mass or less, the transparency of the curable resin composition and the obtained molded body is particularly excellent, and 0.01% by mass in order to sufficiently exhibit the effects of the present invention. The above is preferable.

The curable resin composition for molded bodies of the present invention preferably further contains a solvent and / or a release agent. The said solvent should just be a compound which can be used as a solvent of a thermosetting resin, and it is preferable that it is a compound which has a boiling point of 260 degrees C or less under 1 atmosphere.
Below, the compound which has a boiling point of 260 degrees C or less under 1 atmospheric pressure suitable as a solvent and / or a mold release agent is explained in full detail.

The curable resin composition for molded bodies of the present invention preferably further contains a compound having a boiling point of 260 ° C. or lower under 1 atmosphere.
By further containing such a compound, the releasability when the cured product is taken out from the mold can be improved, and the effects of the present invention can be sufficiently exhibited.
The reason why the releasability is improved is as follows. Since the above-mentioned compound has a boiling point of 260 ° C. or less, the compound is likely to change its state when heated, is easily vaporized, and tends to be in a high energy state.
Moreover, such a compound has an action as a solvent for the thermosetting resin, and is compatible with the resin component. Accordingly, when the resin composition is in a molten state by heating during mold molding, it is in a state of being uniformly mixed with additives such as a resin component and a release agent. When the molten resin composition is filled into a mold (injection / coating) and cured, the state is likely to change as described above, and the resin composition moves to the surface side of the mold and precipitates in the resin composition. , A so-called bleed-out occurs, which causes release properties.

The above-mentioned compound can remarkably enhance the effect of the silicon compound (the bleed-out speed of the silicon compound is increased, and as a result, the effect of adding the silicon compound is more exhibited). That is, the silicon compound is a substance that has a releasing action enough to be used as a releasing agent and causes bleed out. When this silicon compound is used in combination with a compound having the above specific boiling point, when both compounds bleed out, the compound having the specific boiling point functions to move the specific silicon compound to the surface layer side of the molded body. . That is, a compound having a specific boiling point increases the bleed-out speed of a specific silicon compound, so that the effect exhibited by the silicon compound can be remarkably enhanced, and the mold release property can be improved even in the case of curing in a short time. It can be fully expressed.

The compound having a boiling point of 260 ° C. or less under 1 atm may be a compound having such a boiling point and usable as a solvent for a thermosetting resin. When the boiling point at 1 atm of the compound having the specific boiling point is 260 ° C. or less, the above-described effect of improving releasability becomes more remarkable. The boiling point of a compound having a specific boiling point is preferably lower from the viewpoint of the evaporation rate, and the lower limit of the boiling point under 1 atm is preferably 30 ° C., for example, and more preferably 40 ° C. or more. Thus, as described above, the action mechanism of the compound having a specific boiling point is considered to exhibit a releasing action by transferring (depositing or aggregating) to the surface layer of the molded body. .
In addition, a preferable compound in a compound having a boiling point of 260 ° C. or less under 1 atm is not determined only by the boiling point, but also considers compatibility with the resin composition, a moving speed at the time of molding processing (bleed out speed), and the like. In addition, it is determined by being able to demonstrate the effects of the present invention more.

Examples of the compound having a boiling point of 260 ° C. or less at 1 atm include alcohols, polyhydric alcohol derivatives, carboxylic acids, carboxylic esters, carboxylic anhydrides, ketones, aliphatic hydrocarbons, and aromatics. It is preferably at least one compound selected from the group consisting of aromatic hydrocarbons, more preferably at least one compound selected from the group consisting of alcohols, polyhydric alcohol derivatives, carboxylic acid esters and ketones. Carboxylic acid esters and ketones are preferred.
By containing such a compound as an essential component, the transparency of the curable resin composition for a molded product and the molded product is sufficient, and when releasing using a mold, the mold release property is improved. Thus, the molded body can be easily peeled off from the mold. As a result, continuous production is possible without damaging the surface of the molded body, which is particularly useful as a material for electrical / electronic component materials and optical applications. Such a compound having the specific boiling point has an action as a solvent in the thermosetting resin, and therefore, it is considered that the compound moves to the surface layer of the molded body and exhibits releasability and the like as described above.
Moreover, as a structure of the said compound, any structures, such as linear form, a branched form, and cyclic | annular form, may be sufficient.

The compound having a boiling point of 260 ° C. or lower under 1 atm is at least one compound (A-1) having a boiling point of 150 ° C. or lower under 1 atm, and a compound (A- A form containing at least one of 2) is preferred.
The compound (A-1) having a boiling point of 150 ° C. or lower at 1 atm is more easily gasified than the compound (A-2) having a boiling point of more than 150 ° C. at 1 atm, and the boiling point is 130 ° C. The following is preferable. More preferably, the boiling point is 110 ° C. or lower.
As the compound (A-1) having a boiling point at 1 atm of 150 ° C. or lower, alcohols are preferable. The compound (A-2) having a boiling point of more than 150 ° C. under 1 atm may be a compound having a boiling point of more than 150 ° C. and less than 260 ° C. under 1 atm, but is preferably an alcohol. . More preferred are aliphatic monohydric alcohols having a total carbon number of 6 or more.

As described above, from the viewpoint of the evaporation rate (bleed out rate), it is preferable that the compound having the specific boiling point has a lower boiling point. However, in consideration of an industrial process, the compound having a boiling point exceeding 150 ° C. (A -2) may be preferred. For example, when a resin composition for optical use is molded, a heat defoaming process may be performed during the molding process or prior to the molding process.
During such heat defoaming treatment, the compound (A-1) having a relatively low boiling point may evaporate, and when the molten resin is filled (injected / coated) into the mold, The amount of the compound (A-1) is reduced, or in some cases, the compound (A-1) is not included, and the release property of the compound (A-1) itself and the bleed-out speed of the release agent described above There is a risk that the effect of increasing

On the other hand, since the compound (A-2) having a relatively high boiling point is difficult to evaporate, it is easy to control the content of the specific compound in the molded body even in the case of performing the heat defoaming treatment as described above. .
Therefore, when sufficient release properties can be obtained even if the molded product does not contain a compound having a specific boiling point, or when heat defoaming treatment at a low temperature is possible, the compound (A-1 ) Only. However, when it is preferable that a compound having a specific boiling point is contained in the molded body, or when it is used for an optical application requiring heat defoaming treatment as described above, the compound (A-2) Is preferably contained, and it is more preferred that both the compound (A-1) and the compound (A-2) are contained. Further, by using the compound (A-1) and the compound (A-2) in combination, the resin composition containing them sufficiently exhibits the effect of containing the specific compound regardless of the molding processing conditions. It will be a thing.

The alcohols may be monohydric or polyhydric alcohols having a boiling point of 260 ° C. or less under 1 atmosphere. It is preferable that carbon number is 1-12. As a result, the functions and effects of the present invention can be exhibited more sufficiently, and the basic properties such as heat resistance and the functions such as the optical characteristics such as transparency can be made sufficiently excellent in the releasability. More preferably, the total carbon number of alcohol is 2-12, More preferably, it is 3-8.
Examples of the alcohols include aliphatic alcohols, aromatic alcohols having an aromatic ring such as benzyl alcohol, and polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, carbitol, and glycerin. These may be used alone or in combination of two or more.
Among these alcohols, aliphatic alcohols are particularly preferable, and among the aliphatic alcohols, saturated aliphatic alcohols are preferable. The total number of carbon atoms is preferably 1 to 12, more preferably 2 to 12, and further preferably 3 to 12. In consideration of compatibility with the resin composition, the total carbon number is preferably 3 to 8. Considering the industrial process, the total carbon number is preferably 6 to 12 because of good controllability in the defoaming treatment. In particular, it is more preferable that the total number of carbon atoms is 6 to 8 because both the compatibility and the good controllability in the defoaming treatment are provided. Specific examples of saturated aliphatic alcohols having a total carbon number of 6 to 8 include cyclohexanol, methylcyclohexanol, 1-hexanol, 1-heptanol, 2-heptanol, octyl alcohol, 2-ethylhexanol and the like. Can be mentioned. These may be used alone or in combination of two or more.

Specific examples of the aliphatic alcohols include, for example, as the compound (A-1), methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butanol, 1-amyl alcohol, and the like. Is mentioned.
Moreover, as a compound (A-2), a C6-C12 aliphatic alcohol is mentioned, Especially a C6-C12 aliphatic monohydric alcohol is preferable. Specifically, carbons such as 1-hexanol, 4-methyl-2-pentanol, cyclohexanol and the like having 6 carbon atoms, 1-heptanol, 2-heptanol, 3-heptanol, methylcyclohexanol, benzyl alcohol, etc. A compound having 7 carbon atoms, a compound having 8 carbon atoms such as octyl alcohol (1-octanol) and 2-ethylhexanol (2-ethylhexyl alcohol), a compound having 9 carbon atoms such as 1-nonyl alcohol and isononyl alcohol, Examples include compounds having 10 carbon atoms such as 1-decyl alcohol and 2-decyl alcohol, compounds having 11 carbon atoms such as 1-undecyl alcohol, and compounds having 12 carbon atoms such as 1-dodecanol (lauryl alcohol). . Of these, cyclohexanol, methylcyclohexanol, 1-hexanol, 1-heptanol, 2-heptanol, octyl alcohol, and 2-ethylhexanol having 6 to 8 carbon atoms are particularly preferable.
The above-mentioned compound (A-1) and compound (A-2) may be used alone or in combination of two or more.

Although the said polyhydric alcohol derivative should just have a boiling point of 260 degrees C or less under 1 atmosphere, it is preferable that a total carbon number is 1-12, and it is more preferable that it is 2-12. More preferably, it is -8. As a result, the functions and effects of the present invention can be exhibited more sufficiently, and the basic properties such as heat resistance and the functions such as the optical characteristics such as transparency can be made sufficiently excellent in the releasability.
Specific examples of the polyhydric alcohol derivative include, for example, as compound (A-1), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monomethyl. Examples include ether acetate.
In addition, examples of the compound (A-2) include ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, polyhydric alcohol ether compounds such as ethylene glycol dibutyl ether, propylene glycol dimethyl ether and cellosolve, ethylene glycol methyl ether acetate And polyhydric alcohol ether esters such as propylene glycol methyl ether acetate, and polyhydric alcohol ester compounds such as ethylene glycol monoacetate and ethylene glycol diacetate.
These may be used alone or in combination of two or more.

The carboxylic acids may be monovalent or polyvalent carboxylic acids having a boiling point of 260 ° C. or less at 1 atmosphere. The total carbon number is preferably 1-9. Thereby, the effect of this invention can be exhibited more fully. The total carbon number is more preferably 2-8, and still more preferably 2-7. Specific examples of the carboxylic acids include, for example, compounds (A-1) such as aliphatic carboxylic acids having 1 to 3 carbon atoms such as formic acid, acetic acid and propionic acid.
Moreover, as a compound (A-2), carbon number 4 such as butyric acid, pentanoic acid (valeric acid), hexanoic acid (caproic acid), octanoic acid (caprylic acid), 2,2-dimethylpropionic acid (pivalic acid), etc. ˜9 aliphatic carboxylic acids and the like. Among these, aliphatic carboxylic acids having 4 to 9 carbon atoms are preferable.
These may be used alone or in combination of two or more.

As said carboxylic acid ester, what has a boiling point of 260 degrees C or less under 1 atmosphere and has one or more carboxylic acid ester groups should just be used. The total number of carbon atoms is preferably 1 to 12, (1) carboxylic acid ester obtained from the above alcohols and carboxylic acid, (2) methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol, etc. A carboxylic acid ester obtained by a combination of an alcohol having 1 to 7 carbon atoms and the above carboxylic acid; (3) a carboxylic acid having 1 to 18 carbon atoms such as acetic acid, propionic acid, hexanoic acid, butanoic acid and the above alcohols; Carboxylic acid esters obtained in combination are preferred. These may be used alone or in combination of two or more.

The compound (A-1) in the carboxylic acid ester has 1 to 5 carbon atoms such as methyl acetate, ethyl acetate, isopropyl acetate, n-butyl acetate, s-butyl acetate, amyl acetate, isoamyl acetate, and allyl acetate. Of fatty alcohols such as methyl propionate and propionate of aliphatic alcohols having 1 to 4 carbon atoms such as methyl propionate and n-butyl propionate; methyl formate, formic acid-n-propyl, formic acid-n-butyl, formic acid Examples thereof include aliphatic formic acid esters having 1 to 5 carbon atoms such as amyl.
Further, examples of the compound (A-2) include acetic acid esters of aliphatic alcohols having 6 or more carbon atoms such as acetic acid-n-hexyl, acetic acid-2-ethylhexyl, cyclohexyl acetate, benzyl acetate, methylcyclohexyl acetate, octyl acetate; In addition to propionic acid esters of aliphatic alcohols having 5 or more carbon atoms such as isoamyl acid and benzyl propionate; formic acid esters of aliphatic alcohols having 6 or more carbon atoms such as hexyl formate and benzyl formate; Examples include propyl, amyl captylate, methyl caprate, ethyl caprate and the like.
Of these, isopropyl acetate, octyl acetate and the like are preferable. Particularly preferred is isopropyl acetate.

The carboxylic acid anhydrides may have any boiling point of 260 ° C. or less under 1 atm and one or more carboxylic acid anhydride groups, but preferably have 1 to 7 carbon atoms in total. . Examples of the compound (A-1) include acetic anhydride, and examples of the compound (A-2) include carboxylic acid anhydrides having 3 to 7 carbon atoms such as propionic anhydride, maleic anhydride, butyric anhydride, and isobutyric anhydride. Etc.
These may be used alone or in combination of two or more.

The ketones may have any boiling point of 260 ° C. or less under 1 atm and one or more ketone groups, but the total number of carbon atoms is preferably 1-12.
Examples of the compound (A-1) include acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, 4-methyl-3-penten-2-one (methyl oxide), diethyl ketone, di- Examples include n-propyl ketone, diisopropyl ketone, ethyl-n-butyl ketone, acetylacetone (2,4-pentadione), N-methylpyrrolidone and the like.
Further, as the compound (A-2), diisobutyl ketone, methyl-n-amyl ketone, methyl-n-hexyl ketone, methyl-n-hexyl ketone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), Examples include holon, cyclohexanone, methylcyclohexanone, isophorone (isoacetophenone), and acetophenone.
Among these, acetone, methyl ethyl ketone, methyl isobutyl ketone, N-methylpyrrolidone and the like are preferable, and methyl ethyl ketone is particularly preferable. These may be used alone or in combination of two or more.

The aliphatic hydrocarbons may be aliphatic hydrocarbons having a boiling point of 260 ° C. or less at 1 atmosphere, but the total carbon number is preferably 1-12. For example, cyclic hydrocarbons are preferable.
The aromatic hydrocarbons may be hydrocarbons having a boiling point of 260 ° C. or lower under 1 atm and having one or more aromatic groups, but the total number of carbons is preferably 7-12. .
In the aliphatic and aromatic hydrocarbons, examples of the compound (A-1) include hexane, heptane, octane, cyclohexane, cyclopentane, cyclohexene, benzene, toluene, ethylbenzene, xylene, styrene, and the like. Hexane, cyclohexane, Toluene, xylene and the like are preferable. Examples of the compound (A-2) include nonane, decane, dodecane, decalin, dipentene, tetralin, cyclohexylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, and cymene. These may be used alone or in combination of two or more.

It is a preferable embodiment of the present invention that the compound having a boiling point of 260 ° C. or less under 1 atm is contained in an amount of 0.01 to 5% by mass with respect to 100% by mass of the curable resin composition for molded bodies. .
If the ratio of the compound having the specific boiling point is less than 0.01% by mass, there is a possibility that the effect of improving releasability, which is the effect of adding this compound, may not be sufficiently exerted. When exceeding, when the mold is used, the followability of the resin composition to the mold is impaired, and the molded body is swollen and used as an optical molded body. May decrease and the homogeneity as a molded body may be lost.
In the present invention, it is more preferably 0.05% by mass or more and 4% by mass or less, more preferably 0.1% by mass or more and 3% by mass or less in that the effect of the compound having the specific boiling point is easily exhibited. More preferably, it is as follows.

The curable resin composition for molded bodies of the present invention preferably further contains a release agent.
The mold release property is improved by including the mold release agent. Moreover, when used together with the compound having the specific boiling point, when curing the curable resin composition for molded bodies using a mold, the compound having the specific boiling point increases the bleedout speed of the release agent, The effect of adding the release agent will be more exhibited. Thereby, when hardening the curable resin composition for molded objects of this invention using a metal mold | die, a hardened | cured material (molded object) can be easily peeled from a metal mold | die. Further, the appearance can be controlled without causing damage to the surface of the cured product, and transparency can be further expressed. The obtained molded body is particularly useful as a material in electrical / electronic component materials and optical applications.
The mold release agent is a mold release agent usually used in the technical field and may be dissolved (compatible) or dispersed in an epoxy resin, but can be dissolved (compatible) in a thermosetting resin. Those are preferred. Further, considering that the release agent is present on the surface layer of the cured product (molded product) and exhibits releasability, a compound having a boiling point exceeding 260 ° C. at 1 atm is an essential component of the present invention. This is a preferred embodiment. In the present specification, “having a boiling point exceeding 260 ° C. under 1 atm” includes non-volatile substances having no boiling point under 1 atm.
The mold release agent in the curable resin composition for molded bodies of the present invention contains a compound having a boiling point exceeding 260 ° C. under 1 atm, and further has the following configuration (1) and / or (2): The form is preferred.

(1) The said mold release agent is a form which uses at least 1 sort (s) of compounds chosen from the group which consists of alcohols, carboxylic acids, carboxylic acid esters, carboxylate salts, and carboxylic anhydrides as an essential component. (2) The said mold release agent is a solid form at 20 degreeC.
Above all, the release agent is at least one of the compounds (B1) to (B3) described later at 20 ° C., in which the release agent is a compound having the above-mentioned (1) and (2) forms as essential components. And a solid form as an essential component is more preferable. That is, the above-mentioned mold release agent is an essential component comprising at least one compound having 13 or more carbon atoms selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylates and carboxylic anhydrides, A form in which the compound having 13 or more carbon atoms is solid at 20 ° C. is more preferable. More preferred is a form that is solid at 30 ° C., and still more preferred is a form that is solid at 50 ° C.
Hereinafter, the modes (1) and (2) will be described in detail.

(1) The release agent in the curable resin composition for molded bodies of the present invention is at least one selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylic acid salts, and carboxylic acid anhydrides. It is preferable to use this compound as an essential component.
More preferably, the release agent has at least one compound selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, and carboxylates as an essential component. More preferably, the mold release agent has at least one compound selected from the group consisting of alcohols, carboxylic acids and carboxylic acid esters as an essential component. Particularly preferably, the releasing agent is in a form having carboxylic acids as essential components.

In the following, the release agent is an alcohol having a total carbon number of 13 or more (B-1); a carboxylic acid having a total carbon number of 10 or more, a carboxylate having a total carbon number of 6 or more, and a total carbon number of 8 or more. Carboxylic anhydrides (B-2); carboxylic acid esters (B-3) having a total carbon number of 13 or more will be described. One or more of these can be preferably used as the release agent.

The alcohol having a total carbon number of 13 or more (B-1) may be any monovalent or polyhydric alcohol having a boiling point exceeding 260 ° C. under 1 atm and a total carbon number of 13 or more, In particular, an aliphatic monohydric alcohol is preferable. Specifically, aliphatic alcohols such as tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, palmityl alcohol, margaryl alcohol, stearyl alcohol, nonadecyl alcohol, eicosyl alcohol, myristyl alcohol, cetyl alcohol, etc. Is preferred. These may be used alone or in combination of two or more. Among these, stearyl alcohol is more preferable.

The carboxylic acids (B-2) may be monovalent or polyvalent carboxylic acids having a boiling point exceeding 260 ° C. at 1 atm and a total carbon number of 10 or more. The carboxylic acids are preferably aliphatic carboxylic acids. More preferably, it is a saturated aliphatic carboxylic acid. Further, it is preferably an aliphatic carboxylic acid having a total carbon number of 12 or more. More preferably, the total carbon number is 13 or more. Specifically, lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, 1-heptadecanoic acid, stearic acid, nonadecanoic acid, eicosanoic acid, 1-hexacosanoic acid, behenic acid and the like are preferable. These may be used alone or in combination of two or more. More preferred are lauric acid and stearic acid. More preferred is stearic acid.

The carboxylates (B-2) may be monovalent or polyvalent carboxylates having a boiling point exceeding 260 ° C. under 1 atm and a total carbon number of 6 or more. The carboxylates (B-2) are preferably aliphatic carboxylates. More preferably, it is an aliphatic carboxylate having a total carbon number of 10 or more. More preferably, it has 13 or more carbon atoms. Carboxylic acid salt obtained by combining the above carboxylic acid (B-2) with one selected from the group consisting of amine, sodium, potassium, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc, tin Etc. are suitable. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of zinc stearate, magnesium stearate and zinc 2-ethylhexanoate is preferable.
The carboxylic acid anhydrides (B-2) may be carboxylic acid anhydrides having a boiling point exceeding 260 ° C. under 1 atm and a total carbon number of 8 or more. The carboxylic acid anhydride is preferably an aliphatic carboxylic acid anhydride. More preferably, it is an aliphatic carboxylic acid anhydride having a total carbon number of 10 or more. More preferably, the total carbon number is 13 or more. Specific examples include succinic anhydride and phthalic anhydride. These may be used alone or in combination of two or more.
Among the above-mentioned compounds, stearic acid compounds such as stearic acid and stearic acid esters are more preferable. Thus, the curable resin composition for molded bodies of the present invention preferably contains a stearic acid compound. More preferred is stearic acid.

The carboxylic acid esters (B-3) may be any carboxylic acid ester having a boiling point exceeding 260 ° C. under 1 atm and a total carbon number of 13 or more. (1) The alcohols (B— 1) and carboxylic acid esters obtained from carboxylic acids (B-2), (2) alcohols having 1 to 7 carbon atoms such as methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol and the above carboxylic acids ( Carboxylic acid ester obtained by combination with B-2), (3) Combination of carboxylic acid having 1 to 7 carbon atoms such as acetic acid, propionic acid, hexanoic acid, butanoic acid and the above alcohols (B-1) Carboxylic acid ester obtained by (1) is suitable. Preferable carboxylic acid is the same as the preferable form mentioned above in the said carboxylic acid (B-2). Of these, stearic acid methyl ester and stearic acid ethyl ester are preferred. These may be used alone or in combination of two or more.
A form in which the release agent has a boiling point exceeding 260 ° C. under 1 atm and the carboxylic acid ester having a total carbon number of 13 or more is solid at 20 ° C. is a preferred embodiment of the present invention. In other words, carboxylic acid esters having a boiling point exceeding 260 ° C. under 1 atm and a total carbon number of 13 or more are a preferred form.

The mold release agent in the curable resin composition for molded bodies of the present invention is at least one carbon number selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylic acid salts, and carboxylic acid anhydrides. It is preferable to use 13 or more compounds as essential components.
More preferably, the compound has 15 or more carbon atoms. More preferably, it is 18 or more.
The upper limit of the carbon number is preferably 36, for example. More preferably, it is 24, and further preferably 20.
If it has a certain amount of long chain in such a range, it exhibits the effects of the present invention, and exhibits excellent peelability without impairing the basic performance such as heat resistance and the optical properties such as transparency. it can. In addition, it is relatively easy to obtain and can be economical.
Any structure such as linear, branched, and cyclic structures may be used, but a linear structure is preferred.

(2) The release agent in the curable resin composition for molded bodies of the present invention is preferably solid at 20 ° C. More preferably, it is solid at 25 ° C., more preferably it is solid at 30 ° C., and particularly preferably it is solid at 50 ° C.
For example, the release agent in the curable resin composition for molded bodies of the present invention is preferably solid at 50 ° C.
When a mold release agent having such characteristics is used, the effect of improving the bleed-out speed of the mold release agent by the specific compound in the present invention becomes remarkable at the time of mold molding curing. For example, when the molding temperature is low, a release agent having a high melting point is usually difficult to bleed out, but when used in combination with a compound having a boiling point of 260 ° C. or less under the above-mentioned 1 atmosphere, the above-mentioned compound releases the release agent. This is considered to be because it is more easily transferred to the surface side of the molded body and the bleed out speed is remarkably improved. In addition, the release agent deposited and agglomerated on the surface side of the molded body has the above-mentioned characteristics, so that it becomes easier to solidify as the temperature of the molded body decreases, and the mold release agent becomes a state of being deposited on the surface. It is thought that the sex will be greatly improved. Thereby, it is possible to make the releasability remarkably excellent while sufficiently maintaining the basic performance such as heat resistance and the optical characteristics such as transparency.

Specific examples of the compounds (A-1) to (A-2) having a boiling point of 260 ° C. or less under 1 atm and the compounds (B-1) to (B-3) and their melting points, boiling points, etc. Tables 1 and 2 below show.
In Tables 1 and 2 below, A-1 represents a compound having a boiling point of 150 ° C. or lower under 1 atm. A-2 represents a compound having a boiling point of more than 150 ° C. and 260 ° C. or less under 1 atmosphere. B-1 represents an alcohol having a boiling point exceeding 260 ° C. B-2 represents a carboxylic acid having a boiling point exceeding 260 ° C, a carboxylate having a boiling point exceeding 260 ° C, or a carboxylic acid anhydride having a boiling point exceeding 260 ° C. B-3 represents a carboxylic acid ester having a boiling point exceeding 260 ° C. MEK means methyl ethyl ketone. The boiling point is measured at 1 atm unless otherwise specified.

It is preferable that the specific compound and / or the specific release agent remain in the molded product after the molding is completed.
Thereby, sufficient releasability can be obtained even at the end of molding.
Its presence can be confirmed by performing measurement with a pyrolysis GC-Mass (gas chromatograph mass) spectrum on a molded body obtained by molding.
That is, this invention is also a molded object containing the silicon compound which has a polyoxyalkylene chain and / or an aryl group, and / or the compound which has a boiling point of 260 degrees C or less under 1 atmosphere.
The preferable form is the same as the preferable form in the curable resin composition for molded bodies of the present invention and the molded body. For example, a molded body containing a silicon compound having a polyoxyalkylene chain and / or an aryl group is more preferable.

The curable resin composition for molded bodies of the present invention contains an epoxy resin. The epoxy resin is not particularly limited as long as it exhibits the effects of the present invention, but it is preferably excellent in compatibility with components other than the epoxy resin in the resin composition and uniformly dispersed. For example, in plastic lens applications, processing is easier than lenses made of inorganic glass and the like, and the size and shape can be freely changed, which is suitable for mass production. Epoxy resins are not widely used at present because they are more difficult to process than thermoplastic resins, but in the present invention, for example, epoxy resins are also suitable by using the above-mentioned specific compounds. Can be used.

The epoxy resin is not particularly limited as long as it has a thermosetting property and contains a resin having a molecular weight from high molecular weight to about monomer. As the form of the epoxy resin, for example, (1) a form comprising a liquid or solid epoxy resin, (2) a liquid or solid epoxy resin and an epoxy compound having a lower molecular weight than this resin component or a solvent (non-curable), etc. And (3) a form containing a liquid or solid non-curable resin and an epoxy compound having a molecular weight lower than that of the resin component. As a form of said (3), the form containing the oligomer component of acrylic resins, such as PMMA (polymethylmethacrylate), a (meth) acrylate monomer, etc. can be mentioned, for example.

The epoxy resin can be cured in a short time, but the curable resin composition for molded bodies of the present invention achieves both releasability and transparency even when cured in a short time. Therefore, the effect of the present invention is remarkably exhibited. In addition, while having workability equivalent to that of a conventional thermosetting plastic material, it exhibits heat resistance comparable to that of inorganic glass, and can exhibit excellent characteristics such as excellent molding and workability.

The epoxy resin is a compound having at least one epoxy group. In the present specification, the “epoxy group” means a group containing an oxirane ring which is a 3-membered ether. Specifically, a glycidyl group containing an epoxy group or an epoxy group structure is preferred. As the epoxy group, an epoxy group such as an epoxycyclohexyl group, a glycidyl group such as a glycidyl ether group, and a glycidyl ester group are preferable.
The epoxy group-containing compound preferably contains at least one selected from the group consisting of an aliphatic epoxy compound, a hydrogenated epoxy compound, an alicyclic epoxy compound, and an aromatic epoxy compound.

As the aliphatic epoxy compound, an aliphatic glycidyl ether type epoxy resin is suitable, and one or more of these can be used in combination.
Specific 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 Those obtained by a condensation reaction, those having a propylene glycol skeleton, an alkylene skeleton, an oxyalkylene skeleton, etc. It is suitable.
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.

As the hydrogenated epoxy compound, a polyfunctional glycidyl ether compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton (hereinafter also simply referred to as “polyfunctional glycidyl ether compound”). Is preferred. Specifically, a hydrogenated product of an aromatic polyfunctional glycidyl ether compound such as a bisphenol-type epoxy resin is suitable, and one or more of these can be used in combination.
More preferred are hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol S type epoxy resins, hydrogenated bisphenol F type epoxy resins, and the like. More preferred are hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins. Further, complete or partially hydrogenated aromatic epoxy compounds are preferred. The aromatic epoxy compound includes an aromatic glycidyl ether compound.

As the alicyclic epoxy compound, a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group (hereinafter also simply referred to as “polyfunctional alicyclic epoxy compound”) is suitable. Specifically, an epoxy resin having an epoxycyclohexane skeleton (epoxycyclohexane group), an epoxy resin in which an epoxy group is added directly or via a hydrocarbon group to a cyclic aliphatic hydrocarbon, and the like are suitable. Two or more kinds can be used in combination. More preferably, it is an epoxy resin having an epoxycyclohexane skeleton.
Examples of the epoxy resin having an epoxycyclohexane skeleton include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, epsilon-caprolactone-modified 3,4-epoxycyclohexylmethyl 3 ′, 4′-epoxycyclohexanecarboxylate, Bis- (3,4-epoxycyclohexyl) adipate and the like are preferable.

Examples of the alicyclic epoxy compound other than the epoxy resin having the epoxycyclohexane skeleton include 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, tri Examples include alicyclic epoxides such as hetero ring-containing epoxy resins such as glycidyl isocyanurate.
The aromatic epoxy compound is preferably 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, and these can be used alone or in combination. . More preferably, it is an epoxy and / or glycidyl compound (fluorene compound) having a fluorene skeleton. Moreover, although the refractive index can be increased by using a brominated compound of an aromatic epoxy compound, the Abbe number slightly increases, and it is preferably used depending on the application. That is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, an epoxy resin having a fluorene skeleton, an aromatic epoxy resin having a bromo substituent are suitable.

Specific examples of the aromatic epoxy compound include bisphenol A type epoxy resin, bisphenol F type epoxy resin, fluorene epoxy (manufactured by Osaka Gas Chemical Company) on-coat EX-1020 or Ogsol EG210, fluorene epoxy (Osaka Gas Chemical Company). Manufactured) On-coat EX-1010 or Ogsol PG is preferred, and one or more of these can be used in combination. More preferable are bisphenol A type epoxy resin and fluorene epoxy (Osaka Gas Chemical Co., Ltd.) Ogsol EG-210.
Among them, the aliphatic glycidyl ether type epoxy resin and the epoxy resin having an epoxycyclohexane skeleton are more preferably used for the purpose of suppressing the appearance deterioration during light irradiation.

Among the epoxy group-containing compounds, alicyclic epoxy compounds, hydrogenated epoxy compounds, aliphatic epoxy compounds, and aromatic epoxy compounds are preferable in this order.
Specifically, as the alicyclic epoxy compound, a polyfunctional alicyclic epoxy compound having an alicyclic epoxy group (hereinafter also simply referred to as “polyfunctional alicyclic epoxy compound”) is preferable.
As the hydrogenated epoxy compound, a polyfunctional glycidyl ether compound having a glycidyl ether group directly or indirectly bonded to a saturated aliphatic cyclic hydrocarbon skeleton (hereinafter also simply referred to as “polyfunctional glycidyl ether compound”) is preferable. It is.
As the aliphatic epoxy compound, an aliphatic glycidyl ether type epoxy resin is suitable. The preferred form of the aliphatic glycidyl ether type epoxy resin is as described above.
As the aromatic epoxy compound, an aromatic glycidyl ether compound is suitable. Examples of the aromatic glycidyl ether compound include an epibis type glycidyl ether type epoxy resin, a high molecular weight epibis type glycidyl ether type epoxy resin, and a novolac / aralkyl type glycidyl ether type epoxy resin.

As the above-mentioned epibis type glycidyl ether type epoxy resin, those obtained by a condensation reaction of bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and epihalohydrin are suitable.
The high molecular weight epibis type glycidyl ether type epoxy resin is obtained by further subjecting the above epibis type glycidyl ether type epoxy resin to an addition reaction with bisphenols such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and the like. Is preferred.

As the above-mentioned novolak aralkyl type glycidyl ether type epoxy resin, phenol, cresol, xylenol, naphthol, resorcin, catechol, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol and other phenols and formaldehyde, acetoaldehyde, propionaldehyde, Polyhydric phenols obtained by condensation reaction of benzaldehyde, hydroxybenzaldehyde, salicylaldehyde, dicyclopentadiene, terpene, coumarin, paraxylylene glycol dimethyl ether, dichloroparaxylylene, bishydroxymethylbiphenyl, etc. are further condensed with epihalohydrin. What is obtained by this is suitable.

As the aromatic epoxy compound, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol and the like, an aromatic crystalline epoxy resin obtained by a condensation reaction of epihalohydrin, and the above bisphenols and tetramethylbiphenol, High molecular weight polymer of aromatic crystalline epoxy resin obtained by addition reaction of tetramethylbisphenol F, hydroquinone, naphthalene diol, etc .; glycidyl obtained by condensation reaction of tetrahydrophthalic acid, hexahydrophthalic acid, benzoic acid and epihalohydrin 1 type (s) or 2 or more types, such as ester type epoxy resin, can be used.

Among these, a polyfunctional alicyclic epoxy compound and a polyfunctional hydrogenated epoxy compound are more preferable because the curing rate of the curable resin composition is high. Thus, since a high curing rate can be exhibited, if the amount of catalyst is the same, a cured product can be obtained in a shorter time.

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

The curable resin composition of the present invention preferably contains an epoxy resin having an Abbe number of 45 or more. The epoxy resin is not particularly limited as long as it has an Abbe number of 45 or more and exhibits the effects of the present invention.
As content of the epoxy resin whose said Abbe number is 45 or more, it is preferable that 1 mass% or more is contained in all the epoxy resins. The content of the epoxy resin having an Abbe number of 45 or more is more preferably 5% by mass or more, and still more preferably 10% by mass or more. In particular, for high Abbe number optical applications, 60% by mass or more is preferable, and 70% by mass or more is more preferable. For low Abbe number optical applications, 1-70% by weight is preferred. More preferably, it is 10-60 mass%, More preferably, it is 20-50 mass%.
When the curable resin composition of this invention contains the epoxy resin whose Abbe number is 45 or more, it is preferable that the curable resin composition containing the said compound contains a cationic curing catalyst. The cationic curing catalyst will be described later.
The preferred form of the epoxy resin having an Abbe number of 45 or more is as described above as the preferred form of the epoxy compound.

Specifically, an alicyclic epoxy compound and a hydrogenated epoxy compound are suitable as the epoxy resin having an Abbe number of 45 or more.
Among these, more preferred are alicyclic epoxy compounds; hydrogenated bisphenol A type epoxy resins, hydrogenated bisphenol S type epoxy resins, hydrogenated bisphenol F type epoxy resins, and the like, and even more preferred are alicyclic epoxy compounds. is there. Moreover, when using the said specific silicon compound, an alicyclic epoxy compound is suitable also from the point of the stability of the curable resin composition, and the hardening characteristic at the time of making it harden | cure.

By using an alicyclic epoxy resin as the epoxy resin, the Abbe number can be improved, the optical characteristics can be improved, and the epoxy resin can be suitably used for various applications.
As the alicyclic epoxy resin, CELL-2021P, Celoxide 2081, EHPE-3150 (trade names, all manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable. Thus, the said epoxy resin is also one of the preferable forms of this invention for the curable resin composition for molded objects which makes an alicyclic epoxy resin essential. The alicyclic epoxy resin may be contained in the epoxy resin, and the content thereof is not particularly limited, but is preferably 40% by mass or more in the total epoxy resin. More preferably, it is 60% by mass or more, still more preferably 80% by mass or more, and particularly preferably substantially all are alicyclic epoxy resins. Thereby, the effect of this invention can be exhibited more fully.

The thermosetting resin composition in the present invention may contain an alicyclic compound other than an epoxy compound having an Abbe number of 45 or more.
Examples of the alicyclic compound other than the epoxy compound having an Abbe number of 45 or more include, for example, alicyclic modified neopentyl glycol (meth) acrylate (“R-629” or “R-644” manufactured by Nippon Kayaku Co., Ltd.). An alicyclic acrylate having an oxygen atom and / or a nitrogen atom in the structure such as tetrahydrofurfuryl (meth) acrylate and morpholinoethyl (meth) acrylate; an alicyclic monofunctional maleimide such as N-cyclohexylmaleimide; N , N′-methylene bismaleimide, N, N′-ethylene bismaleimide, N, N′-trimethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N′-dodecamethylene bismaleimide, 1,4 -Alicyclic bismaleimides such as dimaleimidocyclohexane and the like, and one or more of these Can be used.

[Flexible ingredients]
In the said curable resin composition for molded objects, a flexible component can be appropriately contained for the purpose of improving mechanical strength or the like as long as the effects of the present invention are not impaired. By including a flexible component, it can be set as the curable resin composition for molded objects with a sense of unity. Examples of the flexible component include (1) a form that is a flexible component made of a compound different from the epoxy resin, and (2) a form in which one of the epoxy resins is a flexible component. However, it can be suitably applied.
The content of the flexible component is not particularly limited and may be appropriately selected. Usually, it selects from the range of 0.01-50 mass% with respect to 100 mass% of curable resin composition for molded objects, Preferably, it selects from the range of 0.1-20 mass%.
As the flexible component, specifically, a compound having an oxyalkylene skeleton represented by — [— (CH ₂ ) _n —O—] _m — (n is 2 or more, m is an integer of 1 or more. N is preferably an integer of 2 to 12, and m is an integer of 1 to 1000. More preferably, n is an integer of 3 to 6, and m is an integer of 1 to 20. As the flexible component, a compound having an oxyalkylene skeleton and having an epoxy group is preferable. Among them, a compound having an oxybutylene skeleton and an epoxy group is preferable, and examples of industrial products include YL-7217 (epoxy equivalent 437, liquid epoxy resin) manufactured by Japan Epoxy Resin Co., Ltd.
In addition, other preferable compounds as the flexible component include, for example, hydrogenated epoxy compounds such as YL-7170 (YX-8040) (epoxy equivalent 1000, hydrogenated bisphenol type epoxy resin) manufactured by Japan Epoxy Resin; Japan Aromatic epoxy compounds such as JER1007 (epoxy equivalent 1750-2200, bisphenol A type epoxy resin) manufactured by Epoxy Resin; EHPE3150 (solid at room temperature) high molecular weight alicyclic solid epoxy resin manufactured by Daicel Chemical Industries; An epoxy compound such as an epoxy resin having an alkylene skeleton having 4 or more carbon atoms such as Celoxide 2081 (liquid at normal temperature) manufactured by Kogyo Co., Ltd. is exemplified.
YL-7170 (YX-8040) manufactured by Japan Epoxy Resin Co., Ltd. and JER1007 manufactured by Japan Epoxy Resin Co. may be preferably used from the viewpoint of high molecular weight.
In addition, liquid rubber such as liquid nitrile rubber, polymer rubber such as polybutadiene, and fine particle rubber having a particle size of 100 nm or less are also preferable.
More preferably, it is a compound containing a curable functional group at the terminal, side sheath, main chain skeleton or the like. As described above, a curable resin composition for a molded body containing a curable functional group as the flexible component is also one of the preferred embodiments of the present invention. The above-mentioned “curable functional group” refers to a “functional group that cures with heat or light such as an epoxy group (a group that causes a resin composition to undergo a curing reaction)”.

Among the compounds containing a curable functional group, an epoxy resin is particularly preferable, and an epoxy resin containing an oxybutylene skeleton is more preferable.
As described above, the curable resin composition for molded bodies of the present invention preferably contains a flexible component. More preferably, a form including an alicyclic curable material including a flexible material (preferably epoxy) is more preferable. As the flexible component, an epoxy resin is particularly preferable.

As the average number of epoxy groups per molecule of the epoxy resin, usually two are used, but in some cases, three or more may be used.

The molded body curable resin composition is also a molded body curable resin composition containing an epoxy resin, and the molded body curable resin composition is prepared with two or more epoxy resins. Form is preferred. By preparing in such a form, continuous production is possible, and an epoxy resin having a sense of unity, high strength, high transparency and heat resistance can be obtained. The curable resin composition for molded bodies having such characteristics can be suitably used as an optical material. For example, it is useful as a lens material (optical material) having a transmittance at 500 nm of 80% or more. Material can be provided.

The above two or more types of epoxy resins preferably have a resin having a molecular weight of 700 or more and an epoxy resin having a molecular weight lower than that of the resin. Among them, those having a molecular weight of 700 or more and less than 700 are preferable. What is essential is more preferable. Moreover, it is preferable that it is the curable resin composition for molded objects containing the said 2 or more types of epoxy resin. By having a molecular weight of 700 or more (high molecular weight epoxy resin, high molecular material) and a material having a molecular weight of less than 700 (low molecular weight epoxy resin, low molecular material) as essential, it is possible to reduce viscosity during production and The effect of improving the strength will be obtained.

The curable resin composition for molded bodies preferably contains a high molecular material and a low molecular weight material. However, as a preparation method thereof, a low molecular weight material (and other components as necessary) is used. The method of mixing and adding a polymer material is preferred. By mixing in this manner, a suitable resin composition can be obtained without increasing the viscosity of the curable resin composition for molded bodies. Further, the familiarity of the polymer material with the resin composition can be improved. Thus, it is a method for producing a curable resin composition for molded bodies containing an epoxy resin, and the production method includes a step of mixing and preparing two or more types of epoxy resins. A method for producing a resin composition is also one of the preferred embodiments of the present invention. More preferable as such a production method is a form in which the two or more types of epoxy resins essentially require a molecular weight of 700 or more (high molecular material) and a molecular weight of less than 700 (low molecular material). .

The method for measuring the molecular weight is preferably the same as described above.
As a ratio (mass ratio) of the polymer material having a molecular weight of 700 or more and a low molecular material having a molecular weight of less than 700, 10 to 90% of the polymer material having a molecular weight of 700 or more is included with respect to the entire resin composition. It is preferable. More preferably, it is 20-80%, More preferably, it is 30-70%.
The two or more types of epoxy resins are preferably two or more types of epoxy resins. Among these, it is preferable to include an alicyclic epoxy resin.

[Low Abbe number and high refractive index]
In the above resin composition and molded product, when a resin having a low Abbe number and a high refractive index is obtained, it is preferable to use an epoxy resin component having a large amount of unsaturated bonds. That is, a curable resin composition containing an epoxy resin, wherein the curable resin composition has an unsaturated bond amount of 40% by mass or more with respect to 100% by mass of the cured product after curing. Is preferred.
The “unsaturated bond amount” as used herein means the total amount of unsaturated bonds contained in the cured product. When components (other components) other than the epoxy resin have an unsaturated bond, unsaturated bonds of other components are also included in the total amount.
The resin composition preferably has 40% by mass or more of unsaturated bonds with respect to 100% by mass of the cured product (also referred to as a cured product) after curing. Here, the amount of unsaturated bonds means carbon atoms, sulfur atoms, nitrogen atoms, boron atoms, silicon atoms, phosphorus atoms, germanium atoms, oxygen atoms, and hydrogen atoms and halogen atoms to be added. The total mass. That is, it is the total mass of atoms that form unsaturated bonds contained in 100% by mass of the cured body, and hydrogen atoms and halogen atoms that are bonded to the atoms. Specifically, when it has a —CH ₂ CH ₂ CHCl—CH═CCl—CH ₂ CH ₂ — structure, the amount of unsaturated bonds means the total mass of the CH═CCl moiety.
Moreover, when a carbon atom forms an aromatic ring, the amount of unsaturated bonds shall represent the mass% of the aromatic ring contained in 100 mass% of hardening bodies. In this case, in order to obtain the total amount of unsaturated bonds when the aromatic ring has a substituent, an aromatic composed of carbon atoms and hydrogen atoms is excluded, not including the mass of the substituents having no unsaturated bond. Only the mass of the ring is included in the calculation of the total amount of unsaturated bonds. When a halogen atom is bonded as a substituent to the aromatic ring, the total amount of unsaturated bonds including the halogen atom is calculated from the above definition. In the present invention, a form in which the unsaturated bond is constituted by an aromatic ring is one of the preferred forms.

In the epoxy resin, it is essential that the epoxy resin has an aromatic ring, and the amount of the aromatic ring is preferably 40% by mass or more with respect to 100% by mass of the cured product after curing, but the Abbe number is 35 The following is preferable. The Abbe number being 35 or less means that “the average value of the Abbe numbers of all epoxy resins is 35 or less”, and an epoxy resin having an Abbe number exceeding 35 may be included. The curable resin composition for a low Abbe number preferably includes an epoxy resin component having an Abbe number of 45 or more, and the average value of the Abbe numbers of all epoxy resins is preferably 35 or less. On the other hand, if the epoxy resin component having an Abbe number of 45 or more, which is an essential component, is not included, the cation curing rate is not increased, and the productivity may not be sufficient. The proportion of the epoxy resin component having an Abbe number of 45 or more is preferably 1% by mass or more in 100% by mass of the epoxy resin component. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 20 mass% or more. By setting the Abbe number to 35 or less (the average value of the Abbe numbers of all epoxy resins is 35 or less), when the curable resin composition is used for optical applications, the optical properties can be improved. If the Abbe number exceeds 35, the wavelength dispersion of light may not be increased, sufficient optical characteristics may not be exhibited, and the material may not be suitable for various optical applications. Further, when the curable resin composition of the present invention is cured and used as an optical member (for example, a lens), the effect is remarkably exhibited when the Abbe is 35 or less. Specifically, by using the optical member (lens) having a low Abbe number in combination with a lens having a high Abbe number in the present invention, the effect of reducing light dispersion, increasing the resolution, and preventing bleeding is exhibited. . Such excellent optical characteristics become more prominent as the difference in Abbe number of the combined lenses increases. The difference in the Abbe number of the lens is preferably 20 or more, but generally the Abbe number of the lens is in the range of 20 to 70, and a lens having an Abbe number of 20 to 40 is the mainstream as a high Abbe number lens. Therefore, it is not easy to combine lenses having Abbe numbers different by 20 or more. In order to increase the Abbe number difference as much as possible, it is effective to reduce the Abbe number of a low Abbe number lens.
As described above, when a plurality of lenses are used in combination in optical applications, it is desirable that the difference in the Abbe number of the lenses is large. However, for example, when a lens having an Abbe number of 33.5 and a lens having an Abbe number of 36.3 are used, the difference between the Abbe numbers of these lenses is 2.8, but the difference is about 2.8. Even so, in optical applications, a significant difference in terms of effect occurs.

In the above epoxy resin, the Abbe number can be made 35 or less by appropriately combining suitable forms as described later. The Abbe number is preferably 35 or less, more preferably 34 or less, still more preferably 33.5 or less, and particularly preferably 30 or less. The epoxy resin is not particularly limited as long as it has an Abbe number of 35 or less (the average value of the Abbe numbers of all epoxy resins is 35 or less). For example, an epoxy resin having an Abbe number of 35 or less is 40% of all epoxy resins. It is preferably contained in an amount of not less than mass%. More preferably, the proportion of the epoxy resin having an Abbe number of 35 or less is 60% by mass or more, more preferably 80% by mass or more, and the upper limit is 99% by mass (substantially all having an Abbe number of 35 or less). It is.

Examples of the epoxy resin component having an Abbe number of 35 or less include a polyhydric phenol compound, a compound having a polymerizable unsaturated bond, and an aromatic epoxy (also referred to as “aromatic epoxy compound”) alone, or two or more kinds thereof. It can be used as a mixture. It is preferable to make the aromatic epoxy compound indispensable from the viewpoint that the optical properties can be excellent and it can be suitably used for various applications. Thus, the said curable resin composition which uses an aromatic epoxy compound as the said epoxy resin is also one of the preferable forms of this invention.
As content of the said aromatic epoxy compound, it is preferable that it is 60 mass% or more in 100 mass% of epoxy resin components. More preferably, it is 80 mass% or more. In addition, the upper limit of content is 99 mass%.
The Abbe number can be evaluated using a refractometer. For example, DR-M2 (refractometer, trade name, manufactured by Atago Co., Ltd.) is preferably used as the refractometer for evaluation at 20 ° C.

The thermosetting resin composition for molded bodies of the present invention may further contain a thermosetting resin other than an epoxy resin. Examples of the thermosetting resin other than the epoxy resin include a polyhydric phenol compound and a compound having a polymerizable unsaturated bond.
As the polyhydric phenol compound, those having a structure in which aromatic skeletons having at least one phenolic hydroxyl group are bonded via an organic skeleton having 2 or more total carbon atoms can be suitably used. . In the polyhydric phenol compound, the aromatic skeleton is an aromatic ring having at least one phenolic hydroxyl group. This aromatic skeleton is a moiety having a phenol type structure, and a phenol type, hydroquinone type, naphthol type, anthracenol type, bisphenol type, biphenol type, and the like are suitable. Of these, the phenol type is preferred. Further, these sites having a phenol type structure or the like may be appropriately substituted with an alkyl group, an alkylene group, an aralkyl group, a phenyl group, a phenylene group, or the like.

In the above polyhydric phenol compound, the organic skeleton means a part that binds the aromatic ring skeletons constituting the polyhydric phenol compound and requires carbon atoms. The organic skeleton having 2 or more carbon atoms preferably has a ring structure. The ring structure is a structure having a ring such as an aliphatic ring or an aromatic ring, and the ring is preferably a cyclopentane ring, a cyclohexane ring, a benzene ring, a naphthalene ring, an anthracene ring or the like. Furthermore, the organic skeleton preferably has a ring structure containing a nitrogen atom such as a triazine ring or a phosphazene ring and / or an aromatic ring, and particularly preferably has a triazine ring and / or an aromatic ring. The polyhydric phenol compound may have an aromatic skeleton or an organic skeleton other than those described above, and the aromatic skeleton having at least one phenolic hydroxyl group is an organic skeleton having 1 carbon atom (methylene ) May be simultaneously bonded.

The compound having a polymerizable unsaturated bond may be any compound having a polymerizable unsaturated bond, but one or more selected from the group consisting of a (meth) acryloyl group, a vinyl group, a fumarate group, and a maleimide group. It is preferable that it is a compound which has these groups. That is, it is preferably at least one compound selected from the group consisting of a compound having a (meth) acryloyl group, a compound having a vinyl group, a compound having a fumarate group, and a compound having a maleimide group. In the present invention, the (meth) acryloyl group means an acryloyl group and a methacryloyl group, and when it has an acryloyl group, it has a vinyl group in the acryloyl group. Does not have an acryloyl group and a vinyl group, but has an acryloyl group. The fumarate group means a group having a fumarate structure, that is, a group having a fumarate ester structure.

The curable resin composition for molded bodies of the present invention may further contain a non-curable component such as a thermoplastic resin. Moreover, what contains non-curable components, such as a thermoplastic resin, and a low molecular weight curable compound as a thermosetting resin can also be used. Examples of the thermoplastic resin include polyethylene, polypropylene, polystyrene, acrylonitrile / styrene copolymer (AS resin), ABS resin made of acrylonitrile / butadiene / styrene, vinyl chloride resin, (meth) acrylic resin, polyamide resin, and acetal resin. , Polycarbonate resin, polyphenylene oxide, polyester, polyimide and the like.
As the low molecular weight curable compound used in combination with these thermoplastic resins, a polyphenol compound, a compound having a polymerizable unsaturated bond, and an epoxy resin can be appropriately selected from the examples exemplified above. do it.
Moreover, when using together noncurable components, such as a thermoplastic resin, and a low molecular weight curable compound, the said thermosetting resin is 90 mass with respect to 100 mass% of curable resin compositions for molded objects. % Or more is preferable. More preferably, it is 95 mass% or more, More preferably, it is 98 mass% or more.

The curable resin composition for molded bodies of the present invention preferably further contains a curing agent.
Especially, it is preferable that the curable resin composition for molded objects of the present invention further contains a heat latent cationic curing catalyst.
Although the curing reaction proceeds in a short time by cationic curing, the curable resin composition for molded bodies of the present invention can sufficiently exhibit the effects of the present invention even under such conditions. it can.
Thermal latent cationic curing catalyst is also called thermal acid generator, thermal latent curing agent, thermal latent cation generator, cationic polymerization initiator, and the compound containing cationic species is excited by heating, and the thermal decomposition reaction is carried out. When it occurs and reaches the curing temperature, it exhibits a substantial function as a curing agent. Unlike the acid anhydrides, amines, phenolic resins, etc., which are generally used as curing agents, the heat latent cationic curing catalyst can be used even if it is contained in the resin composition. Resin composition with excellent handling properties that can exhibit excellent effects by sufficiently accelerating the curing reaction as an action of the heat-latent cationic curing catalyst without causing a significant increase in viscosity or gelation. Can be provided.
By using such a heat-latent cationic curing catalyst, for example, even when an epoxy resin that cures at room temperature is used, curing can be prevented from proceeding at room temperature. It becomes easy to handle. Moreover, the moisture resistance of the obtained molded body is dramatically improved, and the excellent optical properties of the molded body are maintained even in a harsh use environment, and can be suitably used for various applications. Normally, if moisture is contained in the resin composition or its molded product (cured product), the moisture causes turbidity due to its low refractive index, but if a heat-latent cationic curing catalyst is used, excellent moisture resistance is exhibited. Since it can do, such turbidity is suppressed and it can use suitably for optical uses, such as a lens. 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, but these phenomena occur in the presence of air and moisture. This is considered to be caused by the generation of oxygen radicals due to the effects of UV irradiation or heat ray exposure. Improved moisture resistance suppresses moisture absorption to the molded body, and also suppresses generation of oxygen radicals due to UV irradiation or heat ray exposure. Demonstrate.

The thermal latent curing catalyst is, for example, the following general formula (2);
_{^{(R 1 a R 2 b R}} 3 c R 4 d Z) + m (AXn) -m (2)
(Wherein, 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 a 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 a net charge of a halide complex ion. N is the number of halogen elements in the halide complex ion It is preferable that it is what is represented by this.

In general, the heat-latent cationic curing catalyst represented by the general formula (2) generates cations at the curing temperature. The curing temperature is preferably 25 to 250 ° C. More preferably, it is 60-200 degreeC, More preferably, it is 80-180 degreeC.
Further, as the curing condition, the curing temperature may be changed stepwise. For example, after maintaining at a predetermined temperature and time in a mold for the purpose of improving productivity in producing a cured product of the resin composition, the resin composition is taken out from the mold and left in an air or inert gas atmosphere. Heat treatment is also possible. In this case, the curing temperature is preferably 25 to 250 ° C. More preferably, it is 60-200 degreeC, More preferably, it is 80-180 degreeC. The holding time is preferably 10 seconds to 5 minutes, for example. More preferably, it is 30 seconds-5 minutes, More preferably, it is 1 minute-3 minutes.

Specific examples of the anion (AXn) ^-m of the general formula (2) include tetrafluoroborate (BF ₄ ⁻ ), hexafluorophosphate (PF ₆ ⁻ ), hexafluoroantimonate (SbF ₆ ⁻ ), hexafluoro Examples include arsenate (AsF ₆ ⁻ ) and hexachloroantimonate (SbCl ₆ ⁻ ).
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 examples of the thermal latent cationic curing catalyst include diazonium salt types such as AMERICURE series (manufactured by American Can), ULTRASET series (manufactured by Adeka), and WPAG series (manufactured by Wako Pure Chemical Industries); UVE series (general)・ Iodonium salt types such as 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); CYRACURE series (union) Carbide), UVI series (General Electric), FC series (3M), CD series (Satomer), Optomer SP series, Optomer CP series (Adeka), Sun Aid SI Over's (Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), sulfonium salt type such as CPI series (manufactured by San-Apro Ltd.).

The curable resin composition for molded bodies of the present invention is preferably one that is released with a strength (peeling strength) of 4 × 10 ⁻² N / m ² or less when cured and removed from the mold.
In the said curable resin composition for molded objects, when the mold is released with a strength of 4 × 10 ⁻² N / m ² or less, it can be easily peeled in the technical field and can be manufactured with high productivity in the manufacturing process. It means that it is evaluated that continuous production of a molded body can be performed. If the mold release strength exceeds 4 × 10 ⁻² N / m ² , it cannot be produced with good productivity and may not be excellent in economic efficiency. The peel strength is preferably 2 × 10 ⁻² N / m ² or less, more preferably 1 × 10 ⁻² N / m ² or less, and further preferably 1 × 10 ⁻³ N / m ² or less. Particularly preferably, it is 1 × 10 ⁻⁴ N / m ² or less.
The above-mentioned peel strength is a necessary condition for continuous production of a molded product, and is released at a temperature of 150 ° C. or less at which a side reaction occurs at a certain degree of material hardness (4 × 10 ⁻² N / m ² or less) in a short time. Preferably). Such peel strength (material hardness) can be evaluated as follows, for example. The resin composition is cured at a height of 1 mm in a SUS304 substrate shape at 140 ° C. for 2.5 minutes, cooled within 30 seconds at 30 ° C., and a cutter (manufactured by NT Corporation, body model number: L-) 500, the blade model number: BL-150P) can be pressed with a desired force (for example, a peel strength of 4 × 10 ⁻² N / m ² ) to evaluate the ease of release. The force with a peel strength of 4 × 10 ⁻² N / m ² is calculated as a value when a load of 1.5 kg is applied to the interface between the 2 cm long resin and SUS304 using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was set to 0.04 cm ² .

As a method for curing the curable resin composition for molded bodies of the present invention, various methods such as thermosetting can be suitably used. In addition, as described above, cationic curing is preferable because the effects of the present invention can be sufficiently exerted even under conditions in which the curing reaction proceeds in a short time. Further, as a molding method (curing method), it is preferable to cure by casting. For example, a curable resin composition for molded bodies is mixed with a curing agent and other materials as required to make one liquid, and the above mixed liquid is filled into a mold that matches the shape of the cured product (injection / coating) Then, a method of curing and then removing the cured product from the mold is preferably used. In the casting method, since the solvent is usually not used, the effect of the present invention is more fully exhibited.
In such a method, it is preferable that the viscosity of the curable resin composition for a curable molded body mixed with a curing agent or the like is not significantly increased in consideration of handling. As the viscosity that is easy to handle, for example, the viscosity of the curable resin composition for molded bodies after being stored at 25 ° C. for 3 days as compared to immediately after mixing is preferably 200% or less. If this viscosity exceeds 200%, filling of the liquid into the mold (injection / coating) may be difficult, and the fluidity in the mold may be adversely affected. More preferably, it is 180% or less, More preferably, it is 150% or less. Thus, a curable resin composition for molded bodies in which the rate of increase in viscosity of the mixture in one liquid is 200% or less after storage at 25 ° C. for 3 days is also a preferred embodiment of the present invention. One.

As a method for producing a cured product by curing the curable resin composition for molded bodies, a method usually used when curing a resin composition containing an epoxy resin can be suitably used. It can be set as a hardened | cured material by thermosetting using a hardening | curing agent. Although a manufacturing method can be selected suitably, what makes a hardening reaction of the above-mentioned curable resin composition for molded objects in a short time is preferred, and it is a method of making it harden within 5 minutes and manufacturing a hardened material. preferable. Specifically, the curable resin composition for molded bodies is mixed with a curing agent and other materials as required to form one liquid, and the mixed liquid is filled (injected) into a mold that matches the shape of the cured product.・ Coating) and curing within 5 minutes. By performing curing using a mold in a short time, when a compound having a boiling point of 260 ° C. or less is used as the above-mentioned specific compound, its evaporation is sufficiently suppressed and the effects of the present invention are sufficiently exhibited. It is possible to make the method excellent in economic efficiency.
Since the curable resin composition for molded bodies of the present invention can achieve both releasability and transparency even when curing in a short time, the effects of the present invention are more remarkably exhibited. In other words, the method can be economical.
When the curing time (curing time using a mold) exceeds 5 minutes, the compound having a boiling point of 260 ° C. or lower evaporates and is not substantially contained in the cured product. There is a risk that the effect of will not be fully demonstrated. Accordingly, the curing time is more preferably within 4 minutes, further preferably within 3.5 minutes, and most preferably within 3 minutes. Although it can set suitably as said hardening temperature according to the resin composition etc. to harden | cure, it is preferable that it is 80-200 degreeC. More preferably, it is 100-180 degreeC, More preferably, it is 110-150 degreeC. Specifically, it is preferable to cure at 140 ° C. for 3 minutes.
In the said hardening method, it should just be the hardness which can be taken out from a metal mold | die and can keep a shape, and the rate of a shape change when it extrudes with the force of 1 * 10 < ^-3 > N / m < ² > or more is 10% or less of hardening strength (Hardness) is preferred. The ratio of the shape change is preferably 1% or less, more preferably 0.1% or less, and still more preferably 0.01% or less.

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

The resin composition of the present invention may further contain an additive in addition to the above-mentioned resin. Examples of the additive include a curing accelerator, a reactive diluent, a saturated compound having no unsaturated bond, and a pigment. , Dyes, antioxidants, UV absorbers, light stabilizers, plasticizers, non-reactive compounds, chain transfer agents, thermal polymerization initiators, anaerobic polymerization initiators, polymerization inhibitors, inorganic fillers and organic fillers, cups Adhesion improvers such as ring agents, heat stabilizers, antibacterial / antifungal agents, flame retardants, matting agents, antifoaming agents, leveling agents, wetting / dispersing agents, antisettling agents, thickeners / sagging agents, Contains anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, desiccant, IR (infrared) cut agent, antifouling agent, antistatic agent, conductive agent (electrostatic aid) Good.

Hereinafter, the method for curing the resin composition of the present invention will be described. For curing the resin composition of the present invention, a conventionally known method can be employed depending on the properties of the resin used.
As described above, the epoxy resin of the resin composition of the present invention can be cured by thermosetting using a curing agent. As the curing agent, it is preferable to use the above-described thermal latent curing catalyst thermal latent cationic curing catalyst. Examples of curing agents other than the heat latent cationic curing catalyst include acid anhydrides such as methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, pyromellitic anhydride, and methylnadic acid; Various phenol resins such as phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, dicyclopentadiene phenol resin, phenol aralkyl resin, terpene phenol resin; various phenols and various such as hydroxybenzaldehyde, crotonaldehyde, glyoxal Various phenol resins such as a polyhydric phenol resin obtained by a condensation reaction with aldehydes; one or more of BF ₃ complexes, sulfonium salts, imidazoles and the like can be used. Moreover, the said epoxy resin can also be hardened with a polyhydric phenol compound.

In curing the curable resin composition for molded bodies containing the epoxy resin, a curing accelerator can be used. For example, triphenylphosphine, tributylhexadecylphosphonium bromide, tributylphosphine, tris (dimethoxyphenyl) One or more of organic phosphorus compounds such as phosphine are suitable. As said hardening temperature, 70-200 degreeC is preferable. More preferably, it is 80-150 degreeC.

In curing the resin composition containing the epoxy resin, the above-described additives may be further added and cured.
The resin composition of this invention can obtain a molding by the hardening method mentioned above.
This invention is also a molded object formed by shape | molding the curable resin composition for molded objects mentioned above.
The preferable forms of the raw material, the curing method, etc. of the molded body of the present invention are the same as the above-mentioned preferable forms in the curable resin composition for molded bodies of the present invention.

The molded product of the present invention is excellent in various optical characteristics. For example, the turbidity of the molded body is preferably 20% or less. Thus, the resin composition in which the turbidity of the cured product of the resin composition is 20% or less is also a preferred embodiment of the present invention. More preferably, it is 18% or less, More preferably, it is 15% or less. The turbidity of the molded body is preferably 5% or less. More preferably, it is 2% or less, More preferably, it is 1% or less.
As transparency, it is preferable that the light transmittance in the visible light region (region having a wavelength of 360 to 780 nm) of the molded body is 75% or more. More preferably, it is 80% or more, More preferably, it is 85% or more, Most preferably, it is 87% or more.
In the above molded body, a wide range of numerical values is required for the refractive index and Abbe number of the molded body depending on the optical design of the applied optical system. The light transmittance of the cured product can be measured by a method according to JIS K7361-1, the turbidity can be measured by JIS K7136, and the refractive index / Abbe number can be measured by a method according to JIS K7142.
The moisture absorption rate (saturated absorption rate in air at 30 ° C. and 40% relative humidity) after the PCT (pressure cooker test) of the molded body varies depending on the curing conditions, but by optimizing the curing conditions. It is preferable to make it 1.0% or less. More preferably, it is 0.5% or less, More preferably, it is 0.2% or less.

Regarding the heat resistance of the molded article, it is preferable that the appearance does not change at all such as the occurrence of cracks, and the change rate of total light transmittance / turbidity is 20% or less. More preferably, it is 15% or less, More preferably, it is 10% or less.

The present invention is a method for producing a molded body from a curable resin composition for molded bodies containing an epoxy resin, wherein the production method further comprises a silicon compound having a polyoxyalkylene chain and / or an aryl group. It is also the manufacturing method of a molded object including the process of shape | molding the curable resin composition for molded objects contained as.
The preferable forms of the raw material, reaction conditions, etc. of the manufacturing method of the molded object of this invention are the same as the preferable form mentioned above in the curable resin composition for molded objects of this invention, and a molded object.

As described above, the molded article exhibits excellent optical properties such as transparency, and can be suitably used for various applications such as optical applications, optical device applications, display device applications, and the like. Specifically, eyeglass lenses, camera lenses, filters, diffraction gratings, prisms, light guides, light beam condensing lenses and light diffusion lenses, watch glasses, transparent glasses such as cover glasses for display devices, cover glasses, etc. Optical applications; Photosensors, photoswitches, LEDs (Light Emitting Diodes), light-emitting elements, optical waveguides, multiplexers, duplexers, disconnectors, optical splitters, optical fiber adhesives, etc .; Liquid crystal display (LCD), organic EL (Electro Luminescence), PDP (Plasma Display Panel) and other display element substrates, color filter substrates, touch panel substrates, display protective films, display backlights, light guide plates, antireflection films, anti-reflection films A display device such as a cloudy film is suitable.
The shape of the cured product can be appropriately set depending on the application, and is not particularly limited. Examples of the shape of the molded product such as a deformed product, a film, a sheet, and a pellet are also included.
Moreover, since the curable resin composition for molded bodies of the present invention is excellent in releasability, a cured product having a large surface area per unit volume is preferable. The surface area relative to the unit volume in the cured product is preferably (surface area) / (unit volume) = 0.1 mm ² / mm ³ or more, for example. More preferably, it is not ^{1 mm} 2 / mm ³ or more, still more preferably ^{3 mm} 2 / mm ³ or more. Moreover, a preferable upper limit is 100 mm < ² > / mm < ³ >. Thereby, the effect of this invention is exhibited notably. More preferably, the ratio of mold release surface area (mm ² ) / unit volume (mm ³ ) is in the above range. In addition, the said mold release surface area (mm < ² >) means the area which the metal mold | die and hardened | cured material are contacting after taking out from a metal mold | die after hardening of a resin composition.
Examples of the cured product having a large surface area relative to the volume include a minute cured product and a thin film.
Moreover, since it is excellent in optical properties such as transparency, it is suitable for applications such as lens molding, and is particularly suitable for applications such as micro optical systems. Examples of the micro optical system include an imaging lens for a mobile phone, a digital camera, and a pickup lens. Since such a molded body is prepared by fine processing, curing is completed in a short time. In the curable resin composition for molded bodies according to the present invention, the effect of the present invention is more remarkably exhibited because both mold release and transparency can be achieved even when curing is performed in a short time. Will be. Further, when a specific compound includes a compound having a boiling point of 260 ° C. or less under 1 atm, evaporation of this compound can be suppressed, and the effects of the present invention can be exhibited more remarkably.

The curable resin composition for molded bodies, the molded body and the production method thereof according to the present invention have the above-described configuration, and the molded body has excellent basic performance such as heat resistance, and also has releasability when taken out from the mold. Curable resin composition for molded body, molded body, which can be compatible with optical properties such as transparency, and is useful as an optical application, an optical device application, a display device application, a machine part material, an electric / electronic part material, etc. It is the manufacturing method.

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

Example 1
Preparation of curable resin composition for molded body In a four-necked flask equipped with a gas inlet, a cooling tube, and a stirring rod, a liquid epoxy resin CELL-2021P as an epoxy resin (alicyclic epoxy resin, trade name, Daicel Chemical Industries, Ltd.) 30 parts), EHPE-3150 (alicyclic epoxy resin, trade name, Daicel Chemical Industries, Ltd.) 20 parts, and Ogsol EG210 (aromatic epoxy resin, trade name, Osaka Gas Chemical Co., Ltd.) 45 parts Then, 0.5 part of stearic acid was charged as a release agent, and stirred well at 130 ° C. to make it uniform. Thereafter, 5 parts of KF-56 (straight silicone oil [parting agent] in which part of the side chain of the polysiloxane dissolved in the epoxy resin is a phenyl group, trade name, manufactured by Shin-Etsu Silicone Co., Ltd.) as a silicon compound was added, Stirred uniformly.
A compound having a boiling point of 260 ° C. or lower under 1 atm was added at 70 ° C. after adding a release agent, and further stirred uniformly. After cooling the obtained liquid to 40 ° C., Sun Aid SI-80L (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) as a heat latent cationic curing catalyst was added so as to be 0.6 parts with respect to the total weight. And mixed uniformly to obtain a preparation.

Preparation of molded body The resin composition (hereinafter, also referred to as preparation liquid) prepared as described above is heated at 50 ° C. as necessary to perform degassing under reduced pressure, and poured into a mold at 140 ° C. Curing for 3 minutes was performed. And the hardened | cured material was made to peel from a metal mold | die and it took out, and the casting board (coating film) with a thickness of 250 micrometers which is a molded object was obtained.
The composition of the resin composition in Example 1 is shown in Table 3 below.

Various physical properties were measured by the following methods using the preparation solution and the molded body (casting plate).
Physical properties <Releasability>
The molded product according to the present invention is required to achieve a certain degree of material hardness in a short time at a temperature of 250 ° C. or lower at which a side reaction occurs, as a necessary condition for continuous production of the molded product. Therefore, the prepared solution was applied on a SUS304 substrate to a height (thickness) of 1 mm using an applicator and cured under conditions of 140 ° C. and 2.5 minutes. Then, a cutter (manufactured by NT, body model number: L-500, blade model number: BL-150P) is applied to the interface between the cured resin (coating film) and the SUS304 substrate with a force of 4 × 10 ⁻² N / m ² . The resin cured by pressing was peeled off, and the ease of peeling was evaluated to evaluate the releasability.
The force of peel strength 4 × 10 ⁻² N / m ² applies a load of 1.5 kg to the interface between the SUS304 substrate and the resin with a height (thickness) of 1 mm and a length of 2 cm formed on the SUS304 substrate. It is calculated as the value when added using a cutter. In addition, the area where the load of the blade edge of the cutter is applied was 0.04 cm ² . Moreover, the width | variety of a coating film is 2 cm, and the ratio (surface area) / (volume) of a mold release surface area and unit volume is 1 mm < ² > / mm < ³ >.
Evaluation of releasability was performed in the following 8 stages.
8 (strong, difficult to remove)>7>6>5>4>3>2> 1 (weak, easy to peel)
That is, in the above test, the lower the numerical value, the better the releasability. If the evaluation rank is a numerical value of 7 or less, it is a level that can be applied to optical applications as an optical product such as a lens that requires a precise surface shape on the order of several μm. Continuous production of the optical product Was judged to be a possible level.

<Transparency>
Transparency refers to the haze value at 25 ° C. of the resin composition (preparation solution) before curing and the resin composition (cured product) after curing using a turbidimeter (Nippon Denshoku Co., Ltd., NDH2000). Transmittance) was measured and evaluated in five stages as follows. In addition, those in which turbidity that was clearly unsuitable for optical use was visually observed were described in the table below together with the liquid turbidity for the prepared liquid and the solid turbidity for the cured product, together with the following evaluation. Moreover, if the rank of the said evaluation was a numerical value of 4 or less, it was judged that it was a level applicable to an optical use as optical products, such as a lens by which the precise | minute surface shape in order of several micrometers is requested | required.
(Preparation solution): The preparation solution was poured into a cell having an optical path length of 1 cm, and haze was measured using the turbidimeter.
(Hardened product): The haze of the 250 μm-thick molded body was measured using the turbidimeter.
(Evaluation): In consideration of the haze values of both the prepared solution and the cured product measured as described above, transparency was evaluated in five stages as follows.
5 (cloudy)>4>3>2> 1 (transparent)

<Viscosity>
The measurement of the viscosity was performed on the resin composition before adding the curing agent using an R / S rheometer (manufactured by Brookfield, USA) under the conditions of 40 ° C. and rotation speed D = 1 / s. An RC25-1 measuring jig was used at a viscosity of 20 Pa · s or more, and an RC50-1 jig was used at a viscosity of less than 20 Pa · s.
Moreover, about the thing whose viscosity at the rotational speed D = 1 / s cannot be measured, the value of rotational speed D = 5-100 / s was extrapolated and evaluated as the viscosity of a resin composition.

<Evaluation of refractive index and Abbe number>
The refractive index and Abbe number were measured in accordance with JIS K7142, and the following methods were used.
The refractive index was measured for the cured product (molded product having a thickness of 250 μm) using a refractometer (Atago Co., Ltd., DR-M2) at a measurement wavelength of 486 nm, 589 nm, and 656 nm at 20 ° C. .
The Abbe number was measured on the cured product (molded product having a thickness of 250 μm) using a refractometer (DR-M2 manufactured by Atago Co., Ltd.) at 20 ° C.
The measurement and evaluation results of the various physical properties described above are shown in Table 4 below.

Also in Examples 2 to 21, the composition and the like of the resin composition were changed as shown in Table 3 below. And other than that was carried out similarly to Example 1, and prepared the curable resin composition for molded objects, and a molded object, and measured various above-mentioned physical properties. The obtained evaluation results are shown in Table 4 below.

Examples 22-42
A compound having a specific boiling point was used in addition to the silicon compound having a specific organic group, and the composition of the resin composition was as shown in Table 5. And other than that was carried out similarly to Example 1, and prepared the curable resin composition for molded objects, and a molded object, and measured various physical properties mentioned above.
The obtained evaluation results are shown in Table 6 below.

For the molded bodies of Examples 30, 32, 38, and 42 described above (curing conditions: 1 mm thick resin composition was cured at 140 ° C. for 2.5 minutes), pyrolysis GC-Mass spectrum measurement was performed. The equipment and measurement conditions used for the measurement are shown below.
(apparatus)
GC-Mass: Polaris Q manufactured by ThermoQuest
Thermal decomposition apparatus: PY2020D manufactured by Frontier Lab
(conditions)
Thermal decomposition temperature: 260 ° C., gas: He 1 ml / mm
Column (0.25 mm inner diameter × 30 m, film thickness 0.25 μm, TRACE ^™ TR-5MS GC column)
(result)
In the molded bodies of Examples 30, 32, 38, and 42, silicon was confirmed by elemental analysis. In addition, peaks of dodecanol, stearic acid, and epoxy decomposition product were observed. From this measurement result, in the molded bodies of Examples 30, 32, 38 and 42, in addition to the silicon compound having a specific organic group in the present invention, a compound having a specific boiling point, a release agent, and thermosetting It became clear that a functional resin was contained. As is apparent from Table 6, the molded bodies of Examples 30, 32, 38, and 42 are excellent in releasability.

Comparative Examples 1-15
Table 7 shows the composition of the resin composition without using the specific silicon compound in the present invention. And other than that was carried out similarly to Example 1, and prepared the curable resin composition for molded objects, and a molded object, and measured various physical properties mentioned above.
In addition, the silicon compound which does not melt | dissolve in a thermosetting resin was prepared similarly to an epoxy resin, and it stirred uniformly at 130 degreeC, and was made uniform.
The obtained evaluation results are shown in Table 8 below.

Examples 43 and 44
In addition to the silicon compound having a specific organic group, a compound having a specific boiling point was used, and the composition of the resin composition was as shown in Table 9. As a silicon compound having a specific organic group, in Example 43, BYK-333 (manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane solution) is used, and in Example 44, BYK-307 (Big Chemie Japan, Inc.) is used. Manufactured, polyether-modified polydimethylsiloxane). As a compound having a specific boiling point, octanol was used. Otherwise, the curable resin composition for molded bodies and the molded body were prepared in the same manner as in Example 1, and various physical properties described above were measured. The obtained evaluation results are shown in Table 9 below.

In addition, in the following Table 3-Table 9, the numerical value in () represents a mass part. The “melting point” means the melting point of the curable resin composition for molded bodies. Furthermore, abbreviations and trade names represent the following.

(Silicon compound having an aryl group and / or a polyalkylene glycol chain)
KF-56 (trade name, straight silicone oil in which part of the side chain of polysiloxane is a phenyl group [release agent], weight average molecular weight 1.75 × 10 ³ , manufactured by Shin-Etsu Silicone)
KF-6004 (trade name, modified silicone oil introduced with an organic group having a polyoxyethylene chain and a polyoxypropylene chain at both ends [release agent], weight average molecular weight 7.7621 × 10 ⁴ , manufactured by Shin-Etsu Silicone Co., Ltd. )
HIVAC-F-4 (trade name, straight silicone oil in which part of the side chain of polysiloxane is a phenyl group [release agent], weight average molecular weight 1.51 × 10 ³ , manufactured by Shin-Etsu Silicone)
BYK-333 (trade name, manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane solution [siloxane compound])
BYK-307 (trade name, manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane [siloxane compound])

(Compound having a boiling point of 260 ° C. or less under 1 atm)
MEK: Methyl ethyl ketone (thermal latent cationic curing catalyst)
SI-80L: Sun-Aid SI-80L (thermal latent cationic curing catalyst [aromatic sulfonium salt], trade name, manufactured by Sanshin Chemical Industry Co., Ltd.)
SI-100L: Sun-Aid SI-100L (thermal latent cationic curing catalyst [aromatic sulfonium salt], trade name, manufactured by Sanshin Chemical Industry Co., Ltd.)
(Epoxy resin)
CELL-2021P (alicyclic epoxy resin, trade name, manufactured by Daicel Chemical Industries)
Celoxide 2081 (alicyclic epoxy resin, trade name, manufactured by Daicel Chemical Industries)
EHPE-3150 (alicyclic epoxy resin, trade name, manufactured by Daicel Chemical Industries)
Ogsol EG210 (Aromatic epoxy resin (fluorene epoxy compound), trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
Ogsol PG100 (Aromatic epoxy resin (fluorene epoxy compound), trade name, manufactured by Osaka Gas Chemical Co., Ltd.)
JER828EL (Aromatic epoxy resin (bisphenol A epoxy resin), trade name, manufactured by Japan Epoxy Resin Co., Ltd.)
(Silicon compound that does not dissolve in thermosetting resin)
KS-707 (trade name, solution type silicone oil, manufactured by Shin-Etsu Silicone)
KF-96 (trade name, oil type silicone oil, manufactured by Shin-Etsu Silicone)
KF-412 (trade name, oil type silicone oil, manufactured by Shin-Etsu Silicone)
KF-53 (trade name, straight silicone oil in which part of the side chain of polysiloxane is a phenyl group, manufactured by Shin-Etsu Silicone)
KF-54 (trade name, straight silicone oil in which part of the side chain of polysiloxane is a phenyl group, weight average molecular weight 2.27 × 10 ⁴ , manufactured by Shin-Etsu Silicone)
X-22-169AS (trade name, both-end type / alicyclic epoxy-modified silicone oil introduced with an alicyclic epoxy skeleton at both ends, weight average molecular weight 6.85 × 10 ³ , manufactured by Shin-Etsu Silicone)
X-22-163 (Brand Name, Both End Type / Epoxy Modified Silicone Oil Introduced with Aliphatic Epoxy Skeleton at Both Ends, Weight Average Molecular Weight 1.15 × 10 ⁵ , Shin-Etsu Silicone)
SF 8421 (trade name, silicone oil, manufactured by Toray Dow Corning Silicone)

(Dispersant)
PLACCEL FM-1 (manufactured by Daicel Chemical Industries, Ltd.)
(Radical curing catalyst)
Purptil O (trade name, manufactured by NOF Corporation, radical generator)

From the examples and comparative examples described above, it was found that the critical significance of the numerical range of the present invention can be said as follows. That is, the curable resin composition for a molded body contains a silicon compound having a polyoxyalkylene chain and / or an aryl group as an essential component, so that it is possible to achieve both releasability and optical properties such as transparency. It was found that the effect was excellent and the effect was remarkable. Furthermore, since an epoxy resin excellent in basic performance such as heat resistance is used as a thermosetting resin, the above-mentioned curable resin composition for molded bodies has basic performance such as heat resistance in addition to the above characteristics. It is clear that

Further, when Example 7 using a silicon compound having a polyoxyalkylene chain and / or an aryl group is compared with Comparative Example 2 not containing this compound, in Example 7, the releasability is 2. On the other hand, in Comparative Example 2, the releasability is 8.
Thus, in Example 7, it is a level which can manufacture a molded object continuously, but in Comparative Example 2, a molded object cannot be manufactured continuously.

Moreover, when Example 6 using a specific silicon compound is compared with Comparative Examples 6 to 9 using a silicon compound that does not dissolve in a thermosetting resin, Example 6 has a releasability of 6 and is transparent. However, in Comparative Examples 6 to 9, the resin solution is turbid and inferior in transparency.
Thus, it is clear that the silicon compound to be blended in the curable resin composition in the present invention has both releasability and transparency by using a silicon compound having a specific organic group. .

In Examples 1 to 21, as long as a silicon compound having a polyoxyalkylene chain and / or an aryl group is included, it is compatible with the resin composition and sufficient optical properties such as transparency are obtained. The mechanism that can also exert the releasing action is the same. Therefore, it can be said that if the resin composition contains a silicon compound having a polyoxyalkylene chain and / or an aryl group, the advantageous effects of the present invention are manifested.
Further, when Example 9 containing only a specific silicon compound is compared with Example 30 containing a specific silicon compound and a compound having a specific boiling point, the release property is improved in Example 30. it is obvious. The same applies to Example 10 and Example 29, Example 12 and Example 29, Example 10 and Example 30. Thereby, in this invention, it can be said that a mold release property further improves by including both the specific silicon compound and the compound with a specific boiling point.

Moreover, in the Example mentioned above, as a silicon compound which has a polyoxyalkylene chain and / or an aryl group, the silicon compound which has a phenyl group or the silicon compound which has an organic group which has a polyoxyethylene chain and a polyoxypropylene chain is used. As long as it is a silicon compound having a polyoxyalkylene chain and / or an aryl group, it is compatible with the resin composition and has a releasing action after sufficient optical properties such as transparency. The mechanism that can fully exhibit is the same. Therefore, if a silicon compound having a polyoxyalkylene chain and / or an aryl group is contained, it can be said that the advantageous effects of the present invention are surely exhibited. In the case where at least a silicon compound having a polyoxyethylene chain and / or a phenyl group is contained, the advantageous effects of the present invention are sufficiently demonstrated by the above-described examples and comparative examples, and the technical significance of the present invention is supported. It has been.

In view of the above, the curable resin composition of the present invention is industrially produced as a molded product and used in applications such as optical applications, optical device applications, display device applications, mechanical component materials, and electrical / electronic component materials. It is clear that it has the outstanding effect of being able to.

In the examples and comparative examples described above, stearic acid is used as a release agent. However, as long as it is a release agent, the release agent has a release agent by being transferred more quickly to the surface layer of the resin composition. The mechanism that can fully exhibit the mold action is the same. Therefore, if the release agent contains a compound having a boiling point of 260 ° C. or higher, it can be said that the advantageous effects of the present invention are surely exhibited. At least in the case of preparing a molded body using a compound having a boiling point exceeding 260 ° C. as the release agent, the advantageous effects of the present invention are sufficiently demonstrated by the above-described examples and comparative examples, and the technology of the present invention. The significance is supported.

Claims (8)

A curable resin composition for a molded body containing an epoxy resin,
The curable resin composition for molded bodies further contains a silicon compound having a polyoxyalkylene chain and / or an aryl group as an essential component. The curable resin composition for molded bodies according to claim 1, wherein the silicon compound is a polysiloxane compound having a structural unit derived from disubstituted siloxane. The curable resin composition for molded bodies according to claim 1 or 2, wherein the silicon compound has a weight average molecular weight of 500 or more and 100,000 or less. The curable resin composition for molded bodies according to any one of claims 1 to 3, wherein the curable resin composition for molded bodies further contains a compound having a boiling point of 260 ° C or lower under 1 atm. object. The curable resin composition for molded bodies according to any one of claims 1 to 4, wherein the curable resin composition for molded bodies further contains a thermal latent curing catalyst. A molded body obtained by molding the curable resin composition for molded bodies according to claim 1. A molded product comprising a silicon compound having a polyoxyalkylene chain and / or an aryl group, and / or a compound having a boiling point of 260 ° C. or less under 1 atm. A method for producing a molded body from a curable resin composition for molded bodies containing an epoxy resin,
The production method includes a step of molding a curable resin composition for a molded product, which further contains a silicon compound having a polyoxyalkylene chain and / or an aryl group as an essential component. .