JP2009299074A - Curable resin composition for molded body, molded body and method for producing same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition for molded bodies which is excellent in basic performances such as heat resistance, allows molded bodies to have sufficient optical properties such as transparency, and is excellent in mold release characteristics in removing molded bodies from molds during molding, and to provide a molded body molding the composition and a method for producing the same. <P>SOLUTION: The curable resin composition for molded bodies includes a thermosetting resin. The curable resin composition for molded bodies includes a compound having a boiling point of 260°C or below under one atm. as an essential component. <P>COPYRIGHT: (C)2010,JPO&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 the digital camera module is mounted on a mobile phone or the like, the size of the digital camera module has been reduced and the cost has been reduced. Therefore, instead of the conventionally used inorganic glass, polymethyl methacrylate, polycarbonate, The adoption of lenses made of plastic materials such as polycycloolefins 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 applying to these applications, considering the high temperature exposure in summer, etc., long-term heat resistance, that is, heat resistance superior to conventional plastic materials, is required. 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, the thermosetting resin composition obtained by such a production method cannot provide sufficient transparency that can be used in optical applications and the like. 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. In addition, 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, and thickening suppression effect. In addition, there has been room for improvement to sufficiently improve the optical characteristics such as transparency after preventing the mixing of impurities during mixing of the bead mill. 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. In addition, it has been desired to produce a molded body with high productivity by improving the releasability when taking out the cured product from the mold. Furthermore, since transparency and releasability have a contradictory relationship in which when one is increased, the other is decreased, there is room for improvement.
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. 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 Unexamined Patent Publication 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 can have sufficient optical properties such as transparency, and at the time of molding, when taken out from a mold. It is an object of the present invention to provide a curable resin composition for molded bodies that can be excellent in releasability, a molded body formed by molding the same, and a method for producing the same.

The inventors of the present invention have studied variously about a curable resin composition for molded bodies that is excellent in basic performance such as heat resistance, and as a curable resin composition for molded bodies containing a specific compound as an essential component, It has been 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. Moreover, by using such a resin composition, the obtained molded body has not only high basic performance such as strength and heat resistance, but also sufficient optical properties such as Abbe number and refractive index. It has been found that the resin composition is excellent in transparency and can be suitably used for optical applications. Moreover, in such a resin composition, it discovered that the effect of a mold release agent can be improved significantly by using a mold release agent together. Furthermore, the curable resin composition for molded bodies of the present invention has a heat resistance that cannot be achieved by a thermoplastic resin alone, and it has been conceived that the above problems can be solved brilliantly. Such resin compositions are used in various applications such as optical applications such as lenses, optical device applications, display device applications, mechanical component materials, electrical / electronic component materials, automotive component materials, civil engineering and building materials, and molding materials. It has also been found that it can be suitably applied.

It has also been found that in mold molding in which a resin composition is cured by using a mold, the followability of the resin composition to the mold is improved. In mold molding, particularly when lens molding or the like is performed, it is important to prevent the molded body from swelling, and in order to prevent this swelling, followability of the resin composition to the mold is required. The inventors of the present invention can improve the followability of the resin composition to the mold at the time of mold molding as described above by including the specific compound in the curable resin composition for molded bodies. As a result, it was found that the curable resin composition for molded bodies of the present invention can be suitably used for lens molding and the like, because the swelling of the molded body can be prevented thereby. The specific compound can also be used as a solvent. In the conventional mold molding using a curable resin composition for molded bodies, a solvent is not usually added in order to give the resin composition followability to the mold. Is not substantially contained.
Furthermore, when this curable resin composition for molded bodies is applied to a system where curing is completed in a short time, such as in the production of micromolded bodies having a minute shape, molding is performed while preventing evaporation of the specific compound. It has also been found that a specific compound can be contained in the body, whereby the releasability from the mold can be further improved. The curable resin composition for molded bodies of the present invention has been found to be useful particularly for imaging lenses such as for mobile phones and digital cameras, and for micro-optical systems such as pick-up lenses, and has reached the present invention. is there.

That is, the present invention is a curable resin composition for molded bodies containing a thermosetting resin, and the curable resin composition for molded bodies includes a compound having a boiling point of 260 ° C. or less under 1 atmosphere. 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 compound having a boiling point of 260 ° C. or less at 1 atm in the molded article obtained from the curable resin composition for molded articles.
The present invention further relates to a method for producing a molded body from a curable resin composition for molded bodies containing a thermosetting resin, wherein the production method essentially comprises a compound having a boiling point of 260 ° C. or less under 1 atm. 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, in order 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 compound or the like so as to achieve the effects of the present invention.
The present invention is described in detail below.

In the curable resin composition for molded bodies of the present invention, a thermosetting resin is contained, and a compound having a boiling point of 260 ° C. or less under 1 atm is further contained as an essential component. Hereinafter, a compound having a boiling point of 260 ° C. or less under 1 atm is sometimes referred to as “a compound having a specific boiling point” or “a specific compound”. A specific compound may be used independently and may be used in combination of multiple.
The curable resin composition for molded bodies of the present invention can improve releasability when taking out a cured product from a mold in mold molding by further containing such a specific compound as an essential component. Thus, the operational effects of the present invention are fully 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, it easily changes its state when heated. That is, it is a compound that is easily vaporized and is likely 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.

In the above-described mold molding, a mold release agent is used to improve the mold release property. The release agent is compatible with the resin component, and preferably exhibits the above-described bleed-out and exhibits release properties upon curing. The faster the bleed-out speed of the release agent, the shorter the release time. Therefore, productivity can be improved.
In the present invention, when the compound having a specific boiling point described above is contained in the resin composition, when the compound causes bleed-out, the mold release agent also exhibits an action of transferring to the surface layer side of the mold. As a result, the bleed-out speed of the release agent is increased, and even in the case of curing in a short time, the release property can be sufficiently exhibited to improve the productivity. Further, it is considered that the release agent is more likely to be manifested on the surface layer side of the mold, so that the effect of the release agent is more easily exhibited. Furthermore, since the mold release property of the mold release agent is improved, the amount of the mold release agent used can be reduced.
As described above, the compound having the specific boiling point can remarkably enhance the effect of the release agent, and a preferable form of the release agent used together with the compound will be described later.

As described above, the compound having a boiling point of 260 ° C. or lower under 1 atm has optical characteristics such as transparency while maintaining basic performance such as heat resistance in the curable resin composition for molded bodies of the present invention. It is excellent and can improve the releasability when cured and taken out from the mold. As a result, the curable resin composition for molded bodies of the present invention is excellent in basic properties such as heat resistance and optical characteristics such as transparency when formed into molded bodies, and when cured and taken out from the mold. Since is excellent in releasability, a molded body can be continuously produced with high productivity in the production process.

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. Preferred are at least one compound selected from the group consisting of these compounds, selected from the group consisting of alcohols, polyhydric alcohol derivatives, carboxylic acid esters and ketones. More preferably, it is at least one, and carboxylic acid esters and ketones are particularly preferable.
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 a specific boiling point has a function as a solvent for the thermosetting resin, and therefore, as described above, it produces a bleedout that migrates to the surface layer of the molded body and exhibits releasability and the like. It is done.
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 when the heat defoaming treatment is performed 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. The total number of carbon atoms is preferably 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. The total carbon number of the alcohol is more preferably 2 to 12, and still more preferably 3 to 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.

Of 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 still more preferably 3 to 12. In consideration of compatibility with the resin composition, the total carbon number is preferably 3 to 8. Considering an 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.

In the present invention, the compound having a boiling point of 260 ° C. or lower under 1 atm is preferably 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 content of the compound having a specific boiling point is less than 0.01% by mass, the effect of improving the releasability, which is the effect of adding the compound, may not be sufficiently exhibited, and the content is If it exceeds 5% by mass, the followability of the resin composition to the mold will be impaired at the time of molding the mold, and the molded body will be swollen and used as an optical molded body. It is because there exists a possibility that the homogeneity as a molded object may be lost. The content of the compound having a specific boiling point is more preferably 0.05% by mass or more and 4% by mass or less, and further preferably 0.1% by mass or more and 3% by mass or less.

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. In addition, as described above, when the curable resin composition for a molded body is cured using a mold, the compound having a specific boiling point increases the bleeding-out speed of the mold release agent, so that the effect of adding the mold release agent is increased. Will be demonstrated more. As a result, the cured product (molded product) can be easily peeled off from the mold, and the appearance can be controlled without causing damage to the surface of the cured product to further develop transparency. The obtained molded body is particularly useful as a material in electrical / electronic component materials and optical applications.
The release agent is a release agent usually used in the technical field and may be any one that dissolves (compatible) or disperses in the thermosetting resin, but dissolves (compatible) in the thermosetting resin. What can be done is 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 of more than 260 ° C. under 1 atm, and any one of the following forms (1) to (4): One or a combination thereof is preferred.

(1) The mold release agent has at least one compound selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylates and carboxylic anhydrides as an essential component. (2) The said mold release agent is a solid form at 20 degreeC. (3) The said mold release agent is a form which uses a silicon compound as an essential component. (4) The release agent includes a substance having a weight molecular weight of 500 or more and 100,000 or less.

Hereinafter, the modes (1) to (4) will be described in detail.
In the form of (1) above, the release agent contains at least one compound selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylates and carboxylic anhydrides as an essential component. It is. In this form, it is more preferable that the release agent contains at least one compound selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters and carboxylates as an essential component. It is more preferable that at least one compound selected from the group consisting of acid esters is an essential component, and a form having a carboxylic acid as an essential component is particularly preferable.

Further, the release agent is at least one compound selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylates and carboxylic anhydrides, and has a total carbon number of 13 or more. It is preferable that The total carbon number is more preferably 15 or more, and still more preferably 18 or more. The upper limit of the total carbon number is, for example, preferably 36, more preferably 24, and still more preferably 20.
By having the total number of carbons in such a range, if the compound has a certain amount of long chains, the effects of the present invention will be exerted, and the basic performance such as heat resistance and the optical properties such as transparency will be impaired. And excellent peelability can be exhibited. Moreover, the said compound which has such a carbon number is comparatively easy to acquire, and is excellent also in economical efficiency.
In addition, the structure of these compounds may be any structure such as linear, branched, and cyclic, but the linear structure is particularly preferable.

Moreover, in the above-described compound, it is more preferable that the release agent has a boiling point exceeding 260 ° C. under 1 atm and has the following total carbon number. That is, the compound having 13 or more carbon atoms (B-1); a carboxylic acid having 10 or more carbon atoms, a carboxylate having 6 or more carbon atoms, and a carboxylic acid anhydride having 8 or more carbon atoms in total ( It is preferable that at least one compound selected from the group (B-1 to B-3) consisting of B-2); a carboxylic acid ester having 13 or more total carbon atoms (B-3); These compounds can preferably contain one type or two or more types in the release agent.

Hereinafter, alcohols having 13 or more carbon atoms (B-1); carboxylic acids having 10 or more carbon atoms, carboxylates having 6 or more carbon atoms, and carboxylic acid anhydrides having 8 or more carbon atoms (B-2) ); Carboxylic acid ester (B-3) having 13 or more carbon atoms will be described.

The alcohol having 13 or more carbon atoms (B-1) may be any monovalent or polyhydric alcohol having a boiling point exceeding 260 ° C. under 1 atm and having 13 or more carbon atoms, Aliphatic monohydric alcohols are preferred. 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 are suitable. It is. 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. under 1 atm and having 10 or more carbon atoms. The carboxylic acids are preferably aliphatic carboxylic acids, more preferably saturated aliphatic carboxylic acids. Moreover, it is preferable that carbon number is 12 or more, and it is more preferable that it 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, and lauric acid is particularly preferable. Stearic acid is more preferable, and stearic acid is still more preferable. These may be used alone or in combination of two or more.

The carboxylates (B-2) may be monovalent or polyvalent carboxylates having a boiling point exceeding 260 ° C. under 1 atm and having 6 or more carbon atoms. The carboxylates (B-2) are preferably aliphatic carboxylates, more preferably aliphatic carboxylates having 10 or more carbon atoms, and particularly preferably aliphatic carboxylates having 13 or more carbon atoms. . In the present invention, a combination of the carboxylic acid (B-2) and one selected from the group consisting of amine, sodium, potassium, magnesium, calcium, manganese, iron, cobalt, nickel, copper, zinc, and tin. The carboxylate obtained by (1) is preferred. 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 any carboxylic acid anhydride having a boiling point exceeding 260 ° C. under 1 atm and having 8 or more carbon atoms. The carboxylic acid anhydride is preferably an aliphatic carboxylic acid anhydride. More preferably, it is an aliphatic carboxylic anhydride having 10 or more carbon atoms. More preferably, it has 13 or more carbon atoms. 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 a carboxylic acid ester obtained from the carboxylic acid (B-2), (2) an alcohol having 1 to 7 carbon atoms such as methanol, ethanol, propanol, heptanol, hexanol, glycerin, benzyl alcohol and the carboxylic acid. Carboxylic acid ester obtained in 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.
The 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 one of preferred embodiments of the present invention. One. 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.

Next, the mode (2) will be described.
In the form (2), the release agent is solid at 20 ° C. In this embodiment, the release agent is more preferably solid at 25 ° C., more preferably solid at 30 ° C., and particularly 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 atm, the release agent depends on the compound. 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.

Next, the form (3) will be described.
In the form (3), the release agent contains the silicon compound (B-4) as an essential component. In this embodiment, the silicon compound (B-4) is preferably a polysiloxane compound. 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 usually liquid at 50 ° C.
The polysiloxane compound is preferably a polysiloxane having a structural unit composed of a disubstituted siloxane described later. In other words, a polysiloxane compound having a disubstituted siloxane unit as a structural unit is preferable. 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” is also referred to as “disubstituted siloxane unit”, “bifunctional siloxane”, and “bifunctional siloxane unit”.

The silicon compound (B-4) preferably has an aryl group and / or a polyoxyalkylene chain. At this time, the aryl group and / or the polyoxyalkylene chain is bonded to at least one silicon constituting the silicon compound. Thereby, it becomes possible to make the compatibility and releasability of the silicon compound (B-4) and other components in the curable resin composition for molded articles excellent.
The silicon compound (B-4) may be, for example, one having one silicon atom (also referred to as a monomer in the present specification) or one having two or more silicon atoms (in the present specification). , Also referred to as a polymer).

The monomer of the silicon compound (B-4) may be any monomer in which a polyoxyalkylene chain and / or an aryl group is bonded to one silicon constituting the silicon compound. For example, the polyoxyalkylene chain and / or aryl 2 substituents in which two groups are bonded, 2 substituents in which a polyoxyalkylene chain and another substituent are each bonded, and 2 substituents in which an aryl group and another substituent are bonded to each other. (For example, dialkoxysilane etc.).
In addition, a tri-substituted product (for example, trialkoxysilane) in which three polyoxyalkylene chains and / or aryl groups are bonded, two polyoxyalkylene chains and / or aryl groups and one other substituent are bonded. A tri-substituted product, a tri-substituted product in which one polyoxyalkylene chain and two other substituents are bonded, or a tri-substituted product in which one aryl group and two other substituents are bonded may be used (for example, mono-substituted). Alkoxysilane, etc.). Among these disubstituted or trisubstituted products, dialkoxysilane having a polyoxyalkylene chain and / or aryl group, and monoalkoxysilane having a polyoxyalkylene chain and / or aryl group are preferred, and these are used alone. You may use, and may use 2 or more types together. Specifically, triphenylmethoxysilane and / or phenylmethyldiethoxysilane are particularly suitable.
As the polymer of the silicon compound, 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 ( In the present specification, it is also referred to as polysiloxane).

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 polymer of the silicon compound (B-4) has two or more silicon atoms having a siloxane bond, and a polyoxyalkylene chain and / or an aryl group is bonded to at least one silicon atom constituting the siloxane bond. It is preferable that it is a polysiloxane compound. The smallest polymer is a dimer, for example, one represented by the following formula (1).

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

The other substituents other than the polyoxyalkylene chain and the aryl group in the silicon compound (B-4) are organic groups that are bonded to silicon of the silicon compound and may be any one that does not hinder the effects of the present invention. Nonhydrolyzable 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 said silicon compound (B-4), it is preferable that 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. By setting it as such content, the curable resin composition and the molded object obtained will become especially excellent in transparency. If the content of the silicon compound (B-4) is less than 0.01% by mass, the above effect may be insufficient. If it exceeds 10% by mass, the resin may be difficult to cure. is there. More preferably, it is 0.01-5 mass%, More preferably, it is 0.1-2 mass%.

(Polymer structure and raw materials)
Examples of the polymer structure in the silicon compound (B-4) include a chain shape, a ladder shape, a cage shape, and a particle shape. Examples of the chain shape include a linear shape having no branch and a branched linear shape. In the present invention, a form in which the molecular structure is a chain shape is preferable. More preferably, it is a form that is linear without branching. The polymer of the silicon compound (B-4) having such a structure is preferably produced by, for example, the following method.
Linear (unbranched linear); hydrolysis / condensation product of dialkoxysilane (main chain), or hydrolysis / condensation of dialkoxysilane (main chain) and monoalkoxysilane (terminal) as required object.
Chain (branched linear): co-hydrolyzed condensate of dialkoxysilane (main chain) and trialkoxysilane, co-hydrolyzed condensate of dialkoxysilane (main chain) and tetraalkoxysilane, di- Cohydrolyzed condensate of alkoxysilane (main chain), trialkoxysilane and 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 containing these as main components.
In any of the cases described above, it is preferable to produce a polymer having the above structure by using an alkoxysilane having a silicon atom bonded to a polyoxyalkylene chain and / or an aryl group as an essential component. The alkoxysilane is at least one selected from the group consisting of monoalkoxysilane, dialkoxysilane and trialkoxysilane.

As described above, the silicon compound (B-4) preferably has a disubstituted siloxane unit in the molecule, in other words, preferably has a disubstituted siloxane unit, and is particularly preferably the polysiloxane compound. . The number of disubstituted siloxane units in the molecule is preferably 60% or more, more preferably 80% or more, and more preferably 90% or more, assuming that all silicon atoms are 100%. preferable.

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, silicone oil in which part of the side chain of the polysiloxane is a phenyl group (trade name KF-56, manufactured by Shin-Etsu Chemical Co., Ltd.), (trade name HIVAC-F-4, Shin-Etsu Chemical Co., Ltd.)], and modified silicone oils (trade name KF-6004, manufactured by Shin-Etsu Chemical Co., Ltd.) in which organic groups having a polyoxyethylene chain and a polyoxypropylene chain are introduced at both ends, etc. May be used alone or in combination of two or more.

Next, the form (4) will be described.
In the form (4), the release agent contains a substance having a weight average molecular weight of 500 or more and 100,000 or less. If the weight average molecular weight is less than 500, the effects of the present invention may not be sufficiently exhibited. If it exceeds 100,000, the compatibility with the resin component becomes poor, and the effects of the present invention may not be fully exhibited. More preferably, it is 1000 or more and 10,000 or less.
By including a substance having such a weight average molecular weight, the releasability can be remarkably improved while sufficiently maintaining basic performance such as heat resistance and optical characteristics such as transparency. This is because the compound having a boiling point of 260 ° C. or less under 1 atm mentioned above significantly improves the bleed-out speed of a release agent containing a substance having such a weight average molecular weight, and the releasability is remarkable. This is considered to be because
In addition, as a measuring method of the weight average molecular weight of a mold release agent, the following method can be used, for example.

When the release agent is a silicon compound (B-4), the weight average molecular weight is preferably 500 or more and 100,000 or less, more preferably 1000 to 90,000, and 1500 to 80,000. More preferably. By using the silicon compound (B-4) having such a weight average molecular weight, the effect of the present invention having excellent releasability can be exhibited more remarkably.
In addition, as a measuring method of a weight average molecular weight, 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 (GPC). Measurement is preferably performed under the following conditions using HLC-8220GPC (trade name, manufactured by Tosoh Corporation).
<Measurement conditions of 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).

In the present invention, among the forms described above, a form in which the mold release agent contains the compound in the form (1) and (2) as an essential component is more preferable. This form is a form in which at least one of the compounds (B-1) to (B-3), which is a solid at 20 ° C., is an essential component. That is, the release agent is at least one selected from the group consisting of alcohols, carboxylic acids, carboxylic acid esters, carboxylates and carboxylic anhydrides, and a compound having a total carbon number of 13 or more. It is an essential component and the compound is in a solid state at 20 ° C. In this form, the compound is more preferably in the form of a solid at 30 ° C., and more preferably in the form of a solid at 50 ° C.

Moreover, the form which uses the compound which is the said form of said (3) and (4) as an essential component is also one of the preferable forms in this invention. This form is an aspect in which at least one of the silicon compounds (B-4) having a weight average molecular weight of 500 or more and 100,000 or less is an essential component. That is, it is more preferable that the release agent contains the silicon compound (B-4) as an essential component and the silicon compound (B-4) has a weight average molecular weight of 500 or more and 100,000 or less.

Moreover, the form which uses the compound which is the form of said (1) and the compound which is the form of said (3) as an essential component, in other words, at least 1 sort (s) of compound (B-1)-(B-3), and silicon | silicone. The form which uses at least 1 sort (s) of a compound (B-4) as an essential component is more preferable. And the form which uses the compound which is the form of said (2) and the compound which is the form of (4) as an essential component is more preferable. Furthermore, the form which uses as an essential component the compound which is the form of said (1) and (2) and the compound which is said (3) and (4) form is especially preferable.

In the curable resin composition for molded bodies of the present invention, the content of the release agent having the above-described form is 0.01% with respect to 100% by mass of the curable resin composition for molded bodies of the present invention. It is preferable that it is 10 mass% or less. When the content of the release agent is less than 0.01% by mass, the content of the release agent may be insufficient, and when it 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%.

Here, the specific examples and melting points of the compounds (A-1) to (A-2) having the boiling point of 260 ° C. or less under 1 atm and the compounds (B-1) to (B-4) described above. Tables 1 and 2 below show boiling points and the like. In Table 1 and Table 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 atm. B-1 represents an alcohol having a boiling point exceeding 260 ° C. B-2 represents a carboxylic acid, a carboxylate salt or a carboxylic acid anhydride having a boiling point exceeding 260 ° C. B-3 represents carboxylic acid esters having a boiling point exceeding 260 ° C. B-4 means a silicon compound. MEK means methyl ethyl ketone. The boiling point is measured under 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, the present invention provides a molded product obtained by using the molded product obtained from the curable resin composition for molded products of the present invention, wherein a compound having a boiling point of 260 ° C. or less at 1 atmosphere is contained. is there. The preferable form is the same as the preferable form in the curable resin composition for molded bodies and the molded body of the present invention.

The above-mentioned “molded body obtained from a curable resin composition for molded bodies” is, for example, a molded body formed by molding a curable resin composition for molded bodies, particularly a molded body formed by die molding. Is preferred. The curable resin composition for molded bodies of the present invention contains a thermosetting resin. The thermosetting resin is not particularly limited as long as it exhibits the effects of the present invention, but is excellent in compatibility with components other than the thermosetting resin in the resin composition, and the components are uniform in the thermosetting resin. It is preferable to be dispersed in Thermosetting resins are not widely used at present because of difficulties in processing compared to thermoplastic resins, but in the present invention, for example, the above-mentioned specific compounds and specific release agents are used. By using it, even a thermosetting resin can be suitably used. Therefore, the resin composition of the present invention can be applied to, for example, plastic lens applications, and is easier to process than lenses made of inorganic glass, and can be freely changed in size and shape, and mass-produced. Also suitable.

The thermosetting resin is not particularly limited as long as it has thermosetting properties and contains a resin having a molecular weight of high molecular weight to about monomer. Examples of the thermosetting resin include (1) a liquid or solid curable resin, (2) a liquid or solid curable resin, and a curable compound or solvent having a lower molecular weight than the resin component. And a form containing (3) a liquid or solid non-curable resin and a curable compound having a lower molecular weight than 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 thermosetting resin is preferably a cationic curable resin (hereinafter also referred to as “cationic curable compound” or “resin component having a cationic polymerizable group”).
The cationic curable resin is a compound having at least one cationic polymerizable group in the molecule, and in the present invention, a compound having two or more cationic polymerizable groups is preferable. More preferably, it is a polyfunctional cation curable compound having two or more cationically polymerizable groups.

By containing the cationic curable resin, the curable resin composition for molded bodies of the present invention can achieve a curing reaction (cationic polymerization reaction) in a shorter time and can increase the curing rate. Moreover, it can fully suppress that the compound and mold release agent which have the above specific boiling point evaporate, and are not substantially contained in hardened | cured material, and the effect of this invention is exhibited more notably. become. In addition, while having workability equivalent to that of conventional thermosetting plastic materials, it exhibits heat resistance comparable to inorganic glass, can exhibit excellent properties such as excellent moldability and workability, and can be cured. The product is excellent in releasability (release strength).
The cationic curable resin is not particularly limited, but an epoxy resin (hereinafter also referred to as “epoxy compound” or “epoxy group-containing compound”) is preferable.

Examples of cationically polymerizable groups that can provide such effects include glycidyl groups such as glycidyl ether groups and glycidyl ester groups; hydrogenated products of aromatic glycidyl ether compounds, and glycidyl bonded to fully or partially saturated aliphatic cyclic hydrocarbons. Preferred are an ether group; an oxetane group; a dioxolane group; a trioxane group; an epoxy group containing an alicyclic epoxy group such as an epoxycyclohexane group; a vinyl ether group; a styryl group.
Among the above cationic polymerizable groups, in an optical resin composition such as a lens, a glycidyl ether group bonded directly or indirectly to an alicyclic epoxy group or a saturated aliphatic cyclic hydrocarbon is preferable. By having these cationic polymerizable groups, a curable resin composition having an excellent curing rate can be obtained. In particular, an alicyclic epoxy group is preferable. Of the alicyclic epoxy groups, an epoxycyclohexane group is preferred. The curing characteristics of the cationic polymerizable group are affected not only by the type of group but also by the organic skeleton to which the group is bonded.

By containing the cationic curable resin, a curing reaction (cationic polymerization reaction) can be achieved in a shorter time, and the curing rate can be increased. In addition, it is possible to sufficiently prevent the compound having a boiling point of 260 ° C. or less and the release agent from being evaporated at 1 atm and being substantially not contained in the cured product, and the effect of the present invention is more remarkable. Will be demonstrated. In addition, while having workability equivalent to that of conventional thermosetting plastic materials, it exhibits heat resistance comparable to inorganic glass, can exhibit excellent properties such as excellent moldability and workability, and can be cured. The product is excellent in releasability (release strength). The cationic curable resin is not particularly limited, but an epoxy resin (hereinafter also referred to as “epoxy compound” or “epoxy group-containing compound”) is preferable.

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, and an aromatic glycidyl ether compound is preferred. 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 according to the application.

In the present invention, among the above-mentioned aromatic epoxy compounds, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a fluorene skeleton (fluorene epoxy resin), aromatic epoxy resin having a bromo substituent and the like are suitable. Bisphenol A type epoxy resin and fluorene epoxy resin are particularly suitable. These can be used alone or in combination of two or more.
Specifically, 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 (manufactured by Osaka Gas Chemical Company) on coat EX-1010 or Ogsol PG or the like is preferable, 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.
In particular, when light irradiation or the like is performed at the time of curing of a molded body as described later, when the purpose is to suppress the appearance deterioration during light irradiation, the above aliphatic glycidyl ether type epoxy resin or epoxy resin having an epoxy cyclohexane skeleton is used. Are more preferably used.

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 epibis type glycidyl ether type epoxy resins, high molecular weight epibis type glycidyl ether type epoxy resins, and novolak / aralkyl type glycidyl ether type epoxy resins.
As said epibis type glycidyl ether type epoxy resin, what is obtained by condensation reaction of bisphenols, such as bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, and epihalohydrin, for example is suitable.
The high molecular weight epibis type glycidyl ether type epoxy resin 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 resin, tetramethylbiphenol, tetramethylbisphenol F, hydroquinone, naphthalenediol and the like, and 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.

Since the above-mentioned epoxy resin can be cured in a short time, the mold releasability and transparency can be obtained even when the curable resin composition for molded bodies of the present invention is cured in a short time. The effect of the present invention of achieving both is remarkably exhibited. Among these, a polyfunctional alicyclic epoxy compound and a polyfunctional hydrogenated epoxy compound are preferable because the curing rate of the curable resin composition is high. If the catalyst amount is the same, a cured product can be obtained in a shorter time. it can. For the purpose of suppressing appearance deterioration during light irradiation, the above aliphatic glycidyl ether type epoxy resins and epoxy resins having an epoxycyclohexane skeleton are more preferably used.

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 a thermosetting resin having an Abbe number of 45 or more. The thermosetting 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.
The content of the thermosetting resin having an Abbe number of 45 or more is preferably 1% by mass or more in the total thermosetting resin. More preferably, the content of the thermosetting resin having an Abbe number of 45 or more is 5% by mass or more, more preferably 10% by mass or more in the total thermosetting resin. In particular, for optical applications that require a high Abbe number, the content of the thermosetting resin having an Abbe number of 45 or more is preferably 60% by mass or more in the total thermosetting resin, and more preferably. Is 70% by mass or more. For optical applications that may have a low Abbe number, the content of the thermosetting resin having an Abbe number of 45 or more is preferably 1 to 70% by mass in the total thermosetting resin. More preferably, it is 10-60 mass%, More preferably, it is 20-50 mass%.

The thermosetting resin having an Abbe number of 45 or more is more preferably a cationic curable resin, and even more preferably an epoxy resin. Moreover, it is preferable that the curable resin composition containing the thermosetting resin whose Abbe number is 45 or more contains a cationic curing catalyst. The cationic curing catalyst will be described later.
The thermosetting resin having an Abbe number of 45 or more is preferably a compound having at least one cation polymerizable group in the molecule, more preferably an epoxy compound. 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, as the thermosetting resin having an Abbe number of 45 or more, an alicyclic epoxy compound and a hydrogenated epoxy compound are preferable.
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 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. As described above, a curable resin composition for a molded body which essentially includes an alicyclic epoxy resin is also one of the preferred embodiments of the present invention. The alicyclic epoxy resin only needs to be contained in the thermosetting resin constituting the curable resin composition for molded bodies, and the content thereof is not particularly limited, but is 40% by mass or more in the total thermosetting resin. Preferably there is. More preferably, the content 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.). ); Alicyclic acrylate having an oxygen atom and / or a nitrogen atom in the structure such as tetrahydrofurfuryl (meth) acrylate and morpholinoethyl (meth) acrylate; alicyclic monofunctional maleimides 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, Examples thereof include alicyclic bismaleimides such as 4-dimaleimidocyclohexane, 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; Examples include epoxy compounds having an alkylene skeleton having a total carbon number of 4 or more, such as Celoxide 2081 (liquid at normal temperature) manufactured by Kogyo Co., Ltd .;
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. Thus, 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 a thermosetting resin, and the molded body curable resin composition includes two or more types of thermosetting resins. The form prepared in is preferred. By preparing in such a form, continuous production is possible, and a thermosetting resin having a sense of unity, high strength, 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 two or more types of thermosetting resins preferably include a resin having a molecular weight of 700 or more and a thermosetting 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. The thing which makes a thing essential is more preferable. Moreover, it is preferable that it is a curable resin composition for molded objects containing this 2 or more types of thermosetting resin. By having a molecular weight of 700 or more (high molecular weight organic resin, high molecular material) and a material having a molecular weight of less than 700 (low molecular weight organic resin, low molecular material), it is possible to reduce the viscosity during production and to increase the mechanical strength of products The effect of improvement is 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 a thermosetting resin, the production method comprising a step of preparing by mixing two or more kinds of thermosetting resins. A method for producing a body curable resin composition is also one of the preferred embodiments of the present invention. More preferably, the above two or more types of thermosetting resins require that the molecular weight is 700 or more (polymer material) and less than 700 (low molecular material). It is a form. The method for measuring the molecular weight is preferably the same as described above.

As a ratio (mass ratio) between the polymer material having a molecular weight of 700 or more and a low molecular material having a molecular weight of less than 700, the polymer material having a molecular weight of 700 or more is 10% to 90% with respect to the entire resin composition. It is preferably included. More preferably, it is 20-80%, More preferably, it is 30-70%.
The two or more types of thermosetting 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 resin composition and the molded body, when a resin having a low Abbe number and a high refractive index is obtained, it is preferable to use a thermosetting resin having a large amount of unsaturated bonds. That is, it is a curable resin composition containing a thermosetting resin, and the curable resin composition has a unsaturated bond amount of 40% by mass or more with respect to 100% by mass of the cured product after curing. Compositions are 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 thermosetting resin have unsaturated bonds, 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, the total mass of atoms forming unsaturated bonds contained in 100% by mass of the cured product, and hydrogen atoms and halogen atoms 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. That is, when the aromatic ring has a substituent, in order to obtain the total amount of unsaturated bonds, the aromatic ring composed of carbon atoms and hydrogen atoms is excluded, including the mass of substituents not having unsaturated bonds. Only the mass of 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 mass of 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 thermosetting resin, it is preferable that the thermosetting resin has an aromatic ring, and the amount of the aromatic ring is 40% by mass or more with respect to 100% by mass of the cured product after curing. It is preferable that it is 35 or less. An Abbe number of 35 or less means that “the average value of the Abbe number of all thermosetting resins is 35 or less”, and a thermosetting resin having an Abbe number exceeding 35 is included. May be. The curable resin composition for a low Abbe number preferably includes a thermosetting resin having an Abbe number of 45 or more, and the average value of the Abbe numbers of all thermosetting resins is preferably 35 or less. On the other hand, as described above, the thermosetting resin preferably includes a thermosetting resin having an Abbe number of 45 or more as a component. If a thermosetting resin having an Abbe number of 45 or more is not included, the cationic curing rate does not increase, and the productivity may not be sufficient. The proportion of the thermosetting resin having an Abbe number of 45 or more is preferably 1% by mass or more in 100% by mass of the thermosetting resin. More preferably, it is 5 mass% or more, More preferably, it is 10 mass% or more, Most preferably, it is 20 mass% or more. In the present invention, by setting the Abbe number of the thermosetting resin to 35 or less (the average value of the Abbe number of all thermosetting resins is 35 or less), when the curable resin composition is used for optical applications, It can be excellent in optical characteristics. If the Abbe number of the thermosetting resin exceeds 35, there is a possibility that the wavelength dispersion of light cannot be increased, and sufficient optical characteristics may not be exhibited, so that it may not be a material 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 that the Abbe is 35 or less is remarkably exhibited. 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. 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. However, in optical applications, a significant difference occurs in terms of effects.

In the said thermosetting resin, an Abbe number can be 35 or less by combining suitably the suitable forms which are mentioned 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 thermosetting 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 thermosetting resins is 35 or less) as described above. For example, the Abbe number is 35 or less. It is preferable that 40 mass% or more of the thermosetting resin is contained in the total thermosetting resin. The ratio of the thermosetting resin having an Abbe number of 35 or less is more preferably 60% by mass or more, still more preferably 80% by mass or more, and the upper limit is 99% by mass.

Examples of the thermosetting resin having an Abbe number of 35 or less include a polyphenol 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. Can be used as a mixture. Among these, it is preferable to make an aromatic epoxy compound essential because it can be excellent in optical properties and can be suitably used for various applications. Thus, the said curable resin composition which uses an aromatic epoxy compound as the said thermosetting 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 thermosetting resins, It is more preferable that it is 80 mass% or more, It is especially 99 mass%. preferable.
The Abbe number can be evaluated using a refractometer. For example, DR-M2 (trade name, manufactured by Atago Co., Ltd.) is preferably used as the refractometer for evaluation at 20 ° C.

As the thermosetting resin in the curable resin composition for molded bodies of the present invention, a polyphenol compound or a compound having a polymerizable unsaturated bond can be used.
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 ratio of the said thermosetting resin is with respect to 100 mass% of curable resin compositions for molded objects, It is preferable that it is 90 mass% or more. 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 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 (thermal latent curing agent). Thermal latent cation curing catalyst is also called thermal latent cation generator and cationic polymerization initiator. When a compound containing a cationic species is excited by heating to cause a thermal decomposition reaction and reach a curing temperature, The substantial function of is demonstrated. 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 a thermosetting resin that cures at room temperature is used, curing can be prevented from proceeding at room temperature. The reaction can be easily handled. 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. It is thought that this is 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 suppresses generation of oxygen radicals due to ultraviolet irradiation or exposure to heat rays. Therefore, the molded body has excellent heat resistance for a long time without causing yellowing or strength reduction. Demonstrate sex.

The thermal latent cationic 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, for the purpose of improving productivity in producing a cured product of the resin composition, the mold is held in the mold at a predetermined temperature and time, and then taken out of the mold and placed in an inert gas atmosphere such as air or nitrogen. It is also possible to place and heat-treat. 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 it is released with a strength of 4 × 10 ⁻² N / m ² or less, it can be easily peeled off 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 is possible. If the 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 with a certain degree of material hardness (4 × 10 ⁻² N / m ² or less) in a short time at a temperature of 150 ° C. or less at which a side reaction occurs. ) Is preferable. 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 NTT Corporation, main body model number: L) at the interface between the resin and SUS304. -500, 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 and photocuring can be suitably used. Moreover, it is preferable that the shaping | molding method is what hardens | cures 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 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 not usually used, the effect of the present invention is more fully exhibited.
As described above, cationic curing is preferred because the effects of the present invention can be sufficiently exerted even under conditions where the curing reaction proceeds in a short time.

In such a method, it is preferable that the viscosity of the curable resin composition for molded bodies mixed with a curing agent or the like does not increase remarkably 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. As described above, the curable resin composition for molded bodies has a viscosity increase rate of the mixture in one liquid of 200% or less compared with that immediately after mixing after being stored at 25 ° C. for 3 days. Compositions are also one preferred form of the invention.

As a method for producing a cured product by curing the curable resin composition for a molded body, a commonly used method can be suitably used. For example, the composition is cured by thermosetting using a curing agent. It can be a thing. The production method can be appropriately selected according to the type of the resin composition as will be described later, but it is preferable to cure the curable resin composition for molded bodies in a short time, and to cure within 5 minutes. Thus, a method for producing a cured product is preferred. Specifically, the curable resin composition for molded bodies is mixed with a curing agent and other materials as necessary 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 the curing using a mold in a short time, it becomes possible to sufficiently suppress the evaporation of the compound having a boiling point of 260 ° C. or less and to fully exhibit the effects of the present invention, and is excellent in economic efficiency. Method.

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 after curing within 5 minutes as described above, the cured product is taken out of the mold and post-cured (baked). 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. In addition, since it is not necessary to use a mold, there is an advantage that a large amount of products can be post-cured in a small area.
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 of the post cure depends on the curing temperature, but is preferably 1 to 48 hours. 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 a thermosetting resin of the resin composition of the present invention, for example, when an epoxy resin is contained, a cured product can be obtained by thermosetting using a curing agent as described above. As the curing agent, it is preferable to use the thermal latent cationic curing catalyst described above. 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.

When a polyhydric phenol compound is contained as the thermosetting resin of the curable resin composition for molded bodies of the present invention, a cured product can be obtained by thermosetting using a curing agent. Examples of the curing agent include a compound having at least two epoxy groups (also referred to as an epoxy resin curing agent), and the compound having at least two epoxy groups has an average of 2 or more in one molecule. An epoxy resin having an epoxy group is suitable, and the above-mentioned various polyfunctional epoxy resins can be used.

The blending mass ratio of the polyhydric phenol compound and the epoxy resin curing agent (polyhydric phenol compound / epoxy resin curing agent) is preferably 30/70 or more, and 70/30 or less. It is preferable that If it is less than 30/70, the mechanical properties and the like of the formed cured product may be lowered, and if it exceeds 70/30, the flame retardancy may be insufficient. More preferably, it is 35/65 or more and 65/35 or less. A curing accelerator may be used for the curing. Examples of the curing accelerator include imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole; 2,4,6-tris (dimethylaminomethyl). ) Amines such as phenol, benzylmethylamine, DBU (1,8-diazabicyclo [5.4.0] -7-undecene), DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea) An organic phosphorus compound such as tributylphosphine, triphenylphosphine, and tris (dimethoxyphenyl) phosphine is preferable.

Examples of the curing method in the case of containing a compound having a polymerizable unsaturated bond as the thermosetting resin of the resin composition of the present invention include a curing method by irradiation with active energy rays and a curing method by heat. The resin composition of the invention has an intrinsic spectral sensitivity in the range of 200 to 400 nm, and can be polymerized by irradiating with ultraviolet or visible light having a wavelength of 180 to 500 nm in the absence of a photolatent radical curing catalyst. Particularly, since light having wavelengths of 254 nm, 308 nm, 313 nm, and 365 nm is effective for curing, a curing method by irradiation with active energy rays is preferable. Further, the resin composition of the present invention can be cured in air and / or in an inert gas.

The resin composition containing the compound having a polymerizable unsaturated bond can be cured by irradiation with an active energy ray other than the above-described ultraviolet ray or visible ray, and generates a radically active species as the active energy ray. In addition to the ultraviolet rays or visible rays described above, ionizing radiation such as electron beams, α rays, β rays, and γ rays, microwaves, high frequencies, infrared rays, laser beams, and the like are suitable. The absorption wavelength of the compound that generates radically active species may be selected as appropriate.

As a light generation source of ultraviolet or visible light having a wavelength of 180 to 500 nm, low pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, mercury-xenon lamp, excimer lamp, short arc A lamp, helium / cadmium laser, argon laser, excimer laser, sunlight and the like are suitable. The irradiation time of ultraviolet light or visible light having a wavelength of 180 to 500 nm may be appropriately set depending on the wavelength irradiation amount of the active energy ray, but is preferably 0.1 microsecond to 30 minutes, and preferably 0.1 millisecond to 1 minute. Is more preferable.

In the curing by irradiation with the active energy ray, a known and commonly used photolatent radical curing catalyst may be added and cured in order to perform the curing reaction more efficiently. As a compounding quantity of the said photolatent radical curing catalyst, it is preferable that it is 0.1 mass part-10 mass parts with respect to 100 mass parts of thermosetting resins of this invention. If it is less than 0.1 parts by mass, the photopolymerization may not proceed efficiently. On the other hand, if it exceeds 10 parts by mass, there is no further effect of improving the curing rate, and conversely, curing is insufficient. There is a fear.

Examples of the photolatent radical curing catalyst include an intramolecular bond cleavage type photolatent radical curing catalyst, an intramolecular hydrogen abstraction type photolatent radical curing catalyst, and the like. Examples of the intramolecular bond cleavage type photolatent radical curing catalyst include diethoxyacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-methyl-2-morpholino (4 -Thiomethylphenyl) propan-1-one ("Irgacure 907" manufactured by Ciba-Geigy), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one ("Darocur 1173" manufactured by Merck & Co.), 1-hydroxycyclohexyl phenyl ketone ("Irgacure 184" manufactured by Ciba-Geigy), 1- (4-isopropylphenyl) -2-hydroxy-2 -Methylpropan-1-one ("Darocur 1116" manufactured by Merck & Co.), benzyl dimethyl Luketal ("Irgacure 651" manufactured by Ciba-Geigy), oligo {2-hydroxy-2-methyl-1- "4- (1-methylvinyl) phenyl" propane "(" Esacure KIP100 "manufactured by Ramberty), 4- (2-acryloyl-oxyethoxy) phenyl-2-hydroxy-2-propyl ketone (acetophenone series such as “ZLI3331” manufactured by Ciba-Geigy Co., Ltd., benzoin derivatives such as benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin alkyl, etc. -A mixture of hydroxycyclohexyl phenyl ketone and benzophenone ("Irgacure 500" manufactured by Ciba-Geigy), 2,4,6-trimethylbenzoyldiphenylphosphine oxide ("Lucirin TPO" manufactured by BASF), Acylphosphine oxides such as acylphosphine oxide (“CGI1700” manufactured by Ciba-Geigy), benzyl and benzyl derivatives, methylphenylglyoxyester, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) Benzophenone (“BTTB” manufactured by NOF Corporation) is suitable.

Examples of the intramolecular hydrogen abstraction type photolatent radical curing catalyst include benzophenone, methyl o-benzoylbenzoate and alkyl o-benzoylbenzoate, 4-phenylbenzophenone, 4,4′-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl. Benzophenones such as -4′-methyl-diphenyl sulfide, acrylated benzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 3,3′-dimethyl-4-methoxybenzophenone, Thioxanthone series such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, Michler ketone, aminobenzophene such as 4,4'-diethylaminobenzophenone Non-based, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone and the like are preferable.

Other compounds that can be used as the photolatent radical curing catalyst include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1 -[4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-hydroxy-2-methyl-1-phenyl-propan-1-one and derivatives thereof, 4-dimethylaminobenzoic acid ester, 1, 1-dialkoxyacetophenone, benzophenone and benzophenone derivatives, alkyl benzoylbenzoate, bis (4-dialkylaminophenyl) ketone, benzyl and benzyl derivatives, benzoin and benzoin derivatives, benzoin alkyl ether, 2-hydroxy-2-methylpropiophenone , Thioxa And thioxanthone derivatives, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis (2,6-dimethoxybenzoyl)- 2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylphenyl) -phenylphosphine oxide and the like are suitable.

As the photopolymerization initiator photolatent radical curing catalyst, a photocationic polymerization initiator can also be used. Examples of the photocationic polymerization initiator include triphenylsulfonium hexafluoroantimonate, triphenylsulfonium phosphate, p- (phenylthio) phenyldiphenylsulfonium hexafluoroantimonate, p- (phenylthio) phenyldiphenylsulfonium hexafluorophosphate, 4-chloro. Phenyldiphenylsulfonium hexafluorophosphate, 4-chlorophenyldiphenylsulfonium hexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide Bishexafluoroantimonate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) be Zen] -Fe- hexafluorophosphate, diaryliodonium hexafluoroantimonate and the like. These can be easily obtained from the market. For example, SP-150, SP-170 (manufactured by Asahi Denka); Irgacure 261 (manufactured by Ciba-Geigy); UVR-6974, UVR-6990 (manufactured by Union Carbide) CD-1012 (manufactured by Satomer) and the like are suitable. Among these, it is preferable to use an onium salt as the photocationic polymerization initiator. Further, as the onium salt, it is preferable to use at least one of a triarylsulfonium salt and a diaryliodonium salt.

In the curing by irradiation with the active energy ray, it is preferable to use a photosensitizer in combination. It is preferable that the compounding quantity of the said photosensitizer is 0.1-20 mass% with respect to 100 mass% of resin compositions of this invention. If it is less than 0.1% by mass, the photopolymerization may not proceed efficiently, and if it exceeds 20% by mass, it may hinder the transmission of ultraviolet rays into the coating film, resulting in insufficient curing. . More preferably, it is 0.5-10 mass%.

Examples of the photosensitizer include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and benzoic acid (2-dimethylamino). ) Amines such as ethyl, ethyl 4-dimethylaminobenzoate (n-butoxy), 2-ethylhexyl 4-dimethylaminobenzoate and the like are suitable.
In curing the resin composition containing the polymerizable unsaturated compound, the above-described additives may be further added and cured.
The curable resin composition for molded bodies of the present invention can be obtained by a molding method described above.
This invention is also a molded object formed by shape | molding the curable resin composition for molded objects mentioned above.
The preferred forms of the raw material resin composition and the curing method of the molded body of the present invention are the same as the preferred forms of the curable resin composition for molded body of the present invention and the curing method, respectively.

The present invention is a method for producing a molded body from a curable resin composition for molded bodies containing a thermosetting resin, wherein the production method further requires a compound having a boiling point of 260 ° C. or less at 1 atm. 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.
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.

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 molded product, a wide range of numerical values is required for the refractive index and Abbe number of the molded product 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 after PCT (pressure cooker test) of the molded body (saturated moisture absorption rate in air at 30 ° C. and 40% relative humidity) 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.

As described above, when the molded product exhibits excellent optical properties such as transparency, it 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.

Especially, since it is excellent in optical characteristics, such as transparency, it is suitable for uses such as lens molding, and is particularly suitable for uses 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 of the present invention, it is possible to achieve both releasability and transparency even when curing in a short time, and thus the effects of the present invention are more prominently exhibited. Will be. Moreover, as described above, evaporation of a compound having a boiling point of 260 ° C. or lower under the above-mentioned 1 atm can be suppressed, and the effects of the present invention can be exhibited more remarkably.

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 the 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.

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 A liquid epoxy resin CELL-2021P (alicyclic epoxy resin, trade name, Daicel Chemical Co., Ltd.) as a thermosetting resin in a four-necked flask equipped with a gas inlet, a cooling tube, and a stirring rod Kogyo Co., Ltd.) 30 parts, EHPE-3150 (alicyclic epoxy resin, trade name, manufactured by Daicel Chemical Industries) 20 parts, and Ogsol EG210 (aromatic epoxy resin, trade name, manufactured by Osaka Gas Chemical Co., Ltd.) 50 And 0.5 part of stearic acid as a release agent were added and stirred well at 130 ° C. to make it uniform. Thereafter, the temperature was lowered to 70 ° C. Next, 0.5 part of isopropyl acetate was added as a compound having a boiling point of 260 ° C. or lower under 1 atm, and stirred uniformly. After cooling, a slightly yellow and transparent viscous liquid was obtained.
After this liquid was cooled to 40 ° C., Sun Aid SI-80L (trade name, manufactured by Sanshin Chemical Industry Co., Ltd.) was added as a heat-latent cationic curing catalyst so as to be 0.6 parts with respect to the total mass. Mixed.

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 hardened | cured material was peeled from the metal mold | die 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.

Examples 2-23
In Examples 2 to 15 and Examples 17 to 23, silicon compounds having specific organic groups in addition to compounds having specific boiling points were used, and the compositions of the resin compositions were as shown in Tables 3 and 5. The silicon compound was charged in the same manner as the epoxy resin, and stirred well at 130 ° C. to make it uniform. 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 Example 16, the composition of the resin composition was shown in Table 5 without using a silicon compound having a specific organic group. 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 evaluation results obtained in Examples 2 to 23 are shown in Table 6 and Table 8 below.

Comparative Examples 1-16
Table 4 shows the composition of the resin composition without using a compound having a specific boiling point 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. The obtained evaluation results are shown in Table 7 below.

For the molded bodies of Examples 10, 12, and 20 (curing condition: 1 mm thick resin composition was cured at 140 ° C. for 2.5 minutes), pyrolysis GC-Mass (gas chromatograph mass) spectrum measurement was performed. went. The apparatus 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 10, 12, and 20, peaks of dodecanol, stearic acid, and epoxy decomposition product were observed.
In addition, silicon was confirmed by elemental analysis.
From this measurement result, it became clear that the specific compound, mold release agent, and thermosetting resin in the present invention were contained in the molded bodies of Examples 10, 12, and 20. In addition, as is apparent from Tables 6 and 8, the molded bodies of Examples 10, 12, and 20 are all excellent in releasability.

Examples 24-36, Reference Examples 1-3
The types of compounds having specific boiling points were changed as shown in Table 9, and the composition of the resin composition was shown in Table 9. 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 9 below.

Comparative Example 17
Instead of a compound having a specific boiling point, hexadecanol (1-hexadecanol, boiling point 344 ° C.), which is a compound having a boiling point exceeding 260 ° C. under 1 atm, is used. Table 9 shows the composition of the resin composition. As shown. 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 9 below.

Examples 37, 38
A siloxane compound was used as the silicon compound having a specific organic group, and the composition of the resin composition was as shown in Table 10. As the siloxane compound, BYK-333 (manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane solution) is used in Example 37, and BYK-307 (manufactured by Big Chemie Japan, polyether-modified polydimethylsiloxane) is used in Example 38. Was used. These siloxane compounds were charged in the same manner as the epoxy resin, and stirred well at 130 ° C. to make it uniform.
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 11 below.

Example 39
An oxetane compound was blended so that the composition of the resin composition was as shown in Table 10, and the resin composition was prepared as follows.
0.5 parts octanol, 50 parts Ogsol EG-210 (Osaka Kawamaki Co., Ltd., fluorene epoxy resin), 45 parts JER828EL (Japan Epoxy Resin Co., bisphenol A epoxy resin), EHO (Ube Industries, Ltd., 3- 5 parts of ethyl-3-hydroxymethyloxetane) and 0.5 part of stearic acid were mixed at 100 ° C. After cooling, add 1 part of Sun-Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd., thermal acid generator), and perform mixing and defoaming using a self-revolving centrifugal mixing device (manufactured by Shinky Co., Ltd., Kentaro Awatori). Thus, a resin composition was prepared. Using this resin composition, a molded body was prepared in the same manner as described above, and various physical properties and the like were measured.
The obtained measurement results are shown in Table 11.

Example 40
As shown in Table 10, the composition of the resin composition is 0.1 parts of BYK-333 which is a siloxane compound (polyether modified polydimethylsiloxane solution, manufactured by Big Chemie Japan Co.) as a silicon compound having a specific organic group. did. Other than that, a molded body was prepared in the same manner as in Example 39, and various physical properties and the like were measured.
The obtained measurement results are shown in Table 11.

Example 41
An oxetane resin, a radical polymerization generator, and a siloxane compound were added to make the composition of the resin composition as shown in Table 10, and a molded body was prepared as follows, and various physical properties were measured.
Octanol 0.5 part, Ogsol EA-0200 (Osaka Gas Chemical Co., fluorene acrylate) 50 parts, JER828EL (Japan Epoxy Resin Co., bisphenol A epoxy resin) 30 parts, Eternacoll @ OXBP (Ube Industries, Oxetane resin) ) 20 parts and 0.5 parts of stearic acid were mixed at 100 ° C. After cooling, 0.5 part of Sun-Aid SI-80L (manufactured by Sanshin Chemical Industry Co., Ltd., thermal acid generator), 0.1 part of BYK-333 (manufactured by Big Chemie Japan Co., polyether-modified polydimethylsiloxane solution) and Perptil A resin composition was prepared by adding 1 part of O (manufactured by NOF Corporation, radical generator) and carrying out mixing and defoaming using a self-revolving centrifugal mixing apparatus (manufactured by Shinky Co., Ltd., Nertaro Awatori). .
Using the obtained resin composition, a molded body was prepared in the same manner as in Example 1, and various physical properties and the like were measured. In addition, hardening of the resin composition was performed in nitrogen atmosphere.
The obtained measurement results are shown in Table 11.

Reference Example 42
Aromatic epoxy resin (JER828EL, manufactured by Japan Epoxy Resin, bisphenol A epoxy resin), oxetane resin, and heat latent cationic curing catalyst (Sun Aid SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) The composition of the product was as shown in Table 10. And other than that was carried out similarly to Example 41, and prepared the resin composition and the molded object, and measured various physical properties. In addition, hardening of the resin composition was performed in nitrogen atmosphere.
The obtained measurement results are shown in Table 11.

Example 43
A radical polymerization initiator and a heat-latent cationic curing catalyst (Sun-Aid SI-80L, manufactured by Sanshin Chemical Industry Co., Ltd.) were not blended. Solution, manufactured by Ciba-Geigy Co.) was added, and the composition of the resin composition was as shown in Table 10. And other than that was carried out similarly to Example 41, and prepared the resin composition and the molded object, and measured various physical properties. However, the resin composition was cured by photocuring in a nitrogen atmosphere. That is, using an exposure machine (MA-60F, manufactured by Mikasa Co., Ltd.) using a high-pressure mercury lamp as a light source, irradiation was performed with ultraviolet light with an exposure energy of 9 J / cm ^{2 at} an illuminance of 10 mW / cm ² for 15 minutes.
The obtained measurement results are shown in Table 11.

Comparative Example 17
Table 10 shows the composition of the resin composition without blending octanol, which is a compound having a specific boiling point. Other than that, a molded body was prepared in the same manner as in Example 39, and various physical properties and the like were measured.
The obtained measurement results are shown in Table 11.

Comparative Example 18
Table 10 shows the composition of the resin composition without blending octanol, which is a compound having a specific boiling point, and an oxetane compound. Other than that, an attempt was made to prepare a molded body in the same manner as in Example 39, but the resin composition did not cure.
The obtained measurement results are shown in Table 11.

In the table below, “melting point” means the melting point of the curable resin composition for molded bodies. Moreover, the numerical value in () represents a mass part. Furthermore, abbreviations and trade names represent the following.
(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.)

(Thermosetting 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.)
Ogsol EA-0200 (fluorene acrylate, 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 having an aryl group and / or a polyalkylene glycol chain)
KF-56 (straight silicone oil whose part of the side chain of the polysiloxane is a phenyl group [release agent], weight average molecular weight 1.75 × 10 ³ , trade name, manufactured by Shin-Etsu Silicone)
KF-6004 (modified silicone oil introduced with an organic group having polyoxyethylene chain and polyoxypropylene chain at both ends [release agent], weight average molecular weight 7.7621 × 10 ⁴ , trade name, manufactured by Shin-Etsu Silicone Co., Ltd. )
HIVAC-F-4 (straight silicone oil whose part of the side chain of the polysiloxane is a phenyl group [release agent], weight average molecular weight 1.51 × 10 ³ , trade name, 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])

(Silicon compound that does not dissolve in thermosetting resin)
KS-707 (solution type silicone oil, trade name, manufactured by Shin-Etsu Silicone)
KF-96 (oil type silicone oil, trade name, manufactured by Shin-Etsu Silicone)
KF-412 (oil type silicone oil, trade name, manufactured by Shin-Etsu Silicone)
KF-53 (straight silicone oil in which part of the side chain of the polysiloxane is a phenyl group, trade name, 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)

(Oxetane compound)
EHO (trade name, 3-ethyl-3-hydroxymethyloxetane, manufactured by Ube Industries, Ltd.)
OXBP (trade name, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, oxetane resin, manufactured by Ube Industries, Ltd.)
(Radical curing catalyst)
Purptil O (trade name, manufactured by NOF Corporation, radical generator)
(Photolatent cationic curing catalyst)
SP-172 (trade name, manufactured by Asahi Denka)
(Photolatent radical curing catalyst)
Irgacure 189 (trade name, manufactured by Ciba Geigy)
(Dispersant)
PLACCEL FM-1 (manufactured by Daicel Chemical Industries, Ltd.)

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. In other words, the curable resin composition for molded bodies contains a compound having a boiling point of 260 ° C. or less under 1 atm as an essential component, thereby advantageously achieving 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 having excellent basic performance such as heat resistance is used as the thermosetting resin, the curable resin composition for molded bodies has basic performance such as heat resistance in addition to the above characteristics. It is clear that they have both.

Regarding the technical significance of the upper limit of the numerical range, Example 1 using isopropyl acetate, which is a compound having a boiling point of 260 ° C. or less at 1 atm in the present invention, and a boiling point of 260 ° C. or less at 1 atm. Comparative Example 2 in which no compound was used, and comparison using hexadecanol, which is a compound having a boiling point of 260 ° C. or less at 1 atm instead of using a compound having a boiling point of 260 ° C. or less at 1 atm It is clear when comparing with Example 17. In addition, Example 1, Comparative example 2, and Comparative example 17 are common in the point which uses a stearic acid as a composition of the curable resin to be used, or mold release property.
In Example 1, the releasability is 5, whereas in Comparative Example 2 and Comparative Example 17, the releasability is 8.
Thus, in Example 1, it is a level which can manufacture a molded object continuously, However, In the comparative example 2 and the comparative example 17, a molded object cannot be manufactured continuously.

More specifically, when Examples 27 and 30 to 34 and Comparative Example 2 are compared, in Comparative Example 2 that does not contain octanol, which is a compound having a specific boiling point, the releasability is 8, It cannot be manufactured continuously. In contrast, in Example 34 containing 0.01% by mass of octanol, the releasability is 7 and the releasability is improved, and a lens that requires a precise surface shape on the order of several μm is required. It was a level that can be applied to optical use like an optical product such as the above, and a level at which the optical product can be continuously manufactured. Moreover, in Example 33 in which octanol is contained in an amount of 0.1% by mass with respect to 100% by mass of the resin composition, the releasability is improved to 4, which is a level at which continuous production of a molded product can be satisfactorily performed. ing. Furthermore, in Example 27 in which octanol is contained in an amount of 0.5% by mass relative to 100% by mass of the resin composition, the releasability is improved to 2, and in Example 31 in which 3% by mass is contained, The releasability is improved to 1, and the releasability is such that it can be suitably used in optical applications and the like.

In Reference Example 1 in which 10% by mass of octanol is contained with respect to 100% by mass of the resin composition and in Reference Example 2 in which 6% by mass of octanol is contained, there is (bubbles) in the evaluation of releasability. Bubbles in the molded body are generated when the gas (air) in the resin composition cannot be completely degassed at the time of mold molding. However, even if such bubbles are generated in the molded body, they can be used depending on the use of the molded body as long as the molded body can be continuously manufactured by having sufficient releasability.
Further, in Comparative Example 15 in which a compound having a specific boiling point is not contained, the evaluation that the releasability is 2 is obtained, but the transparency is inferior, and it cannot be used for the above optical use.

In Examples 39 and 40, an aromatic epoxy resin (fluorene epoxy resin and bisphenol A epoxy resin) is a main component as a curable resin. However, since an oxetane compound is used in combination, the refractive index is 1.6. In addition, the result was excellent in curability. In Examples 41 and 43, since an aromatic epoxy resin (bisphenol A epoxy resin) and fluorene (meth) acrylate are used in combination as curable resins, both have a high refractive index of 1.6 and are cured. The result was excellent.
Since the cured products obtained in Examples 39, 40, 41, and 43 are composed of a resin composition containing a compound having a boiling point of 260 ° C. or less under 1 atm, all are evaluated for releasability. Has a rank of 3 or less and excellent releasability, and also has excellent transparency.
Moreover, since Example 40 contained the silicon compound (siloxane compound) which has an oxyalkylene chain | strand further in the resin composition, it became a result excellent in the release property compared with Example 39.
In the resin composition of Comparative Example 19, the curable resin consists only of an aromatic epoxy resin (fluorene epoxy resin and bisphenol A epoxy resin), but under the above-described curing conditions, that is, heating at 140 ° C. for 3 minutes in a short time. As a result, it was not cured sufficiently.

On the other hand, in Comparative Example 18, as a result of adding a small amount of oxetane compound to the aromatic epoxy resin similar to Comparative Example 19 as a curable resin in the resin composition, the curability was improved and the refractive index was 1.6. A cured product having a high refractive index was obtained. However, the evaluation of releasability has a rank of 8, which is a result that cannot be said to be sufficient for optical applications such as lenses, and has a problem level for continuous molding.

In Example 41, Reference Example 42, and Example 43, fluorene (meth) acrylate is used as the curable resin, so that it has excellent curability and a high refractive index of 1.6 or more. Since the viscosity of the resin composition was low compared with the reference example 42, Example 41 and 43 using together the group epoxy resin was excellent in workability. Moreover, the evaluation of releasability was rank 1, which was the highest rank.

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 a compound having a boiling point of 260 ° C. or lower is contained in the release agent, 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 (14)

A curable resin composition for an optical molded body, comprising a cationic curable compound, a compound having a boiling point of 260 ° C. or lower under 1 atm, a release agent, and a cationic curing catalyst,
The compounds having a boiling point of 260 ° C. or less under 1 atm are alcohols, polyhydric alcohol derivatives, carboxylic acids, carboxylic acid esters obtained from monohydric alcohols and carboxylic acids, carboxylic acid anhydrides, ketones, aliphatic hydrocarbons. And at least one compound selected from the group consisting of aromatic hydrocarbons,
The polyhydric alcohol derivative is a polyhydric alcohol ether compound, a polyhydric alcohol ether ester or a polyhydric alcohol ester compound (however, those corresponding to the polyhydric alcohol ether ester are excluded from the polyhydric alcohol ester compound). And
The content of the compound having a boiling point of 260 ° C. or less under 1 atm is 0.01 to 5% by mass with respect to 100% by mass of the resin composition,
The mold release agent has a boiling point exceeding 260 ° C. under 1 atm, an alcohol having 13 or more carbon atoms, a carboxylic acid having 13 or more carbon atoms, a carboxylic acid ester having 13 or more carbon atoms, or a carboxylic acid having 13 or more carbon atoms. An essential component is at least one compound selected from the group consisting of a salt and a carboxylic acid anhydride having 13 or more carbon atoms,
Content of this mold release agent is 0.01 mass% or more and 10 mass% or less with respect to 100 mass% of this resin composition, The curable resin composition for optical molded bodies characterized by the above-mentioned. The curable resin composition for optical molded bodies according to claim 1, wherein the cationic curing catalyst is a heat latent cationic curing catalyst. 3. The curable resin composition for an optical molded body according to claim 1, wherein the cationic curable compound is an epoxy group-containing compound, a glycidyl ether group-containing compound, and / or an oxetane group-containing compound. . The cation curable compound is a compound having an alicyclic epoxy group and / or a compound having a glycidyl ether group bonded directly or indirectly to a saturated aliphatic cyclic hydrocarbon. The curable resin composition for optical molded bodies according to 1 or 2. The curable resin composition for optical molded bodies according to claim 1 or 2, wherein the cationic curable compound is a polyfunctional alicyclic epoxy compound and / or a polyfunctional hydrogenated epoxy compound. The curable resin composition for an optical molded body according to claim 1, wherein the optical molded body is a lens. The curable resin composition for an optical molded body according to claim 1, wherein the optical molded body is a molded body formed by die molding. The curable resin composition for an optical molded body according to claim 6 or 7, wherein the optical molded body is a micro optical lens. The curable resin composition for an optical molded body according to any one of claims 6 to 8, wherein the optical molded body is a light beam condensing lens, a light diffusion lens, an imaging lens, or a pickup lens. The compound having a boiling point of 260 ° C. or less under 1 atm is at least one selected from the group consisting of alcohols, polyhydric alcohol derivatives, carboxylic acids, carboxylic acid esters obtained from monohydric alcohols and carboxylic acids, and ketones. The curable resin composition for optical molded bodies according to any one of claims 1 to 9. The curable composition for optical molded bodies according to any one of claims 1 to 10, wherein the compound having a boiling point of 260 ° C or lower under 1 atm includes a compound having a boiling point exceeding 150 ° C under 1 atm. Resin composition. The curable resin composition for optical molded bodies according to claim 11, wherein the compound having a boiling point exceeding 150 ° C. under 1 atm is an alcohol. The curable resin composition for optical molded bodies according to claim 12, wherein the alcohol is an aliphatic monohydric alcohol having a total carbon number of 6 or more. An optical molded body obtained by molding the curable resin composition for an optical molded body according to any one of claims 1 to 13.