JP2013043985A - Curable resin composition and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition without breaking or cracks in curing, and able to give a highly hard cured product with low hygroscopicity, a small expansion coefficient due to environmental temperature and further having excellent moldability, and to provide the cured product useful for various usages such as optical materials.SOLUTION: The curable resin composition includes a polysiloxane compound and vinyl compound, wherein the vinyl compound includes a polyfunctional compound including an aliphatic cyclic skeleton, and/or a compound including an isocyanuric acid skeleton.

Description

The present invention relates to a curable resin composition and a cured product. More specifically, a curable resin composition useful as a raw material for various uses such as optical materials, molding materials, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, and cured products obtained by curing the same. About.

Curable resin compositions that can be cured by heat or active energy rays include, for example, optical materials, molding materials, mechanical parts, electrical / electronic parts, automobile parts, civil engineering and building materials, paint materials, adhesive materials, etc. Various applications for various uses have been studied, and a curable resin composition having excellent characteristics required for each use has been developed. Such a curable resin composition is also useful as an optical lens material in an imaging device or the like because it can exhibit transparency. In the optical field, for example, a digital camera module is mounted on a mobile phone or the like, and there is a demand for downsizing and cost reduction. As a material for imaging lenses, resin lenses are increasingly used instead of conventional inorganic glass. Yes. Also, in recent years, application to applications that can be used outdoors, such as in-vehicle cameras, surveillance cameras, and display elements (LEDs, etc.), has also been studied, but in outdoor applications, resistance to external environments such as dust and cleaning liquid That is, a high level of wear resistance is required.

As the curable resin composition, conventionally, a highly functional polyfunctional (meth) acrylate compound is used as a main component. A cured product obtained by using this compound has sufficient hardness, but on the other hand, it is brittle and has a high curing shrinkage rate, so that cracks and cracks are likely to occur during curing. Therefore, for example, it was not suitable for manufacturing a molded body such as a resin lens or a thick film product. Therefore, a cured molded article containing a specific metalloxane component and an organic resin component is disclosed as a cured product having sufficient hardness and excellent heat resistance and optical characteristics (see Patent Document 1).

By the way, when using the hardened | cured material of a curable resin composition for each use, the humidity in a use environment may affect a physical property. For example, when a cured product is used as an optical material or an electrical / electronic component, when the refractive index fluctuates due to moisture absorption (water absorption), the volume expands, or is subjected to a solder reflow process, the moisture absorption component in the cured product is reduced. When heated, bulges may occur. Therefore, the cured product is required to have sufficiently low hygroscopicity (also referred to as low water absorption) so that the required physical properties can be stably exhibited.

International Publication No. 2011/034138

As described above, various curable resin compositions have been studied, but curable resin compositions that can be more adapted to recent needs, that is, cracks and cracks during curing are sufficiently suppressed, with high hardness, Moreover, there is still no curable resin composition that can provide a cured product exhibiting sufficiently low hygroscopicity, and there is room for improvement in this respect.

The present invention has been made in view of the above-mentioned present situation, has no cracks or cracks at the time of curing, has high hardness, is excellent in low moisture absorption, and is low in moisture absorption under high humidity conditions. Can provide a cured product in which expansion (volume expansion) is sufficiently suppressed, has excellent moldability, and has such characteristics, and is useful for various applications such as optical materials. It aims at providing hardened | cured material.

The present inventor has made various studies on the curable resin composition. When the composition is a compound in which a polysiloxane compound is blended with a vinyl compound, the shrinkage at the time of curing is alleviated, and the occurrence of cracks and cracks at the time of curing is suppressed. Furthermore, it has been found that when a vinyl compound is specified as one containing a predetermined compound, a cured product having excellent low hygroscopicity and low expansion rate (volume expansion) due to environmental humidity can be obtained. In addition, such a resin composition containing a vinyl compound and a polysiloxane compound can control the surface hardness of a cured product, for example, the surface hardness so that it can be suitably applied to outdoor use that is a severe use environment. In addition to being able to give a cured product having high wear resistance, that is, excellent wear resistance, it is also excellent in moldability (also called processability and moldability). It has also been found that a cured product such as the above film can be provided with good moldability. Further, such a resin composition can be suitably applied to an optical material in particular, and among them, it is found that it can be preferably used for a lens application because the refractive index and Abbe number required for the lens application can be controlled. The present invention has been achieved. The cured product obtained from the resin composition of the present invention is low in hygroscopicity, has a small expansion coefficient due to environmental humidity, and is excellent in surface hardness. Therefore, it can be suitably used for lens applications, particularly imaging lens applications.

That is, the present invention is a curable resin composition containing a polysiloxane compound and a vinyl compound, and the vinyl compound is a cured product containing an aliphatic cyclic skeleton-containing polyfunctional compound and / or an isocyanuric acid skeleton-containing compound. It is an adhesive resin composition.
The present invention is also a cured product obtained by curing the curable resin composition.
The present invention is described in detail below. In addition, what combined two or three or more of the preferable forms of this invention described in a paragraph below is also a preferable form of this invention.

<Curable resin composition>
The curable resin composition of the present invention (hereinafter also referred to as “resin composition”) contains a polysiloxane compound and a vinyl compound, but may contain other components as long as these are essential components. May be. Each component can be used alone or in combination of two or more.

In the curable resin composition, the blending mass ratio of the polysiloxane compound and the vinyl compound (polysiloxane compound / vinyl compound) is not particularly limited, but is preferably 5 to 95/95 to 5, for example. It is. Within this range, a cured product having high heat resistance, that is, difficult to be colored and having a sufficient hardness can be obtained with good moldability. More preferably, it is 10-90 / 90-10 as said mixing | blending mass ratio, More preferably, it is 20-80 / 80-20.

In the resin composition, in order to suppress cracking at the time of curing, the unsaturated double bond concentration (the double bond concentration derived from the vinyl compound contained in 1 g of the resin composition) is 4 mmol / g or less. It is preferable that More preferably, it is 3.3 mmol / g or less, More preferably, it is 3 mmol / g or less. In order to obtain a cured product having sufficient hardness, the unsaturated double bond concentration is preferably 0.4 mmol / g or more. More preferably, it is 0.8 mmol / g or more, More preferably, it is 1.5 mmol / g or more.

In the above resin composition, in order to improve moldability (ease of processing, mold transferability), the storage elastic modulus G ′ (G prime) exhibited by the molded body (cured product) at the molding (curing) temperature is 5 It is preferred that it is greater than or equal to megapascal. More preferably, it is 15 megapascals or more, More preferably, it is 20 megapascals or more.
The storage elastic modulus G ′ can be obtained by performing dynamic viscoelasticity measurement (DMA) (measurement mode: shear mode) in the process of raising the temperature to the molding (curing) temperature using the resin composition as a sample.

The amount of the siloxane bond in the resin composition is preferably 5% by mass or more in terms of the Si content in 100% by mass of the finally obtained cured product. More preferably, it is 7 mass% or more, More preferably, it is 12 mass% or more. Moreover, a preferable upper limit is 22 mass% or less, More preferably, it is 18 mass% or less.

-Polysiloxane compound-
In the curable resin composition, the polysiloxane compound is a polymer having a siloxane bond (Si—O—Si bond) in one molecule. That is, it is a polymer having at least a structural unit containing a siloxane bond (referred to as a siloxane unit).

The polysiloxane compound usually has a structure in which 0 to 3 organic groups are bonded to each silicon (Si) atom constituting the siloxane bond. Those having a structure formed by bonding organic groups are preferred. That is, those having an R—Si bond (R represents an organic group) are preferred.
In such a form, R represents an organic group, but is preferably an optionally substituted hydrocarbon group. The hydrocarbon group may have a chain (straight chain or branched chain) structure or a cyclic structure. Moreover, the group which has an unsaturated bond may be sufficient, and the group which does not have an unsaturated bond, ie, a saturated hydrocarbon group, may be sufficient.

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

The hydrocarbon group may have 1 or more carbon atoms, but is preferably 2 or more. As a result, the compatibility with the vinyl compound is improved, and since it is homogeneously mixed, it is possible to obtain a cured product that is superior in low hygroscopicity, and also has high transparency as required for lens applications and the like. A cured product can be obtained. More preferably, it is 3 or more. Moreover, 20 or less is preferable from a viewpoint which makes hardness of hardened | cured material sufficient, More preferably, it is 10 or less. A hydrocarbon group having a mercapto group is particularly preferable, and a hydrocarbon group having 3 carbon atoms and having a mercapto group is most preferable.
In addition, when the said hydrocarbon group has group containing carbon as a substituent, it is suitable for it to exist in the said range as the total carbon number including the carbon number of the substituent.

Among the hydrocarbon groups, an aliphatic hydrocarbon group is preferable, and an aliphatic hydrocarbon group that does not include an aromatic ring is particularly preferable. Thereby, it becomes possible to obtain a cured product having excellent light resistance and heat-resistant colorability.

The hydrocarbon group may also have a substituent. The substituent is not particularly limited, for example, mercapto group, halogen element, alkoxy group, hydroxyl group, sulfonic acid group, aldehyde group, carbonyl group, carboxyl group, amino group, imino group, isocyanate group, cyano group, azo group, Examples include an ester group (ester bond), an ether group (ether bond), and the like. However, it is preferable that the hydrocarbon group does not have an amino group, a hydroxyl group, a carboxyl group, or an ester group (ester bond). That is, it is preferable not to have a group with high hydrophilicity or a hydrolyzable group, and this makes it possible to obtain a cured product that is more excellent in low hygroscopicity.

Preferably, the polysiloxane compound has a structure in which 50% by mass or more of Si atoms are bonded to an aliphatic hydrocarbon group having 3 or more carbon atoms with respect to 100% by mass of all Si atoms contained in the polysiloxane compound. It is. The aliphatic hydrocarbon group here may be substituted. That is, in the polysiloxane compound, 50% by mass or more of Si atoms are R′-Si bonds (R ′ is an optionally substituted carbon) with respect to 100% by mass of all Si atoms contained in the polysiloxane compound. It represents an aliphatic hydrocarbon group having a number of 3 or more. Especially, it is more preferable that Si atom which comprises R'-Si bond is 60 mass% or more with respect to 100 mass% of all Si atoms. Further, as described above, R ′ is preferably an aliphatic hydrocarbon group having no aromatic ring, and an aliphatic hydrocarbon having no amino group, hydroxyl group, carboxyl group and ester group (ester bond). It is also suitable that it is a group.

The molecular structure of the polysiloxane compound is not particularly limited, but usually, a chain structure (linear or branched), a ladder structure, a cyclic structure, a cage structure and a particulate structure are exemplified. Among these, a chain shape, a ladder shape, and a cage shape are preferable from the viewpoint of high compatibility with a vinyl compound. Furthermore, from the viewpoint of obtaining a cured product having high compatibility and higher optical transparency and mechanical properties, a chain shape and a ladder shape are more preferable, and a ladder shape is particularly preferable. In particular, when a ladder-like polysiloxane compound is used, releasability, controllability of optical properties (transparency, Abbe number, refractive index, etc.), mechanical properties, etc. can be added with a small amount compared to the case of using other structures. The characteristics can be further improved. That is, (1) the cured product (molded product) can be easily released from the molded mold after curing (excellent mold release properties), (2) transparency of the curable resin composition, Abbe number, The refractive index can be strictly controlled (excellent controllability), (3) the transparency, Abbe number and refractive index of the cured product can be strictly controlled (excellent controllability), (4) curing Additive effects such as excellent mechanical properties (high modulus of elasticity and high fracture strength) can be exhibited.
The polysiloxane compound may be liquid at room temperature or may be solid.

As a weight average molecular weight of the said polysiloxane compound, 3000 or more are preferable and it is preferable that it is 30,000 or less. If it is less than 3000, the resulting cured product tends to be brittle, and the handleability may not be sufficient. If it exceeds 30,000, the viscosity of the resin composition will be too high, and the moldability and handleability will not be sufficient, and the compatibility with resin components such as vinyl compounds will not be sufficient. There is a fear. More preferably, it is 4000 or more, More preferably, it is 5000 or more, More preferably, it is 25000 or less, More preferably, it is 20,000 or less.
The weight average molecular weight is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).
The weight average molecular weight can be measured by gel permeation chromatography (column: TSKgel SuperMultipore HZ-N 4.6 ^* 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard).

The polysiloxane compound preferably contains a mercapto group in one molecule depending on required physical properties. That is, the polysiloxane compound is preferably a mercapto group-containing polysiloxane compound. Such a mercapto group-containing polysiloxane compound is excellent in compatibility with a vinyl compound, and the mercapto group can react with a vinyl group (for example, (meth) acryloyl group, etc.). Thus, a highly transparent cured product can be obtained, which is particularly suitable for applications such as optical materials.
The mercapto group-containing polysiloxane compound is a polymer having a mercapto group (SH group) and a siloxane bond (Si—O—Si bond) in one molecule. That is, it is a polymer having at least a structural unit containing a mercapto group and a siloxane bond (referred to as a mercapto group-containing siloxane unit).

The content ratio of the mercapto group-containing siloxane unit is preferably 40 mol% or more with respect to 100 mol% of the total amount of siloxane units constituting the mercapto group-containing polysiloxane compound, although it depends on the application to which it is applied. is there. As a result, the compatibility with the vinyl compound becomes more sufficient, and a cured product that is more excellent in transparency and homogeneity can be obtained, and the moldability of the resin composition becomes more satisfactory. More preferably, it is 50 mol% or more. Moreover, although an upper limit is 100 mol%, in order to obtain hardened | cured material with higher surface hardness, it is preferable that it is 90 mol% or less, More preferably, it is 80 mol% or less.
In addition, the content rate (mol%) of a mercapto group containing siloxane unit can be calculated | required by the content rate (mol%) of a mercapto group containing silane compound with respect to 100 mol% of total amounts of the silane compound which is a raw material.

The mercapto group-containing siloxane unit is preferably in a form in which a mercapto group is bonded to a silicon atom via a hydrocarbon chain from the viewpoint of excellent compatibility with a vinyl compound. As the hydrocarbon chain, a chain saturated hydrocarbon chain (alkylene chain) is preferable, and a linear saturated hydrocarbon chain is particularly preferable. The hydrocarbon chain is preferably a hydrocarbon chain having 1 to 10 carbon atoms, more preferably a hydrocarbon chain having 1 to 6 carbon atoms, still more preferably a hydrocarbon chain having 2 to 4 carbon atoms, particularly preferably. It is a hydrocarbon chain having 3 carbon atoms. The preferred number of carbon atoms is the same when the hydrocarbon chain is a chain saturated hydrocarbon chain or when it is a straight chain saturated hydrocarbon chain.

The polysiloxane compound in the resin composition can be obtained, for example, by hydrolyzing and dehydrating and condensing a silane compound. The hydrolysis and dehydration condensation methods are not particularly limited, and can be performed by ordinary methods.

The silane compound may include a silane compound having a mercapto group (referred to as a mercapto group-containing silane compound), or may be composed only of a silane compound not including a mercapto group (also referred to as another silane compound). However, as described above, in order to obtain a more homogeneous and transparent cured product, it is preferable to include a mercapto group-containing silane compound. In this case, the said silane compound may consist only of a mercapto group containing silane compound, and may contain another silane compound. That is, the mercapto group-containing polysiloxane compound may be a co- (hydrolysis) condensate of a mercapto group-containing silane compound and another silane compound. In the case of a co-hydrolyzed condensate, the content ratio of the mercapto group-containing silane compound contained in the raw material is preferably 40 mol% or more with respect to 100 mol% of the total amount of silane compounds. More preferably, it is 50 mol% or more. Moreover, although an upper limit is 100 mol%, it is preferable that it is 90 mol% or less, More preferably, it is 80 mol% or less.

The mercapto group-containing silane compound is a silane compound having at least one mercapto group in the molecule. For example, the following general formula (1):
_{^{(R 1) m -Si- (OR}} 2) n (1)
(In the formula, R ¹ is the same or different and represents a hydrocarbon group and may have a substituent. R ² is the same or different and represents a hydrocarbon group and has a substituent. Provided that at least one of m R ¹ and n R ² is a group containing a mercapto group, and m and n represent the number of each group bonded to Si, And a number of 0 to 4, provided that m + n = 4).

In the general formula (1), R ^{1 s} are the same or different and represent a hydrocarbon group, and among them, an alkyl group, an aryl group, or an aralkyl group is preferable, and two or more of these may be included. . Moreover, it is preferable that carbon number is 1-20. More preferably, it is 1-10, More preferably, it is 1-6.
Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, and 2-ethyl. Chain alkyl group such as xyl group, n-octyl group, lauryl group, stearyl group; cycloalkyl group such as cyclopropyl group, cyclobutyl group, cyclohexyl group, bicyclohexyl group; one of hydrogen atoms of chain alkyl group A group in which part or all are substituted with a cycloalkyl group; a group in which some or all of the hydrogen atoms of a cycloalkyl group are substituted with a chain alkyl group; and the like.
Examples of the aryl group include a phenyl group, a naphthyl group, an anthranyl group and the like, and a group in which part or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylphenyl group (toluyl group), Dimethylphenyl group (xylylene group), diethylphenyl group, etc.).
Examples of the aralkyl group include a benzyl group and the like, and a group in which some or all of these hydrogen atoms are substituted with an alkyl group (for example, a methylbenzyl group).

Among R ¹ , an alkyl group is preferable, and an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a pentyl group, and a hexyl group is preferable. This makes it possible to further reduce curing shrinkage.
R ¹ may have a substituent. Further, it may be a chain (linear or branched) structure or a cyclic structure.

In the general formula (1), R ² represents a hydrocarbon group, but is preferably an alkyl group, an aryl group, or an aralkyl group, and may have two or more of these. Moreover, it is suitable that carbon number is 1-20. More preferably, it is 1-8, More preferably, it is 1-3.
Specific examples of the alkyl group, aryl group and aralkyl group are the same as those described above for R ¹ .
Among the R ² , an alkyl group (that is, a form in which the R ² O group is an alkoxy group) is preferable, and among them, the number of carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, and a pentyl group. 1-5 alkyl groups are preferred. This makes it possible to further reduce curing shrinkage. More preferred is an alkyl group having 1 to 3 carbon atoms, and particularly preferred is a methyl group or an ethyl group (that is, a form in which the R ² O group is a methoxy group or an ethoxy group).
R ² may have a substituent. Further, it may be a chain (linear or branched) structure or a cyclic structure.

In the general formula (1), m and n are each a number of 0 to 4 (provided that m + n = 4), but n is 1, 2 or 3 from the viewpoint of compatibility with the vinyl compound. Preferably it is. n is more preferably 2 or 3. The form in which n is 2 or 3 and R ² is an alkyl group, that is, the compound represented by the general formula (1) is a mercapto group-containing dialkoxysilane compound or a mercapto group-containing trialkoxysilane. The form which is a compound is still more preferable. Moreover, when it is going to obtain hardened | cured material with high surface hardness, for example, the hardened | cured material whose pencil hardness mentioned later is 6H or more, it is suitable to use a mercapto group containing trialkoxysilane compound.

In the general formula (1), at least one of m R ¹ and n R ² is a group containing a mercapto group, but at least one of R ¹ is a group having a mercapto group. preferable. More preferably, at least one of R ¹ is an alkyl group having a mercapto group at the terminal. Moreover, it is suitable that the mercapto group which the compound represented by the said General formula (1) has is 1-2 in 1 molecule. More preferably, it is one.
Incidentally, when R ¹ is a group having a mercapto group in R ¹ having the mercapto group, the number of carbon atoms constituting the hydrocarbon group is preferably from 1 to 10, more preferably number of carbon atoms is 1 to 6, more preferably 2 to 4 carbon atoms, and particularly preferably 3 carbon atoms. In R ¹ having a mercapto group, the hydrocarbon group is preferably a chain saturated hydrocarbon group (alkyl group), and is preferably a linear saturated hydrocarbon group (alkyl group). The preferred number of carbon atoms is the same when the hydrocarbon group is an alkyl group. That is, as R ¹ having a mercapto group, a mercaptopropyl group is particularly preferable.

As the compound represented by the general formula (1), 3-mercaptopropyltrialkoxysilane and 3-mercaptopropylmethyldialkoxysilane are particularly preferable. The alkoxy group in these compounds is the same as R ² O in the general formula (1) described above, and is preferably an alkoxy group having 1 to 5 carbon atoms. More preferably, it is a C1-C3 alkoxy group, Most preferably, it is a methoxy group or an ethoxy group.

As said other silane compound, if it is a silane compound which does not contain a mercapto group, it will not specifically limit. For example, the following silane compounds etc. are mentioned and 1 type (s) or 2 or more types can be used.
Alkoxy such as methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane Silanes;
Vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane;
(meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane;
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3, 4-epoxycyclohexyl) epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane;
N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-amino Aminosilanes such as propyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane;
Thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

Among these, alkoxysilanes are suitable, but the number of alkoxysilane groups possessed by the compound may be 1 to 4. That is, any of a tetraalkoxysilane compound, a trialkoxysilane compound, a dialkoxysilane compound, and a monoalkoxysilane compound may be used, but from the viewpoint of compatibility with a vinyl compound, a trialkoxysilane compound and a dialkoxy Silane compounds are preferred. Among the above-mentioned alkoxysilanes, methyltrimethoxysilane and dimethyldimethoxysilane are preferable because they are inexpensive and excellent in industrial availability, and are three-dimensionally difficult to impair the effect of the mercapto group of the cocondensate. is there. In addition, when it is going to obtain hardened | cured material with high surface hardness, for example, the hardened | cured material whose pencil hardness mentioned later is 6H or more, it is suitable to use a trialkoxysilane compound.

-Vinyl compounds-
In the curable resin composition, the vinyl compound is an aliphatic cyclic skeleton-containing polyfunctional compound (also referred to as a polyfunctional vinyl compound having an aliphatic cyclic skeleton) and / or an isocyanuric acid skeleton-containing compound (isocyanuric acid skeleton). Also referred to as a vinyl-based compound). That is, the vinyl compound includes at least one compound selected from the group consisting of an aliphatic cyclic skeleton-containing polyfunctional compound and an isocyanuric acid skeleton-containing compound.
The vinyl compound is preferably a radical polymerizable compound. The vinyl compound is preferably a monomer or an oligomer.

The vinyl compound preferably contains a (meth) acryloyl group from the viewpoint of excellent light resistance, hardness and the like. That is, the vinyl compound is preferably a (meth) acrylate compound, and includes a polyfunctional (meth) acrylate compound having an aliphatic cyclic skeleton and / or a (meth) acrylate compound having an isocyanuric acid skeleton. Is preferred.
The (meth) acrylate compound is a general term for a methacrylate compound (a compound having a methacryloyl group) and an acrylate compound (a compound having an acryloyl group), but the acrylate compound is more reactive and has better curability. More preferable.

= Polyfunctional vinyl compound having an aliphatic cyclic skeleton =
The polyfunctional vinyl compound having an aliphatic cyclic skeleton is a compound having an aliphatic cyclic skeleton and containing two or more polymerizable unsaturated double bonds (C = C) in one molecule. The aliphatic cyclic skeleton may be one kind or two or more kinds.

Examples of the aliphatic cyclic skeleton include monocyclic structures such as a cyclohexyl structure and a cyclodecanyl structure; and polycyclic rings such as an adamantyl structure, an isobornyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure, a dicyclodecanyl structure, and a tricyclodecanyl structure. Structure; etc. are preferred. Thereby, it is easy to obtain the molded object (hardened | cured material) which is more excellent in low moisture absorption, has a small expansion coefficient by environmental humidity, and is further excellent in light resistance and heat resistance. Among these, a polycyclic structure is preferable, and a tricyclodecanyl structure is more preferable.

Specific examples of the polyfunctional vinyl compound having an aliphatic cyclic skeleton include, for example, cyclohexyldi (meth) acrylate, 4-tert-butylcyclohexyldi (meth) acrylate, cyclohexanedimethanoldi (meth) acrylate, isobornyldi ( (Meth) acrylate, adamantyl di (meth) acrylate, dicyclopentanyl di (meth) acrylate, dicyclopentenyl di (meth) acrylate, dicyclopentenyloxyethyl di (meth) acrylate, tricyclodecane methanol di (meth) acrylate And tricyclodecane dimethanol di (meth) acrylate.

The weight average molecular weight of the polyfunctional vinyl compound having the aliphatic cyclic skeleton is preferably, for example, 100 or more and 10,000 or less. When the weight average molecular weight is 100 or more, shrinkage during curing is further reduced, and a crack-free cured product can be provided more. Further, when the weight average molecular weight is 10,000 or less, the moldability (ease of processing, mold transferability) of the resin composition is further improved. More preferably, it is 200 or more and 8000 or less as said weight average molecular weight, More preferably, it is 250 or more and 5000 or less.
The weight average molecular weight is a molecular weight in terms of polystyrene and can be measured by gel permeation chromatography (column: TSKgel SuperMultipore HZ-N 4.6 ^* 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard). .

= Vinyl compound having an isocyanuric acid skeleton = The vinyl compound having an isocyanuric acid skeleton is a compound containing an isocyanuric acid skeleton and one or more polymerizable unsaturated double bonds in one molecule. A compound containing two or more polymerizable unsaturated double bonds (isocyanuric acid skeleton-containing polyfunctional compound) is preferable. The isocyanuric acid skeleton may be one kind or two or more kinds. Specifically, the following general formula (2):

(In the formula, R ³ is the same or different and represents a hydrogen atom or a methyl group. R ⁴ is the same or different and represents —O—, —CO— or an alkanediyl group, and is contained in the alkanediyl group. And at least one methylene group may be replaced by —O— or —CO—.

In the general formula (2), examples of the alkanediyl group represented by R ⁴ include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. Linear alkanediyl groups such as nonamethylene group and decamethylene group; 1-methylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1 -Branched alkanediyl groups such as methylpentamethylene group, 2-methylpentamethylene group and 3-methylpentamethylene group.

The alkanediyl group represented by R ⁴ preferably has 1 to 10 carbon atoms. More preferably, it is 5 or less, More preferably, it is 3 or less, Especially preferably, it is 1, ie, a methylene group.

R ⁴ may also be a group in which at least one methylene group (—CH ₂ —) contained in the alkanediyl group is replaced by —O— or —CO—. For example, — (CH ₂ ) _{2 -O -, - (CH 2} ) 5 -CO-O -, - (O- (CH 2) 2) x -O-CO- (x is an integer of 1~5.), - (O- _{(CH 2) 5) y -O} -CO- (y can be mentioned represent.) such as an integer of 1 to 5.

The vinyl compound having an isocyanuric acid skeleton represented by the above general formula (2) is preferably, for example, triallyl isocyanurate, tri (meth) acryl isocyanurate, isocyanuric acid ethylene oxide-modified tri (meth) acrylate, ethoxylated isocyanurate. Isocyanuric acid skeleton-containing polyfunctional compounds such as acid tri (meth) acrylate (also referred to as tris (2-acryloyloxyethyl) isocyanurate) and ε-caprolactone-modified tris- (2-acryloxyethyl) isocyanurate are exemplified.

The vinyl compound having an isocyanuric acid skeleton is preferably 100 or more and 10,000 or less, for example. When the weight average molecular weight is 100 or more, shrinkage during curing is further reduced, and a crack-free cured product can be provided more. Further, when the weight average molecular weight is 10,000 or less, the moldability (ease of processing, mold transferability) of the resin composition is further improved. More preferably, it is 200 or more and 8000 or less as said weight average molecular weight, More preferably, it is 250 or more and 5000 or less.
The weight average molecular weight can be measured in the same manner as described above for the polyfunctional vinyl compound having an aliphatic cyclic skeleton.

= Other vinyl compounds =
The resin composition also has a vinyl compound other than the above-described polyfunctional vinyl compound having an aliphatic cyclic skeleton and a vinyl compound having an isocyanuric acid skeleton (that is, neither an aliphatic cyclic skeleton nor an isocyanuric acid skeleton). 1 type (s) or 2 or more types may be included. Such vinyl compounds are also referred to as “other vinyl compounds”.
The content ratio of the other vinyl compound is, for example, the total amount of the vinyl compound contained in the resin composition (polyfunctional vinyl compound having an aliphatic cyclic skeleton, vinyl compound having an isocyanuric acid skeleton, and others. The total amount of vinyl-based compounds) is preferably 80% by mass or less with respect to 100% by mass. More preferably, it is 70 mass% or less, More preferably, it is 60 mass% or less. Moreover, it is preferable that it is 10 mass% or more from a viewpoint of raising the hardness of a hardening molded object, More preferably, it is 30 mass% or more.

The weight average molecular weight of the other vinyl compound is preferably 100 or more and 10,000 or less, for example. When the weight average molecular weight is 100 or more, shrinkage during curing is further reduced, and a crack-free cured product can be provided more. Further, when the weight average molecular weight is 10,000 or less, the moldability (ease of processing, mold transferability) of the resin composition is further improved. More preferably, it is 200 or more and 8000 or less as said weight average molecular weight, More preferably, it is 250 or more and 5000 or less.
The weight average molecular weight can be measured in the same manner as described above for the polyfunctional vinyl compound having an aliphatic cyclic skeleton.

The other vinyl compound is particularly limited as long as it is a compound containing one or more polymerizable unsaturated double bonds in one molecule and has neither an aliphatic cyclic skeleton nor an isocyanuric acid skeleton. However, as described above, a compound containing a (meth) acryloyl group, that is, a (meth) acrylate compound is preferable. Specifically, for example, an aliphatic (meth) acrylate compound and an aromatic (meth) acrylate compound are suitable. Thus, the form in which the vinyl-type compound contained in the said resin composition contains at least 1 sort (s) further selected from the group which consists of an aliphatic (meth) acrylate compound and an aromatic (meth) acrylate compound is also this book. This is one of the preferred forms of the invention.
As described above, among the methacrylate compound and the acrylate compound, the acrylate compound is more preferable because it has high reactivity and excellent curability.
The other vinyl compound is also preferably a polyfunctional vinyl compound containing two or more polymerizable unsaturated double bonds in one molecule. More preferably, it is a polyfunctional (meth) acrylate compound. The number of polymerizable unsaturated double bonds contained in one molecule is preferably 2 or more, more preferably 3 or more, and preferably 10 or less.

(I) Aliphatic (meth) acrylate compound The aliphatic (meth) acrylate compound is a compound having neither an aliphatic cyclic skeleton nor an isocyanuric acid skeleton, and having an aliphatic hydrocarbon group in the main chain. And a compound having a (meth) acryloyl group at at least one molecular end or side chain. For example, (i) an aliphatic (meth) acrylate oligomer, (ii) an aliphatic (meth) acrylate monomer Can be mentioned. Among them, it is preferable to use at least an aliphatic (meth) acrylate oligomer, and more preferably to use at least a urethane (meth) acrylate oligomer described later.

(i) Aliphatic (meth) acrylate oligomer The aliphatic (meth) acrylate oligomer may be an oligomer having at least one (meth) acryloyl group in one molecule. In order to obtain an excellent cured product, it is preferably a polyfunctional oligomer having two or more (meth) acryloyl groups in one molecule. More preferably, it is a trifunctional or higher functional oligomer having 3 or more (meth) acryloyl groups.

The aliphatic (meth) acrylate oligomer preferably has an aliphatic hydrocarbon group in the main chain and a non-hydrocarbon group in the main chain and / or side chain. When the oligomer has such a structure, the resulting cured product is excellent in transparency and durability. Non-hydrocarbon groups include, for example, carbon and carbon atoms in the structure such as urethane bonds (—O—C (═O) —N (H) —) and ester bonds (—O—C (═O) —). The site has at least one atom other than hydrogen and does not contain a hydrocarbon in the structure.
The aliphatic (meth) acrylate oligomer may have a non-hydrocarbon group only in one of the main chain and the side chain, or have a non-hydrocarbon group in both the main chain and the side chain. It may be.

In the form where the aliphatic (meth) acrylate oligomer has a non-hydrocarbon group in the main chain, the main chain has an organic skeleton including an aliphatic hydrocarbon group and a non-hydrocarbon group.
Examples of the organic skeleton having an aliphatic hydrocarbon group and a non-hydrocarbon group in the main chain include a urethane skeleton having an aliphatic hydrocarbon group (R) and a urethane bond (—O—C (═O ) -N (H) -R-); an ester skeleton having an aliphatic hydrocarbon group (R) and an ester bond (-O-C (= O) -R-); an aliphatic hydrocarbon group (R) 1 such as an ether skeleton having an ether bond (—O—R—); a carbonate skeleton having an aliphatic hydrocarbon group (R) and a carbonate bond (—O—C (═O) —O—R—); Species or two or more are preferred.
The ether skeleton includes an oxyalkylene skeleton (—RO—) composed of an oxyalkylene group.

The form of the aliphatic (meth) acrylate oligomer having a non-hydrocarbon group in the side chain is, for example, a (meth) acrylate (co) polymer skeleton composed of a (co) polymer of a (meth) acrylate monomer. An oligomer having

The aliphatic (meth) acrylate oligomer also has at least one skeleton selected from the group consisting of urethane skeleton, ester skeleton, ether skeleton, carbonate skeleton, and (meth) acrylate (co) polymer skeleton. It is preferable to have it. When the oligomer has such a skeleton, the obtained cured product is further excellent in transparency, durability, and the like.
More preferably, it has at least one skeleton selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton and a carbonate skeleton, and among them, it is selected from the group consisting of a urethane skeleton, an ester skeleton and an ether skeleton. It is preferred to have at least one skeleton.
More preferably, it has two or more of a urethane skeleton, an ester skeleton, an ether skeleton, or a carbonate skeleton, that is, a polyurethane skeleton, a polyester skeleton, a polyether skeleton, or a polycarbonate skeleton.
Particularly preferably, it has at least two skeletons selected from the group consisting of a urethane skeleton, an ester skeleton, an ether skeleton and a carbonate skeleton. Among them, a urethane skeleton and other organic skeletons having a non-hydrocarbon group ( For example, (poly) ester skeleton, (poly) ether skeleton, (poly) carbonate skeleton, (meth) acrylate (co) polymer skeleton, etc.). Most preferably, it has a urethane skeleton and a (poly) ester skeleton.

It is particularly preferred that the aliphatic (meth) acrylate-based oligomer contains a urethane skeleton in the main chain because the resulting cured product is excellent in mechanical strength and the like. Further, if the oligomer contains an ester skeleton, an ether skeleton or a carbonate skeleton in the main chain, in particular, a polyester skeleton, a polyether skeleton or a polycarbonate skeleton, the refractive index of the obtained cured product is used for the protective part of the display device. Because it is close to the refractive index of acrylic resin (plate) and glass, glass used for light source lamps, acrylic resin (plate) and polycarbonate resin (plate) used for light guide plate, transparency and light transmission Efficiency can be further increased.
In this specification, an aliphatic (meth) acrylate-based oligomer having a urethane skeleton in the main chain is also referred to as a “urethane (meth) acrylate oligomer”, and in addition to the urethane skeleton, for example, an ester skeleton or an ether skeleton All the aliphatic (meth) acrylate oligomers having other organic skeletons and the like are classified as “urethane (meth) acrylate oligomers”. That is, for example, even if it has an ester skeleton or an ether skeleton in the molecule, it is included in the “urethane (meth) acrylate oligomer” if it further has a urethane skeleton.

The urethane (meth) acrylate oligomer can be obtained, for example, as a reaction product of an isocyanate compound obtained by reacting a polyol and diisocyanate and a (meth) acrylate monomer having a hydroxyl group. In addition, the reaction conditions normally used can be employ | adopted for this reaction.
Examples of the polyol include aliphatic polyester polyols, aliphatic polyether polyols, and aliphatic polycarbonate diols. When an aliphatic polyester polyol is used as the polyol, a urethane (meth) acrylate oligomer having a urethane skeleton and an ester skeleton in the structure is obtained. Similarly, when an aliphatic polyether polyol is used as the polyol, a urethane (meth) acrylate oligomer having a urethane skeleton and an ether skeleton in the structure is obtained, and when an aliphatic polycarbonate diol is used as the polyol, the urethane skeleton is included in the structure. And a urethane (meth) acrylate oligomer having a carbonate skeleton.

The method for producing the aliphatic polyester polyol is not particularly limited. For example, even when an aliphatic diol and an aliphatic dicarboxylic acid or an aliphatic dicarboxylic acid chloride are subjected to a polycondensation reaction, the diol or the dicarboxylic acid is esterified and transesterified. You may make it react. For this reaction, reaction conditions that are usually used can be employed.
Examples of the aliphatic diol include alkylene glycols such as ethylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, and tetrapropylene glycol. It is preferable to use 1 type (s) or 2 or more types.
As the aliphatic dicarboxylic acid, it is preferable to use one or more of adipic acid, succinic acid, glutaric acid, pimelic acid, sebacic acid, azelaic acid, maleic acid and the like.

As said aliphatic polyether polyol, 1 type (s) or 2 or more types of polyalkylene oxides, such as polyethylene oxide, polypropylene oxide, and ethylene oxide propylene oxide random copolymerization, can be used.

The aliphatic polycarbonate diol can be obtained, for example, by a transesterification reaction between a low molecular carbonate compound and an aliphatic diol.
As the low molecular carbonate compound, dimethyl carbonate can be used.
Examples of the aliphatic diol include 1,4-butanediol, 1,6-hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and diethylene glycol. Aliphatic hydrocarbon diols such as propylene glycol, 2-ethyl-1,3-hexanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanediol, and polyoxyethylene glycol One type or two or more types can be used.

As the diisocyanate, a linear or cyclic aliphatic diisocyanate can be used. Typical examples include hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated xylylene diisocyanate, and one or more of these can be used.

Examples of the (meth) acrylate monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 3-hydroxybutyl acrylate, polyethylene glycol monoacrylate, pentaerythritol triacrylate, and dipentaerythritol penta. An acrylate, dipentaerythritol hexaacrylate, etc. are mentioned, These 1 type (s) or 2 or more types can be used.

Specific examples of the urethane (meth) acrylate oligomer include, for example, EBECRYL 230, 270, 9260, 8296 (manufactured by Daicel Cytec); CN 9893, 9788, 983, 980, 981, 991, 9006, 9010, 9178 (manufactured by Sartomer) ); UF-8001G (manufactured by Kyoeisha); UV-7640B, 7550B, 6100B, 3310B, 3200B, 3000B, 3700B, 3520TL, 3210EA, 1700B (manufactured by Nippon Gosei Kagaku); UN-904, 908 (manufactured by Negami Kogyo Co., Ltd.) And the like.
In the present specification, a compound or the like having a name of a manufacturer or a sales company represents a trade name.

Among the aliphatic (meth) acrylate oligomers, an oligomer having a polyester skeleton (also referred to as “polyester (meth) acrylate oligomer”) and an oligomer having a polyether skeleton (also referred to as “polyether (meth) acrylate oligomer”). .) May have other skeletons other than the urethane skeleton in addition to the ester skeleton and ether skeleton in the structure, and may have a (meth) acryloxy group at the end of the structure. You may have.
Specific examples of the polyester (meth) acrylate oligomer include CN294, CN2280, CN2270, CN2297, CN2470 (manufactured by Sartomer), and the like.

Among the ether skeletons in the aliphatic (meth) acrylate oligomers having the ether skeleton (for example, (poly) ether (meth) acrylate oligomers and urethane (meth) acrylate oligomers having an ether skeleton), oxyalkylene skeletons (oxy Although it does not specifically limit as an alkylene chain), For example, it is suitable that it is a C1-C30 oxyalkylene chain.

In the oligomer having the (meth) acrylate (co) polymer skeleton, the (meth) acrylate (co) polymer skeleton has a structure obtained by (co) polymerizing any aliphatic (meth) acrylate monomer. For example, in addition to the aliphatic (meth) acrylate oligomer, a structure formed by (co) polymerizing one type or two or more types of aliphatic (meth) acrylate monomers to be described later can be used. Among these, in order to obtain a molded article having excellent adhesiveness, the aliphatic (meth) acrylate monomer forming the (meth) acrylate (co) polymer skeleton is an aliphatic chain having 4 or more carbon atoms. Monomer having hydrocarbon group, monomer having aliphatic cyclic structure, monomer having heterocyclic structure, monomer having neopentyl structure and / or alkylene glycol structure (oxyalkylene chain), and (meth) acryloyl group in one molecule It is preferable to use at least one monomer selected from the group consisting of monomers having a polar group and other polar groups. Furthermore, it is preferable that the (meth) acrylate-based (co) polymer skeleton contains 50% by mass or more of the above preferred monomer with respect to 100% by mass of the total amount of monomers forming the (meth) acrylate-based (co) polymer skeleton. .
Specific examples of the preferable monomer are the same as the compounds exemplified in the aliphatic (meth) acrylate monomer described later.

The aliphatic (meth) acrylate oligomer may contain an aromatic ring in the structure as long as the light resistance and heat resistance of the molded article are not impaired. For example, when the total amount of the aliphatic (meth) acrylate oligomer is 100% by mass, the oligomer total amount is preferably included in a range where the mass ratio of the aromatic ring is 20% by mass or less. More preferably, it is 10 mass% or less, More preferably, it is 5 mass% or less, Most preferably, it is 0 mass%, ie, it does not contain an aromatic ring.

(ii) Aliphatic (meth) acrylate monomers As the aliphatic (meth) acrylate monomers, aliphatic (meth) acrylate compounds other than the aliphatic (meth) acrylate oligomers described above can be used.
In addition, the aliphatic (meth) acrylate compound used as a raw material of the said aliphatic (meth) acrylate type oligomer can also be used as an aliphatic (meth) acrylate type monomer. That is, since the aliphatic (meth) acrylate compound used as a raw material does not correspond to the aliphatic (meth) acrylate oligomer itself, “aliphatic (meth) acrylate compound other than aliphatic (meth) acrylate oligomer” It corresponds to.

Examples of the aliphatic (meth) acrylate monomer include a monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms and a monomer having an aliphatic cyclic structure (however, it corresponds to the above-mentioned aliphatic cyclic skeleton-containing polyfunctional compound) A monomer having a heterocyclic structure (excluding those corresponding to the above-mentioned compounds containing an isocyanuric acid skeleton), a monomer having a neopentyl structure and / or an alkylene glycol structure (oxyalkylene chain), 1 Monomers having a (meth) acryloyl group and other polar groups in the molecule are preferred. The (meth) acrylate having such a structure is a monomer that gives a molded article excellent in durability (light resistance, heat resistance, and moisture resistance). More preferably, it is a monomer having a (meth) acryloyl group and another polar group in one molecule. Since such a monomer is excellent in compatibility with the mercapto group-containing polysiloxane compound, the obtained cured product is excellent in transparency and homogeneity.

Among the aliphatic (meth) acrylate monomers, the aliphatic chain hydrocarbon group in the aliphatic (meth) acrylate monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms is not particularly limited. An alkyl group or an alkenyl group having a number of 4 or more is preferable. Although the upper limit of the carbon number is not particularly limited, for example, a carbon number of 12 or less is preferable. More preferably, it is an alkyl group having 4 to 12 carbon atoms.
Specific examples of the aliphatic (meth) acrylate monomer having an aliphatic chain hydrocarbon group having 4 or more carbon atoms include alkyl (such as n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate). Meth) acrylate; alkenyl (meth) acrylates such as 2-butenyl (meth) acrylate and 4-pentenyl (meth) acrylate. Among these, n-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate are preferable.

Examples of the aliphatic cyclic structure in the aliphatic (meth) acrylate monomer having an aliphatic cyclic structure include, for example, a monocyclic structure such as a cyclohexyl structure; an isobornyl structure, a dicyclopentanyl structure, a dicyclopentenyl structure, a dicyclodecanyl structure, A polycyclic structure such as a tricyclodecanyl structure or an adamantyl structure is preferred. Thereby, it is easy to obtain a molded body (cured product) having low hygroscopicity and further excellent in light resistance and heat resistance. Among these, a polycyclic structure is more preferable, and a tricyclodecanyl structure is particularly preferable.

Specific examples of the aliphatic (meth) acrylate monomer having an aliphatic cyclic structure include monofunctional (meth) acrylates such as cyclohexyl (meth) acrylate and 4-tert-butylcyclohexyl (meth) acrylate. , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecane methanol (meth) acrylate, etc. Can be mentioned. Among these, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate are preferable. More preferred are cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and adamantyl (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate monomer having the heterocyclic structure include PT810 manufactured by Ciba Specialty Chemicals; ERL4234, 4299, 4221, 4206 manufactured by UCC, and the like.

Specific examples of the aliphatic (meth) acrylate monomer having the neopentyl structure and the aliphatic (meth) acrylate monomer having a neopentyl structure and an alkylene glycol structure include, for example, neopentyl (meth) acrylate, neopentyl di (meth) ) Acrylate, neopentyl glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, and the like. Among these, neopentyl glycol di (meth) acrylate and ethoxylated neopentyl glycol di (meth) acrylate are preferable. More preferred is neopentyl glycol di (meth) acrylate.

Specific examples of the aliphatic (meth) acrylate monomer having an alkylene glycol structure include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,12-dodecanediol, neopentyl glycol, ethoxylated neopentyl glycol, propoxylated neopentyl glycol and other alkylene glycols, diols Examples include (meth) acrylate and di (meth) acrylate. More specifically, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butane Examples include diol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,12-dodecanediol di (meth) acrylate.

Among these, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, and tripropylene glycol glycol (meth) acrylate and di (meth) acrylate are preferable. If the alkylene glycol chain is too long, the hygroscopicity of the resulting cured product may not be sufficiently reduced, and if the alkylene glycol chain is too short, the resulting molded article may have insufficient elasticity. More preferred are di (meth) acrylates of any of these glycols. Specific examples of such di (meth) acrylates of glycol include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, and propylene glycol di (meth). Preferred are acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate and the like. More preferred are diethylene glycol di (meth) acrylate and dipropylene glycol di (meth) acrylate. Among these, more preferred are diacrylates of any of these glycols.
Of the aliphatic (meth) acrylate monomers having an alkylene glycol structure, those having a repeating structure of an oxyalkylene chain and having a weight average molecular weight of 1000 or more are structurally equivalent to the aliphatic (meth) This also applies to acrylate oligomers.

The aliphatic (meth) acrylate monomer having a (meth) acryloyl group and other polar group in one molecule is one (meth) acryloyl group and one or more other polar groups in the structure. It only has to have. When the monomer has two or more other polar groups, the other polar groups may be the same or different from each other.
The other polar group is not particularly limited as long as it is a polar group (bond), but is preferably a polar group having an oxygen atom. Examples of polar groups having an oxygen atom include hydroxyl groups, urethane groups (bonds), ester groups (bonds), ether groups (bonds), carbonate groups (bonds), and functional groups having these polar groups. . Among these, a hydroxyl group and a functional group having a hydroxyl group are preferable. A hydrocarbon group having a hydroxyl group is more preferable, and a hydroxyalkyl group having 1 to 3 carbon atoms is still more preferable.
Note that a polar group containing a (meth) acryloyl group in the structure, such as a (meth) acryloxyalkyl group, is also included in the other polar groups. In addition, the aliphatic (meth) acrylate monomer having a heterocyclic structure described above and the aliphatic (meth) acrylate monomer having an alkylene glycol structure also have a (meth) acryloyl group and another polar group in one molecule. It corresponds to the aliphatic (meth) acrylate monomer which it has.

Preferable specific examples of the aliphatic (meth) acrylate monomer having a (meth) acryloyl group and another polar group in one molecule are, for example, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, tetrahydrofurfuryl acrylate. , Pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, 2- (2-ethoxyethoxy) ethyl acrylate (ethyl carbitol acrylate), caprolactone acrylate, neopentyl glycol diacrylate, ethoxylated (9) tri And methylolpropane triacrylate. Among these, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tetrahydrofurfuryl acrylate, and ethyl carbitol acrylate are preferable.

(II) Aromatic (meth) acrylate compound The aromatic (meth) acrylate compound is a compound having an aromatic ring skeleton in the main chain and a (meth) acryloyl group at at least one molecular terminal. As the aromatic ring skeleton, for example, bisphenol skeletons such as bisphenol A, S, and F structures; fluorene skeletons and the like are suitable.
Examples of the (meth) acrylate compound having a bisphenol skeleton include ethylene oxide adduct di (meth) acrylate of bisphenol A, bisphenol A diglycidyl ether (meth) acrylic acid adduct, and the like.
As the (meth) acrylate compound having the fluorene skeleton, a compound having a structure in which a (meth) acryloyl group is bonded to the fluorene skeleton directly or via an oxyalkylene chain (monooxyalkylene chain or polyoxyalkylene chain). In particular, a so-called polyfunctional fluorene (meth) acrylate having a number of bonds of (meth) acryloyl groups (including those via an oxyalkylene chain) to the fluorene skeleton of 2 or more is preferable. Specific examples include Ogsol EA-0200, EA-0500, EA-1000 (manufactured by Osaka Gas Chemical Co., Ltd.).

-Other ingredients-
It is preferable that the resin composition also contains a polymerization initiator.
As the polymerization initiator, a radical polymerization initiator is preferably used.

The radical polymerization initiator is not particularly limited as long as it is a compound capable of generating radicals and initiating the polymerization, and examples thereof include the following compounds.
1,1′-azobis (cyclohexane-1-carbonitrile), 1,1′-azobis-1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, phenylazotriphenylmethane, 2,2 ′ -Azobis- (2-methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis-2-methyl Azo initiators such as methyl propionate, dimethyl 2,2′-azobisisobutyrate, 2,2′azobis-2-methylvaleronitrile;
Benzoyl peroxide, acetyl peroxide, tert-butyl peroxide, propionyl peroxide, lauroyl peroxide, tert-butyl peroxide, tert-butyl perbenzoate, tert-butyl hydroperoxide, tert-butyl peroxypivalate, 1, 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, t-butylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-amylper Peroxide based initiators such as isononanoate, t-amyl peroxyacetate, t-amyl peroxybenzoate;
2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxy Ethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2- Methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1 -Butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Alkyl phenone initiators such;
Acylphosphine oxide-based initiators such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide;
Titanocene initiators such as bis (η ⁵ -2,4-cyclopentadien-1-yl) bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium;
1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Il]-, oxime ester initiators such as 1- (O-acetyloxime).

The content of the polymerization initiator may be appropriately selected depending on the polymerization system (curing system), the type of polymerization initiator used, the type of vinyl compound, and the like. For example, when a radical polymerization initiator is used, the content of the radical polymerization initiator is preferably 0.01 parts by weight or more with respect to 100 parts by weight of the total amount of vinyl compounds. This is because the curing can be performed sufficiently and the curing time can be shortened. More preferably, it is 0.1 weight part or more, More preferably, it is 0.2 weight part or more. The upper limit is preferably 10 parts by weight or less. If the amount exceeds 10 parts by weight, the optical properties of the cured product may be deteriorated due to the residue of the radical polymerization initiator. More preferably, it is 5 parts by weight or less, more preferably 3 parts by weight or less, and particularly preferably 2 parts by weight or less.

The resin composition can also contain a solvent as necessary for the purpose of adjusting the viscosity of the resin composition.
The solvent is not particularly limited and may be any organic solvent that is usually used. However, those that dissolve the above-described vinyl compound are suitable. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; hydrocarbons such as toluene and xylene; alcohols such as butanol and 2-ethylhexyl alcohol; ethylene glycol, diethylene glycol, (di) ethylene glycol methyl ether, (di) Glycols such as ethylene glycol ethyl ether, (di) ethylene glycol acetate, (di) ethylene glycol diacetate, (di) ethylene glycol methyl ether acetate, propylene glycol, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol methyl ether acetate And derivatives thereof (ether, ester); esters such as ethyl acetate and butyl acetate;
The solvent may cause bubbles in the cured product when the resin composition is polymerized to obtain a cured product, and when used in a large amount, the viscosity of the resin composition becomes too low, resulting in a cured product. In some cases, the controllability of the film thickness and shape cannot be made sufficient. Therefore, when a solvent is used, the content thereof is preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass or less, and still more preferably, with respect to 100% by mass of the total resin composition. Is 5% by mass or less, more preferably 1% by mass or less. The amount is particularly preferably 0.1% by mass or less, and most preferably 0% by mass, that is, no solvent is used.

In addition to the components described above, the resin composition further includes, for example, a polyfunctional thiol compound, inorganic fine particles, a reactive diluent, a saturated compound having no unsaturated bond, and a pigment unless the effects of the present invention are impaired. , 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, One or more of anti-coloring agent, emulsifier, anti-slip / scratch agent, anti-skinning agent, drying agent, antifouling agent, antistatic agent, conductive agent (electrostatic aid), photosensitizer, etc. May be contained.

<Hardened product>
The present invention is also a cured product obtained by curing the curable resin composition.
The cured product is obtained from the curable resin composition described above, and thus has no cracks or cracks, has high hardness and low water absorption, has a small expansion coefficient due to environmental humidity, and has mechanical properties. And optical characteristics can be sufficiently exhibited. Such a cured product is preferably a mold molded body (also referred to as a mold molded body), but may be a film shape such as a film or a sheet or a pellet shape.
In addition, in this invention, the hardened | cured material of a thick film can also be implement | achieved suitably. For example, the film thickness (thickness) of the film-shaped cured product (cured film) is preferably 10 μm or more, more preferably 15 μm or more, still more preferably 20 μm or more, and particularly preferably 21 μm or more. Moreover, it is preferable that it is 5000 micrometers or less, More preferably, it is 2000 micrometers or less.

As the curing method (polymerization method) of the resin composition, various methods such as thermal curing and photocuring (curing by irradiation with active energy rays) can be suitably used, and the thermal curing is about 30 to 400 ° C. It is preferable to cure in the temperature range, and the photocuring is preferably cured in the range of the integrated light amount of 10 to 10,000 mJ / cm ² .

Specific examples of the curing method for the resin composition include, for example, a method in which the resin composition is applied onto a substrate, polymerized (cured), and then the cured product is peeled off from the substrate, or the resin Examples include a method of casting the composition into a mold and curing it, and then releasing the cured product (mold molding method). The method can be appropriately selected according to the shape of the target cured product. . For example, when obtaining a film-shaped cured product (sheet-shaped cured product or the like), it is preferable to employ a molding method by coating in that it can be easily molded into a film shape. As a base material used, polymer films, such as PET, are mentioned, for example. Moreover, what is necessary is just to employ | adopt a metal mold molding method, when obtaining a metal mold body.
Curing may be performed in one step, or may be performed in two steps, such as primary curing (preliminary curing) and secondary curing (main curing). For example, when molding such as a lens is required, a demolding operation is required. However, a primary curing is performed before the demolding operation and a secondary curing is performed after the demolding operation. A molding method (hereinafter also referred to as “two-stage curing method”) is preferably employed.

As the above-mentioned two-stage curing method, as a first step corresponding to primary curing, a step of thermally curing the resin composition at 80 to 200 ° C. or a step of photocuring, and a second step corresponding to secondary curing, It is preferable to employ a method including a step of thermally curing the cured product obtained in the first step at a temperature exceeding 200 ° C. and not exceeding 500 ° C. In addition, you may further include the other process performed by a normal shaping | molding (molding) process.

In the first step, when thermosetting is performed, the curing temperature is preferably 80 to 200 ° C. More preferably, it is 100 degreeC or more, More preferably, it is 160 degreeC or less.
The curing time in the thermosetting step is preferably, for example, within 10 minutes, more preferably within 5 minutes, and even more preferably within 3 minutes. Further, it is preferably 10 seconds or longer, more preferably 30 seconds or longer.

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

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

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

What is necessary is just to set suitably the irradiation time of the said active energy ray irradiation, ie, the hardening time in the hardening process by an active energy ray, according to the kind, irradiation amount, etc. of an active energy ray. For example, the irradiation time of ultraviolet rays or visible rays having a wavelength of 180 to 500 nm is preferably 0.1 microseconds to 30 minutes, and more preferably 0.1 milliseconds to 10 minutes.

The first step is also preferably a curing step using a mold made of metal, ceramic, glass, resin or the like (referred to as “mold”). The curing process using a mold may be a curing process normally performed by a mold molding method such as an injection molding method, a compression molding method, a casting molding method, or a sandwich molding method. If it is a hardening process using such a metal mold | die, it is excellent in various physical properties, such as abrasion resistance, low shrinkage, dimensional accuracy, and mold transfer property, and there is no coloring and a transparent molded object (cured material). Easy to manufacture.

When the first step is a curing step using a mold, it is preferable to perform the demolding step after the first step and before the second step. The mold including the demolding process, that is, the cured product obtained in the first process is taken out from the mold, and the taken cured product is used for the next second process, whereby the expensive mold is effectively rotated (recycled). ) And the life of the mold can be extended, and a molded product can be obtained at low cost.
In this case, the resin composition is a one-component composition containing a curing agent and other components as necessary, and the one-component composition is filled into a mold that matches the shape of the target molded article (injection / A method in which the cured product is taken out from the mold after coating and the like is suitably used.

In the second-stage curing method, in the second step, the cured product obtained in the first step (preferably, the cured product taken out from the mold by the demolding step) is heat-cured at a temperature exceeding 150 ° C. and not more than 500 ° C. It is preferable to make it. More preferably, it is 200 degreeC or more, More preferably, it is 220 degreeC or more, Most preferably, it is 250 degreeC or more, Most preferably, it is 270 degreeC or more. Moreover, More preferably, it is 400 degrees C or less.
The curing time in the second step is not particularly limited as long as the curing rate of the obtained molded body is sufficient, but considering the production efficiency, for example, it is preferably set to 30 minutes to 30 hours. . More preferably, it is 1 to 10 hours.

The second step can also be performed in any atmosphere of air and / or an inert gas atmosphere such as nitrogen. In particular, the second step is preferably performed in an atmosphere having a low oxygen concentration. For example, it is preferable to carry out in an inert gas atmosphere having an oxygen concentration of 10% by volume or less. More preferably, it is 3 volume% or less, More preferably, it is 1 volume% or less, Especially preferably, it is 0.5 volume% or less, Most preferably, it is 0.3 volume% or less. Further, the curing temperature may be changed stepwise within a temperature range exceeding 150 ° C. and 500 ° C. or less.

The strength of the cured product obtained by the above two-stage curing method may be a strength that can be taken out of the mold and keep the shape. For example, the ratio of the shape change when extruded with a force of 1 kgf / cm ² or more is The compressive strength is preferably 10% or less. The ratio of the shape change is more preferably 1% or less, still more preferably 0.1% or less, and particularly preferably 0.01% or less.

The cured product obtained by curing the curable resin composition of the present invention preferably has a water absorption of 0.85% or less. More preferably, it is 0.8% or less, More preferably, it is 0.7% or less. Moreover, the water absorption rate of the said hardened | cured material is 0.85% or more normally.
The water absorption rate is preferably measured by a method defined in JIS K6911 (General Test Method for Thermosetting Plastics, 2006). Specifically, it can be measured by the following method.
<Measurement method of water absorption>
The dimensions of the test specimen are 50 mm in diameter and 3 mm in thickness. As pretreatment, the test piece is dried for 24 hours in a thermostatic bath maintained at 50 ° C. Furthermore, the dried test piece is cooled to 23 ° C. with a desiccator containing silica gel, and the mass of the test piece is measured to the unit of 1 mg. Next, the test piece is immersed in distilled water at 23 ° C. for 24 hours and then taken out, wiped with a dry Kimwipe, and the mass after water absorption is measured to the nearest 1 mg. Then, the water absorption is calculated by the following formula.
A = (W2-W1) / W1 × 100
here,
A: Water absorption rate (%)
W1: Mass of test specimen before water absorption (g)
W2: Mass of test piece after water absorption (g)

The cured product preferably has a water absorption linear expansion coefficient of 0.22% or less. More preferably, it is 0.20% or less, More preferably, it is 0.18% or less. Moreover, a water absorption linear expansion coefficient is 0.22% or more normally.
The water absorption linear expansion coefficient can be measured by, for example, the following method.
<Measurement method of water absorption linear expansion coefficient>
The thickness of the test piece is measured immediately after measuring the test piece mass in the water absorption test described above. Thickness is measured to 1 micrometer unit using a micrometer. The water absorption expansion coefficient is calculated from the following formula.
B = (T2-T1) / T1 × 100
here,
B: Water absorption linear expansion coefficient (%)
T1: Thickness (mm) of test piece before water absorption
T2: Thickness (mm) of test piece after water absorption

The cured product preferably has a refractive index of 1.40 to 1.65. When the refractive index is in such a range, the cured product can be suitably used for an optical lens or the like. The refractive index of the cured product is more preferably 1.45 or more, further preferably 1.47 or more, and particularly preferably 1.50 or more. On the other hand, the upper limit is more preferably 1.60 or less.
The refractive index can be measured using a refractometer (Atago Co., Ltd., DR-M2).

The cured product preferably has an Abbe number of 45 or more. Thereby, the wavelength dispersion of light can be reduced, the resolution can be increased, and the optical characteristics can be improved. If it is less than 45, for example, bleeding may be observed, sufficient optical characteristics may not be exhibited, and a material suitable for an optical lens may not be obtained. The Abbe number is more preferably 46 or more, and still more preferably 47 or more. The upper limit of the Abbe number is not particularly limited, but is preferably 55 or less.
The Abbe number can be measured using a refractometer (Atago Co., Ltd., DR-M2).

The cured product preferably has a pencil hardness of 4H or more. Thus, since it is a hardened | cured material with high surface hardness, ie, excellent abrasion resistance, it can apply suitably also for the outdoor use use which is a more severe use environment. As said pencil hardness, More preferably, it is 5H or more, More preferably, it is 6H or more, More preferably, it is 7H or more, Most preferably, it is 9H or more. The above hardness is preferable for lens applications, particularly for imaging lens applications.
The pencil hardness can be measured using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho) in accordance with JIS-K5600-5-4 (established in 1999) with a load of 1000 g.

In order for the cured product to be a cured product having a high surface hardness, the amount of siloxane bonds in the cured product is 5% by mass or more in terms of the Si content in 100% by mass of the cured product. Is preferred. More preferably, it is 7 mass% or more, More preferably, it is 12 mass% or more. Moreover, since there exists a possibility that the intensity | strength of hardened | cured material may not become enough when there is too much quantity of the siloxane bond in hardened | cured material, a preferable upper limit is 22 mass% or less, More preferably, it is 18 mass% or less.

The cured product of the present invention is free from cracks and cracks, has high hardness and low hygroscopicity, has a small expansion coefficient due to environmental humidity, and can sufficiently exhibit mechanical characteristics and optical characteristics. Further, due to the resin composition having excellent moldability, the cured product has excellent mold transferability, and can be processed into a fine shape with high accuracy. Such a cured product is useful for various uses such as materials for paints and adhesives in addition to electric / electronic members, optical members, molded members, machine parts, automobile parts, civil engineering and building materials. Among them, it can be suitably used for an optical member, and is extremely useful particularly for optical lens applications requiring transparency and homogeneity, especially for imaging lens applications. Thus, an optical lens using a cured product obtained by curing the curable resin composition is also one preferred embodiment of the present invention.

Examples of the optical lens include eyeglass lenses; (digital) cameras, mobile phone cameras, in-vehicle cameras, surveillance cameras and other camera imaging lenses; light beam condensing lenses (optical pickup lenses), LED lenses And the like. Among these, a camera imaging lens, a light beam condensing lens, and a light diffusion lens are preferable, and a camera imaging lens is more preferable. Among camera imaging lenses, imaging lenses such as a mobile phone camera imaging lens and a digital camera imaging lens are preferable. Moreover, it is preferable that it is a micro optical lens.
In addition, when the said hardened | cured material is an optical member, the said curable resin composition may contain the other component suitably according to the use of the optical member. Specifically, UV absorber, IR cut agent, reactive diluent, pigment, washing agent, antioxidant, light stabilizer, plasticizer, non-reactive compound, chain transfer agent, thermal polymerization initiator, anaerobic polymerization Initiators, light stabilizers, polymerization inhibitors, antifoaming agents and the like are suitable.

Since the curable resin composition of the present invention has the above-described configuration, it provides a cured product that is free from cracks and cracks during curing, has high hardness, low hygroscopicity, and has a small expansion coefficient due to environmental humidity. It is something that can be done. Therefore, if such a curable resin composition is used, it has a high level of wear resistance and the like that can be suitably applied to outdoor use applications and physical contact applications, and is excellent in low moisture absorption. A cured product (molded article) useful for various uses such as an optical member can be obtained.

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%”.

Synthesis example 1
Synthesis of polysiloxane (1) (mercapto group-containing siloxane unit / other structural unit = 100% / 0% (molar ratio))
A 4-neck 1 L separable flask equipped with a gas inlet, a condenser, a thermometer, and a stirring rod was charged with 900 g of 3-mercaptopropyltrimethoxysilane and 63.3 g of formic acid, and was purged with nitrogen. The temperature was kept at 50 ° C. in an oil bath, and 165.2 g of water was added over 60 minutes with stirring. The reaction solution was heated to distill off methanol produced by hydrolysis and perform condensation. It heated until internal temperature became 150 degreeC, and also reduced pressure to 1 kPa, and the volatile component was distilled off. The reaction solution was cooled to 40 ° C. to obtain 616.78 g of a polysiloxane compound (referred to as polysiloxane (1)).

Synthesis example 2
Synthesis of polysiloxane (2) (mercapto group-containing siloxane unit / other structural unit = 75% / 25% (molar ratio))
3-mercaptopropyltrimethoxysilane (726 g), methyltrimethoxysilane (167.64 g), and formic acid (68.06 g) were charged into a 4-neck 1 L separable flask equipped with a gas inlet, a condenser, a thermometer, and a stirring rod, and replaced with nitrogen. It was. The temperature was kept at 50 ° C. in an oil bath, and 177.62 g of water was added over 60 minutes with stirring. The reaction solution was heated to distill off methanol produced by hydrolysis and perform condensation. It heated until internal temperature became 150 degreeC, and also reduced pressure to 1 kPa, and the volatile component was distilled off. The reaction solution was cooled to 40 ° C. to obtain 586.05 g of a polysiloxane compound (referred to as polysiloxane (2)).

Synthesis example 3
Synthesis of polysiloxane (3) (mercapto group-containing siloxane unit / other structural unit = 50% / 50% (molar ratio))
A four-neck 1L separable flask equipped with a gas inlet, a condenser, a thermometer, and a stirring rod was charged with 552 g of 3-mercaptopropyltrimethoxysilane, 382.95 g of methyltrimethoxysilane, and 77.64 g of formic acid, and purged with nitrogen. It was. The temperature was kept at 50 ° C. in an oil bath, and 202.64 g of water was added over 60 minutes with stirring. The reaction solution was heated to distill off methanol produced by hydrolysis and perform condensation. It heated until internal temperature became 140 degreeC, and also reduced pressure to 1 kPa, and the volatile component was distilled off. The reaction solution was cooled to 40 ° C. to obtain 579.3 g of a polysiloxane compound (referred to as polysiloxane (3)).

Production Example 1 (resin composition (1))
To 80 parts of polysiloxane (1) obtained in Synthesis Example 1, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 14 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 6 parts of tricyclodecane dimethanol diacrylate KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd.) were added thereto and mixed until uniform. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. Thus, a resin composition (1) was obtained.

Production Example 2 (resin composition (2))
In Production Example 1, except that the addition amount of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate KAYARAD R-684 was changed to the amount shown in Table 2, respectively, as in Production Example 1, A resin composition (2) was obtained.

Production Example 3 (resin composition (3))
In Production Example 1, except that the addition amount of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate KAYARAD R-684 was changed to the amount shown in Table 2, respectively, as in Production Example 1, A resin composition (3) was obtained.

Production Example 4 (resin composition (4))
To 80 parts of the polysiloxane (2) obtained in Synthesis Example 2, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 14 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 6 parts of tricyclodecane dimethanol diacrylate KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd.) were added thereto and mixed until uniform. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (4) was obtained.

Production Example 5 (resin composition (5))
In Production Example 4, except that the addition amount of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate KAYARAD R-684 was changed to the amount shown in Table 2, respectively, in the same manner as in Production Example 4, A resin composition (5) was obtained.

Production Example 6 (resin composition (6))
In Production Example 4, except that the addition amount of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate KAYARAD R-684 was changed to the amount shown in Table 2, respectively, in the same manner as in Production Example 4, A resin composition (6) was obtained.

Production Example 7 (resin composition (7))
To 80 parts of polysiloxane (3) obtained in Synthesis Example 3, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 6 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 14 parts of tricyclodecane dimethanol diacrylate KAYARAD R-684 (manufactured by Nippon Kayaku Co., Ltd.) were added thereto and mixed until uniform. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (7) was obtained.

Production Example 8 (resin composition (8))
To 80 parts of polysiloxane (1) obtained in Synthesis Example 1, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 10 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts of tricyclodecane dimethanol diacrylate (NK ester DCP, Shin Nakamura Chemical Co., Ltd.) were added and mixed until uniform. . Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (8) was obtained.

Production Example 9 (resin composition (9))
To 80 parts of the polysiloxane (2) obtained in Synthesis Example 2, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 14 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 6 parts of tricyclodecane dimethanol diacrylate (NK ester DCP, Shin Nakamura Chemical Co., Ltd.) were added and mixed until uniform. . Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (9) was obtained.

Production Example 10 (resin composition (10))
In Production Example 9, the same procedures as in Production Example 9 were conducted except that the addition amounts of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate (NK ester DCP) were changed to the amounts shown in Table 2, respectively. A resin composition (10) was obtained.

Production Example 11 (resin composition (11))
In Production Example 9, using polysiloxane (3) obtained in Synthesis Example 3 instead of polysiloxane (2), the addition amount of light acrylate DPE-6A and tricyclodecane dimethanol diacrylate (NK ester DCP) A resin composition (11) was obtained in the same manner as in Production Example 9 except that the amounts were changed to those shown in Table 3, respectively.

Production Example 12 (resin composition (12))
To 80 parts of polysiloxane (1) obtained in Synthesis Example 1, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. Here, 10 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 10 parts of tris (2-acryloyloxyethyl) isocyanurate (funcryl FA-731A, manufactured by Hitachi Chemical Co., Ltd.) are added uniformly. Mix until. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (12) was obtained.

Production Example 13 (resin composition (13))
To 80 parts of the polysiloxane (2) obtained in Synthesis Example 2, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. Here, 14 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) and 6 parts of tris (2-acryloyloxyethyl) isocyanurate (funcryl FA-731A, manufactured by Hitachi Chemical Co., Ltd.) are added uniformly. Mix until. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a resin composition (13) was obtained.

Production Example 14 (resin composition (14))
Production Example 13 except that the addition amounts of light acrylate DPE-6A and tris (2-acryloyloxyethyl) isocyanurate (funcryl FA-731A) were changed to the amounts shown in Table 3, respectively. In the same manner as in Example 13, a resin composition (14) was obtained.

Production Example 15 (resin composition (15))
Production Example 13 except that the addition amounts of light acrylate DPE-6A and tris (2-acryloyloxyethyl) isocyanurate (funcryl FA-731A) were changed to the amounts shown in Table 3, respectively. In the same manner as in Example 13, a resin composition (15) was obtained.

Comparative Production Example 1 (Comparative resin composition (c1))
To 80 parts of polysiloxane (1) obtained in Synthesis Example 1, 0.005 part of Q-1301 (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.5 parts of propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Showa Denko KK) Part of the mixture was added and mixed until uniform. 20 parts of light acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.) was added thereto and mixed until uniform. Furthermore, 0.3 part of Perhexyl I (manufactured by NOF Corporation) was added and mixed until uniform. In this way, a comparative resin composition (c1) was obtained.

Comparative Production Example 2 (Comparative resin composition (c2))
In Comparative Production Example 1, a comparative resin composition (c2) was obtained in the same manner as Comparative Production Example 1 except that the polysiloxane (2) obtained in Synthesis Example 2 was used instead of the polysiloxane (1). It was.

Comparative Production Example 3 (Comparative resin composition (c3))
In Comparative Production Example 1, a comparative resin composition (c3) was obtained in the same manner as in Comparative Production Example 1, except that the polysiloxane (3) obtained in Synthesis Example 3 was used instead of the polysiloxane (1). It was.

The details of the vinyl compounds used in each production example are shown in Table 1.

Example 1
(First step)
The resin composition (1) obtained in Production Example 1 was sandwiched between two metal plates of SUS304 (manufactured by Nippon Test Panel Co., Ltd., surface No. 800) having a 1 mm gap, and cast-molded. After being cured by heating at 140 ° C. for 2 minutes, the mold was removed.
(Second step)
The cured body after the first step was heated at about 15 ° C./min under N ₂ atmosphere (performed at an oxygen concentration of 0.0 to 0.3% by volume unless otherwise specified), and reached the maximum. Heat treatment was performed at a temperature of 290 ° C. for 180 minutes, and then the temperature was lowered to 50 ° C. at about 1 ° C./min.

Examples 2 to 15 and Comparative Examples 1 to 3
Instead of the resin composition (1) obtained in Production Example 1, the resin compositions (2) to (15) obtained in Production Examples 2 to 15 and the comparative resin composition (c1) obtained in Comparative Production Examples 1 to 3 ) To (c3) were used, and the curing treatment was performed in the same manner as in Example 1.

About the secondary hardened | cured material (hardened | cured material obtained at the 2nd process) obtained in Examples 1-15 and Comparative Examples 1-3, the water absorption rate, the water absorption expansion coefficient, and pencil hardness (surface hardness) were evaluated. The results are shown in Tables 2 and 3. The water absorption rate and the water absorption expansion rate were measured by the measurement methods described above. Pencil hardness (surface hardness) was measured by the following method.
<Pencil hardness (surface hardness)>
It measured based on JIS-K5600-5-4 (1999 establishment) using the pencil scratch hardness tester (made by Yasuda Seiki Seisakusho). The load was 1000 g.

In Tables 2 and 3, “SH / Me” represents the ratio (molar ratio) of mercapto group-containing siloxane unit / methyl group-containing siloxane unit (siloxane unit in which CH ₃ is directly bonded to Si atom).

From the results of the above Examples and Comparative Examples, the cured products obtained in Examples 1 to 15 are all excellent in pencil hardness of 4H or higher and surface hardness, compared with the cured products obtained in Comparative Examples 1 to 3, It was found that the low hygroscopicity and the water absorption coefficient of expansion were low. Moreover, although not shown in the table | surface, it was confirmed that all the hardened | cured material obtained in Examples 1-15 is transparent (judgment by visual observation).

Claims (4)

A curable resin composition comprising a polysiloxane compound and a vinyl compound,
The curable resin composition, wherein the vinyl compound includes an aliphatic cyclic skeleton-containing polyfunctional compound and / or an isocyanuric acid skeleton-containing compound. The curable resin composition according to claim 1, wherein the vinyl compound has a (meth) acryloyl group. The polysiloxane compound has a structure in which 50% by mass or more of Si atoms are bonded to an aliphatic hydrocarbon group having 3 or more carbon atoms with respect to 100% by mass of all Si atoms contained in the polysiloxane compound. The curable resin composition according to claim 1 or 2. A cured product obtained by curing the curable resin composition according to claim 1.