KR102165729B1 - Low viscosity agent of high refractive index polymerizable compound and polymerizable composition containing the same - Google Patents

Abstract

[Problem] A high refractive index low viscosity agent and a polymerizable composition containing the same are provided, which breaks the trade-off between low Abbe and low viscosity, and exhibits little loss of refractive index when blended.
[Solution] A compound having a solid state at 23°C and a melting point of less than 100°C under 1013.25 hPa, the viscosity at 100°C is 10 mPa·s or less, and the D line of the cured product (589.3 nm), a compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in the D line (589.3 nm) of the cured product is used as a low viscosity agent for a high refractive index polymerizable compound. Way.

Description

Low viscosity agent of high refractive index polymerizable compound and polymerizable composition containing the same

The present invention relates to a low viscosity agent, and more particularly, to a low viscosity agent useful as a high refractive index diluent capable of achieving a low viscosity of a polymerizable optical material having a high refractive index.

Resin lenses are used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras, and are required to have excellent optical properties according to the purpose of the electronic devices. In addition, high durability, for example, heat resistance and weather resistance, and high productivity that can be molded in good yield are required in accordance with the usage mode. As a material for a resin lens that satisfies these requirements, for example, a thermoplastic transparent resin such as a polycarbonate resin, a cycloolefin polymer, and a methacrylic resin has been used.

In recent years, in the manufacture of resin lenses, in order to improve yield and production efficiency, and further suppress optical axis shift during lens lamination, from injection molding of thermoplastic resin to compression molding using a liquid curable resin at room temperature. The transition to wafer-level molding is being actively studied.

Meanwhile, a plurality of lenses are used in a high-resolution camera module, and one of them is a wavelength correction lens, and an optical material having high wavelength dispersion, that is, a low Abbe number, is required.

In the case of a material characterized by a low Abbe number, in addition to a high refractive index, high transparency is also required. However, when these optical properties are improved, the viscosity of the material increases, and handling properties are often significantly deteriorated. In general, this is due to the fact that the component contributing to the high refractive index has a high electron density, and thus it is easy to increase the viscosity, and the deterioration of the handling property can be said to be an essential problem in the development of a low Abbe material.

In response to such a problem, for example, a liquid (meth)acrylate having a relatively high refractive index is employed as a diluent, and there is a proposal of a curable composition for a lens material in which the viscosity is reduced and the handling property is improved (Patent Document 1). Further, there is a proposal of a curable composition in which an oxyalkylene group is introduced into a component contributing to a high refractive index, thereby achieving a low viscosity without using a diluent (Patent Document 2).

Japanese Patent Publication No. 2012-255914 Japanese Patent Publication No. 2015-199952

However, in the curable composition (Patent Document 1) using the above-described diluent, the refractive index n _D at 589 nm after photocuring is around 1.61, but the Abbe number ν _D is 25 or more, for example, a low Abbe of 23 or less. It did not meet the demands of Sue. Further, in the curable composition without a diluent (Patent Document 2), the refractive index n _D : 1.60 or more after photocuring was not realized, and the optical properties were not sufficiently satisfied.

As described above, low Abbe and low viscosity are in a trade-off relationship, for example, while realizing a low viscosity of 10,000 mPa·s or less, a high refractive index of 1.60 or more and a low viscosity of 23 or less in the cured product. There is still no optical material that has realized the excellent optical properties called Abbe's number.

In addition, conventional diluents for achieving low viscosity generally have a low refractive index, while optical properties (high refractive index, low Abbe number, high refractive index) required for optical materials such as lens targets for recent high resolution camera modules Since the transparency) is still higher, it is supposed that the combination of a conventional diluent (low viscosity agent) can rather lead to high Abbe of the optical material.

The present invention has been made in view of these circumstances, and provides a high refractive index low viscosity agent and a polymerizable composition containing the same, which breaks the tradeoff between low Abbe and low viscosity, and has a low loss of refractive index when blended. Is to do it as a task.

In order to solve the above problems, the inventors of the present invention have conducted intensive investigations, and as a result, a low Abbe compound having a viscosity of 10 mPa·s or less at room temperature and pressure, and a low viscosity agent for a polymerizable compound having a high refractive index As a result of using as a result, surprisingly, the viscosity of the system was reduced to 10,000 mPa·s or less, or maintained at 10,000 mPa·s or less, and excellent optical properties (low Abbe number, high Refractive index) was found to be realized, and the present invention was completed.

That is, as a first aspect, the present invention is a compound having a solid state at 23°C and a melting point of less than 100°C under 1013.25 hPa, and has a viscosity of 10 mPa·s or less at 100°C. A compound having an Abbe number of 23 or less in the D line (589.3 nm) of the cured product,

It relates to a method of using as a low viscosity agent for a high-refractive-index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in the D line (589.3 nm) of the cured product.

As a second aspect, the low viscosity agent is a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed cyclic hydrocarbon group having a plurality of benzene ring structures (1 to 6 carbon atoms) 6), and a monovalent or divalent hydrocarbon ring group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded by a single bond Having at least one aromatic group selected from the group, and,

A compound having at least one group having a polymerizable double bond selected from the group consisting of a vinyl group, an allyl group, a (meth)allyloxy group and a (meth)acryloyl group,

It relates to the method described in the first aspect.

As a 3rd viewpoint, it is related with the method described in 2nd viewpoint in which the said low viscosity agent is a compound represented by following formula [1].

[Formula 1]

(Wherein, X is a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, a biphenyl group having at least one substituent having a polymerizable double bond, Or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ¹ is a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (may be substituted with an alkyl group having 1 to 6 carbon atoms), or a plurality of Represents a hydrocarbon ring group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) to which the aromatic ring of is directly bonded by a single bond, and R ¹ represents a methyl group, an ethyl group, or an isopropyl group.)

As a 4th viewpoint, it relates to the method described in a 2nd viewpoint in which the said low-viscosity agent is a compound represented by following formula [2].

[Formula 2]

(In the formula, Ar ² represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2,

Y represents a single bond, -OC(=O)- group, or -O- group, and R ² represents a hydrogen atom or a methyl group.)

As a fifth aspect, it relates to the method described in the second aspect, wherein the low viscosity agent is a compound represented by the following formula [3-1] or [3-2].

[Formula 3]

(In the formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.)

As a sixth aspect, as a low viscosity agent of a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in the D line (589.3 nm) of the cured product,

Under 1013.25 hPa, the state of the substance at 23°C is a solid, a compound having a melting point of less than 100°C, the viscosity at 100°C is 10 mPa·s or less, and the cured product at the D line (589.3 nm) It relates to a low viscosity agent comprising a compound having an Abbe number of 23 or less.

As a seventh aspect, (a) 100 parts by mass of a high-refractive-index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in the D line (589.3 nm) of the cured product, and

(b) A compound having a solid state at 23°C and a melting point of less than 100°C under 1013.25 hPa, the viscosity at 100°C is 10 mPa·s or less, and the cured product has a D line (589.3 nm) ) 10 to 500 parts by mass of a low-viscosity agent comprising a compound having an Abbe number of 23 or less

It relates to a polymerizable composition comprising a.

As an eighth aspect, the (a) high refractive index polymerizable compound is a polycondensate of an alkoxysilicon compound A represented by formula [4], and an alkoxysilicon compound A represented by formula [4] and formula [5]. It relates to the polymerizable composition according to the seventh viewpoint containing a reactive polysiloxane containing at least one of the polycondensate of the alkoxysilicon compound B to be used.

[Formula 4]

(Wherein, X is a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, a biphenyl group having at least one substituent having a polymerizable double bond, Or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ³ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (the number of carbon atoms It may be substituted with an alkyl group of 1 to 6), or a hydrocarbon ring group in which a plurality of aromatic rings are directly bonded by a single bond (may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ³ is It represents a methyl group, an ethyl group, or an isopropyl group.)

[Formula 5]

(In the formula, Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (may be substituted with an alkyl group having 1 to 6 carbon atoms), or Represents a hydrocarbon ring group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded by a single bond, and R ⁴ represents a methyl group, an ethyl group, or an isopropyl group.),

As a ninth aspect, it relates to the polymerizable composition according to the seventh aspect, wherein the (a) high refractive index polymerizable compound contains a fluorene compound represented by formula [6].

[Formula 6]

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² are each independently a phenylene group which may have a substituent or a naphthalenediyl group which may have a substituent And L ³ and L ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms, and m and n each independently represent 0 or a positive integer satisfying 0≦m+n≦40. )

As a tenth aspect, the (a) high refractive index polymerizable compound is a compound represented by the following formula [7-1], a compound having a structural unit represented by the formula [7-2], and formula [7-2] It relates to the polymerizable composition according to the seventh aspect, selected from the group consisting of a compound having a structural unit represented by and a structural unit represented by formula [7-3].

[Formula 7]

(In the formula, each of two Qs is the same group, and represents a group selected from the group consisting of a vinyloxy group, an allyloxy group, and a (meth)acryloyloxy group, and two p's each have an integer of 0 to 3, Show.)

[Formula 8]

(In the formula, Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.)

As an eleventh aspect, it relates to the polymerizable composition according to any one of the seventh to tenth aspects, further comprising a polymerizable diluent in which the state of the substance is liquid at 23°C under (c)1013.25 hPa. .

As a twelfth viewpoint, it relates to a cured product of the polymerizable composition according to any one of the seventh to eleventh viewpoints.

As a thirteenth viewpoint, it relates to a material for a high refractive index resin lens comprising the polymerizable composition according to any one of the seventh to eleventh viewpoints.

As a 14th viewpoint, it relates to a resin lens produced from the polymerizable composition according to any one of the 7th to 11th viewpoints.

As a fifteenth aspect, the step of filling the polymerizable composition according to any one of the seventh to eleventh aspects into the space between the support and the mold to be bonded, or the space inside the dividable mold, and the filled composition It relates to a method for producing a molded article including a step of photopolymerizing by exposure to light.

As a sixteenth aspect, the fifteenth aspect further includes a step of removing the obtained photopolymer from the filled space and releasing it, and a step of heating the photopolymer before, midway or after the release. It relates to the manufacturing method described in the viewpoint.

As a 17th viewpoint, it relates to the manufacturing method as described in a 15th viewpoint or a 16th viewpoint, wherein the molded article is a lens for a camera module.

The present invention is a compound having a solid state at 23° C. and a melting point of less than 100° C. under 1013.25 hPa, the viscosity at 100° C. is 10 mPa·s or less, and the cured product has a D line (589.3 nm) by using a compound having an Abbe number of 23 or less as a low viscosity agent and using it for a high refractive index polymerizable compound, the viscosity of the system is reduced to 10,000 mPa·s or less or maintained at 10,000 mPa·s or less, In addition, excellent optical properties (low Abbe number, high refractive index) can be realized in the cured product of this system.

In addition, the polymerizable composition of the present invention achieves low viscosity by blending the low viscosity agent, improves its handling properties, and the cured product is used as a lens for an optical device, for example, a high-resolution camera module. Desirable optical properties (low Abbe number, high refractive index) can be achieved.

Accordingly, the material for a high refractive index resin lens of the present invention comprising the polymerizable composition can be suitably used as a lens for a high resolution camera module.

Furthermore, since the polymerizable composition of the present invention has a viscosity that can be handled sufficiently in a solvent-free form by the blending of this low viscosity agent, it can be molded by applying compression processing (imprint technology) of a mold such as a mold. In addition, the mold release property after molding is also excellent, and a molded article can be suitably produced.

Furthermore, according to the manufacturing method of the present invention, since the polymerizable composition to be used has excellent handling properties, a molded article, particularly a lens for a camera module, can be efficiently manufactured.

1 is a diagram showing a ¹ H NMR spectrum of dimethoxy(phenanthrene-9-yl)(4-vinylphenyl)silane obtained in Production Example 1. FIG.
FIG. 2 is a diagram showing a ¹ H NMR spectrum of trimethoxy(9-phenanthryl)silane obtained in Production Example 3. FIG.

The present invention is a compound having a solid state at 23° C. and a melting point of less than 100° C. under 1013.25 hPa, the viscosity at 100° C. is 10 mPa·s or less, and the cured product has a D line (589.3 nm), a compound having an Abbe number, that is, ν _D of 23 or less, as a low viscosity agent for a high refractive index polymerizable compound described later, and the low viscosity agent is also an object of the present invention.

Hereinafter, the details of the present invention will be described.

<<Low viscosity agent>>

The low viscosity agent of the present invention, as described above, is a solid substance at 23°C under 1013.25 hPa (that is, atmospheric pressure), has a melting point of less than 100°C, and has a viscosity of 10 mPa·s or less at 100°C, And the cured product is not particularly limited as long as it is a compound having an Abbe number of 23 or less in the D line (589.3 nm).

Examples of the low viscosity agent include compounds each having at least one group having an aromatic group and a polymerizable double bond. Herein, the polymerizability refers to a property in which a part of a molecule chemically reacts by external stimuli such as heat or light, and causes a polymerization reaction by cleavage or decomposition.

As the compound, specifically, a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed cyclic hydrocarbon group having a plurality of benzene ring structures ( It may be substituted with an alkyl group), and a monovalent or divalent hydrocarbon ring aggregation group in which a plurality of aromatic rings are directly bonded by a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms). Compounds having at least one selected aromatic group, and having at least one group having a polymerizable double bond selected from the group consisting of a vinyl group, an allyl group, a (meth)allyloxy group and a (meth)acryloyl group. I can.

In the aromatic group, as a monovalent or divalent condensed cyclic hydrocarbon group having a plurality of benzene ring structures, for example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, And monovalent or divalent groups derived from fluorene.

In addition, as a monovalent or divalent hydrocarbon ring group group in which a plurality of aromatic rings are directly bonded by a single bond, for example, biphenyl, terphenyl, quarterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, diphenylfluorene And monovalent or divalent groups derived from.

On the other hand, in the phenyl group or phenylene group, the monovalent or divalent condensed cyclic hydrocarbon group and the monovalent or divalent hydrocarbon ring aggregate group, examples of the alkyl group having 1 to 6 carbon atoms that may have as a substituent include, for example, a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group. have.

Among these aromatic groups, phenyl group, naphthyl group, from the viewpoint of achieving solubility, the effect in maintaining viscosity reduction or low viscosity, and excellent optical properties (high transparency, high refractive index, low Abbe number) in the formulation, A phenanthryl group is mentioned as a preferable group.

As a specific example of the compound having at least one group each having a specific aromatic group and a polymerizable double bond, a compound represented by the following formula [1] can be mentioned.

[Formula 9]

In the formula [1], X is a phenyl group having at least one group having a polymerizable double bond, a naphthyl group having at least one group having a polymerizable double bond, a biphenyl group having at least one group having a polymerizable double bond, Or a phenanthryl group having at least one group having a polymerizable double bond, and Ar ¹ is a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (may be substituted with an alkyl group having 1 to 6 carbon atoms), or a plurality of The aromatic ring represents a hydrocarbon ring group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) directly bonded by a single bond, and R ¹ represents a methyl group, an ethyl group, or an isopropyl group.

As a phenyl group having at least one group having a polymerizable double bond represented by X, for example, 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 4-vinyloxyphenyl group, 4-allylphenyl group, 4- Allyloxyphenyl group and 4-isopropenylphenyl group are mentioned.

As a naphthyl group having at least one group having a polymerizable double bond represented by X, for example, 4-vinylnaphthalen-1-yl group, 5-vinylnaphthalen-1-yl group, 6-vinylnaphthalen-2-yl group, 5-vinyloxynaphthalen-1-yl group, 5-allylnaphthalen-1-yl group, 4-allyloxynaphthalen-1-yl group, 5-allyloxynaphthalen-1-yl group, 8-allyloxynaphthalen-1-yl group, 5 -Isopropenylnaphthalen-1-yl group is mentioned.

Examples of the biphenyl group having at least one group having a polymerizable double bond represented by X include 4'-vinyl-[1,1'-biphenyl]-2-yl group, 4'-vinyl-[1, 1'-biphenyl]-3-yl group, 4'-vinyl-[1,1'-biphenyl]-4-yl group, 4'-vinyloxy-[1,1'-biphenyl]-4-yl group, 4'-allyl-[1,1'-biphenyl]-4-yl group, 4'-allyloxy-[1,1'-biphenyl]-4-yl group, 4'-isopropenyl-[1,1 '-Biphenyl]-4-yl group.

As the phenanthryl group having at least one group having a polymerizable double bond represented by X, for example, 3-vinylphenanthrene-9-yl group, 7-vinylphenanthrene-9-yl group, 10-vinylphenanthrene-9 -Yl group, 7-vinylphenanthren-2-yl group, 6-vinylphenanthren-3-yl group, 10-vinylphenanthren-3-yl group, 3-vinyloxyphenanthrene-9-yl group, 3-allylphenanthrene- 9-yl group, 3-allyloxyphenanthrene-9-yl group, and 3-isopropenylphenanthrene-9-yl group are mentioned.

The X is preferably a phenyl group having at least one group having a polymerizable double bond, and more preferably a vinylphenyl group.

As a condensed cyclic hydrocarbon group having a plurality of benzene ring structures represented by Ar ¹ , for example, 1 derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene. The flag of the family is mentioned.

In addition, as a hydrocarbon ring group in which a plurality of aromatic rings are directly bonded by a single bond, for example, a monovalent group derived from biphenyl, terphenyl, quarterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene Can be raised.

On the other hand, in the condensed cyclic hydrocarbon group and the hydrocarbon ring aggregation group, examples of the alkyl group having 1 to 6 carbon atoms that may have as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group are mentioned.

The Ar ¹ is preferably a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.

Specific examples of the compound represented by the above formula [1] include, for example, dimethoxy(9-phenanthryl)(4-vinylphenyl)silane, diethoxy(9-phenanthryl)(4-vinylphenyl)silane. , Diisopropoxy (9-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4-vinylnaphthalen-1-yl) silane, dimethoxy (9-phenanthryl) (4' -Vinyl-[1,1'-biphenyl]-4-yl)silane, dimethoxy(9-phenanthryl)(3-vinylphenanthrene-9-yl)silane, dimethoxy(1-naphthyl)(4 -Vinylphenyl)silane, dimethoxy(2-naphthyl)(4-vinylphenyl)silane, dimethoxy(2-phenanthryl)(4-vinylphenyl)silane, dimethoxy(3-phenanthryl)(4-vinyl) Phenyl) silane, dimethoxy (9-phenanthryl) (4-vinylphenyl) silane, and [1,1'-biphenyl]-4-yldimethoxy (4-vinylphenyl) silane, but limited to this. It does not become.

Further, as a specific example of the compound having at least one of the specific aromatic group and a group having a polymerizable double bond, a compound represented by the following formula [2] can be mentioned.

[Formula 10]

In the above formula [2], Ar ² represents a q-valent aromatic hydrocarbon residue, q represents 1 or 2, Y represents a single bond, -OC(=O)- group, or -O- group, and R ² represents It represents a hydrogen atom or a methyl group.

The q-valent aromatic hydrocarbon residue in Ar ² is a group excluding q hydrogen atoms from benzene, a condensed cyclic hydrocarbon having a plurality of benzene ring structures, or a hydrocarbon ring aggregate in which a plurality of aromatic rings are directly bonded by single bonds. These may be mentioned, and these may be substituted with an alkyl group having 1 to 6 carbon atoms.

Specifically, a phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed cyclic hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms) May be), or a monovalent or divalent hydrocarbon ring group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) in which a plurality of aromatic rings are directly bonded by a single bond.

Examples of the phenyl group that may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ² include, for example, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4,6-trimethylphenyl group , 4-tert-butylphenyl group, and examples of the phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms include a phenylene group, a 2,4-methylphenylene group, and a 2,5-methylphenylene group , 2,4,5-trimethyl-1,3-phenylene group, and 2-tert-butyl-1,4-phenylene group.

As a monovalent or divalent condensed cyclic hydrocarbon group having a plurality of benzene ring structures represented by Ar ² , for example, naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, flu Or a monovalent or divalent group derived from orene.

In addition, as a monovalent or divalent hydrocarbon ring group group in which a plurality of aromatic rings are directly bonded by a single bond, for example, biphenyl, terphenyl, quarterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, diphenylfluorene And monovalent or divalent groups derived from.

On the other hand, in the condensed cyclic hydrocarbon group and the hydrocarbon ring aggregation group, examples of the alkyl group having 1 to 6 carbon atoms that may have as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group are mentioned.

Specific examples of the compound represented by the above formula [2] include, for example, 1-vinylnaphthalene, 2-vinylnaphthalene, 2-isopropenylnaphthalene, 2,7-bis(4-vinylphenyl)naphthalene, and naphthalene. And 1-ylmethyl (meth)acrylate and naphthalen-2-ylmethyl (meth)acrylate.

Examples of the low viscosity agent according to the present invention include compounds represented by the following formulas [3-1] to [3-4], and among them, formulas [3-1] and [3-2] The compound represented by the formula [3-1] is particularly preferred from the viewpoint of realizing the effect of reducing and maintaining the viscosity and excellent optical properties (low Abbe's number).

[Formula 11]

In the above formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.

The low-viscosity agent according to the present invention can suitably use a commercially available compound.

In addition, for example, an ester compound containing a (meth)acryloyl group, such as a compound represented by formula [3-4], can be prepared by a conventional method, and alcohol and (meth)acrylic acid halide are triethylamine Or it can be prepared by esterification reaction in the presence of pyridine.

In addition, the compound represented by the above formulas [3-1] and [3-3] (the compound represented by the above formula [1]) can be prepared by a conventional method, for example, an alkoxysilane compound and Conventional Grignard reaction, in which an organoalkoxysilane compound is obtained by reacting a Nyar reagent, or a conventional coupling reaction, in which an organoalkoxysilane compound is obtained by reacting an alkoxyhydrosilane compound and an arylhalide using a transition metal catalyst It can be manufactured as

Specifically, a Grignard reagent having an Ar ¹ group: Ar ¹ -Mg-Hal and a trialkoxysilane compound having an aromatic cyclic group having a polymerizable double bond: X-Si(OR ¹ ) ₃ are reacted, or polymerization Grignard reagent having an aromatic ring group having a double bond: X-Mg-Hal and a trialkoxysilane compound having an Ar ¹ group: Ar ¹ -Si(OR ¹ ) ₃ to react, polymerization represented by formula [1] A silane compound can be obtained (the above Ar ¹ , X and R ¹ have the same meaning as in the above formula [1], and Hal represents a halogen atom).

The Grignard reagent is obtained by reaction of an aryl halide: Ar ¹ -Hal or X-Hal with magnesium.

The preparation of the Grignard reagent and the reaction of the Grignard reagent and the alkoxysilane compound may be carried out in an organic solvent. Examples of the organic solvent used herein include ether solvents such as diethyl ether, tetrahydrofuran, and tert-butyl methyl ether; And inert organic solvents such as hydrocarbon solvents such as hexane, toluene, and xylene. These organic solvents may be used alone or in combination of two or more.

The production temperature and reaction temperature are preferably in the range of 0 to 200°C, particularly 20 to 150°C.

In addition, if oxygen is present in the reaction system of the Grignard reagent or the reaction system between the Grignard reagent and the alkoxysilane compound, the Grignard reagent reacts with oxygen in the manufacturing and reaction steps, causing the yield of the polymerizable silane compound to be reduced. Therefore, these are preferably carried out in an inert atmosphere such as nitrogen or argon.

The low-viscosity agent may be used alone or in combination of two or more.

<<High refractive index polymerizable compound>>

The low viscosity agent according to the present invention is used for a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index in the D line (589.3 nm) of the cured product, that is, n _D of 1.60 or more.

The high refractive index polymerizable compound is not particularly limited as long as it has a polymerizable group as described above and has a high refractive index of 1.60 or more in the cured product, for example, specific reactive polysiloxane shown below, or specific Fluorene compounds are mentioned.

<Reactive polysiloxane>

The reactive polysiloxane is at least one of a polycondensate of an alkoxysilicon compound A represented by formula [4], and a polycondensation product of an alkoxysilicon compound A represented by formula [4] and an alkoxysilicon compound B represented by formula [5]. Includes.

[Alkoxy Silicon Compound A]

[Formula 12]

In the above formula [4], X is a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, and having at least one substituent having a polymerizable double bond. A biphenyl group or a phenanthryl group having at least one substituent having a polymerizable double bond, Ar ³ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (It may be substituted with an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring group in which a plurality of aromatic rings are directly bonded by a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), R ³ represents a methyl group, an ethyl group, or an isopropyl group.

As a specific example of X in the above formula [4], in the compound represented by the above formula [1], the group mentioned as the group X in this formula [1] can be mentioned, and in particular, in the group X in the formula [1], In this case, the groups mentioned as preferred groups are mentioned.

Moreover, as a specific example of Ar ⁴ in said formula [4], the group mentioned as the group Ar ¹ in said formula [1] is mentioned, In particular, the group mentioned as a preferable group in the group Ar ¹ in formula [4] is mentioned. I can.

And as a specific example of the compound represented by said formula [4], the compound mentioned as a specific example of the compound represented by said formula [1] is mentioned.

[Alkoxy Silicon Compound B]

[Formula 13]

In formula [5], Ar ⁴ is a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (may be substituted with an alkyl group having 1 to 6 carbon atoms) , Or a hydrocarbon ring group in which a plurality of aromatic rings are directly bonded by a single bond (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and R ⁴ represents a methyl group, an ethyl group, or an isopropyl group.)

As a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms represented by Ar ⁴ , for example, a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4,6-trimethylphenyl group And 4-tert-butylphenyl group.

As a condensed cyclic hydrocarbon group having a plurality of benzene ring structures represented by Ar ⁴ , for example, 1 derived from naphthalene, phenanthrene, anthracene, triphenylene, pyrene, chrysene, naphthacene, biphenylene, and fluorene. The flag of the family is mentioned.

In addition, as a hydrocarbon ring group in which a plurality of aromatic rings are directly bonded by a single bond, for example, a monovalent group derived from biphenyl, terphenyl, quarterphenyl, binaphthalene, phenylnaphthalene, phenylfluorene, and diphenylfluorene Can be raised.

On the other hand, in the condensed cyclic hydrocarbon group and the hydrocarbon ring aggregation group, examples of the alkyl group having 1 to 6 carbon atoms that may have as a substituent include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, cyclopentyl group, n-hexyl group, and cyclohexyl group are mentioned.

The Ar ⁴ is preferably a condensed cyclic hydrocarbon group having a plurality of benzene ring structures (which may be substituted with an alkyl group having 1 to 6 carbon atoms), and more preferably a phenanthryl group.

Specific examples of the compound represented by the above formula [5] include, for example, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, trimethoxy (p-tolyl) silane, and trimethoxy (1 -Naphthyl)silane, triethoxy(1-naphthyl)silane, triisopropoxy(1-naphthyl)silane, trimethoxy(2-naphthyl)silane, triethoxy(2-naphthyl)silane , Triisopropoxy(2-naphthyl)silane, trimethoxy(2-phenanthryl)silane, trimethoxy(3-phenanthryl)silane, trimethoxy(9-phenanthryl)silane, triethoxy( 9-phenanthryl)silane, triisopropoxy(9-phenanthryl)silane, [1,1'-biphenyl]-4-yltrimethoxysilane, [1,1'-biphenyl]-4-yl Triethoxysilane and [1,1'-biphenyl]-4-yltriisopropoxysilane, but are not limited thereto.

As the alkoxysilicon compound constituting the reactive polysiloxane, in addition to the alkoxysilicon compound A represented by formula [4], when the alkoxysilicon compound B represented by formula [5] is included, the polycondensation reaction of these alkoxysilicon compounds The required mixing molar ratio is not particularly limited, but for the purpose of stabilizing the physical properties of the cured product, usually, the range of 9 mol or less of the alkoxysilicon compound B is preferable to 1 mol of the alkoxysilicon compound A. More preferably, it is a range of 1.5 mol or less. When the molar ratio of the alkoxysilicon compound B to the number of moles of the alkoxysilicon compound A is 9 or less, a sufficient crosslinking density is obtained, dimensional stability against heat is improved, and a light having a higher refractive index and a lower Abbe number is You can get the cargo.

The alkoxysilicon compound A and the alkoxysilicon compound B described above can be suitably selected and used as necessary, and a plurality of types of compounds may be used in combination, respectively. In this case, the ratio of the total molar amount of the alkoxysilicon compound A and the total molar amount of the alkoxysilicon compound B is within the above range.

[Acid or basic catalyst]

The polycondensation reaction of the alkoxysilicon compound A represented by the above formula [4], or an alkoxysilicon compound comprising the alkoxysilicon compound A represented by the above formula [4] and the alkoxysilicon compound B represented by the above formula [5] The polycondensation reaction of is suitably carried out in the presence of an acid or basic catalyst.

The type of the catalyst used for the polycondensation reaction is not particularly limited as long as it is dissolved in a solvent described below or is uniformly dispersed, and may be appropriately selected and used if necessary.

Examples of the catalyst that can be used include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid and oxalic acid; Examples of basic compounds include alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, quaternary ammonium salts, and amines; NH ₄ F and NR ₄ F are mentioned as a fluoride salt. Meanwhile, R is at least one group selected from the group consisting of a hydrogen atom, a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclic alkyl group having 3 to 12 carbon atoms.

These catalysts may be used alone or in combination of multiple types.

Examples of the acidic compound include hydrochloric acid, nitric acid, sulfuric acid, acetic acid, oxalic acid, and boric acid.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and triethylamine. I can.

Examples of the fluoride salt include ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride.

Among these catalysts, preferably used is one or more selected from the group consisting of hydrochloric acid, acetic acid, potassium hydroxide, calcium hydroxide, barium hydroxide and tetraethylammonium hydroxide.

The amount of the catalyst used is 0.01 to 10% by mass, preferably 0.1 to 5% by mass, based on the total mass of the alkoxysilicon compound. The reaction proceeds more favorably by setting the amount of the catalyst to be 0.01% by mass or more. In addition, if economic efficiency is considered, 10 mass% or less is sufficient.

[Polycondensation reaction]

The reactive polysiloxane (polycondensate) has one feature of the structure of the alkoxysilicon compound A, and the reactive group (polymerizable double bond) contained in the alkoxysilicon compound A is easily polymerized by a radical or a cation. , After polymerization (after curing) shows high heat resistance.

The hydrolysis polycondensation reaction of the alkoxysilicon compound A or the hydrolysis polycondensation reaction of the alkoxysilicon compound A and the alkoxysilicon compound B can be carried out without a solvent, but use of tetrahydrofuran (THF), which will be described later. It is also possible to use a solvent that is inert to the alkoxy silicon compound described above as the reaction solvent. In the case of using a reaction solvent, there is an advantage in that the reaction system can be made uniform and a more stable polycondensation reaction can be performed.

Although the synthesis reaction of the reactive polysiloxane may be performed without a solvent as described above, there is no problem even if a solvent is used to make the reaction more homogeneous. The solvent is not particularly limited as long as it does not react with the alkoxysilicon compound to be used and dissolves the polycondensate.

Examples of such a reaction solvent include ketones such as acetone and methyl ethyl ketone (MEK); Aromatic hydrocarbons such as benzene, toluene, and xylene; Ethers such as tetrahydrofuran (THF), 1,4-dioxane, diisopropyl ether, and cyclopentylmethyl ether (CPME); Glycols such as ethylene glycol, propylene glycol, and hexylene glycol; Glycol ethers such as ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve, and diethyl carbitol; Amides, such as N-methyl-2-pyrrolidone (NMP) and N,N-dimethylformamide (DMF), are mentioned. These solvents may be used alone or in combination of two or more.

The reactive polysiloxane used in the present invention is an alkoxy silicon compound A represented by formula [4] or an alkoxy silicon compound A represented by formula [4] and an alkoxy silicon compound B represented by formula [5]. It is obtained by carrying out hydrolysis polycondensation of a silicon compound in the presence of an acid or a basic catalyst. The reaction temperature required for hydrolysis polycondensation is 20 to 150°C, more preferably 30 to 120°C.

The reaction time is not particularly limited as long as the increase in the molecular weight of the polycondensate is completed and the molecular weight distribution is stabilized, and more specifically, it is several hours to several days.

After completion of the polycondensation reaction, it is preferable that the obtained reactive polysiloxane is recovered by any method such as filtration or solvent distillation, and appropriately subjected to purification treatment as necessary.

As an example of the method for producing a reactive polysiloxane used in the present invention, an alkoxysilicon compound A represented by formula [4], or an alkoxysilicon compound A represented by formula [4] and an alkoxyl group represented by formula [5] A method obtained by polycondensing an alkoxysilicon compound containing the silicon compound B in the presence of a base and removing the base using a cation exchange resin is mentioned.

The base and its use amount may be one or more compounds selected from the group consisting of the above-described basic compounds and fluoride salts, and the use amount thereof, preferably potassium hydroxide, calcium hydroxide, barium hydroxide and tetraethylammonium hydroxide. At least one selected from the group consisting of can be used as the base.

In addition, the reaction conditions and the like used for the polycondensation reaction and the reaction solvent can be those described above.

And after the reaction is completed, an ion exchange resin having a sulfo group as an ionic group is preferably used as the cation exchange resin used to remove the base.

As the cation exchange resin, a styrene-based (styrene-divinylbenzene copolymer), an acrylic-based material having a commonly used parent structure may be used. Further, any of a strongly acidic cation exchange resin having a sulfo group as an ionic group and a weakly acidic cation exchange resin having a carboxy group as an ionic group may be used. Furthermore, as the form of the cation exchange resin, various things such as granular, fibrous, and membrane can be used. These cation exchange resins are commercially available and can be used suitably.

Among them, a strongly acidic cation exchange resin having a sulfo group as an ionic group is preferably used.

As a commercially available strong acid cation exchange resin, for example, Amberlite (registered trademark) 15, 200, 200C, 200CT, 252, 1200H, IR120B, IR120H, IR122 Na, East IR124, East IRC50, East IRC86, East IRN77, East IRP-64, East IRP-69, East CG-50, East CG-120, Amberjet (registered trademark) 1020, East 1024, East 1060, East 1200 , Dong 1220, Amber List (registered trademark) 15, Dong 15DRY, Dong 15JWET, Dong 16, Dong 16WET, Dong 31WET, Dong 35WET, Dong 36, DowX (registered trademark) 50Wx2, Dong 50Wx4, Dong 50Wx8, Dong DR- 2030, DR-G8, HCR-W2, 650C UPW, G-26, 88, M-31, N-406, DowX (registered trademark) Monosphere (registered trademark) 650C, East 88 , M-31, 99K/320, 99K/350, 99Ca/320, Dow X Marathon (registered trademark) MSC, C [above, manufactured by Dow Chemical]; DIAION (registered trademark) EXC04, East HPK25, East PK208, East PK212, East PK216, East PK220, East PK228L, East RCP160M, East SK1B, East SK1BS, East SK104, East SK110, East SK112, East SK116, East UBK510L, UBK555 [above, manufactured by Mitsubishi Chemical Corporation]; Rewatit (registered trademark) MonoPlus S100 and MonoPlus SP112 [above, made by LANXESS] are mentioned.

In addition, as a commercially available weakly acidic cation exchange resin, for example, Amberlite (registered trademark) CG-50, copper FPC3500, copper IRC50, copper IRC76, copper IRC86, copper IRP-64, Dowex (registered trademark) MAC -3 [above, manufactured by Dow Chemical]; Diaion (registered trademark) CWK30/S, copper WK10, copper WK11, copper WK40, copper WK100, copper WT01S [above, manufactured by Mitsubishi Chemical Corporation].

The polycondensation compound obtained by this reaction has a weight average molecular weight Mw of 500 to 100,000, preferably 500 to 30,000, measured in terms of polystyrene by GPC, and a degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) ) Is 1.0-10.

On the other hand, the reactive polysiloxanes, a compound having a siloxane unit represented by [X (Ar ¹⁾ SiO] at least, for example, represented by [X (Ar ¹⁾ SiO] and [Ar _² SiO _^3/2] It is a compound which has a crosslinked structure which has at least a siloxane unit.

<Fluorene compound>

The fluorene compound is a compound represented by the following formula [6].

[Formula 14]

In the above formula [6], R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² are each independently a phenylene group which may have a substituent or a phenylene group which may have a substituent Represents a naphthalenediyl group, L ³ and L ⁴ each independently represent an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and m and n are each independently, 0≤ It represents 0 or a positive integer satisfying m+n≤40.

As the phenylene group which may have a substituent represented by L ¹ and L ² , for example, o-phenylene group, m-phenylene group, p-phenylene group, 2-methylbenzene-1,4-diyl group, 2 -Aminobenzene-1,4-diyl group, 2,4-dibromobenzene-1,3-diyl group, and 2,6-dibromobenzene-1,4-diyl group are mentioned.

In addition, as the naphthalenediyl group which may have a substituent represented by L ¹ and L ² , for example, 1,2-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 1 And an 8-naphthalenediyl group, a 2,3-naphthalenediyl group, and a 2,6-naphthalenediyl group.

Examples of the alkylene group having 1 to 6 carbon atoms represented by L ³ and L ⁴ include methylene group, ethylene group, trimethylene group, 1-methylethylene group, tetramethylene group, 1-methyltrimethylene group, 1 ,1-dimethylethylene group, pentamethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene Group, 1-ethyltrimethylene group, hexamethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltetramethylene Group, 2,2-dimethyltetramethylene group, 1-ethyltetramethylene group, 1,1,2-trimethyltrimethylene group, 1,2,2-trimethyltrimethylene group, 1-ethyl-1-methyltrimethylene group And 1-ethyl-2-methyltrimethylene group. Among these, a group corresponding to an alkylene group having 2 or 3 carbon atoms is more preferable as L ³ and L ⁴ .

In the compound represented by formula [6], m and n are each independently preferably a case where 0≦m+n≦30 is satisfied, and more preferably a case where 2≦m+n≦20 is satisfied.

As a specific example of the compound represented by the above formula [6], for example, 9,9-bis(4-(2-(meth)acryloyloxyethoxy)phenyl)-9H-fluorene, orgsol (Registered trademark) EA-0200, EA-0300, EA-F5003, EA-F5503, EA-F5510, EA-F5710, GA-5000 [above, manufactured by Osaka Gas Chemical Co., Ltd.], NK Ester A-BPEF [manufactured by Shin-Nakamura Chemical Co., Ltd.], but is not limited thereto. (On the other hand, in the present invention, the (meth)acryloyl group refers to both acryloyl and methacryloyl groups. Say.).

In addition, the compound suitable as a high refractive index polymerizable compound is a compound represented by the following formula [7-1], a compound having a structural unit represented by formula [7-2], and a compound represented by formula [7-2]. It is a compound having a structural unit and a structural unit represented by formula [7-3].

[Formula 15]

In formula [7-1], two Qs are each the same group, and represent a group selected from the group consisting of a vinyloxy group, an allyloxy group and a (meth)acryloyloxy group, and two p's are each equal to 0 to Represents an integer of 3.

[Formula 16]

In formulas [7-2] and [7-3], Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.

In particular, compounds suitable as high refractive index polymerizable compounds are compounds represented by the following formula [7-1-1], compounds having a structural unit represented by formula [7-2-1], and formula [7-2- It is a compound having a structural unit represented by 1] and a structural unit represented by formula [7-3-1].

[Formula 17]

[Formula 18]

The high refractive index polymerizable compound may be used alone or in combination of two or more.

<<polymerizable composition>>

The present invention also targets a polymerizable composition comprising 100 parts by mass of the (a) high refractive index polymerizable compound and 10 to 500 parts by mass of the (b) low viscosity agent.

In the above-described polymerizable composition, (a) a high refractive index polymerizable compound, and (b) a low viscosity agent may each be used alone or in combination of two or more.

The polymerizable composition may further contain (c) a polymerizable diluent in which the substance is in a liquid state at 23°C under 1013.25 hPa, and (d) a polymerization initiator.

<(c) Polymerizable diluent>

The polymerizable diluent usable in the polymerizable composition of the present invention is a compound in which the substance is liquid at 23°C under 1013.25 hPa, and is also referred to as a liquid diluent. The polymerizable diluent can be used for the purpose of 1) adjusting the viscosity of the polymerizable composition and 2) adjusting the crosslinking density at the time of curing the polymerizable composition. By using a polymerizable diluent, the effect of reducing and maintaining the viscosity of the above-described low-viscosity agent can be further enhanced.

As a polymerizable diluent, for example, 1,3-butanedioldi(meth)acrylate, 1,4-butanedioldi(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol Di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, Tricyclo[5.2.1.0 ^2,6 ]decanedimethanoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropanetetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, Dipentaerythritol hexa(meth)acrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, glycerin di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth) Acrylate, bis((meth)acryloyloxyethyl)hydroxyethyl isocyanurate, benzyl(meth)acrylate, 2-phenoxyethyl(meth)acrylate, 2-phenoxybenzyl(meth)acrylate , 3-phenoxybenzyl (meth)acrylate, 4-phenoxybenzyl (meth)acrylate, 2-(2-biphenylyloxy)ethyl (meth)acrylate, 2-(3-biphenylyloxy) Ethyl (meth)acrylate, 2-(4-biphenylyloxy)ethyl (meth)acrylate, ethoxylated o-phenylphenol (meth)acrylate, diethylene glycol monophenyl ether (meth)acrylate, polyethylene glycol Monophenyl ether (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, neopentyl glycol benzoate (meth)acrylate, and divinylbenzene.

The polymerizable diluent can be obtained as a commercial item, and specific examples thereof include NK ester 701A, copper A-DCP, copper A-DON-N, copper A-HD-N, copper A-NOD-N, copper DCP, copper DOD-N, copper HD-N, copper NOD-N, copper NPG, copper A-TMM-3, copper A-TMM-3L, copper A-TMM-3LMN, copper A-TMPT, copper TMPT, copper A-TMMT, AD-TMP, A-DPH, A-9550, A-9530, ADP-51EH, ATM-31EH, UA-7100, A-LEN-10 [above, Shinnakamura Chemical Co., Ltd.], KAYARAD (registered trademark) T-1420, D-330, D-320, D-310, DPCA-20, DPCA-30, DPCA-60, DPCA-120, Copper TMPTA, copper PET-30, copper DPHA, copper DPHA-2C [above, Japan Explosives Co., Ltd. product] can be mentioned.

When using a polymerizable diluent, a polymerizable diluent may be used alone or in combination of two or more. In addition, the addition amount is 10 to 500 parts by mass based on 100 parts by mass of the component (a), and when the entire polymerizable composition is 100 parts by mass, it is preferably 0.1 to 40 parts by mass, and 5 to 30 parts by mass. More preferable. If it is added in excess of 30 parts by mass, a drop in the refractive index may occur, and the high refractive index, which is the main purpose of the present invention, may not be maintained in some cases.

<(d) polymerization initiator>

The polymerizable composition of the present invention may further include a polymerization initiator. As the polymerization initiator, both a photopolymerization initiator and a thermal polymerization initiator can be used.

As a photoinitiator, for example, alkylphenones, benzophenones, Michler's ketones, acylphosphine oxides, benzoyl benzoates, oxime esters, tetramethylthiuram monosulfides, thioxane Tons are mentioned.

In particular, photo-cleavable photo-radical polymerization initiators are preferred.

Commercially available optical radical polymerization initiators include, for example, IRGACURE (registered trademark) 184, wing 369, wing 651, wing 500, wing 819, wing 907, wing 784, wing 2959, wing CGI1700, wing CGI1750, wing CGI1850. , East CG24-61, East TPO, Darocur (registered trademark) 1116, East 1173 [above, BASF Japan Corporation], ESACURE KIP150, East KIP65LT, East KIP100F, East KT37, East KT55, East KTO46, East KIP75[ As mentioned above, the Lamberti company make] is mentioned.

As a thermal polymerization initiator, azos and organic peroxides are mentioned, for example.

As a commercially available azo-based thermal polymerization initiator, for example, V-30, V-40, V-59, V-60, V-65, V-70 [above, manufactured by Wako Pure Chemical Industries, Ltd.] Can be lifted.

In addition, as commercially available organic peroxide-based thermal polymerization initiators, for example, Percadox (registered trademark) CH, copper BC-FF, copper 14, copper 16, Trigonox (registered trademark) 22, copper 23, and 121, Kayaester (registered trademark) P, Copper O, Kayabutyl (registered trademark) B [above, manufactured by Kayakuakzo Co., Ltd.], Perhexa (registered trademark) HC, Percumyl (registered trademark) H, Perocta ( Registered trademark) O, perhexyl (registered trademark) O, copper Z, perbutyl (registered trademark) O, and copper Z [above, manufactured by Nichiyu Corporation], but are not limited thereto.

When a polymerization initiator is added, the polymerization initiator may be used singly or in combination of two or more. In addition, the addition amount is 0.1 to 20 parts by mass, more preferably, based on 100 parts by mass of the total amount of the polymerizable component, that is, the component (a) and the component (b) (additionally (c) component as necessary) It is 0.3 to 10 parts by mass.

<Other additives>

Further, the polymerizable composition of the present invention is, if necessary, as long as the effect of the present invention is not impaired, for example, a chain transfer agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a leveling agent, a rheology modifier, a silane coupling agent, etc. It may contain adhesion aids, pigments, dyes, and antifoaming agents.

As the chain transfer agent, for example, as a thiol compound, methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, 3-mercaptopropionic acid 3-methoxybutyl, 3-mer Captopropionate n-octyl, 3-mercaptopropionate stearyl, 1,4-bis(3-mercaptopropionyloxy)butane, 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolethantris (3-mercaptopropionate), trimethylolethantris (3-mercaptobutyrate), trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetris (3-mercaptobutyrate), pentaerythritol Tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptobutyrate) ), mercaptocarboxylic acid esters such as tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, and tris[2-(3-mercaptobutyryloxy)ethyl]isocyanurate; Ethanethiol, 2-methylpropane-2-thiol, n-dodecanthiol, 2,3,3,4,4,5-hexamethylhexane-2-thiol (tert-dodecanthiol), ethane-1,2 -Alkyl thiols such as dithiol, propane-1,3-dithiol, and benzyl thiol; Aromatic thiols such as benzenethiol, 3-methylbenzenethiol, 4-methylbenzenethiol, naphthalene-2-thiol, pyridin-2-thiol, benzoimidazole-2-thiol, and benzothiazole-2-thiol; Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; As disulfide compounds, such as silane-containing thiols such as 3-(trimethoxysilyl)propane-1-thiol and 3-(triethoxysilyl)propane-1-thiol, diethyldisulfide, dipropyldisulfide, diisopropyl Disulfide, dibutyldisulfide, di-tert-butyldisulfide, dipentyldisulfide, diisopentyldisulfide, dihexyldisulfide, dicyclohexyldisulfide, didecyldisulfide, bis(2,3,3,4,4,5-hexa) Alkyl disulfides such as methylhexan-2-yl) disulfide (di-tert-dodecyldisulfide), bis(2,2-diethoxyethyl) disulfide, bis(2-hydroxyethyl) disulfide, and dibenzyl disulfide; Aromatic disulfides such as diphenyldisulfide, di-p-tolyldisulfide, di(pyridin-2-yl)pyridyldisulfide, di(benzoimidazol-2-yl)disulfide, and di(benzothiazol-2-yl)disulfide Ryu; Thiuram disulfides, such as tetramethyl thiuram disulfide, tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, and bis(pentamethylene) thiuram disulfide, and α-methylstyrene dimers.

When a chain transfer agent is added, a chain transfer agent may be used alone or in combination of two or more. In addition, the addition amount is 0.01 to 20 parts by mass, more preferably, based on 100 parts by mass of the total amount of the polymerizable component, that is, the component (a) and the component (b) (additionally (c) component as necessary) It is 0.1 to 10 parts by mass.

Examples of the antioxidant include phenolic antioxidants, phosphoric acid antioxidants, sulfide antioxidants, and the like. Among them, phenolic antioxidants are preferred.

As a phenolic antioxidant, for example, IRGANOX (registered trademark) 245, copper 1010, copper 1035, copper 1076, copper 1135 [above, BASF Japan Co., Ltd. product], Sumirizer (registered trademark) GA-80, Copper GP, Copper MDP-S, Copper BBM-S, Copper WX-R [above, Sumitomo Chemical Co., Ltd.], Adeka Staff (registered trademark) AO-20, Copper AO-30, Copper AO-40, Copper AO-50, copper AO-60, copper AO-80, copper AO-330 [above, made by ADEKA Co., Ltd.] are mentioned.

In the case of adding an antioxidant, the antioxidant may be used alone or in combination of two or more. In addition, the addition amount is 0.01 to 20 parts by mass, more preferably, based on 100 parts by mass of the total amount of the polymerizable component, that is, the component (a) and the component (b) (additionally (c) component as necessary) It is 0.1 to 10 parts by mass.

<Method of preparing a polymerizable composition>

The method for preparing the polymerizable composition of the present embodiment is not particularly limited. As a preparation method, for example, (a) component and (b) component, and if necessary, (c) component and (d) component are mixed in a predetermined ratio, and if necessary, other additives are further added and mixed. Then, a method of making a homogeneous solution, of each of these components, for example, by mixing some of the components (a) and (b) to make a homogeneous solution, then adding the remaining components, and other additives as necessary And a method of further adding and mixing to obtain a homogeneous solution, or a method of using a common solvent further in addition to these components.

In the case of using a solvent, the proportion of the solid content in the present polymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 50% by mass, or 1 to 30% by mass. %, or 1 to 25% by mass. Here, the solid content excludes the solvent component from all components of the polymerizable composition.

In addition, it is preferable to use the solution of the polymerizable composition after filtering using a filter or the like having a pore diameter of 0.1 to 5 μm.

<<hardened cargo>>

A cured product can be obtained by exposing the polymerizable composition to light (photocuring) or heating (thermosetting), and the present invention also targets a cured product of the polymerizable compound.

Examples of the light beam to be exposed include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, for example, sunlight, chemical lamps, low pressure mercury lamps, high pressure mercury lamps, metal halide lamps, xenon lamps, and UV-LEDs can be used. Further, post-baking may be performed after exposure to stabilize the physical properties of the cured product. The post-baking method is not particularly limited, but is usually carried out in a range of 50 to 260°C for 1 to 120 minutes using a hot plate or an oven.

Although it does not specifically limit as a heating condition in thermosetting, Usually, it is suitably selected in the range of 50-300 degreeC, 1 to 120 minutes. In addition, although it does not specifically limit as a heating means, For example, a hot plate and an oven are mentioned.

The cured product obtained by curing the polymerizable composition of the present invention has a high refractive index of 1.620 or more at a wavelength of 589.3 nm (D line), and further, it is possible to prepare a cured product having an Abbe number of 23 or less. It can be expected that the occurrence of cracks and peeling from the support can be suppressed and dimensional stability can be expected. Therefore, it can be suitably used as a material for a high refractive index resin lens.

<<molded body>>

The polymerizable composition of the present invention can be easily produced in parallel with the formation of a cured product by using a conventional molding method such as compression molding (imprint, etc.), mold, injection molding, and blow molding. . The molded article obtained in this way is also an object of the present invention.

As a method of manufacturing a molded article, for example, a process of filling the polymerizable composition of the present invention into a space between the support and the mold to be joined, or the space inside the dividable mold, a process of exposing the filled composition to photopolymerization And a method including a step of removing the obtained photopolymer from the filled space and releasing it, and a step of heating the photopolymer before, intermediate or after the release.

The step of exposure and photopolymerization can be carried out by applying the conditions shown in the above-described <<cured product>>.

The conditions for the heating step are not particularly limited, but are usually appropriately selected in the range of 50 to 260° C. and 1 to 120 minutes. In addition, although it does not specifically limit as a heating means, For example, a hot plate, an oven, etc. are mentioned.

The molded article produced by this method can be suitably used as a module lens for a camera.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

On the other hand, in Examples, the apparatus and conditions used for preparation of a sample and analysis of physical properties are as follows.

(1) Spin coater

Apparatus: Brewer Science, Cee (registered trademark) 200X

(2) UV exposure

Device: Batch UV irradiation device (high pressure mercury lamp 2kW×1 lamp)

(3) ¹ H NMR spectrum

Device: AVANCE III HD from Bruker

Measurement frequency: 500MHz

Solvent: CDCl ₃

Internal standard: Tetramethylsilane (δ=0.00ppm)

(4) Gel permeation chromatography (GPC)

Equipment: Prominence (registered trademark) GPC system manufactured by Shimadzu Corporation

Column: Showa Denko Corporation Shodex (registered trademark) GPC KF-804L and GPC KF-803L

Column temperature: 40℃

Solvent: tetrahydrofuran

Detector: RI

Calibration curve: standard polystyrene

(5) Abbe number ν _D , refractive index n _D

Apparatus A (when measuring the cured film): Multi-incidence spectral ellipsometer VASE manufactured by J.A.Ulam Japan

Apparatus B (when measuring a molded object): Prism coupler model 2010/M manufactured by Metricone

Measurement temperature: room temperature (about 23℃)

(6) melting point

Observation device: Nikon's polarizing microscope ECLIPSE (registered trademark) E600 POL

Heating device: ThermoPlate (registered trademark), automatic stage temperature control system for microscopes manufactured by Tokai Heat Co., Ltd.

Heating rate: 0.5℃/sec

Measurement method: The melting point is the temperature at which part of the sample begins to melt with the naked eye.

(7) viscosity

Equipment: EMS-1000 manufactured by Kyoto Electronics Industries, Ltd.

(8) transmittance

Apparatus: Ultraviolet visible near-infrared spectrophotometer V-670 manufactured by Japan Spectroscopy

Reference: air

In addition, the weak symbol shows the following meaning.

NMA: naphthalen-2-ylmethylacrylate

VN: 2-vinyl naphthalene [manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.]

SPeDMS: Dimethoxy (phenanthrene-9-yl) (4-vinylphenyl) silane

BPOEA: 2-([1,1'-biphenyl]-2-yloxy)ethylacrylate [NK Ester A-LEN-10 manufactured by Shinnakamura Chemical Industries, Ltd.]

BnA: Benzyl acrylate [Osaka Organic Chemical Co., Ltd. Viscoat #160, BZA]

DVB: Divinylbenzene [DVB-810 manufactured by Shinnittetsu Sumikin Chemical Co., Ltd.]

FDA: 9,9-bis(4-(2-acryloyloxyethoxy)phenyl)fluorene [NK Ester A-BPEF manufactured by Shin-Nakamura Chemical Industries, Ltd.]

PheTMS: trimethoxy(9-phenanthryl)silane

STMS: Trimethoxy (4-vinylphenyl) silane [Shin-Etsu Silicone (registered trademark) KBM-1403 manufactured by Shin-Etsu Chemical Industry Co., Ltd.]

TMOS: Tetramethoxysilane [manufactured by Tokyo Chemical Industry Co., Ltd.]

TEAH: 35% by mass aqueous solution of tetraethylammonium hydroxide [manufactured by Aldrich Corporation]

DDT: n-dodecanethiol [thiocalcol 20 manufactured by Kao Corporation]

I184: 1-hydroxycyclohexylphenyl ketone [IRGACURE (registered trademark) 184 manufactured by BASF Japan Co., Ltd.]

TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [IRGACURE (registered trademark) TPO manufactured by BASF Japan]

PGMEA: Propylene glycol monomethyl ether acetate

THF: tetrahydrofuran

[Preparation Example 1] Preparation of dimethoxy (phenanthrene-9-yl) (4-vinylphenyl) silane (SPeDMS)

To a 1 L reaction flask equipped with a condenser, 15.7 g (0.65 mol) of a magnesium cutting piece [manufactured by Kanto Chemical Co., Ltd.] was put, and air in the flask was replaced with nitrogen using a nitrogen balloon. Here, a mixture of 151.2 g (0.58 mol) of 9-bromophenanthrene [manufactured by Tokyo Chemical Industry Co., Ltd.] and 518 g of THF was added dropwise at room temperature (about 23° C.) for 1 hour, followed by stirring for 1 hour. , Grignard reagent was prepared.

To a 2 L reaction flask, 131.9 g (0.58 mol) of STMS and 259 g of THF were added, and air in the flask was replaced with nitrogen using a nitrogen balloon. Here, the Grignard reagent was added dropwise for 30 minutes under reflux (about 66° C.), and refluxed again for 24 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. 1,000 g of hexane was added to the obtained residue, refluxed for 1 hour to dissolve the soluble matter, and then the insoluble matter was filtered off. 750 g of hexane was again added to this insoluble matter, and after dissolving the soluble matter in the same manner, the insoluble matter was filtered off. Each filtrate was mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was recrystallized from 150 g of hexane to obtain 102.4 g (yield 47%) of the target SPeDMS.

¹ H NMR spectrum of the obtained compound is shown in Fig. 1.

[Preparation Example 2] Preparation of naphthalen-2-ylmethylacrylate (NMA)

To a 200 mL reaction flask, 25.0 g (0.158 mol) of 2-naphthalene methanol [manufactured by Tokyo Chemical Industry Co., Ltd.] and 158 g of THF were added, and the air in the flask was replaced with nitrogen using a nitrogen balloon, and then the temperature was reduced to 0°C. Cooled. To this, 17.58 g (0.174 mol) of triethylamine [manufactured by Tokyo Chemical Industry Co., Ltd.] and 15.73 g (0.174 mol) of acryloyl chloride [manufactured by Tokyo Chemical Industry Co., Ltd.] were added, and room temperature (approximately 23) was added thereto. ℃) for 1 hour. 158 g of water was added to the reaction mixture, and the product was extracted with 158 g of ethyl acetate. A crude product was obtained by distilling off the solvent under reduced pressure using an evaporator from the organic layer. The crude product was purified by silica gel chromatography (hexane/ethyl acetate = 9/1 (mass ratio)) to obtain 21.5 g (yield 64%) of naphthalen-2-ylmethylacrylate as the target product.

From the ¹ H NMR spectrum of the obtained compound, it was confirmed that it was the target structure.

[Preparation Example 3] Preparation of trimethoxy (9-phenanthryl) silane (PheTMS)

To a 500 mL reaction flask equipped with a condenser, 10.4 g (0.43 mol) of a magnesium cutting piece (manufactured by Kanto Chemical Co., Ltd.) was put, and air in the flask was replaced with nitrogen using a nitrogen balloon. Here, a mixture of 100.3 g (0.39 mol) of 9-bromophenanthrene [manufactured by Tokyo Chemical Industry Co., Ltd.] and 346 g of THF was added dropwise at room temperature (about 23° C.) for 1 hour, followed by stirring for 30 minutes. , Grignard reagent was prepared.

To a 1 L reaction flask, 178.0 g (1.17 mol) of TMOS and 346 g of THF were added, and air in the flask was replaced with nitrogen using a nitrogen balloon. Here, the Grignard reagent was added dropwise for 30 minutes at room temperature (about 23°C), and stirred for another 2 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. To the obtained residue, 1,000 g of hexane was added to dissolve the soluble matter, and then the insoluble matter was filtered off. To this insoluble matter, 500 g of hexane was added again, and the insoluble matter was similarly filtered. Each filtrate was mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was distilled under reduced pressure (1 mmHg, 120 to 150°C), and then recrystallized from 389 g of methanol to obtain 74.6 g (yield 64%) of PheTMS.

Fig. 2 shows the ¹ H NMR spectrum of the obtained compound.

[Production Example 4] Preparation of high refractive index polymerizable compound 1 (PSPeDMS)

To a 50 mL reaction flask equipped with a condenser, 1.36 g (3.23 mmol) of TEAH and 12 g of THF were added, and air in the flask was replaced with nitrogen using a nitrogen balloon. Here, a mixture of 29.9 g (80.7 mmol) of SPeDMS prepared according to Preparation Example 1 and 24 g of THF was added dropwise at room temperature (about 23° C.) for 10 minutes, followed by stirring at 40° C. for 16 hours. It was cooled to room temperature (about 23° C.). Next, 6.0 g of a cation exchange resin (Amberist (registered trademark) 15JWET manufactured by Dow Chemical) and 1.2 g of a filtering aid (KC Flock W-100GK manufactured by Japan Paper Corporation) were added to the reaction mixture previously washed with THF. And stirred for 1 hour to stop the reaction. Thereafter, the cation exchange resin and the filter aid were filtered through a membrane filter having a pore diameter of 0.5 μm, and washed again with 30 g of ethyl acetate. Together, the filtrate and washing liquid were added to 897 g of methanol to precipitate a polymer. The precipitate was filtered and dried to obtain 18.9 g of the target high refractive index polymerizable compound 1 (hereinafter, also abbreviated as PSPeDMS).

The weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 610, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number average molecular weight) was 1.2.

[Production Example 5] Preparation of high refractive index polymerizable compound 2 (XPe55)

To a 50 mL reaction flask equipped with a condenser, 0.90 g (2.14 mmol) TEAH, 0.86 g (47.7 mmol) of ion-exchanged water, and 7 g of THF were added, and the air in the flask was replaced with nitrogen using a nitrogen balloon. Here, a mixture of 9.9 g (26.8 mmol) of SPeDMS prepared according to Preparation Example 1, 8.0 g (26.8 mmol) of PheTMS prepared according to Preparation Example 3, and 14 g of THF was prepared at room temperature (about 23° C.) for 10 minutes. It was dripped and stirred at 40 degreeC for 16 hours. It was cooled to room temperature (about 23° C.). Next, 3.6 g of a cation exchange resin (Amberist (registered trademark) 15JWET manufactured by Dow Chemical) and 0.72 g of a filtering aid (KC Flock W-100GK manufactured by Japan Paper Corporation) were added to the reaction mixture previously washed with THF. And stirred for 1 hour to stop the reaction. Thereafter, the cation exchange resin and the filter aid were filtered through a membrane filter having a pore diameter of 0.5 μm, and washed again with 18 g of ethyl acetate. Together, this filtrate and washing liquid were added to 538 g of methanol to precipitate a polymer. The precipitate was filtered and dried to obtain 14.8 g of the target high refractive index polymerizable compound 2 (hereinafter, also abbreviated as XPe55).

The weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 1,000, and the degree of dispersion: Mw/Mn was 1.0.

For SPeDMS and NMA prepared according to Preparation Examples 1 and 2, and VN and BPOEA, the state and viscosity of the substance at 23°C and 100°C under atmospheric pressure were measured. Table 1 shows the results.

100 parts by mass of SPeDMS, NMA, VN, or BPOEA, 1 part by mass of I184, and 233 parts by mass of PGMEA were mixed. This solution was filtered through a PTFE syringe filter having a pore diameter of 0.2 μm to obtain a varnish having a solid content concentration of 30% by mass.

Each varnish was spin-coated on a silicon wafer (1,500 rpm for 30 seconds), and then heated and dried on a hot plate at 80°C for 1 minute. This coating film was exposed to UV light at 20 mW/cm ² for 250 seconds in a nitrogen atmosphere and then heated again on a hot plate at 150° C. for 20 minutes to prepare a cured film having a thickness of 1.0 μm. The Abbe number ν _D of the obtained cured film at a wavelength of 589 nm (D line) was measured. The results are shown together in Table 1.

[Table 1]

[Example 1] Preparation of polymerizable composition 1

(b) 2 parts by mass of VN as the low viscosity agent of the component, 6 parts by mass of the FDA as the high refractive index polymerizable compound of the component (a), and 2 parts by mass of BnA as the polymerizable diluent of the component (c) are mixed at 40°C. It was stirred for 2 hours. Here, 0.1 parts by mass of I184 and 0.07 parts by mass of TPO were added as the polymerization initiator of the component (d), and the mixture was stirred at 40°C for 1 hour. Again, 0.3 parts by mass of DDT was added thereto as a chain transfer agent (reaction accelerator), and stirred at room temperature (about 23° C.) for 2 hours to obtain a polymerizable composition 1 as a uniform transparent varnish.

[Examples 2 to 9, Comparative Examples 1 to 7] Preparation of polymerizable compositions 2 to 16

Except that each formulation was changed as described in Table 2, the same operation as in Example 1 was carried out to prepare polymerizable compositions 2 to 16, respectively. In addition, in Table 2, "part" represents "mass part".

[Table 2]

Table 3 shows the viscosity of each polymerizable composition at 25°C.

[Preparation of cured product and evaluation of optical properties]

Each polymerizable composition was sandwiched between two release-treated glass substrates together with a 1 mm-thick silicone rubber spacer. The interposed polymerizable composition was exposed to UV light for 250 seconds at 20 mW/cm ² . After the cured product was peeled from the glass substrate, it was heated on a hot plate at 150° C. for 20 minutes to prepare a molded article having a diameter of 30 mm and a thickness of 1 mm.

The Abbe number ν _D , the refractive index n _D , and the average transmittance at a wavelength of 400 to 800 nm at a wavelength of 589 nm (D line) of the obtained molded article were measured. The results are also shown in Table 3.

[Table 3]

As shown in Tables 2 and 3, by blending the low viscosity agent of the present invention, compared to the example of no blending of the low viscosity agent, lowering the viscosity and lowering the Abbe number ν _D are realized, and the refractive index n _D and the transmittance Also, a result was obtained that it could be improved to an equivalent or higher value (see Examples 1 and 3 and Comparative Example 1, Example 4 and Comparative Example 2, and Example 5 and Comparative Example 3). On the other hand, in Example 2, low viscosity, high refractive index, and high transmittance were achieved by blending a low viscosity agent, but as the ratio of the high refractive index polymerizable compound to the polymerizable composition decreased, an increase in Abbe number was observed.

In addition, BPOEA, which is a conventional liquid diluent, was able to lower the viscosity or maintain a viscosity of 10,000 mPa·s or less in the same manner as the low viscosity agent of the present invention, but the Abbe number increased (Example 5 and Comparative Example 5, Example 7 And Comparative Example 6, Example 9 and Comparative Example 7). On the other hand, when compared with the example of no blending of the low viscosity agent, the BPOEA resulted in an increase in Abbe's number rather by blending (see Comparative Examples 3 and 5, and Comparative Examples 4 and 7).

[(a) Optical properties of high refractive index polymerizable compound]

100 parts by mass of the FDA, PSPeDMS, XPe55 or BPOEA, 1 part by mass of I184, and 233 parts by mass of PGMEA were mixed. This solution was filtered through a PTFE syringe filter having a pore diameter of 0.2 μm to obtain a varnish having a solid content concentration of 30% by mass.

Each varnish was spin-coated on a silicon wafer (1,500 rpm for 30 seconds), and then heated and dried on a hot plate at 80°C for 1 minute. This coating film was exposed to UV light at 20 mW/cm ² for 250 seconds in a nitrogen atmosphere and then heated again on a hot plate at 150° C. for 20 minutes to prepare a cured film having a thickness of 1.0 μm. The refractive index and Abbe number ν _D of the obtained cured film at a wavelength of 589 nm (D line) were measured. The results are shown in Table 4.

[Table 4]

Claims (17)

Under 1013.25 hPa, the state of the substance at 23°C is a solid, a compound having a melting point of less than 100°C, the viscosity at 100°C is 10 mPa·s or less, and the cured product at the line D at 589.3 nm A compound having an Abbe number of 23 or less,
A method of using as a low viscosity agent for a high refractive index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in a D line of 589.3 nm of the cured product, wherein the low viscosity agent is the following formula [1] A compound represented by ].

(Wherein, X is a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, a biphenyl group having at least one substituent having a polymerizable double bond, Or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ¹ is a condensed cyclic hydrocarbon group having a plurality of benzene ring structures unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, or 1 carbon atom number A plurality of aromatic rings substituted or unsubstituted with an alkyl group of to 6 represent a hydrocarbon ring group in which a single bond is directly bonded, and R ¹ represents a methyl group, an ethyl group, or an isopropyl group.) The method of claim 1,
The method, wherein the low viscosity agent is a compound represented by the following formula [3-1].

(In the formula, R ¹ represents a methyl group, an ethyl group, or an isopropyl group.) (a) 100 parts by mass of a high-refractive-index polymerizable compound having at least one polymerizable double bond and having a refractive index of 1.60 or more in a D line of 589.3 nm of the cured product, and
(b) A compound having a solid state at 23°C and a melting point of less than 100°C under 1013.25 hPa, with a viscosity of 10 mPa·s or less at 100°C, and a D line of 589.3 nm of the cured product 10 to 500 parts by mass of a low viscosity agent comprising a compound having an Abbe number of 23 or less
As a polymerizable composition containing, wherein the high refractive index polymerizable compound is a polycondensate of an alkoxysilicon compound A represented by formula [4], and an alkoxysilicon compound A represented by formula [4] and formula [5]. A polymerizable composition containing a reactive polysiloxane containing at least one of the polycondensate of the alkoxysilicon compound B shown.

(Wherein, X is a phenyl group having at least one substituent having a polymerizable double bond, a naphthyl group having at least one substituent having a polymerizable double bond, a biphenyl group having at least one substituent having a polymerizable double bond, Or a phenanthryl group having at least one substituent having a polymerizable double bond, and Ar ³ is a phenyl group unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, a plurality of unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms Condensed cyclic hydrocarbon group having a benzene ring structure of, or a hydrocarbon ring group in which a plurality of unsubstituted or substituted aromatic rings with an alkyl group having 1 to 6 carbon atoms are directly bonded by a single bond, R ³ is a methyl group, an ethyl group, or It represents an isopropyl group.)

(In the formula, Ar ⁴ is a phenyl group unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plurality of benzene ring structures unsubstituted or substituted with an alkyl group having 1 to 6 carbon atoms, or the number of carbon atoms A plurality of aromatic rings substituted or unsubstituted with 1 to 6 alkyl groups represents a hydrocarbon ring group in which a single bond is directly bonded, and R ⁴ represents a methyl group, an ethyl group, or an isopropyl group.) The method of claim 3,
The (a) high refractive index polymerizable compound is a compound having a structural unit represented by the following formula [7-2], and a structural unit represented by formula [7-2] and a structure represented by formula [7-3] A polymerizable composition selected from the group consisting of compounds having units.

(In the formula, Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group.) The method according to claim 3 or 4,
(c) A polymerizable composition further comprising a polymerizable diluent in which the state of the substance is liquid at 23°C under 1013.25 hPa. A cured product of the polymerizable composition according to claim 3 or 4. A material for a high refractive index resin lens comprising the polymerizable composition according to claim 3 or 4. A resin lens produced from the polymerizable composition according to claim 3 or 4. Comprising the step of filling the polymerizable composition according to claim 3 or 4 into the space between the support and the mold to be joined, or the space inside the dividable mold, and the step of exposing the filled composition to photopolymerize Method of manufacturing a molded article. The method of claim 9,
Further, a manufacturing method comprising a step of removing the obtained photopolymer from the filled space for release, and a step of heating the photopolymer before, midway or after the release. The method of claim 9,
The molded body is a lens for a camera module, a manufacturing method. delete delete delete delete delete delete

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