TWI725190B - Viscosity lowering agent for high refractive index polymerizable compound and polymerizable composition containing the same - Google Patents

Abstract

The present invention provides a low-viscosity agent with a high refractive index that can break the mutual compensation between low Abbe and low viscosity, and with less loss of refractive index when formulated, and a polymerizable composition containing the low-viscosity agent with high refractive index.

The method of the present invention uses a compound that is solid at 1013.25hPa and 23°C, has a melting point of less than 100°C, and has a viscosity of 10mPa‧s or less at 100°C. The cured product has a D line (589.3 nm) A compound with an Abbe number of 23 or less, as a high refractive index polymer compound with at least one polymerizable double bond and a cured product whose D line (589.3nm) has a refractive index of 1.60 or more Agent.

Description

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

The present invention relates to a low-viscosity agent. Specifically, the present invention relates to a low-viscosity agent that can be used as a high-refractive-index diluent that can achieve low-viscosity of a polymerizable optical material with a high refractive index.

Resin lenses can be used in electronic devices such as mobile phones, digital cameras, and in-vehicle cameras. Those who require excellent optical properties for the purpose of applying to their electronic devices. In addition, it conforms to the usage pattern and requires high durability, such as heat resistance and weather resistance, and high productivity that can be formed with good yield. The resin lens material that meets such requirements can use thermoplastic transparent resins such as polycarbonate resins, cycloolefin polymers, and methacrylic resins.

Moreover, in recent years, when manufacturing resin lenses, in order to improve the yield or production efficiency, and to further suppress the deviation of the optical axis when the lens is laminated, research is being carried out. The injection molding of thermoplastic resin is moving toward wafer-level molding obtained by extrusion molding using curable resin that is liquid at room temperature.

In addition, a high-resolution camera module uses a plurality of lenses, and one of the wavelength correction lenses requires optical materials with high wavelength dispersion, that is, low Abbe number.

Among the materials characterized by low Abbe number, in addition to high refractive index, high transparency is still required. However, if the improvement of these optical properties is sought, the viscosity of the material is mostly increased, and the workability is significantly deteriorated. Generally, the component that contributes to the high refractive index has a high electron density. Therefore, due to the fact that the viscosity is easily increased, the deterioration of operability can be regarded as an essential problem in the development of low Abbe materials.

In response to the problem of such a method, there has been proposed a curable composition for lens materials that uses, for example, a liquid (meth)acrylate having a relatively high refractive index as a diluent to achieve low viscosity and improved workability (Patent Document 1 ). In addition, it has been proposed that by introducing an alkylene oxide into a component that contributes to a high refractive index, a curable composition capable of achieving low viscosity can be achieved even without using a diluent (Patent Document 2).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2012-255914 A

[Patent Document 2] JP 2015-199952 No.

However, with the curable composition using the aforementioned diluent (Patent Document 1), although the refractive index n _D at 589 nm after photocuring is about 1.61, the Abbe number ν _D becomes 25 or more, which is not as good as, for example, 23 or less. Low Abbe number requirements. In addition, when the curable composition (Patent Document 2) that does not use a diluent, the refractive index n _D after photocuring cannot be achieved: 1.60 or more, which also fails to sufficiently satisfy the optical characteristics.

As mentioned above, the relationship between low Abbeization and low viscosity is the mutual compensation. For example, it has not been possible to achieve low viscosity below 10000mPa‧s, and at the same time achieve high refractive index above 1.60 and low A below 23 in the hardened material. An optical material with excellent optical properties.

In addition, the thinner used to achieve low viscosity in the past generally has a low refractive index. On the other hand, in recent years, the optical properties required for optical materials such as lenses for high-resolution camera modules (high refractive index/low Abbe number /High transparency) is further improved, so by mixing conventional diluents (low-viscosity reducers), it becomes the one that can cause high Abbeization of optical materials.

The present invention was made in view of such matters, and the subject is to provide a low-viscosity agent with a high refractive index that can break the mutual compensation between low-abbeization and low-viscosity, and has less refractive index loss when blended. The polymerizable composition.

In order to solve the above-mentioned problems, the inventors have worked hard as a result of research and found that a low-Abbe compound that is solid at normal temperature/normal pressure and has a viscosity of 10 mPa·s or less at 100°C is used as a polymerizable compound with high refractive index. The result is surprisingly low viscosity agent, which can reduce the viscosity of the system to below 10000mPa‧s or maintain it below 10000mPa‧s. The system achieves excellent optical properties (low Abbe number, high refractive index) in the cured product of the system, and finally completes the present invention.

That is, the first viewpoint of the present invention relates to a method that uses a compound that is solid at 1013.25hPa and 23℃, has a melting point below 100℃, and has a viscosity of 10mPa‧s at 100℃ Hereinafter, the compound with the D-line (589.3nm) of the cured product having an Abbe number of 23 or less is regarded as a compound having at least one polymerizable double bond, and the refractive index of the D-line (589.3nm) of the cured product is 1.60 or more A low-viscosity agent for high refractive index polymerizable compounds.

The second aspect relates to the method described in the first aspect, wherein the aforementioned low-viscosity agent has at least one phenyl group or phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms, and a plural benzene group. A monovalent or divalent condensed cyclic hydrocarbon group of ring structure (which can be substituted by an alkyl group with 1 to 6 carbon atoms); and a monovalent or divalent hydrocarbon ring assembly group in which plural aromatic rings are directly bonded by a single bond ( Can be substituted by an alkyl group having 1 to 6 carbon atoms) in the group consisting of an aromatic 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.

The third viewpoint is the method described in the second viewpoint, wherein the aforementioned low viscosity reducing agent is a compound represented by the following formula [1].

(式中，X表示：至少具有1個之具有聚合性雙鍵之取代基 的苯基、至少具有1個之具有聚合性雙鍵之取代基的萘基、至少具有1個之具有聚合性雙鍵之取代基的聯苯基，或至少具有1個之具有聚合性雙鍵之取代基的菲基；Ar¹表示具有複數之苯環構造的縮合環烴基(可被碳原子數1至6之烷基取代)，或複數之芳香環以單鍵直接鍵結之烴環集合基(可被碳原子數1至6之烷基取代)；R¹表示甲基、乙基或異丙基。)

(In the formula, X represents: at least one phenyl group having a polymerizable double bond substituent, at least one naphthyl group having a polymerizable double bond substituent, at least one polymerizable double bond A biphenyl group as a substituent of the bond, or a phenanthrenyl group with at least one substituent having a polymerizable double bond; Ar ¹ represents a condensed cyclic hydrocarbon group with a plural benzene ring structure (which may be substituted by 1 to 6 carbon atoms Alkyl substitution), or a hydrocarbon ring group in which multiple aromatic rings are directly bonded with a single bond (which can be substituted by an alkyl group with 1 to 6 carbon atoms); R ¹ represents methyl, ethyl or isopropyl.)

The fourth viewpoint is the method described in the second viewpoint, wherein the aforementioned low-viscosity reducing agent is a compound represented by the following formula [2].

(式中，Ar²表示q價之芳香族烴殘基，q表示1或2， Y表示單鍵、-O-C(=O)-基或-O-基，R²表示氫原子或甲基。)

(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. )

The fifth viewpoint is the method described in the second viewpoint, wherein the aforementioned low viscosity reducing agent is a compound represented by the following formula [3-1] or formula [3-2].

(式中，R¹表示甲基、乙基或異丙基。)

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

The sixth point of view is about a low-viscosity agent, which has at least one polymerizable double bond, and the refractive index of the D line (589.3nm) of the cured product is 1.60 or more The above-mentioned low-viscosity agent for high-refractive-index polymerizable compounds, and it is from the state of a substance at 1013.25hPa and 23℃ to solid, and a compound with a melting point of less than 100℃, the viscosity at 100℃ is 10mPa‧s Hereinafter, the D-line (589.3nm) of the cured product is composed of a compound whose Abbe number is 23 or less.

The seventh point of view relates to a polymerizable composition, which contains: (a) at least one polymerizable double bond, and the cured product has a high refractive index polymerizable with a refractive index of 1.60 or more at the D line (589.3nm) 100 parts by mass of the compound; and (b) From the state of the substance at 1013.25hPa and 23℃ as a solid, a compound with a melting point of less than 100℃, and a viscosity at 100℃ of 10mPa‧s or less, at the D line of the hardened product (589.3 nm) A low-viscosity agent composed of compounds with an Abbe number of 23 or less is 10 to 500 parts by mass.

The eighth aspect relates to the polymerizable composition described in the seventh aspect, wherein the (a) high refractive index polymerizable compound contains a reactive polysiloxane, and the reactive polysiloxane contains: At least one of the polycondensate of the alkoxysilicon compound A and the polycondensate of the alkoxysilicon compound A represented by the formula [4] and the alkoxysilicon compound B represented by the formula [5].

(式中，X表示：至少具有1個之具有聚合性雙鍵之取代基的苯基、至少具有1個之具有聚合性雙鍵之取代基的萘基、至少具有1個之具有聚合性雙鍵之取代基的聯苯基，或至少具有1個之具有聚合性雙鍵之取代基的菲基；Ar³表示可被碳原子數1至6之烷基取代之苯基、具有複數之苯環構造的縮合環烴基(可被碳原子數1至6之烷基取代)，或複數之芳香環以單鍵直接進行鍵結之烴環集合基(可被碳原子數1至6之烷基取代)；R³表示甲基、乙基或異丙基。)

(In the formula, X represents: at least one phenyl group having a polymerizable double bond substituent, at least one naphthyl group having a polymerizable double bond substituent, at least one polymerizable double bond Biphenyl as the substituent of the bond, or phenanthrenyl having at least one substituent with a polymerizable double bond; Ar ³ represents a phenyl group that can be substituted by an alkyl group having 1 to 6 carbon atoms, or benzene having a plural number Condensed cyclic hydrocarbon group of ring structure (which can be substituted by an alkyl group with 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 can be substituted by an alkyl group with 1 to 6 carbon atoms) Substitution); R ³ represents methyl, ethyl or isopropyl.)

[Chemical formula 5] Ar ⁴ -Si(OR ⁴ ) ₃ [5] (In the formula, Ar ⁴ represents a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms, a condensed cyclic hydrocarbon group having a plural benzene ring structure ( It can be substituted by an alkyl group having 1 to 6 carbon atoms), or a hydrocarbon ring group in which multiple aromatic rings are directly bonded by a single bond (which can be substituted by an alkyl group having 1 to 6 carbon atoms); R ⁴ represents methyl , Ethyl or isopropyl.)

The ninth aspect relates to the polymerizable composition described in the seventh aspect, wherein the (a) high refractive index polymerizable compound contains the sulphur compound represented by the formula [6].

(式中，R⁵及R⁶分別獨立地表示氫原子或甲基；L¹及L²分別獨立地表示可具有取代基之伸苯基，或可具有取代基之伸萘二基；L³及L⁴分別獨立地表示碳原子數1至6之伸烷 基，m及n分別獨立地表示滿足0≦m+n≦40之0或正的整數。)

(In the formula, R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group; L ¹ and L ² each independently represent an optionally substituted phenylene group or an optionally substituted naphthalene diyl group; 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.)

The tenth aspect is the polymerizable composition described in the seventh aspect, wherein the (a) high refractive index polymerizable compound is selected from compounds represented by the following formula [7-1], having the formula [7-2] In the group consisting of the compound of the structural unit shown in the formula [7-2] and the compound of the structural unit shown in the formula [7-3].

(式中，2個之Q分別為相同之基，且表示選自由乙烯基氧基、烯丙基氧基及(甲基)丙烯醯基氧基所構成之群中之基，2個之p分別相同地表示0至3之整數。)

(In the formula, two Qs are the same group respectively, and represent a group selected from the group consisting of vinyloxy, allyloxy and (meth)acryloxy, and the two p Each represents the same integer from 0 to 3.)

(式中，Ar⁵及Ar⁶分別獨立地表示苯基、萘基或菲基。)

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

The eleventh viewpoint is the polymerizable composition described in any one of the seventh to the tenth viewpoints, which further contains (c) a polymerizable diluent in a liquid state at 1013.25 hPa and 23°C.

The twelfth viewpoint relates to a cured product, which is a cured product of the polymerizable composition described in any one of the seventh to the eleventh viewpoints.

The 13th viewpoint relates to a material for a high refractive index resin lens, which is composed of the polymerizable composition described in any one of the 7th to the 11th viewpoint.

The fourteenth viewpoint relates to a resin lens, which is produced by the polymerizable composition described in any one of the seventh to the eleventh viewpoints.

The fifteenth viewpoint relates to a method of manufacturing a molded body, which comprises: filling the space between the support body and the mold that are joined to each other with the polymerizable composition described in any one of the seventh to the eleventh viewpoints; or The step of dividing the inner space of the mold; and the step of exposing and photopolymerizing the filled composition.

The 16th viewpoint relates to the manufacturing method of the 15th viewpoint, which further comprises: taking out and demolding the photopolymer from the aforementioned space filled with the obtained photopolymer; and, before, during or after the demolding of the photopolymer Carry out the heating step.

The 17th viewpoint relates to the manufacturing method of the 15th viewpoint or the 16th viewpoint, in which the said molded object is a lens for camera modules.

The present invention is based on the use of high refractive index polymerizable compounds at 1013.25hPa and 23°C. The state of the substance is solid and has a low A compound with a melting point of 100°C and a viscosity at 100°C below 10mPa‧s. The compound whose hardened product has an Abbe number of less than 23 on the D line (589.3nm) can be used as a low-viscosity agent to reduce the viscosity of the system. To below 10000mPa‧s or maintain below 10000mPa‧s, and achieve excellent optical properties (low Abbe number, high refractive index) in the cured product of the system.

In addition, the polymerizable composition of the present invention can achieve low viscosity through the blending of the low viscosity agent, its operability will be improved, and its cured product can be used as an optical device such as a lens for a high-resolution camera module. The optical properties (low Abbe number, high refractive index).

Therefore, the high-refractive-index resin lens material of the present invention composed of the above-mentioned polymerizable composition can be suitably used as a lens for a high-resolution camera module.

Furthermore, the polymerizable composition of the present invention has a sufficiently manageable viscosity in a solvent-free form by the formulation of the low-viscosity agent, so it can be formed by extrusion processing (imprint technology) of molds such as metal molds In addition, the mold releasability from the mold after molding is also excellent, and the molded body can be suitably manufactured.

Furthermore, in the manufacturing method of the present invention, since the above-mentioned polymerizable composition used is excellent in operability, it is possible to efficiently manufacture a molded body, particularly a lens for a camera module.

^{[Fig. 1] Fig. 1 shows the 1} H NMR spectrum of dimethoxy(phenanthryl-9-yl)(4-vinylphenyl)silane obtained in Production Example 1. [Fig.

^{[Fig. 2] Fig. 2 shows the 1} H NMR spectrum of trimethoxy(9-phenanthryl)silane obtained in Production Example 3. [Fig.

[Form to implement invention]

The present invention relates to a method that uses a compound that is solid at 1013.25hPa and 23℃, has a melting point of less than 100℃, and has a viscosity of 10mPa‧s or less at 100℃. The hardened product is The Abbe number of the D line (589.3 nm), that is, _{the compound whose ν D} is 23 or less, is used as a low-viscosity agent for the high-refractive-index polymerizable compound described later, and this low-viscosity agent is also the 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 is as described above, as long as it is a solid substance at 1013.25hPa (that is, atmospheric pressure) at 23°C, has a melting point of less than 100°C, and has a viscosity of 10mPa‧s or less at 100°C, and The cured product has an Abbe number of 23 or less at D line (589.3 nm), and it is not particularly limited.

Examples of the aforementioned low-viscosity agent include compounds each having at least one aromatic group and a group having a polymerizable double bond. Here, the so-called polymerizability refers to the property that a part of the molecule undergoes a chemical reaction by external stimuli such as heat or light, and causes a polymerization reaction by cracking or decomposition.

The above-mentioned compounds can be specifically exemplified: having at least one monovalent or divalent condensed cyclic hydrocarbon group selected from the group consisting of a phenyl group or a phenylene group which may be substituted by an alkyl group having 1 to 6 carbon atoms, and a plural benzene ring structure (which can be A monovalent or divalent hydrocarbon ring group that is substituted by an alkyl group with 1 to 6 carbon atoms), and a monovalent or divalent hydrocarbon ring group in which multiple aromatic rings are directly bonded with a single bond (which can be substituted by an alkyl group with 1 to 6 carbon atoms) The aromatic group in the group constituted by having at least one polymerizable group selected from the group consisting of vinyl, allyl, (meth)allyloxy and (meth)acrylic groups Compounds based on double bonds.

Among the above-mentioned aromatic groups, monovalent or divalent condensed cyclic hydrocarbon groups having a plurality of benzene ring structures include, for example, naphthalene, phenanthrene, anthracene, terphenyl, pyrene, triphenylene, condensed tetraphenyl, and extension A monovalent or divalent radical derived from benzene and pyridium.

In addition, the monovalent or divalent hydrocarbon ring group in which the plural aromatic rings are directly bonded by single bonds can be exemplified by biphenyl, terphenyl, bitetraphenyl, biphenylene, phenylnaphthalene, phenylpyridine, A monovalent or divalent group derived from diphenylpyridine.

In addition, in the above-mentioned phenyl group or phenylene group, monovalent or divalent condensed cyclic hydrocarbon group, and monovalent or divalent hydrocarbon ring group, the alkyl group having 1 to 6 carbon atoms which may have a substituent includes, for example Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, tertiary-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl.

Among these aromatic groups, from the viewpoint of the effect of maintaining solubility, viscosity reduction or low viscosity, and achieving excellent optical properties (high transparency, high refractive index, and low Abbe number) in the formulation In particular, phenyl, naphthyl, and phenanthryl are preferred groups.

A specific example of a compound each having at least one of the above-mentioned specific aromatic group and a group having a polymerizable double bond is a compound represented by the following formula [1].

In the above formula [1], X represents: at least one phenyl group having a polymerizable double bond, at least one naphthyl group having a polymerizable double bond, and at least one polymerizable group A biphenyl group with a double bond, or a phenanthrenyl group with at least one polymerizable double bond; Ar ¹ represents a condensed cyclic hydrocarbon group with a plural benzene ring structure (can be substituted by an alkane with 1 to 6 carbon atoms Group substitution), or a hydrocarbon ring group in which multiple aromatic rings are directly bonded by a single bond (which can be substituted by an alkyl group with 1 to 6 carbon atoms); R ¹ represents a methyl group, an ethyl group or an isopropyl group.

The phenyl group represented by X having at least one polymerizable double bond can include, for example, 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl, 4-vinyloxyphenyl, 4 -Allylphenyl, 4-allyloxyphenyl, 4-isopropenylphenyl.

The naphthyl group represented by X having at least one polymerizable double bond group includes, for example, 4-vinylnaphthyl-1-yl, 5-vinylnaphthyl-1-yl, and 6-vinylnaphthylene-2. -Base, 5-vinyloxynaphthylene-1-yl, 5-allyloxynaphthylene-1-yl, 4-allyloxynaphthylene-1-yl, 5-allyloxynaphthylene-1-yl 1-yl, 8-allyloxynaphthylene-1-yl, 5-isopropenylnaphthylene-1-yl.

The biphenyl group represented by X having at least one group having a polymerizable double bond includes, for example, 4'-vinyl-[1,1'-biphenyl]-2-yl, 4'-vinyl-[1 ,1'-biphenyl]-3-yl, 4'-vinyl-[1,1'-biphenyl]-4-yl, 4'-vinyloxy-[1,1'-biphenyl ]-4-yl, 4'-allyl-[1,1'-biphenyl]-4-yl, 4'-allyloxy-[1,1'-biphenyl]-4-yl , 4'-isopropenyl-[1,1'-biphenyl]-4-yl.

The phenanthrenyl group represented by X having at least one polymerizable double bond group includes, for example, 3-vinylphenanthryl-9-yl, 7-vinylphenanthryl-9-yl, 10-vinylphenanthryl-9 -Base, 7-vinylphenanthryl-2-yl, 6-vinylphenanthryl-3-yl, 10-vinylphenanthryl-3-yl, 3-vinyloxyphenanthryl-9-yl, 3 -Allylphenanthryl-9-yl, 3-allyloxyphenanthryl-9-yl, 3-isopropenylphenanthryl-9-yl.

Among the above-mentioned X, a phenyl group having at least one polymerizable double bond is preferable, and a vinyl phenyl group is more preferable.

The condensed cyclic hydrocarbon group with a plural benzene ring structure represented by Ar ¹ can include, for example, monovalent monovalent derivatives derived from naphthalene, phenanthrene, anthracene, terphenylene, pyrene, triphenylene, fused tetraphenyl, biphenylene, and pyrene base.

In addition, the hydrocarbon ring group in which the plural aromatic rings are directly bonded by single bonds can be exemplified by biphenyl, terphenyl, bitetraphenyl, biphenylnaphthalene, phenylnaphthalene, phenylpyrene, and diphenylpyrene. Derived 1-valent base.

In addition, in the above-mentioned condensed cyclic hydrocarbon group and hydrocarbon ring assembly group, the alkyl group having 1 to 6 carbon atoms that may have as a substituent includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second-butyl, tertiary-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl.

Among the above-mentioned Ar ¹ , a condensed cyclic hydrocarbon group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) having a plural benzene ring structure is preferable, and a phenanthryl group is more preferable.

Specific examples of the compound represented by the above formula [1] include dimethoxy (9-phenanthryl) (4-vinylphenyl) silane, diethoxy (9-phenanthryl) (4-vinyl) Phenyl) silane, diisopropoxy (9-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4-vinyl naphthyl-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, dimethyl Oxy (2-phenanthryl) (4-vinylphenyl) silane, dimethoxy (3-phenanthryl) (4-vinylphenyl) silane, dimethoxy (9-phenanthryl) (4 -Vinylphenyl)silane, [1,1'-biphenyl]-4-yldimethoxy(4-vinylphenyl)silane, but not limited to these.

In addition, specific examples of compounds each having at least one of the above-mentioned specific aromatic group and a group having a polymerizable double bond are compounds represented by the following formula [2].

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; R ² represents a hydrogen atom or methyl.

The q-valent aromatic hydrocarbon residues in Ar ² can be, for example, removed from benzene, a condensed cyclic hydrocarbon having a plural benzene ring structure, or a hydrocarbon ring assembly in which plural aromatic rings are directly bonded with a single bond. The groups of hydrogen atoms may be substituted by alkyl groups having 1 to 6 carbon atoms.

Specifically, a phenyl group or a phenylene group substituted by an alkyl group having 1 to 6 carbon atoms, a monovalent or divalent condensed cyclic hydrocarbon group having a plural benzene ring structure (which can be substituted by a carbon atom number of 1 to 6 Alkyl substitution), or a monovalent or divalent hydrocarbon ring group in which multiple aromatic rings are directly bonded with a single bond (which can be substituted by an alkyl group with 1 to 6 carbon atoms).

The phenyl group represented by Ar ² which may be substituted by an alkyl group having 1 to 6 carbon atoms includes, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4,6-trimethylbenzene Phenyl groups, 4-tert-butylphenyl groups, and phenylene groups that may be substituted with alkyl groups having 1 to 6 carbon atoms include, for example, phenylene groups, 2,4-methylphenylene groups, and 2,5-methyl phenylene groups. Phenylene, 2,4,5-trimethyl-1,3-phenylene, 2-tert-butyl-1,4-phenylene.

Ar ² represents a monovalent or divalent condensed ring hydrocarbon group with a plural benzene ring structure, for example, from naphthalene, phenanthrene, anthracene, tetraphenylene, pyrene, triphenylene, fused tetraphenyl, biphenylene, pyrene The derived monovalent or divalent base.

In addition, the monovalent or divalent hydrocarbon ring assembly group in which plural aromatic rings are directly bonded by single bonds can be exemplified by biphenyl, terphenyl, bitetraphenyl, biphenylene, phenylnaphthalene, and phenylpyridine. , A monovalent or divalent group derived from diphenylpyridine.

In addition, in the above-mentioned condensed cyclic hydrocarbon group and hydrocarbon ring assembly group, the alkyl group having 1 to 6 carbon atoms that may have as a substituent includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second-butyl, tertiary-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl.

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, naphthalene -1-yl methyl (meth) acrylate, naphth-2-yl methyl (meth) acrylate.

The low-viscosity agent of the present invention can be exemplified by the compounds represented by the following formula [3-1] to formula [3-4], wherein the compounds represented by the formula [3-1] and formula [3-2] vary from the viscosity The reduction/maintenance effect and the viewpoint of achieving excellent optical properties (low Abbe number) are preferable, and the compound represented by formula [3-1] is particularly preferable.

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

The low-viscosity agent of the present invention can be suitably used as a commercially available compound.

In addition, for example, the compound represented by the formula [3-4] and the like, the ester compound containing (meth)acryloyl group can be produced by a common method, by making alcohol and (meth)acrylic acid halide in triethylamine or It is produced by esterification in the presence of pyridine.

In addition, the compound represented by the above formula [3-1] and formula [3-3] (the compound represented by the above formula [1]) can be produced by a commonly used method, for example, the alkoxysilane compound is combined with a glycine (Grignard) Reagent reaction to obtain the organic alkoxysilane compound in the past Grignard subreaction; or the alkoxyhydrosilane compound and the aryl halide compound are reacted with a transition metal catalyst to obtain the organic alkoxysilane compound It is manufactured by coupling reaction in the past.

In detail, the ^{sub-reagents with Ar 1} group: Ar ¹ -Mg-Hal, and the trialkoxysilane compound with the aromatic ring group with polymerizable double bond: X-Si(OR ¹ ) ₃ Reaction, or, Gren sub-reagents with aromatic ring groups with polymerizable double bonds: X-Mg-Hal, and ^{trialkoxysilane compounds with Ar 1} groups: Ar ¹ -Si(OR ¹ ) ₃ , The polymerizable silane compound represented by the formula [1] can be obtained (the above Ar ¹ , X, and R ^{1 have the} same meaning as in the aforementioned formula [1], and Hal represents a halogen atom).

The aforementioned Gren sub-reagents can be prepared by halogenating aryl groups: Ar ¹ -Hal or X-Hal, and reacting with magnesium.

The preparation of the above reagent and the reaction between the reagent and the alkoxysilane compound can be carried out in an organic solvent. Examples of the organic solvent used here include ether solvents such as diethyl ether, tetrahydrofuran, and tertiary butyl methyl ether; and inert organic solvents such as hydrocarbon solvents such as hexane, toluene, and xylene. These organic solvents can be used alone or in combination of two or more.

The above-mentioned manufacturing temperature and reaction temperature are preferably in the range of 0 to 200°C, especially 20 to 150°C.

In addition, if oxygen is present during the manufacture of the reagent, or the reaction between the reagent and the alkoxysilane compound, the reagent reacts with oxygen during the production/reaction stage to form the polymerization of the target substance. Because of the decrease in the yield of the silane compound, it can be carried out in an inert environment such as nitrogen and argon.

The aforementioned low-viscosity agent can be used alone or in combination of two or more kinds.

<<High refractive index polymerizable compound>>

The low-viscosity agent of the present invention is a high-refractive-index polymerizable compound having at least one polymerizable double bond and the refractive index of the D line (589.3 nm) of the cured product, that is, n _{D of 1.60 or more.} use.

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

<Reactive Polysiloxane>

The above-mentioned reactive polysiloxane includes: the polycondensate of the alkoxysilicon compound A represented by the formula [4], the alkoxysilicon compound A represented by the formula [4] and the alkane represented by the formula [5] At least one of polycondensates of oxysilicate compound B.

[Alkoxy Silicon Compound A]

In the above formula [4], X represents: at least one phenyl group having a polymerizable double bond substituent, at least one naphthyl group having a polymerizable double bond substituent, and at least one A biphenyl group as a substituent of a polymerizable double bond, or a phenanthryl group having at least one substituent with a polymerizable double bond; Ar ³ represents a phenyl group that may be substituted by an alkyl group having 1 to 6 carbon atoms, and has A condensed cyclic hydrocarbon group composed of plural benzene rings (which can be substituted by 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 can be replaced by a hydrocarbon ring group of 1 to 6 carbon atoms). Alkyl substitution); R ³ represents a methyl group, an ethyl group or an isopropyl group; specific examples of X in the above formula [4] can be exemplified in the compound represented by the aforementioned formula [1], as the formula [ 1] The group of the group X in the formula [1] can be exemplified as a preferable group.

^{In addition, specific examples of Ar 4} in the above formula [4] include, for example, the group as the group Ar ¹ in the aforementioned formula [1], and particularly, for example, the group Ar ¹ in the formula [4] can be cited as The preferred base of the base.

Furthermore, specific examples of the compound represented by the aforementioned formula [4] include compounds which are specific examples of the compound represented by the aforementioned formula [1].

[Alkoxy Silicon Compound B]

[Chemical formula 13] Ar ⁴ -Si(OR ⁴ ) ₃ [5]

In formula [5], Ar ⁴ represents a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms, or a condensed cyclic hydrocarbon group having a plural benzene ring structure (which may be substituted by 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 can be substituted by an alkyl group with 1 to 6 carbon atoms); R ⁴ represents a methyl group, an ethyl group or an isopropyl group. )

The phenyl group represented by Ar ⁴ which may be substituted by an alkyl group having 1 to 6 carbon atoms includes, for example, phenyl, o-tolyl, m-tolyl, p-tolyl, 2,4,6-trimethylbenzene Group, 4-tert-butylphenyl.

The condensed cyclic hydrocarbon group with a plural benzene ring structure represented by Ar ⁴ can include, for example, monovalent monovalent derivatives derived from naphthalene, phenanthrene, anthracene, terphenylene, pyrene, triphenylene, fused tetraphenyl, biphenylene, and pyrene base.

In addition, the hydrocarbon ring group in which the plural aromatic rings are directly bonded by single bonds may be, for example, those derived from biphenyl, terphenyl, bitetraphenyl, biphenylene, phenylnaphthalene, phenylpyrene, and diphenylpyrene. The base of the price of one.

In addition, in the above-mentioned condensed cyclic hydrocarbon group and hydrocarbon ring assembly group, the alkyl group having 1 to 6 carbon atoms that may have as a substituent includes, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, Isobutyl, second-butyl, tertiary-butyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl.

Among the above-mentioned Ar ⁴ , a condensed cyclic hydrocarbon group (which may be substituted with an alkyl group having 1 to 6 carbon atoms) having a plural benzene ring structure is preferable, and a phenanthrene group is more preferable.

Specific examples of the compound represented by the above formula [5] include, for example, trimethoxy (phenyl) silane, triethoxy (phenyl) silane, trimethoxy (p-tolyl) silane, trimethoxy (1 -Naphthyl) silane, triethoxy (1-naphthyl) silane, triisopropoxy (1-naphthyl) silane, trimethoxy (2-naphthyl) silane, triethoxy (2-naphthalene) Group) 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-yltriethoxysilane and [1,1'-biphenyl]-4-yltriisopropoxysilane are not limited to these.

The alkoxy silicon compound constituting the above reactive polysiloxane, in addition to the alkoxy silicon compound A represented by the formula [4], when it contains the alkoxy silicon compound B represented by the formula [5], about this The molar ratio of the polycondensation reaction of the alkoxysilicon compound is not particularly limited, but for the purpose of stabilizing the physical properties of the cured product, generally, the alkoxysilicon compound B9 is used relative to the alkoxysilicon compound A1 molar ratio. The range of less than mol is preferable. More preferably, it is a range of less than 1.5 mol. Compared with the molar ratio of the alkoxysilicon compound A, the molar ratio of the alkoxysilicon compound B is set to 9 or less to obtain a sufficient cross-linking density, and the dimensional stability to heat is improved. Obtain a hardened product with a higher refractive index and a low Abbe number.

The above-mentioned alkoxysilicon compound A and alkoxysilicon compound B can be used by appropriately selecting compounds according to needs, and plural kinds of compounds can also be used in combination. At this time, the molar ratio of the compounding ratio, the ratio of the total molar amount of the alkoxide silicon compound A to the total molar amount of the alkoxide silicon compound B also falls within the above-mentioned range.

[Acid or alkaline catalyst]

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

The type of the catalyst used in the above-mentioned polycondensation reaction is not particularly limited as long as it is dissolved in the solvent described below or uniformly dispersed, and it can be appropriately selected and used according to needs.

Examples of catalysts that can be used include acidic compounds such as 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 and alkaline earth metal hydrogens. Oxides, ammonium hydroxide, quaternary ammonium salts, amines; fluoride salt series include, for example, NH ₄ F and NR ₄ F. Also, here R is composed 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. The base of more than one kind in the group.

These catalysts may be used alone or in combination of plural kinds.

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

The above-mentioned basic compound system includes, for example, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Tetrabutylammonium hydroxide, triethylamine.

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

Among these catalysts, the preferred user 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 0.01-10% by mass, preferably 0.1-5% by mass relative to the total mass of the aforementioned alkoxysilicon compound. If the amount of catalyst used is 0.01% by mass or more, the reaction will proceed more satisfactorily. In addition, if economical efficiency is possible, it is sufficient to use 10% by mass or less.

[Polycondensation reaction]

The above-mentioned reactive polysiloxane (polycondensate) is a feature of the structure of the alkoxysilicon compound A, and the reactive group (polymerizable double bond) contained in the alkoxysilicon compound A is caused by free radicals. Or it is cationically and easily polymerized, and shows high heat resistance after polymerization (after curing).

The hydrolysis polycondensation reaction of the alkoxysilicon compound A, or/and the hydrolysis polycondensation reaction of the alkoxysilicon compound A and the alkoxysilicon compound B can also be carried out without a solvent, but compared to the tetrahydrofuran (THF) described later For the alkoxy silicon compound used in other applications, an inert solvent can also be used as the reaction solvent. When a reaction solvent is used, it is easy to make the reaction system uniform, and has the advantage that a more stable polycondensation reaction can be carried out.

The synthesis reaction of the reactive polysiloxane can be carried out without a solvent as described above, but in order to make the reaction more uniform, there is no problem even if a solvent is used. It is not particularly limited as long as the solvent does not react with the alkoxysilicon compound used, but dissolves the polycondensate.

烷、二異丙基醚、環戊基甲基醚(CPME)等之醚類；乙二醇、丙二醇、己二醇等之二醇類；乙基溶纖劑、丁基溶纖劑、乙基卡必醇、丁基卡必 醇、二乙基溶纖劑、二乙基卡必醇等之二醇醚類；N-甲基-2-吡咯啶酮(NMP)、N,N-二甲基甲醯胺(DMF)等之醯胺類。此等溶劑可一種單獨使用、或混合二種以上使用。 Such reaction solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene, and xylene; tetrahydrofuran (THF), 1,4-bis

Ethers such as alkane, diisopropyl ether, cyclopentyl methyl ether (CPME), etc.; glycols such as ethylene glycol, propylene glycol, hexanediol, etc.; ethyl cellosolve, butyl cellosolve, ethyl card Glycol ethers such as alcohol, butyl carbitol, diethyl cellosolve, diethyl carbitol; N-methyl-2-pyrrolidone (NMP), N,N-dimethyl Dimethamides such as formamide (DMF). These solvents can be used alone or in combination of two or more.

The reactive polysiloxane used in the present invention can be obtained by using the alkoxysilicon compound A represented by the formula [4] or the alkoxysilicon compound A represented by the formula [4] and the formula [5] ] The alkoxysilicon compound of the alkoxysilicon compound B shown in the figure is obtained by hydrolysis and polycondensation in the presence of an acid or alkaline catalyst. The reaction temperature for hydrolysis polycondensation is 20 to 150°C, more preferably 30 to 120°C.

If the increase in the molecular weight of the polycondensate is terminated and the molecular weight distribution is stable for longer than the time required, the reaction time is not particularly limited, and more specifically it is several hours to several days.

After the polycondensation reaction is terminated, the obtained reactive polysiloxane is recovered by any method such as filtration, solvent distillation, etc., and it is preferable to perform an appropriate purification treatment as needed.

As an example of the production method of the reactive polysiloxane used in the present invention, the alkoxysilicon compound A represented by the formula [4] or the alkoxysilicon compound A represented by the formula [4] can be exemplified A method consisting of polycondensation with the alkoxy silicon compound B represented by the formula [5] in the presence of an alkali, and using a cation exchange resin to remove the alkali.

The above-mentioned base and its usage amount can be one or more compounds selected from the group consisting of the above-mentioned basic compounds and fluoride salts, and the usage amount is preferably selected from potassium hydroxide and calcium hydroxide. One or more of the group consisting of barium hydroxide and tetraethylammonium hydroxide is used as a base.

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

Furthermore, after the reaction is terminated, the cation exchange resin used for alkali removal is preferably an ion exchange resin having a sulfonic group as an ionic group.

The above-mentioned cation exchange resin may use a matrix structure generally used such as styrene (styrene-divinylbenzene copolymer) and acrylic. In addition, it may be any one of a strong acid cation exchange resin having a sulfo group as an ionic group, and a weak acid cation exchange resin having a carboxyl group as an ionic group. Furthermore, various forms of the cation exchange resin can be used, such as granular, fibrous, and film-like. Commercially available cation exchange resins can be suitably used.

Among them, it is preferable to use a strongly acidic cation exchange resin having a sulfo group as an ionic group.

Commercially available strong acid cation exchange resins include, for example, Amberlite (registered trademark) 15, Amberlite200, Amberlite200C, Amberlite200CT, Amberlite252, Amberlite1200H, AmberliteIR120B, AmberliteIR120H, AmberliteIR122Na, AmberliteIR124, AmberliteIRC50, AmberliteIRC86, AmberliteIRP-64, AmberliteIRP-64, AmberliteIRP-64, AmberliteCG-50, AmberliteCG-120, Amberjet (registered trademark) 1020, Amberjet1024, Amberjet1060, Amberjet1200, Amberjet1220, Amberlist (registered trademark) 15, Amberlist15DRY, Amberlist15JWET, Amberlist16, Amberlist16WET, Amberlist31WET, Amberlist35WET, Amberlist35WET, Amberlist36WET, Amberlist36WET, Amberlist35WET, Amberlist36WET, Amberlist , Dowex50Wx4, Dowex50Wx8, DowexDR-2030, DowexDR-G8, DowexHCR-W2, Dowex650C UPW, DowexG-26, Dowex88, DowexM-31, DowexN-406, Dowex (registered trademark) Monosphere (registered trademark) 65088, Dowex Monosphere MonosphereM-31, Dowex Monosphere99K/320, Dowex Monosphere99K/350, Dowex Monosphere99Ca/320, Dowex Marathon (registered trademark) MSC, Dowex Marathon C [above, made by Dow Chemical]; Diaion (registered trademark) EXC04, DiaionHPK25, DiaionPK208, DiaionPK212 , DiaionPK216, DiaionPK220, DiaionPK228L, DiaionRCP160M, DiaionSK1B, DiaionSK1BS, DiaionSK104, DiaionSK110, DiaionSK112, DiaionSK116, DiaionUBK510L, DiaionUBK5 55 [above, manufactured by Mitsubishi Chemical Corporation]; Lewatit (registered trademark) MonoPlusS100, Lewatit MonoPlusSP112 [above, manufactured by Lanxess Corporation].

In addition, commercially available weakly acidic cation exchange resins include, for example, Amberlite (registered trademark) CG-50, Amberlite FPC3500, AmberliteIRC50, AmberliteIRC76, AmberliteIRC86, AmberliteIRP-64, Dowex (registered trademark) MAC-3 [above, manufactured by Dow Chemical Company]; Diaion (registered trademark) CWK30/S, DiaionWK10, DiaionWK11, DiaionWK40, DiaionWK100, DiaionWT01S [above, manufactured by Mitsubishi Chemical Corporation].

The polycondensation compound obtained by such a reaction is converted into polystyrene by GPC. The weight average molecular weight Mw is 500-100000, preferably 500-30000, and the degree of dispersion: Mw (weight average molecular weight)/Mn (number) The average molecular weight) is 1.0-10.

In addition, the above-mentioned reactive polysiloxane ^{is a compound having at least a siloxane unit represented by [X(Ar 1} )SiO], for example, it has at least [X(Ar ¹ )SiO] and [Ar ² SiO _3/2 ] The siloxane unit shown is a compound with a cross-linked structure.

<Fructus compound>

The above-mentioned stilbene compound is a compound represented by the following formula [6].

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 each independently represent a substituted phenylene group or a substituted naphthalene diyl group , L ³ and L ⁴ each independently represent an alkylene having 1 to 6 carbon atoms, more preferably an alkylene having 2 or 3 carbon atoms, and m and n each independently represent 0≦m+n≦40的0 or a positive integer.

The ^{phenylene groups represented by L 1} and L ² which may have substituents include, for example, o-phenylene, m-phenylene, p-phenylene, 2-methylbenzene-1,4-diyl, 2 -Aminobenzene-1,4-diyl, 2,4-dibromobenzene-1,3-diyl, 2,6-dibromobenzene-1,4-diyl.

In addition, ^{examples of the naphthalene diyl group represented by L 1} and L ² that may have a substituent include 1,2-naphthalene diyl, 1,4-naphthalene diyl, 1,5-naphthalene diyl, 1, 8-naphthalene diyl, 2,3-naphthalene diyl, 2,6-naphthalene diyl.

The alkylene groups with 1 to 6 carbon atoms represented by L ³ and L ⁴ include, for example, methylene, ethylene, trimethylene, 1-methylethylene, tetramethylene, 1-methyltriethylene Methyl, 1,1-dimethylethylene, pentamethylene, 1-methyltetramethylene, 2-methyltetramethylene, 1,1-dimethyltrimethylene, 1, 2-dimethyl trimethylene, 2,2-dimethyl trimethylene, 1-ethyl trimethylene, hexamethylene, 1-methyl pentamethylene, 2-methyl pentamethylene , 3-methylpentamethylene, 1,1-dimethyltetramethylene, 1,2-dimethyltetramethylene, 2,2-dimethyltetramethylene, 1-ethyl Tetramethylene, 1,1,2-trimethyltrimethylene, 1,2,2-trimethyltrimethylene, 1-ethyl-1-methyltrimethylene, 1-ethyl-2 -Methyl trimethylene. Among these, the group corresponding to the alkylene group having 2 or 3 carbon atoms is more preferable as L ³ and L ⁴ .

In the compound represented by the formula [6], it is preferable that m and n each independently satisfy 0≦m+n≦30, and it is more preferable when it satisfies 2≦m+n≦20.

Specific examples of the compound represented by the above formula [6] include, for example, 9,9-bis(4-(2-(meth)propenyloxyethoxy)phenyl)-9H-茀, Ogsol (registered trademark) )EA-0200, Ogsol EA-0300, Ogsol EA-F5003, Ogsol EA-F5503, Ogsol EA-F5510, Ogsol EA-F5710, Ogsol GA-5000 [above, manufactured by Osaka GAS CHEMICALS], NK ESTER A- BPEF [manufactured by Shinnakamura Chemical Industry Co., Ltd.], but is not limited to these (also in the present invention, the so-called (meth)acryloyl group refers to both of the acryloyl group and the methacryloyl group.).

In addition, compounds suitable as high refractive index polymerizable compounds are the compound represented by the following formula [7-1], the compound having the structural unit represented by the formula [7-2], and the compound having the formula [7-2] The structural unit shown and the compound of the structural unit shown in formula [7-3].

In the formula [7-1], the two Qs respectively represent the same group, which are selected from the group consisting of vinyloxy, allyloxy and (meth)acryloxy, and 2 The p represents the same integer from 0 to 3, respectively.

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.

Compounds particularly suitable as high refractive index polymerizable compounds are the compound represented by the following formula [7-1-1], the compound having the structural unit represented by the formula [7-2-1], and the compound having the formula [7- Compound of the structural unit shown in 2-1] and the structural unit shown in formula [7-3-1].

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

<<Polymerizable composition>>

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

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

The polymerizable composition may further contain (c) a polymerizable diluent that is a liquid at 1013.25 hPa and 23°C, and (d) a polymerization initiator.

<(c) Polymerizable diluent>

The polymerizable diluent that can be used in the polymerizable composition of the present invention is a compound that is liquid at 1013.25 hPa and 23°C, and is also called 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 when the polymerizable composition is cured. From the use of polymerizable diluent, the effect of reducing/maintaining the viscosity of the aforementioned low-viscosity agent can be further improved.

The polymerizable diluent system includes, for example, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 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 ]decane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, Ditrimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, dineopentaerythritol hexa (meth) acrylate, 2-hydroxy-3-propenyloxypropane Methyl methacrylate, glycerol di(meth)acrylate, neopentyl erythritol tri(meth)acrylate, dineopentaerythritol penta(meth)acrylate, bis((meth)acryloyloxy) Ethyl) hydroxyethyl trimeric isocyanate, biphenylmethanyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, 2-phenoxybiphenylmethanyl (meth) Acrylate, 3-phenoxybiphenylmethanyl (meth)acrylate, 4-phenoxybiphenylmethanyl (meth)acrylate, 2-(2-biphenyloxy)ethyl ( Meth) acrylate, 2-(3-biphenyloxy)ethyl (meth)acrylate, 2-(4-biphenyloxy)ethyl (meth)acrylate, ethoxylated o-benzene Base phenol (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, divinylbenzene.

The above-mentioned polymeric diluents can be obtained from commercially available products, and specific examples are NK ESTER 701A, NK ESTERA-DCP, NK ESTERA-DON-N, NK ESTERA-HD-N, NK ESTERA-NOD-N, NK ESTERDCP, NK ESTERDOD-N, NK ESTER HD-N, NK ESTER NOD-N, NK ESTER NPG, NK ESTER A-TMM-3, NK ESTER A-TMM-3L, NK ESTER A-TMM-3LMN, NK ESTERA-TMPT, NK ESTER TMPT, NK ESTER A-TMMT, NK ESTER AD-TMP, NK ESTER A-DPH, NK ESTER A-9550, NK ESTER A-9530, NK ESTER ADP-51EH, NK ESTER ATM-31EH, UA-7100, A -LEN-10 [above, manufactured by Shin Nakamura Chemical Industry Co., Ltd.], KAYARAD (registered trademark) T-1420, KAYARAD-330, KAYARA D-320, KAYARA D-310, KAYARA DPCA-20, KAYARA DPCA-30, KAYARA DPCA-60, KAYARA DPCA-120, KAYARA TMPTA, KAYARA PET-30, KAYARA DPHA, KAYARA DPHA-2C [above, manufactured by Nippon Kayaku Corporation].

When using a polymerizable diluent, one type of polymerizable diluent may be used alone, or two or more types may be used in combination. In addition, the addition amount is preferably 10 to 500 parts by mass relative to 100 parts by mass of the component (a), and when the entire polymerizable composition is 100 parts by mass, 0.1 to 40 parts by mass is preferred, It is more preferably 5-30 parts by mass. If it is added in excess of 30 parts by mass, the refractive index may decrease, and the high refractive index that is the main purpose of the present invention cannot be maintained.

<(d) Polymerization initiator>

The polymerizable composition of the present invention may further contain a polymerization initiator. As the polymerization initiator, any one of a photopolymerization initiator and a thermal polymerization initiator may be used.

The photopolymerization initiator can include, for example, alkylphenols, benzophenones, ketones such as Michler ketones, phosphine oxides, benzyl benzoates, oxime esters, tetrakis Methyl thiolan (THIURAM) monosulfide, thioxanthones.

In particular, a photo-cracking type photo-radical polymerization initiator is preferred.

Commercially available photo radical polymerization initiators include, for example, IRGACURE (registered trademark) 184, IRGACURE 369, IRGACURE 651, IRGACURE 500, IRGACURE 819, IRGACURE 907, IRGACURE 784, IRGACURE 2959, IRGACURE CGI1700, IRGACURE CGI1750, IRGACURE CGI1850, IRGACURE CG24-61, IRGACURE TPO, Darocur (registered trademark) 1116, Darocur 1173 [above, BASFJAPAN (stock) system], ESACURE KIP150, ESACURE KIP65LT, ESACURE KIP100F, ESACURE KT37, ESACURE KT55, ESACURE KTO46, ESACURE KIP75, or more Lamberti Corporation].

Examples of thermal polymerization initiators include azo and organic peroxides.

Examples of commercially available azo-based thermal polymerization initiators include V-30, V-40, V-59, V-60, V-65, and V-70 [above, manufactured by Wako Pure Chemical Industries, Ltd.].

Also commercially available organic peroxide-based thermal polymerization initiators include, for example, Perkadox (registered trademark) CH, Perkadox BC-FF, Perkadox 14, Perkadox 16, Trigonox (registered trademark) 22, Trigonox 23, Trigonox 121, Kayaester (registered trademark) ) P, Kayaester O, Kayabutyl (registered trademark) B [above, manufactured by AKZO Chemicals (Stock)], PERHEXA (registered trademark) HC, PERCUMYL (registered trademark) H, PEROCTA (registered trademark) O, PERHEXYL (registered trademark) O, PERHEXYLZ, PERBUTYL (registered trademark) O, PERBUTYL Z [above, manufactured by NOF Corporation], but not limited to these.

When adding a polymerization initiator, a polymerization initiator can be used individually by 1 type or in mixture of 2 or more types. In addition, the added amount is 0.1-20 parts by mass relative to 100 parts by mass of the total amount of the polymerizable components, that is, the above-mentioned (a) component and (b) component (if desired, further (c) component), and more preferably It is 0.3 to 10 parts by mass.

<Other additives>

Furthermore, as long as the polymerizable composition of the present invention does not impair the effects of the present invention, it may contain, as necessary, chain transfer agents, antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, rheology modifiers, and silane coupling agents. Adhesive additives, pigments, dyes, defoamers, etc.

The above-mentioned chain transfer agent is a thiol compound, for example, methyl hydrothioacetate, methyl 3-hydrothiopropionate, 2-ethylhexyl 3-hydrothiopropionate, and 3-hydrothiopropionate. 3-methoxybutyl propionate, n-octyl 3-hydrothiopropionate, stearyl 3-hydrothiopropionate, 1,4-bis(3-hydrothiopropionyloxy)butane , 1,4-bis(3-hydrothiobutanoyloxy)butane, trimethylolethane ginseng (3-hydrothiopropionate), trimethylolethane ginseng (3-hydrothiobutane Acid ester), trimethylolpropane ginseng (3-hydrothiopropionate), trimethylolpropane ginseng (3-hydrothiobutyrate), neopentylerythritol four (3-hydrothiopropionate) Acid ester), neopentylerythritol four (3-hydrothiobutyrate), dineopentaerythritol land (3-hydrothiopropionate), dineopentaerythritol land (3-hydrothiobutyrate) Acid ester), ginseng [2-(3-hydrothiopropyloxy)ethyl] trimeric isocyanate, ginseng [2-(3-hydrothiobutyloxy) ethyl] trimeric isocyanate, etc. Hydrosulfide carboxylic acid esters; ethane mercaptan, 2-methylpropane-2-mercaptan, n-dodecyl mercaptan, 2,3,3,4,4,5-hexamethylhexane- Alkyl mercaptans such as 2-mercaptan (third-dodecane mercaptan), ethane-1,2-dimercaptan, propane-1,3-dimercaptan, biphenylmethyl mercaptan, etc. Class; Benzene mercaptan, 3-methylbenzene mercaptan, 4-methylbenzene mercaptan, naphthalene-2-mercaptan, pyridine-2-mercaptan, benzimidazole-2-mercaptan, benzothiazole-2 -Aromatic mercaptans such as mercaptans; hydrogen mercaptan alcohols such as 2-hydrothioethanol and 4-hydrosulfan-1-butanol; 3-(trimethoxysilyl)propane-1-sulfur Silane-containing mercaptans such as alcohols, 3-(triethoxysilyl)propane-1-thiol, etc.; for disulfide compounds, for example, diethyl disulfide, dipropyl disulfide Sulfide, diisopropyl disulfide, dibutyl disulfide, di-tertiary butyl disulfide, dipentyl disulfide, diisopentyl disulfide, dihexyl disulfide, Dicyclohexyl disulfide, didecyl disulfide, bis(2,3,3,4,4,5-hexamethylhexane-2-yl) disulfide (two-third-twelve carbon Alkyl disulfide), bis(2,2-diethoxyethyl) disulfide, bis(2-hydroxyethyl) disulfide, bibibenzyl disulfide, etc. Ethers; diphenyl disulfide, two-p-tolyl disulfide, two (pyridin-2-yl) pyridyl disulfide, two (benzimidazol-2-yl) disulfide, two ( Aromatic disulfide such as benzothiazol-2-yl) disulfide; tetramethyl sulfide blue disulfide, tetraethyl sulfide blue disulfide, tetrabutyl sulfide blue disulfide, bis(five Methylene) thioblue disulfide and other thioblue disulfide, α-methylstyrene dimer.

When adding a chain transfer agent, one kind of chain transfer agent may be used alone, or two or more kinds may be mixed and used. In addition, the addition amount is 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the polymerizable components, that is, the above-mentioned (a) component and (b) component (the (c) component to be further added as desired), and more Preferably, it is 0.1 to 10 parts by mass.

Examples of the above-mentioned antioxidant include phenol-based antioxidants, phosphoric acid-based antioxidants, and thioether-based antioxidants. Among them, phenol-based antioxidants are preferred.

Examples of phenolic antioxidants include IRGANOX (registered trademark) 245, IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX 1135 [above, manufactured by BASF JAPAN (stock)], Sumilizer (registered trademark) GA-80, Sumilizer GP, Sumilizer MDP-S, Sumilizer BBM-S, Sumilizer WX-R [above, manufactured by Sumitomo Chemical Co., Ltd.], ADK STAB (registered trademark) AO-20, ADK STABAO-30, ADK STABAO-40, ADK STABAO-50, ADK STABAO-60, ADK STABAO-80, ADK STABAO-330 [above, manufactured by ADEKA].

When the antioxidant is added, one kind of antioxidant may be used alone, or two or more kinds may be mixed and used. In addition, the addition amount is 0.01 to 20 parts by mass relative to 100 parts by mass of the total amount of the above-mentioned (a) component and (b) component (additional (c) component as desired) of the polymerizable components, and more Preferably, it is 0.1 to 10 parts by mass.

<Preparation method of polymerizable composition>

The preparation method of the polymerizable composition of this embodiment is not particularly limited. The preparation method can include, for example, mixing (a) component and (b) component, and as required (c) component and (d) component in a predetermined ratio, and further adding other additives as desired to mix to form a uniform solution The method; among these components, for example, mixing a part of (a) component and (b) component to form a uniform solution, adding the remaining components, and adding other additives as desired A method of mixing to form a uniform solution; or a method of further using common solvents in addition to these ingredients.

When a solvent is used, the ratio of the solid content in the polymerizable composition is not particularly limited as long as the components are uniformly dissolved in the solvent, but for example, it is 1-50% by mass, or 1-30% by mass, or 1~25 quality. Here, the term “solid content” refers to the solvent component removed from all the components of the polymerizable composition.

In addition, the solution of the polymerizable composition is preferably used after being filtered with a filter having a pore diameter of 0.1 to 5 μm or the like.

<<hardened material>>

The polymerizable composition can be exposed (photocured) or heated (thermally cured) to obtain a cured product. The present invention also targets the cured product of the polymerizable compound.

Light for exposure such as ultraviolet rays, electron rays, X-rays. The light source used for ultraviolet radiation can be, for example, sunlight, chemical lamp, low-pressure mercury lamp, high-pressure mercury lamp, metal halide lamp, xenon lamp, UV-LED. In addition, after exposure, in order to stabilize the physical properties of the hardened product, post-baking may be applied. The method of post-baking is not particularly limited, but usually a hot plate, oven, etc., are used in the range of 50 to 260°C for 1 to 120 minutes.

The heating conditions for thermal hardening are not particularly limited, but usually can be appropriately selected within the range of 50 to 300°C for 1 to 120 minutes. In addition, the heating means is not particularly limited, but examples include hot plates and ovens.

The cured product obtained by curing the polymerizable composition of the present invention has a wavelength of 589.3nm (D line) with a refractive index of 1.620 or more. Furthermore, a cured product with an Abbe number of 23 or less can be produced, and it can be suppressed It is expected to have dimensional stability due to cracks caused by heating or peeling from the support, so it can be suitably used as a material for high refractive index resin lenses.

<<Formed body>>

The polymerizable composition of the present invention can be easily produced in parallel with the formation of hardened products by using common molding methods such as compression molding (imprinting, etc.), casting, injection molding, and blow molding. The formed body obtained in this way is also the object of the present invention.

The method of manufacturing a molded body may include, for example, a step of filling the polymerizable composition of the present invention in the space between the support body and the mold that are joined to each other, or the inner space of the mold that can be divided; making the filled composition The step of performing photopolymerization by exposing the object; the step of taking out and demolding from the aforementioned space filled with the obtained photopolymer; and the step of heating the photopolymer before, during or after the demolding.

The steps of performing the above exposure and photopolymerization can be implemented by applying the conditions shown in the above-mentioned <<hardened product>>.

The conditions of the heating step are not particularly limited, but generally, it can be appropriately selected from the range of 50 to 260°C for 1 to 120 minutes. In addition, the heating means is not particularly limited, but for example, a hot plate, an oven, etc. can be mentioned.

The molded body manufactured by such a method can be suitably used as a camera module lens.

[Example]

Hereinafter, examples are given to explain the present invention more specifically, but the present invention is not limited to the following examples.

In addition, in the embodiment, the equipment and conditions used for the preparation of the sample and the analysis of the physical properties are as follows.

(1) Spin coater

Device: Cee (registered trademark) 200X made by Brewer Science

(2) UV exposure

Device: Eyegraphics (stock) system batch type UV irradiation device (high-pressure mercury lamp 2kW×1 lamp)

(3) ¹ H NMR spectrum

Device: AVANCE III HD manufactured by Bruker

Measuring frequency: 500MH z

Solvent: CDCl ₃

Internal benchmark: Tetramethylsilane (δ=0.00ppm)

(4) Gel permeation chromatography (GPC)

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

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

Column temperature: 40℃

Solvent: Tetrahydrofuran

Detector: RI

Calibration line: standard polystyrene

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

Apparatus A (when measuring cured film): Multi-incident angle spectroscopic ellipsometer VASE manufactured by J.A. Woollam Japan

Apparatus B (when measuring molded body): Prism Coupler 2010/M manufactured by Metricon

Measuring temperature: room temperature (about 23℃)

(6) Melting point

Observation device: (Stock) Nikon Polarizing Microscope ECLIPSE (registered trademark) E600 POL

Heating device: (Stock) Tokai Hit, stage automatic temperature control system for microscope ThermoPlate (registered trademark)

Heating rate: 0.5°C/sec

Measurement method: visually, the temperature at which a part of the sample begins to melt is used as the melting point

(7) Viscosity

Device: EMS-1000 manufactured by Kyoto Electronics Industry Co., Ltd.

(8) Penetration rate

Device: Japan Spectrophotometer (Stock) UV-Visible-Near-Infrared Spectrophotometer V-670

Control group: air

In addition, the abbreviated symbols indicate the following meanings.

NMA: Naphth-2-yl methacrylate

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

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

BPOEA: 2-([1,1'-biphenyl]-2-yloxy)ethyl acrylate [NK ESTER A-LEN-10 manufactured by Shinnakamura Chemical Industry Co., Ltd.]

BnA: Biphenylmethyl acrylate [Viscoat #160 manufactured by Osaka Organic Chemical Industry Co., Ltd., BZA]

DVB: Divinylbenzene [DVB-810 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.]

FDA: 9,9-bis(4-(2-propenyloxyethoxy)phenyl) pyridium [NK ESTER A-BPEF manufactured by Shinnakamura Chemical Industry Co., Ltd.]

PheTMS: Trimethoxy (9-phenanthryl) silane

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

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

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

DDT: n-dodecyl mercaptan [thiocatechol 20 manufactured by Kao Co., Ltd.]

I184: 1-Hydroxycyclohexyl phenyl ketone [IRGACURE (registered trademark) 184 manufactured by BASFJAPAN Co., Ltd.]

TPO: Diphenyl (2,4,6-trimethylbenzyl) phosphine oxide [BASFJAPAN (Stock) IRGACURE (registered trademark) TPO]

PGMEA: Propylene glycol monomethyl ether acetate

THF: Tetrahydrofuran

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

A 1L reaction flask equipped with a condenser was filled with 15.7 g (0.65 mol) of magnesium chips [manufactured by Kanto Chemical Co., Ltd.], and the air in the flask was replaced with nitrogen using a nitrogen balloon. In response, 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 dropped at room temperature (about 23° C.) for 1 hour, and further stirred for 1 hour. Prepare Gerenya reagent.

A 2L reaction flask was filled with STMS131.9g (0.58mol) and THF259g, and a nitrogen balloon was used to replace the air in the flask with nitrogen. In this regard, the above-mentioned Grenya reagent was dropped under reflux (approximately 66°C) for 30 minutes, and further refluxed for 24 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. After adding 1000 g of hexane to the obtained residue and refluxing for 1 hour to dissolve the soluble matter, the insoluble matter was filtered. To this insoluble matter, 750 g of hexane was added again, and after dissolving the soluble matter in the same manner, the insoluble matter was filtered. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. The crude product was recrystallized with 150 g of hexane to obtain 102.4 g of the intended SPeDMS (yield 47%).

^{The 1} H NMR spectrum of the obtained compound is shown in FIG. 1.

[Production Example 2] Production of Naphth-2-yl Methacrylate (NMA)

A 200 mL reaction flask was charged with 25.0 g (0.158 mol) of 2-naphthalenemethanol [manufactured by Tokyo Chemical Industry Co., Ltd.] and 158 g of THF, and after replacing the air in the flask with nitrogen using a nitrogen balloon, it was cooled to 0°C. 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 kept at room temperature (about 23°C) Stir for 1 hour. 158 g of water was added to the reaction mixture, and the product was extracted with 158 g of ethyl acetate. The solvent was distilled off under reduced pressure from the organic layer using an evaporator to obtain a crude product. The crude product was purified by silica gel chromatography (hexane/ethyl acetate=9/1 (mass ratio)) to obtain 21.5 g of the target naphthalene-2-yl methacrylate (yield 64%) ).

The target structure was confirmed from the ¹ H NMR spectrum of the obtained compound.

[Production Example 3] Production of Trimethoxy(9-phenanthryl)silane (PheTMS)

A 500 mL reaction flask equipped with a condenser was filled with 10.4 g (0.43 mol) of magnesium chips [manufactured by Kanto Chemical Co., Ltd.], and the air in the flask was replaced with nitrogen using a nitrogen balloon. In this regard, 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 dropped at room temperature (about 23°C) for 1 hour, and further stirred for 30 minutes. Prepare Gerenya reagent.

A 1L reaction flask was filled with 178.0g (1.17mol) of TMOS and 346g of THF, and a nitrogen balloon was used to replace the air in the flask with nitrogen. In this regard, the above-mentioned Grenya reagent was dropped at room temperature (approximately 23° C.) for 30 minutes, and further stirred for 2 hours. From this reaction mixture, THF was distilled off under reduced pressure using an evaporator. After adding 1000 g of hexane to the obtained residue to dissolve the soluble matter, the insoluble matter was filtered. 500 g of hexane was added to this insoluble matter again, and the soluble matter was filtered in the same manner. The respective filtrates were mixed, and hexane was distilled off under reduced pressure using an evaporator to obtain a crude product. After the crude product was evaporated under reduced pressure (1 mmHg, 120 to 150°C), it was recrystallized with 389 g of methanol to obtain 74.6 g of the desired PheTMS (yield 64%).

^{The 1} H NMR spectrum of the obtained compound is shown in FIG. 2.

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

A 50 mL reaction flask equipped with a condenser was charged with 1.36 g (3.23 mmol) of TEAH and 12 g of THF, and a nitrogen balloon was used to replace the air in the flask with nitrogen. In this regard, a mixture of 29.9 g (80.7 mmol) of SPeDMS manufactured according to Manufacturing Example 1 and 24 g of THF was dropped at room temperature (about 23° C.) for 10 minutes, and stirred at 40° C. for 16 hours. Cool this to room temperature (about 23°C). Then, 6.0 g of a cation exchange resin [Amberlist (registered trademark) 15JWET manufactured by Dow Chemical Co., Ltd.] and a filter aid [KCFlock W-100GK manufactured by Nippon Paper Co., Ltd.] 1.2 were added to this reaction mixture. g, stir for 1 hour to stop the reaction. After that, the cation exchange resin and the filter aid were filtered with a filter membrane with a pore diameter of 0.5 μm, and further rinsed with 30 g of ethyl acetate. This filtrate and washing liquid were combined, and they were added to 897 g of methanol to precipitate the polymer. This precipitate was filtered and dried to obtain 18.9 g of the intended 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] Production of high refractive index polymerizable compound 2 (XPe55)

A 50 mL reaction flask equipped with a condenser was filled with 0.90 g (2.14 mmol) of TEAH, 0.86 g (47.7 mmol) of ion-exchanged water, and 7 g of THF, and a nitrogen balloon was used to replace the air in the flask with nitrogen. In this regard, a mixture of 9.9 g (26.8 mmol) of SPeDMS manufactured according to Manufacturing Example 1, PheTMS 8.0 g (26.8 mmol) manufactured according to Manufacturing Example 3, and 14 g of THF was used for 10 minutes at room temperature (about 23°C) Dropped and stirred at 40°C for 16 hours. Cool this to room temperature (about 23°C). Then, 3.6 g of a cation exchange resin [Amberlist (registered trademark) 15JWET manufactured by Dow Chemical Co., Ltd.] and a filter aid [KCFlock W-100GK manufactured by Nippon Paper Co., Ltd.] 0.72 were added to this reaction mixture. g, stir for 1 hour to stop the reaction. After that, the cation exchange resin and the filter aid were filtered with a filter membrane with a pore size of 0.5 μm, and further washed with 18 g of ethyl acetate. The filtrate and the washing liquid were combined, and added to 538 g of methanol to precipitate the polymer. This precipitate was filtered and dried to obtain 14.8 g of the intended high refractive index polymerizable compound 2 (hereinafter, also sometimes referred to as XPe55).

The weight average molecular weight Mw of the obtained compound measured in terms of polystyrene by GPC was 1000, and the degree of dispersion: Mw/Mn was 1.0.

Regarding the SPeDMS, NMA, VN, and BPOEA produced according to Production Examples 1 and 2, the state and viscosity of the substance at 23°C and 100°C under atmospheric pressure were measured. The results are shown in Table 1.

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 with a PTFE pump filter with a pore size of 0.2 μm to obtain a varnish with a solid content of 30% by mass.

Each varnish was spin-coated on a silicon wafer (1500 rpm×30 seconds), and heated and dried on a hot plate at 80°C for 1 minute. This coating film was subjected to UV exposure at 20 mW/cm ² in a nitrogen atmosphere for 250 seconds, and further heated on a hot plate at 150° C. for 20 minutes to produce a cured film with a film thickness of 1.0 μm. _{The Abbe number ν D} of the obtained cured film at a wavelength of 589 nm (line D) was measured. The results are shown in Table 1 together.

[Example 1] Preparation of polymerizable composition 1

Mix 2 parts by mass of VN as a low viscosity agent of component (b), 6 parts by mass of FDA as a high refractive index polymerizable compound of component (a), and 2 parts by mass of BnA as a polymerizable diluent of component (c), in Stir at 40°C for 2 hours. In response to this, 0.1 parts by mass of I184 and 0.07 parts by mass of TPO as the polymerization initiator of the component (d) were added, and the mixture was stirred at 40°C for 1 hour. Furthermore, 0.3 parts by mass of DDT as a chain transfer agent (reaction accelerator) was added, and stirred at room temperature (approximately 23° C.) for 2 hours to prepare a homogeneous transparent varnish polymerizable composition 1.

[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 rest was performed in the same manner as in Example 1, and polymerizable compositions 2 to 16 were prepared, respectively. In addition, in Table 2, "part" means "parts by mass".

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

[Preparation of hardened material and evaluation of optical properties]

Each polymerizable composition and a 1mm thick silicone rubber spacer were sandwiched by two glass substrates with a release process. The polymerizable composition held by this was ^{exposed to 20mW/cm 2} UV for 250 seconds. After peeling the cured product from the glass substrate, it was heated on a hot plate at 150°C for 20 minutes to produce a molded body with a diameter of 30 mm and a thickness of 1 mm.

_{Measure the Abbe's number ν D at} the wavelength of 589 nm (D line) of the obtained molded body, the refractive index n _D , and the average transmittance at the wavelength of 400 to 800 nm. The results are shown in Table 3 together.

As shown in Tables 2 and 3, the low-viscosity agent of the present invention can be formulated to achieve low viscosity and low Abbe number ν _D as compared with the case where the low-viscosity agent is not formulated. In addition, it is related to the refractive index. n _D and transmittance are also the same or can be increased to higher values (refer to Examples 1 and 3 and Comparative Example 1, Example 4 and Comparative Example 2, Example 5 and Comparative Example 3). In addition, in Example 2, although low viscosity, high refractive index and high transmittance can be achieved by the formulation of a low viscosity agent, the proportion of high refractive index polymerizable compounds in the polymerizable composition is reduced, so it can be seen To the rise of Abbe number.

In addition, although BPOEA, which is a conventional liquid diluent, has a lower viscosity or maintains a viscosity of 10000 mPa•s or less like the low-viscosity agent of the present invention, the Abbe number increases (refer to Example 5 and Comparative Example 5, implementation Example 7 and Comparative Example 6, Example 9 and Comparative Example 7). In addition, when compared with the example in which the low viscosity agent is not formulated, BPOEA is compounded, but the result is that the Abbe number can be increased (refer to Comparative Examples 3 and 5, and Comparative Examples 4 and 7).

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

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

Each varnish was spin-coated on a silicon wafer (1500 rpm×30 seconds), and heated and dried on a hot plate at 80°C for 1 minute. This coating film was subjected to UV exposure at 20 mW/cm ² in a nitrogen atmosphere for 250 seconds, and further heated on a hot plate at 150° C. for 20 minutes to produce a cured film with a film 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 together.

Claims (11)

A method used as a low-viscosity agent for high refractive index diluents. It uses a compound that is solid at 1013.25 hPa and 23°C and has a melting point of less than 100°C, and has a viscosity at 100°C. It is 10mPa‧s or less, and the D-line (589.3nm) of the cured product has an Abbe number of 23 or less. As a compound with at least one polymerizable double bond, the D-line (589.3nm) of the cured product A low-viscosity agent for high refractive index polymerizable compounds with a refractive index of 1.60 or more, wherein the low-viscosity agent is a compound represented by the following formula [1];

In the formula, X represents: at least one phenyl group having a polymerizable double bond substituent, at least one naphthyl group having a polymerizable double bond substituent, and at least one polymerizable double bond A biphenyl group as a substituent, or a phenanthrenyl group with at least one substituent having a polymerizable double bond; Ar ¹ represents a condensed cyclic hydrocarbon group with a plural benzene ring structure (which can be substituted by an alkane with 1 to 6 carbon atoms) Group substitution), or a hydrocarbon ring group in which multiple aromatic rings are directly bonded by a single bond (which can be substituted by an alkyl group with 1 to 6 carbon atoms); R ¹ represents a methyl group, an ethyl group or an isopropyl group. Such as the method of item 1 in the scope of the patent application, wherein the aforementioned 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 polymerizable composition comprising: (a) 100 parts by mass of a high-refractive-index polymerizable compound having at least one polymerizable double bond and a cured product having a D-line (589.3nm) refractive index of 1.60 or more; And (b) 10 to 500 parts by mass of a low-viscosity agent composed of a compound each having at least one aromatic group and a group having a polymerizable double bond, wherein the high refractive index polymerizable compound contains reactive Polysiloxane, and the reactive polysiloxane contains: the polycondensate of the alkoxysilicon compound A represented by the formula [4], and the alkoxysilicon compound A represented by the formula [4] and the formula [ 5] At least one of the polycondensates of the alkoxysilicon compound B shown;

In the formula, X represents: at least one phenyl group having a polymerizable double bond substituent, at least one naphthyl group having a polymerizable double bond substituent, and at least one polymerizable double bond A biphenyl group with a substituent or a phenanthryl group with at least one substituent having a polymerizable double bond; Ar ³ represents a phenyl group that can be substituted by an alkyl group having 1 to 6 carbon atoms, and a plural benzene ring Condensed cyclic hydrocarbon group (which can be substituted by an alkyl group with carbon atoms of 1 to 6), or a hydrocarbon ring group in which multiple aromatic rings are directly bonded by a single bond (which can be substituted by an alkyl group with carbon atoms of 1 to 6 ); R ³ represents a methyl group, an ethyl group or an isopropyl group; Ar ⁴ -Si(OR ⁴ ) ₃ [5] In the formula, Ar ⁴ represents a phenyl group that can be substituted by an alkyl group having 1 to 6 carbon atoms, with A condensed cyclic hydrocarbon group composed of plural benzene rings (which can be substituted by 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 (may be substituted by a carbon number of 1 to 6的alkyl substitution); R ⁴ represents methyl, ethyl or isopropyl. Such as the polymerizable composition of item 3 of the scope of patent application, wherein the aforementioned (a) high refractive index polymerizable compound is a compound selected from the structural unit represented by the following formula [7-2] and has the formula [7-2 ] The group consisting of the structural unit shown in the formula [7-3] and the compound of the structural unit shown in the formula [7-3];

In the formula, Ar ⁵ and Ar ⁶ each independently represent a phenyl group, a naphthyl group, or a phenanthryl group. For example, the polymerizable composition of item 3 or 4 in the scope of the patent application further contains (c) a polymerizable diluent that is liquid at 1013.25 hPa and 23°C. A cured product, which is a cured product of a polymerizable composition according to any one of items 3 to 5 in the scope of the patent application. A high-refractive-index resin lens material, which is composed of the polymerizable composition of any one of items 3 to 5 in the scope of patent application. A resin lens, which is made of the polymerizable composition of any one of the 3 to 5 patent applications. A method of manufacturing a molded body, which includes: filling the space between the support body and the mold that are joined with each other with the polymerizable composition of any one of items 3 to 5 in the scope of the patent application, or the interior of the mold that can be divided The step of space; and the step of exposing and photopolymerizing the filled composition. For example, the manufacturing method of item 9 of the scope of patent application, which further comprises: taking out and demolding from the aforementioned space filled with the obtained photopolymer; and heating the photopolymer before, during or after demolding A step of. Such as the manufacturing method of item 9 or 10 in the scope of patent application, wherein the aforementioned molded body is a lens for a camera module.

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