WO2015022965A1

WO2015022965A1 - Polymerizable composition containing reactive silicone compound

Info

Publication number: WO2015022965A1
Application number: PCT/JP2014/071320
Authority: WO
Inventors: 偉大長澤; 健太郎大森; 和宏澤田
Original assignee: 日産化学工業株式会社
Priority date: 2013-08-15
Filing date: 2014-08-12
Publication date: 2015-02-19
Also published as: TW201522391A; JP2016180017A

Abstract

[Problem] To provide a liquid curable resin which does not undergo (yellowish) discoloration even when exposed to a high temperature environment and can be cured into an article having a Tg of 140˚C or higher. [Solution] A polymerizable composition comprising: (a) 100 parts by mass of a reactive silicone compound that is produced by the polycondensation of a diaryl silicic acid compound represented by formula [1] with an alkoxy silicon compound represented by formula [2] in the presence of an acid or a base; and (b) 20 to 100 parts by mass of at least one polymerizable monomer selected from the group consisting of (b1) a compound having a C_3-30 alicyclic group and one radically polymerizable double bond in the molecule and (b2) a maleimide derivative. (In the formula, Ar¹ and Ar² independently represent a phenyl group which may be substituted by a C_1-6 alkyl group; Ar³ represents a phenyl group which has at least one group having a polymerizable double bond, or a naphthyl group which has at least one group having a polymerizable double bond; R¹ represents a methyl group or an ethyl group; R² represents a methyl group, an ethyl group or a vinylphenyl group; and a represents 2 or 3.)

Description

Polymerizable composition comprising a reactive silicone compound

The present invention relates to a polymerizable composition containing a reactive silicone compound, a cured product obtained from the composition, and a method for producing a molded body using the composition.

In recent years, in the display field such as a liquid crystal panel and an organic EL panel, a large screen and high-quality image quality are required. For this reason, studies are being made on controlling the light traveling direction with a microlens array in which a large number of fine lenses are regularly arranged on a substrate, improving screen brightness and opening efficiency, and widening the viewing angle.
As a manufacturing method of the microlens array, a method of molding a resin lens on a glass substrate is common. In particular, a molding method using mold transfer using a solvent-free liquid cured resin is very frequently used because the process array has high reproducibility and a lens array can be manufactured with inexpensive equipment. As such a solvent-free liquid curable resin capable of lens molding, a curable resin composition containing a fluorene-based acrylate whose cured product exhibits a high refractive index of about 1.6 is disclosed (patent) Reference 1).

JP 2010-265346 A

In the device manufacturing process as described above, exposure is often performed at a high temperature of about 200 ° C. such as color filter baking and TFT array manufacturing. Therefore, it is an essential condition that the cured resin used for these applications has a high refractive index and at the same time, is not colored (yellowing) or deformed even when exposed to high temperatures. In particular, in order to suppress deformation due to heating, the glass transition temperature (hereinafter also referred to as Tg) needs to be at least 140 ° C. empirically.
For example, the Tg of the cured product obtained from the composition of Patent Document 1 is as low as 50 to 96 ° C., and it is difficult to use it in a device exposed to high temperatures. Thus, it is difficult to satisfy the above physical properties with a general-purpose cured resin such as an acrylic resin, and a material that satisfies all of these physical properties has been demanded.
An object of the present invention is to provide a liquid curable resin having no coloration (yellowing) even when exposed to a high temperature and having a Tg of a cured product of 140 ° C. or higher.

As a result of intensive studies in order to achieve the above object, the present inventors have found that a reactive silicone compound having a specific structure, an alicyclic group having 3 to 30 carbon atoms in the molecule and one radical as a polymerizable monomer. By combining a compound having a polymerizable double bond and / or a maleimide derivative, there is very little coloration (yellowing) due to heating, and a polymerization property capable of producing a cured product exhibiting a high Tg and a high refractive index. The present inventors have found that a composition can be obtained and completed the present invention.

That is, the present invention provides a first aspect as follows:
(A) 100 parts by mass of a reactive silicone compound obtained by polycondensation of a diaryl silicate compound represented by the formula [1] and an alkoxysilicon compound represented by the formula [2] in the presence of an acid or a base; And (b) (b1) at least one polymerization selected from the group consisting of a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative The present invention relates to a polymerizable composition containing 20 to 100 parts by mass of a polymerizable monomer.

(In the formula, Ar ¹ and Ar ² each independently represent a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms; Ar ³ represents at least one group having a polymerizable double bond) One phenyl group, or a naphthyl group having at least one group having a polymerizable double bond, R ¹ represents a methyl group or an ethyl group, R ² represents a methyl group, an ethyl group, or a vinylphenyl group, a represents 2 or 3.)
As a second aspect, the present invention relates to the polymerizable composition according to the first aspect, wherein (b1) is a (meth) acrylate compound.
As a third aspect, the present invention relates to the polymerizable composition according to the second aspect, wherein (b1) is a compound represented by the formula [3].

(In the formula, R ³ represents a hydrogen atom or a methyl group, L represents a single bond or an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents an alicyclic group having 3 to 30 carbon atoms.)
As a fourth aspect, the present invention relates to the polymerizable composition according to the third aspect, wherein L represents a single bond.
As a fifth aspect, the present invention relates to the polymerizable composition according to any one of the first aspect to the fourth aspect, in which the alicyclic group is an organic group having a crosslinked ring structure.
As a sixth aspect, the organic group is an organic group having at least one bridged ring structure selected from the group consisting of a norbornane ring, an adamantane ring, and a tricyclo [5.2.1.0 ^2,6 ] decane ring. And the polymerizable composition according to the fifth aspect.
As a seventh aspect, the present invention relates to the polymerizable composition according to any one of the first aspect to the sixth aspect, wherein (b2) is a compound represented by the formula [4].

(Wherein R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an optionally substituted aromatic group having 6 to 12 carbon atoms, or a hydroxy group.)
As an eighth aspect, the (b) polymerizable monomer is (b1) a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative. The present invention relates to the polymerizable composition according to any one of the first to seventh aspects.
As a ninth aspect, the (a) reactive silicone compound is obtained by polycondensation of a compound represented by the formula [5] and a compound represented by the formula [6] in the presence of an acid or a base. The polymerizable composition according to any one of the first to eighth aspects, which is a polymerizable silicone compound.

(Wherein R ¹ represents the same meaning as described above.)
As a tenth aspect, the present invention relates to a cured product obtained by photopolymerization or thermal polymerization of the polymerizable composition according to any one of the first to ninth aspects.
As an 11th viewpoint, it is related with the hardening relief pattern obtained from the polymeric composition in any one of a 1st viewpoint thru | or a 9th viewpoint.
As a 12th viewpoint, it is related with the optical lens obtained from the polymeric composition in any one of a 1st viewpoint thru | or a 9th viewpoint.
As a thirteenth aspect, the present invention relates to a high refractive index resin lens material comprising the polymerizable composition according to any one of the first to ninth aspects.
As a fourteenth aspect, a step of filling the polymerizable composition according to any one of the first to ninth aspects into a space between a support and a mold, exposing the filled composition to photopolymerization And a step of releasing the photopolymerized product on the support from the mold, and a step of heating the photopolymerized product together with the support.
As a fifteenth aspect, the present invention relates to the manufacturing method according to the fourteenth aspect, in which the molded body is a microlens array.

According to the present invention, a reactive silicone compound having a specific structure, a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule as a polymerizable monomer, and / or a maleimide derivative Can be combined to obtain a polymerizable composition capable of producing a cured product having very little coloration (yellowing) due to heating and having a high Tg and a high refractive index.
The polymerizable composition of the present invention having the above characteristics can easily mold a cured relief pattern typified by a lens array by various molding methods, and the obtained molded body is required to have a high heat resistance of 200 ° C. or higher. It can be used with high reliability even in a device.

1 is a diagram showing a ¹ H NMR spectrum of the reactive silicone compound obtained in Production Example 1. FIG. FIG. 2 is an SEM image of the microlens array produced in Example 9.

<< Polymerizable composition >>
The present invention provides (a) reactivity obtained by polycondensation of a diaryl silicate compound represented by the above formula [1] and an alkoxy silicon compound represented by the above formula [2] in the presence of an acid or a base. Selected from the group consisting of 100 parts by mass of a silicone compound, (b) (b1) a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative And a polymerizable composition containing 20 to 100 parts by mass of at least one polymerizable monomer.

<(A) Reactive silicone compound>
The (a) reactive silicone compound used in the present invention is a compound obtained by polycondensation of a diaryl silicate compound having a specific structure and an alkoxy silicon compound having a specific structure in the presence of an acid or a base.

[Diaryl silicate compound]
The diaryl silicate compound is a compound represented by the following formula [1].

In the above formula [1], Ar ¹ and Ar ² each independently represent a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms.

Examples of Ar ¹ and Ar ² include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-ethylphenyl group, 4-isopropylphenyl group, 4-tert-butylphenyl group, 3, Examples include 5-dimethylphenyl group, 3,5-diethylphenyl group, 3,5-diisopropylphenyl group, 2,4,6-trimethylphenyl group.
Specific examples of the compound represented by the above formula [1] include diphenylsilanediol, di-p-tolylsilanediol, bis (4-ethylphenyl) silanediol, bis (4-isopropylphenyl) silanediol and the like. However, it is not limited to these.

[Alkoxysilicon compounds]
The alkoxy silicon compound having the specific structure is a compound represented by the following formula [2].

In the above formula [2], Ar ³ represents a phenyl group having at least one group having a polymerizable double bond, or a naphthyl group having at least one group having a polymerizable double bond, and R ¹ is a methyl group Alternatively, it represents an ethyl group, R ² represents a methyl group, an ethyl group or a vinylphenyl group, and a represents 2 or 3.

Examples of the phenyl group having at least one group having a polymerizable double bond represented by Ar ³ include 2-vinylphenyl group, 3-vinylphenyl group, 4-vinylphenyl group, 4-vinyloxyphenyl group, 4 -Allylphenyl group, 4-allyloxyphenyl group, 4-isopropenylphenyl group and the like.
Examples of the naphthyl group having at least one group having a polymerizable double bond represented by Ar ³ include a 4-vinylnaphthalen-1-yl group and a 6-vinylnaphthalen-2-yl group.

Specific examples of the compound represented by the above formula [2] include, for example, trimethoxy (4-vinylphenyl) silane, triethoxy (4-vinylphenyl) silane, dimethoxy (methyl) (4-vinylphenyl) silane, dimethoxybis Examples include (4-vinylphenyl) silane, but are not limited thereto.

The reactive silicone compound (a) is a reactive silicone obtained by polycondensation of a compound represented by the following formula [5] and a compound represented by the following formula [6] in the presence of an acid or a base. Compounds are preferred.

In the above formula [6], R ¹ represents the same meaning as described above.

[Blending ratio of diaryl silicate compound and alkoxy silicon compound]
Although the compounding molar ratio concerning the polycondensation reaction of the diaryl silicic acid compound represented by the formula [1] and the alkoxysilicon compound represented by the formula [2] used for the above-mentioned reactive silicone compound is not particularly limited, a block copolymer is formed. In general, the range of diaryl silicate compound: alkoxy silicon compound = 2: 1 to 1: 2 is preferable. More preferably, the blending ratio is between 1.1: 0.9 and 0.9: 1.1.
The above-mentioned diaryl silicate compound and alkoxy silicon compound can be appropriately selected and used as necessary, and a plurality of types can be used in combination. In this case, the molar ratio of the total molar amount of the diaryl silicate compound and the total molar amount of the alkoxysilicon compound is within the above range.

[Acid or basic catalyst]
The polycondensation reaction between the diaryl silicate compound represented by the above formula [1] and the alkoxysilicon compound represented by the above formula [2] is preferably carried out in the presence of an acid or a basic catalyst.
The type of the catalyst used for the polycondensation reaction is not particularly limited as long as it is dissolved or uniformly dispersed in the solvent described later, and can be appropriately selected and used as necessary.
Examples of catalysts that can be used include B (OR) ₃ , Al (OR) ₃ , Ti (OR) ₄ , and Zr (OR) ₄ as acidic compounds; alkali metal hydroxides as basic compounds, Alkaline earth metal hydroxides, ammonium salts, amines, etc .; Examples of fluoride salts include NH ₄ F, NR ₄ F, and the like. Here, R is 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. One or more groups.
These catalysts can be used alone or in combination of two or more.

Examples of the acidic compound include boric acid, trimethoxyboron, triethoxyboron, tri-n-propoxyboron, triisopropoxyboron, tri-n-butoxyboron, triisobutoxyboron, tri-sec-butoxyboron, Tri-tert-butoxyboron, trimethoxyaluminum, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, triisobutoxyaluminum, tri-sec-butoxyaluminum, tri-tert- Butoxyaluminum, tetramethoxytitanium, tetraethoxytitanium, tetra-n-propoxytitanium, tetraisopropoxytitanium (titanium tetraisopropoxide), tetra-n-butoxytitanium, te Lysobutoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy titanium, tetramethoxy zirconium, tetraethoxy zirconium, tetra-n-propoxy zirconium, tetraisopropoxy zirconium, tetra-n-butoxy zirconium, tetraisobutoxy zirconium, Examples thereof include tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium and the like.

Examples of the basic compound include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine. Etc.

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

Among these catalysts, one or more selected from the group consisting of tetraisopropoxy titanium (titanium tetraisopropoxide), magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide is preferably used.
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 diaryl silicate compound and the alkoxysilicon compound. The reaction proceeds more favorably when the amount of the catalyst used is 0.01% by mass or more. In consideration of economy, the use of 10% by mass or less is sufficient.

[Polycondensation reaction]
The reactive silicone compound according to the present invention is characterized by the structure of the alkoxysilicon compound. The reactive group (polymerizable double bond) contained in the alkoxysilicon compound used in the present invention is easily polymerized radically or ionically (anion, cation), and has high heat resistance after polymerization (after curing). Show.
When such an alkoxysilicon compound and a diarylsilicate compound are polycondensed to obtain a silicone compound having high heat resistance, it is necessary to stop the reaction at an appropriate degree of polymerization so that the product maintains a liquid state. Since the alkoxysilicon compound used in the present invention does not actively hydrolyze, the polycondensation reaction with the diaryl silicate compound is gentle, and the degree of polymerization is easily controlled.
The polycondensation reaction of the alkoxy silicon compound and the diaryl silicate compound by dealcoholization can be carried out in the absence of a solvent, but it is also possible to use a solvent inert to the alkoxy silicon compound such as toluene as the reaction solvent. . When there is no solvent, there is an advantage that the alcohol as a reaction by-product can be easily distilled off. On the other hand, when a reaction solvent is used, there are advantages that the reaction system can be easily made uniform and a more stable polycondensation reaction can be performed.

The reactive reaction of the reactive silicone compound may be performed without a solvent as described above, but there is no problem even if a solvent is used in order to make it more uniform. The solvent is not particularly limited as long as it does not react with the diaryl silicate compound and the alkoxysilicon compound and dissolves the condensate thereof.
Examples of such a reaction solvent include ketones such as acetone and methyl ethyl ketone (MEK); aromatic hydrocarbons such as benzene, toluene and xylene; glycols such as ethylene glycol, propylene glycol and hexylene glycol; ethyl cellosolve Glycol ethers such as butyl cellosolve, ethyl carbitol, butyl carbitol, diethyl cellosolve and diethyl carbitol; amides such as N-methyl-2-pyrrolidone (NMP) and N, N-dimethylformamide (DMF) It is done. These solvents may be used alone or in combination of two or more.

The reactive silicone compound used in the present invention comprises a dealcoholization condensation of a diaryl silicate compound represented by the formula [1] and an alkoxy silicon compound represented by the formula [2] in the presence of an acid or a basic catalyst. Is obtained. The reaction is preferably performed in an inert gas atmosphere such as nitrogen gas for the purpose of preventing moisture from entering. The reaction temperature is 20 to 150 ° C, more preferably 30 to 120 ° C.
The reaction time is not particularly limited as long as it is longer than the time necessary for the molecular weight distribution of the polycondensate to increase and to stabilize the molecular weight distribution, and more specifically, several hours to several days.

After completion of the polycondensation reaction, it is preferable to collect the reactive silicone compound obtained by any method such as filtration and solvent distillation, and appropriately perform a purification treatment as necessary.

The polycondensate obtained by such a reaction has a weight average molecular weight Mw measured in terms of polystyrene by gel permeation chromatography (GPC) of 500 to 10,000, and a dispersity Mw (weight average molecular weight) / Mn (Number average molecular weight) is 1.0 to 10.

<(B) Polymerizable monomer>
The (b) polymerizable monomer used in the present invention comprises (b1) a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative. And at least one polymerizable monomer selected from the group.

[(B1) Compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule]
The compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule used in the present invention is preferably an organic group in which the alicyclic group has a crosslinked ring structure, and a norbornane ring And an organic group having at least one kind of a bridged ring structure selected from the group consisting of an adamantane ring and a tricyclo [5.2.1.0 ^2,6 ] decane ring.

Examples of the alicyclic group having 3 to 30 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 3,3,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, menthyl group, Isobornyl, norbornyl, 1-adamantyl, 2-adamantyl, 2-methyladamantan-2-yl, 2-ethyladamantan-2-yl, tricyclo [5.2.1.0 ^2,6 ] decanyl Groups and the like.
Among them, isobornyl group, norbornyl group, 1-adamantyl group, 2-adamantyl group, 2-methyladamantan-2-yl group, 2-ethyladamantan-2-yl group, tricyclo [5.2.1.0 ^2,6 A decanyl group is preferred.

The compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule used in the present invention is preferably a (meth) acrylate compound, particularly a compound represented by the following formula [3] Is preferred. In the present invention, the (meth) acrylate compound refers to both an acrylate compound and a methacrylate compound. For example, (meth) acrylic acid refers to acrylic acid and methacrylic acid.

In the above formula [3], R ³ represents a hydrogen atom or a methyl group, L represents a single bond or an alkylene group having 1 to 6 carbon atoms, and R ⁴ represents an alicyclic group having 3 to 30 carbon atoms. .

L is, for example, a chain of methylene, ethylene, trimethylene, methylethylene, tetramethylene, 1-methyltrimethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, etc. Or a branched alkylene group; cyclopropane-1,2-diyl group, cyclobutane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,2-diyl group, cyclopentane-1, And cyclic alkylene groups such as a 3-diyl group, a cyclohexane-1,2-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,4-diyl group.
Among these, L is preferably a single bond, a methylene group or an ethylene group, and more preferably a single bond.

Examples of the suitable compound (b1) having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 3, 3,5-trimethylcyclohexyl (meth) acrylate, 4-tert-butylcyclohexyl (meth) acrylate, menthyl (meth) acrylate, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2- Adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantan-2-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate Etc.
Among them, isobornyl (meth) acrylate, norbornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-adamantyl (meth) acrylate, 2-methyladamantan-2-yl (meth) acrylate, 2-ethyladamantane-2- Particularly preferred are yl (meth) acrylate and tricyclo [5.2.1.0 ^2,6 ] decanyl (meth) acrylate.

[(B2) Maleimide derivative]
The maleimide derivative used in the present invention is preferably a compound represented by the following formula [4].

In the above formula [4], R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an optionally substituted aromatic group having 6 to 12 carbon atoms, or a hydroxy group.

Examples of the alkyl group having 1 to 12 carbon atoms represented by R ⁵ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl, isoamyl, neopentyl, tert-amyl, sec-isoamyl, cyclopentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, benzyl, phenethyl, naphthylmethyl Group, naphthylethyl group and the like.
Examples of the aromatic group having 6 to 12 carbon atoms represented by R ⁵ include a phenyl group and a naphthyl group. Examples of the substituent include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group, a halogen atom, and a hydroxy group. Examples of the alkyl group having 1 to 6 carbon atoms as the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. N-pentyl group, isoamyl group, neopentyl group, tert-amyl group, sec-isoamyl group, cyclopentyl group, n-hexyl group, cyclohexyl group and the like. Examples of the alkoxy group having 1 to 6 carbon atoms as the substituent include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group. Group, n-pentyloxy group, isoamyloxy group, neopentyloxy group, tert-amyloxy group, sec-isoamyloxy group, cyclopentyloxy group, n-hexyloxy group, cyclohexyloxy group and the like.
Among these, R ⁵ is preferably a cyclohexyl group or a phenyl group, and more preferably a cyclohexyl group.

The (b) polymerizable monomer comprises both (b1) a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative. It is preferable.

In the present invention, the content of the polymerizable monomer (b) is 20 to 100 parts by mass, more preferably 25 to 60 parts by mass with respect to 100 parts by mass of the (a) reactive silicone compound.

<(C) Polymerization initiator>
The polymerizable composition of the present invention may contain (c) a polymerization initiator in addition to (a) the reactive silicone compound and (b) the polymerizable monomer. As the polymerization initiator, any of a photopolymerization initiator and a thermal polymerization initiator can be used.

Examples of the photopolymerization initiator include alkylphenones, benzophenones, acylphosphine oxides, Michler's benzoylbenzoates, oxime esters, tetramethylthiuram monosulfides, and thioxanthones.
In particular, photocleavable photoradical polymerization initiators are preferred. Examples of the photocleavable photoradical polymerization initiator include those described in the latest UV curing technology (p. 159, publisher: Kazuhiro Takahisa, publisher: Technical Information Association, published in 1991). .
Examples of commercially available radical photopolymerization initiators include IRGACURE (registered trademark) 184, 369, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, and CGI 1850. CG24-61, TPO, Darocur (registered trademark) 1116, 1173 [above, manufactured by BASF Japan Ltd.], ESACURE KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 [ As mentioned above, Lamberti Co.] can be mentioned.

Examples of the thermal polymerization initiator include azos 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.] Etc.
Examples of commercially available organic peroxide thermal polymerization initiators include, for example, Parkadox (registered trademark) CH, BC-FF, 14, 16 and Trigonox (registered trademark) 22, 23, 121. , Kayaester (registered trademark) P, O, Kayabutyl (registered trademark) B [above, manufactured by Kayaku Akzo Co., Ltd.], Perhexa (registered trademark) HC, Parkmill (registered trademark) H, Perocta (registered trademark) O Perhexyl (registered trademark) O, Z, perbutyl (registered trademark) O, Z [above, manufactured by NOF Corporation] and the like, but is not limited thereto.

When a polymerization initiator is added, the polymerization initiators may be used alone or in combination of two or more. The addition amount is 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the (a) reactive silicone compound.

<Other additives>
Furthermore, in the polymerizable composition of the present invention, a reactive diluent, a chain transfer agent, an antioxidant, an ultraviolet absorber, a surfactant, and a leveling agent are added as necessary as long as the effects of the present invention are not impaired. Other components such as an antifoaming agent and an adhesion improver may be added as appropriate.

<Method for Preparing Polymerizable Composition>
The method for preparing the polymerizable composition of the present embodiment is not particularly limited. As a preparation method, for example, the (a) component, the (b) component, and the (c) component as necessary are mixed at a predetermined ratio, and other additives are further added and mixed as desired. Or a method using a conventional solvent in addition to these components.

The ratio of the solid content in the polymerizable composition is not particularly limited as long as each component is uniformly dissolved in the solvent, and is, for example, 1 to 50% by mass, or 1 to 30% by mass, or 1 to 25% by mass. Here, the solid content is obtained by removing the solvent component from all components of the polymerizable composition.

The solution of the polymerizable composition is preferably used after being filtered using a filter having a pore size of 0.05 to 5 μm.

<< cured product >>
The present invention also relates to a cured product obtained by photo or thermal polymerization of the polymerizable composition.
Examples of actinic rays used for photopolymerization include ultraviolet rays, electron beams, and X-rays. As a light source used for ultraviolet irradiation, sunlight, a chemical lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a UV-LED, or the like can be used. In addition, after the photopolymerization, if necessary, post-baking is performed, and specifically, the polymerization can be completed by heating using a hot plate, an oven or the like. The post-baking conditions are not particularly limited, but are usually 50 to 260 ° C. for 1 to 120 minutes.
The heating conditions in the thermal polymerization are not particularly limited, but are usually appropriately selected from the range of 50 to 300 ° C. and 1 to 120 minutes. Moreover, it does not specifically limit as a heating means, For example, a hotplate, oven, etc. are mentioned.

The cured product of the present invention has a refractive index as high as 1.5 or more at a wavelength of 589 nm, and also has a dimensional stability by suppressing the occurrence of yellowing and cracks due to heating. It is useful as a material for a high refractive index resin lens such as an optical lens.

<< Molded Article >>
The hardened | cured material of this invention can be obtained as molded articles, such as a cured film and a laminated body, by coating the said polymeric composition on a base material and carrying out light or thermal polymerization (hardening). Further, for example, various molded bodies can be easily produced by using a conventional molding method such as compression molding, injection molding, blow molding, or vacuum molding.
Examples of the substrate include plastics (polyesters such as polycarbonate, polymethacrylate, polystyrene, and PET (polyethylene terephthalate), polyolefins, epoxy resins, melamine resins, triacetyl cellulose, and ABS resins (acrylonitrile-butadiene-styrene copolymer). AS resin (acrylonitrile-styrene copolymer), norbornene resin, etc.), metal, wood, paper, glass, slate and the like. The shape of these base materials may be a plate shape, a film shape, or a three-dimensional molded body.

The coating method of the polymerizable composition of the present invention includes a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a spray coating method, a bar coating method, a die coating method, an ink jet method, a printing method (letter plate). , Intaglio, lithographic, screen printing, etc.) can be selected as appropriate, and it is desirable to use a bar coating method because of the advantage that it can be applied in a short time and can be uniformly applied easily. The polymerizable composition used here can be suitably used in the form of a varnish.
The thickness of the film formed by coating is usually 0.01 to 50 μm, preferably 0.05 to 30 μm, particularly preferably 0.1 to 30 μm after drying and curing.

As a method for producing a molded body, for example, a step of filling the polymerizable composition in a space between the support and the mold, a step of exposing the filled composition to photopolymerization, and a step on the support And a method for producing a molded article, including a step of releasing the photopolymerized product from the mold and a step of heating the photopolymerized product together with the support.
The molded body obtained by the above production method can be suitably used as a microlens array.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated more concretely, this invention is not limited to the following Example.
In the examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1) ¹ H NMR spectrum apparatus: JNM-ECX300 manufactured by JEOL Ltd.
Measuring solvent: CDCl ₃
Reference substance: Tetramethylsilane (0.00ppm)
(2) Gel permeation chromatography (GPC)
Equipment: HLC-8320GPC manufactured by Tosoh Corporation
Column: Shodex (registered trademark) GPC KF-802.5, GPC KF-803 manufactured by Showa Denko K.K.
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Detector: UV (254 nm)
Calibration curve: Standard polystyrene (3) Stirring and deaerator Machine: Rotating and revolving mixer manufactured by Shinkey Co., Ltd. Awatori Rentaro (registered trademark) ARE-310
(4) UV exposure device: Batch type UV irradiation device (high pressure mercury lamp 2kW x 1 lamp) manufactured by Eye Graphics Co., Ltd.
(5) Light transmittance apparatus: UV-visible spectrophotometer UV-3100 manufactured by Shimadzu Corporation
(6) Glass transition temperature (Tg)
Apparatus: Dynamic viscoelasticity measuring apparatus (DMA) Q800 manufactured by TA Instrument
Deformation mode: Pulling frequency: 1 Hz
Strain: 0.1%
Measurement temperature: 25-250 ° C
Temperature rising rate: 10 ° C./min (7) Refractive index Device: Multi-wavelength Abbe refractometer DR-M4 manufactured by Atago Co., Ltd.
Intermediate liquid: Monobromonaphthalene Measurement temperature: 23 ° C
(8) Nanoimprinter Device: Myeongchang Kiko NM-0801B
Lamp: Toshiba Corporation Short Arc Mercury Lamp (9) SEM Observation Equipment: Field Emission Scanning Electron Microscope S-4800, Hitachi High-Technologies Corporation

Abbreviations represent the following meanings.
ADCP: Tricyclo [5.2.1.0 ^2,6 ] decane dimethanol diacrylate [NK Nakano Chemical Co., Ltd. NK ester A-DCP]
ADM: 1-adamantyl methacrylate [Adamantate (registered trademark) M-104, manufactured by Idemitsu Kosan Co., Ltd.]
BZM: benzyl methacrylate [manufactured by Aldrich]
CHM: N-cyclohexylmaleimide [Imirex (registered trademark) -C, manufactured by Nippon Shokubai Co., Ltd.]
DCPM: Tricyclo [5.2.1.0 ^2,6 ] decanyl methacrylate [manufactured by Hitachi Chemical Co., Ltd., FANCLIL (registered trademark) FA-513M]
EPPA: ethoxylated o-phenylphenol acrylate [manufactured by Shin-Nakamura Chemical Co., Ltd., NK Ester A-LEN-10]
I184: 1-hydroxycyclohexyl = phenyl ketone [IRGACURE (registered trademark) 184 manufactured by BASF Japan Ltd.]
IBA: Isobornyl acrylate [manufactured by Tokyo Chemical Industry Co., Ltd.]
PEBHT: Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) [manufactured by Tokyo Chemical Industry Co., Ltd.]
TPO: Diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide [IRGACURE (registered trademark) TPO manufactured by BASF Japan Ltd.]

[Production Example 1] Production of reactive silicone compound In a 1 L eggplant-shaped flask equipped with a condenser, 177 g (0.80 mol) of diphenylsilanediol [manufactured by Tokyo Chemical Industry Co., Ltd.], trimethoxy (4-vinylphenyl) silane [Shin-Etsu Chemical Co., Ltd.] 179 g (0.80 mol) and 141 g of toluene were charged, and the air in the flask was replaced with nitrogen using a nitrogen balloon. After this reaction mixture was heated to 50 ° C., 0.303 g (1.6 mmol) of barium hydroxide monohydrate [manufactured by Aldrich] was added, and the mixture was further stirred at 50 ° C. for 2 days for dealcohol condensation. The reaction mixture was cooled to room temperature (approximately 25 ° C.), and insoluble matters were removed using a membrane filter having a pore size of 0.2 μm. Using a rotary evaporator, toluene and by-product methanol were distilled off from this reaction mixture under reduced pressure at 50 ° C. to obtain 305 g of a colorless transparent oily reactive silicone compound.
The ¹ H NMR spectrum of the obtained reactive silicone compound is shown in FIG. Moreover, the weight average molecular weight Mw measured by polystyrene conversion by GPC was 1,600, and dispersion degree Mw (weight average molecular weight) / Mn (number average molecular weight) was 1.3.

[Example 1]
[Preparation of polymerizable composition]
32 parts by mass of the reactive silicone compound produced in Production Example 1, 8 parts by mass of DCPM as a monofunctional monomer, 0.2 parts by mass of PEBHT as an antioxidant, and 2 parts by mass of I184 as a polymerization initiator are mixed and stirred at 2000 rpm for 30 minutes. A polymerizable composition was obtained by defoaming.
[Production of cured product (thin film) and evaluation of transmittance reduction by heating]
The polymerizable composition was applied on a glass substrate with an applicator having a gap of 25 μm. This coating film was subjected to UV exposure at 20 mW / cm ² (365 nm detection) for 1 minute in a nitrogen atmosphere, and further heated on a hot plate at 150 ° C. for 10 minutes to produce a cured film.
The obtained cured film was measured for light transmittance at a wavelength of 400 nm before and after a heating test (200 ° C., 3 hours), and evaluated for a decrease in transmittance due to heating. The results are shown in Table 1.
[Production of cured product and evaluation of physical properties]
The above-mentioned polymerizable composition was poured into a 200 μm-thick silicone mold obtained by cutting out a central portion placed on a glass substrate into a rectangle of 30 mm × 5 mm, and another glass substrate was covered from above. The polymerizable composition in the mold sandwiched between these two glass substrates was cured by UV exposure for 1 minute at 20 mW / cm ² (365 nm detection). After curing, the cured product obtained by removing the glass substrate and the mold was further heated in an oven at 150 ° C. for 10 minutes to prepare a cured product.
The obtained cured product was evaluated for the glass transition temperature (Tg) and the refractive index (n _d ) of the D line (wavelength 589 nm). For Tg, the storage elastic modulus E ′ and the loss elastic modulus E ″ are measured by DMA, and the temperature at which the value of tan δ (loss elastic modulus E ″ / storage elastic modulus E ′) obtained from these is maximum is obtained. Was Tg. The results are also shown in Table 1.

[Examples 2 to 8, Comparative Examples 1 to 6]
Operations and evaluations were performed in the same manner as in Example 1 except that each component was mixed with the composition shown in Table 1. The results are also shown in Table 1.

As shown in Table 1, the cured products (Examples 1 to 8) obtained from the polymerizable composition of the present invention all showed a high Tg of 140 ° C. or higher and a high refractive index of 1.56 or higher. Even after heating at 200 ° C. for 3 hours, the decrease in transmittance due to discoloration was 1.5% or less.
On the other hand, in the cured product in which the specific monofunctional monomer is less than the predetermined amount (Comparative Example 1) and the cured product in which the bifunctional monomer is added instead of the specific monofunctional monomer (Comparative Example 5), Tg is 100 ° C. or less. Further, yellowing occurred by heating at 200 ° C. for 3 hours, and the transmittance decreased by 3 to 4%. Moreover, in the hardened | cured material (Comparative Examples 3 and 4) which added the other monofunctional monomer instead of the specific monofunctional monomer, although the fall of the transmittance | permeability was small, Tg was as low as 100 degrees C or less. Furthermore, in the cured product (Comparative Example 2) in which the specific monofunctional monomer exceeds a predetermined amount (Comparative Example 2), the cured product (thin film) is not cured in the cured product (Comparative Example 6) to which the specific monofunctional monomer is added at 200 ° C. for 3 hours The result that a crack entered and the hardened | cured material cracked at the time of preparation was obtained.

[Example 9] Production of microlens array and evaluation of dimensional stability by heating 0.01 g of the polymerizable composition prepared in Example 6 was placed on a glass substrate, and a microlens shape was formed from above using a nanoimprinter. A silicon mold (lens size: φ40 μm × depth 16.5 μm, manufactured by Kyodo International Co., Ltd.) was pressure bonded. This polymerizable composition was cured by UV exposure at 4 mW / cm ² (365 nm detection) for 5 minutes from the glass surface. After curing, the mold was peeled off, and further heated on a hot plate at 150 ° C. for 10 minutes to produce a microlens array on the glass substrate.
When the obtained microlens array was observed with an SEM, it was confirmed that the lens shape was clearly transferred. The SEM image is shown in FIG. Moreover, the lens height (thickness) and lens diameter (lens bottom diameter) before and after the heating test (200 ° C., 3 hours) of this microlens array were measured by cross-sectional SEM observation, and dimensional stability by heating was evaluated. The results are shown in Table 2.

As shown in Table 2, the cured product obtained from the polymerizable composition of the present invention has a very small shape change even after heating at 200 ° C. for 3 hours, and has very high dimensional stability by heating. Results were obtained.

Claims

(A) 100 parts by mass of a reactive silicone compound obtained by polycondensation of a diaryl silicate compound represented by the formula [1] and an alkoxysilicon compound represented by the formula [2] in the presence of an acid or a base; And (b) (b1) at least one polymerization selected from the group consisting of a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative A polymerizable composition comprising 20 to 100 parts by mass of a polymerizable monomer.

(In the formula, Ar 1 and Ar 2 each independently represent a phenyl group which may be substituted with an alkyl group having 1 to 6 carbon atoms; Ar 3 represents at least one group having a polymerizable double bond) One phenyl group, or a naphthyl group having at least one group having a polymerizable double bond, R 1 represents a methyl group or an ethyl group, R 2 represents a methyl group, an ethyl group, or a vinylphenyl group, a represents 2 or 3.)
The polymerizable composition according to claim 1, wherein (b1) is a (meth) acrylate compound.
The polymerizable composition according to claim 2, wherein (b1) is a compound represented by Formula [3].

(In the formula, R 3 represents a hydrogen atom or a methyl group, L represents a single bond or an alkylene group having 1 to 6 carbon atoms, and R 4 represents an alicyclic group having 3 to 30 carbon atoms.)
The polymerizable composition according to claim 3, wherein L represents a single bond.
The polymerizable composition according to any one of claims 1 to 4, wherein the alicyclic group is an organic group having a crosslinked ring structure.
The organic group is an organic group having at least one bridged ring structure selected from the group consisting of a norbornane ring, an adamantane ring, and a tricyclo [5.2.1.0 2,6 ] decane ring. The polymerizable composition as described.
The polymerizable composition according to any one of claims 1 to 6, wherein (b2) is a compound represented by the formula [4].

(Wherein R 5 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an optionally substituted aromatic group having 6 to 12 carbon atoms, or a hydroxy group.)
The (b) polymerizable monomer comprises both (b1) a compound having an alicyclic group having 3 to 30 carbon atoms and one radical polymerizable double bond in the molecule, and (b2) a maleimide derivative. The polymerizable composition according to any one of Items 1 to 7.
The reactive silicone compound (a) is a reactive silicone compound obtained by polycondensation of a compound represented by the formula [5] and a compound represented by the formula [6] in the presence of an acid or a base. The polymerizable composition according to any one of claims 1 to 8.

(Wherein R 1 represents the same meaning as described above.)
A cured product obtained by photo or thermal polymerization of the polymerizable composition according to any one of claims 1 to 9.
A cured relief pattern obtained from the polymerizable composition according to claim 1.
An optical lens obtained from the polymerizable composition according to claim 1.
A material for a high refractive index resin lens comprising the polymerizable composition according to any one of claims 1 to 9.
A step of filling the polymerizable composition according to any one of claims 1 to 9 in a space between a support and a mold, a step of photopolymerizing the filled composition by exposure, a support A method for producing a molded article, comprising the steps of releasing the photopolymerized product from the mold and heating the photopolymerized product together with the support.
The manufacturing method according to claim 14, wherein the molded body is a microlens array.