JP2008247849A - New sulfur-containing ethylenically unsaturated group-containing compound, radiation-curable composition and cured product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-curable composition providing a cured product having high refractive index and high Abbe's number. <P>SOLUTION: The sulfur-containing ethylenically unsaturated group-containing compound is obtained by reacting a sulfur-containing compound represented by formula (1) with a compound having the ethylenically unsaturated group. The radiation-curable composition containing the compound, and the cured product thereof are also provided. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel sulfur-containing ethylenically unsaturated group-containing compound, a radiation curable composition containing the compound, and a cured product. In particular, the present invention relates to a radiation curable composition useful as a material for an optical member, and an optical member made of the cured product.

  In recent years, plastic lenses that are light in weight, have high impact resistance, and can be mass-produced are increasingly used instead of inorganic glass. In the field of spectacle lenses, the proportion of plastic lenses has reached 90%. In the field of such optical lenses, a higher refractive index is being promoted for the purpose of further reducing the thickness of the lens. On the other hand, an Abbe number is one of important optical characteristics. This represents the degree of refractive index difference depending on the wavelength of light, and the higher the Abbe number, the smaller the difference and the better the lens. However, the refractive index and Abbe number of organic materials are in a trade-off relationship, and it has been difficult to improve these simultaneously.

  In addition, optical lenses such as Fresnel lenses and lenticular lenses used in projection televisions have been manufactured by methods such as pressing and casting. However, these methods have a problem of low productivity because they require a long time for heating and cooling during production.

In order to solve such problems, in recent years, it has been studied to manufacture a lens using an ultraviolet curable resin composition. Specifically, by pouring an ultraviolet curable resin composition between a lens-shaped mold and a transparent resin substrate, by irradiating ultraviolet rays from the transparent resin substrate side and curing the composition A lens can be manufactured in a short time.
With the recent thinning and enlargement of projection televisions and video projectors, UV curable resin compositions for forming optical lenses have a high refractive index and so-called blue loss (the screen is bluish). Phenomenon), having excellent mechanical properties, and having an appropriate viscosity (small viscosity suitable for thinning and enlargement) before curing.

  Here, as a resin composition for forming an optical lens, for example, a reaction product of a diol (a) having a specific structure, an aromatic organic polyisocyanate (b), and a hydroxyl group-containing (meth) acrylate (c). There has been proposed a resin composition comprising a urethane (meth) acrylate (A), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C). (Patent Document 1).

A component: bis (acryloxymethyl or methacryloxymethyl) tricyclodecane represented by a specific general formula 40 to 80% by mass, B component: pentaerythritol tetrakis (β-thiopropionate) or pentaerythritol tetrakis ( thioglycolate) 10 to 50 mass%, C component: pentaerythritol triacrylate, trimethylolpropane triacrylate or divinyl benzene 10 to 40 mass%, obtained by polymerizing and curing a mixture of, the refractive index _(N D 20 ° C. ) Is 1.53 or more and an Abbe number (ν _D 20 ° C.) is 40 or more, a high Abbe number lens (particularly a spectacle lens) has been proposed (Patent Document 2).

  However, even with the technologies disclosed in Patent Documents 1 and 2 and the like, both the recent demand for optical lenses such as projection televisions, that is, the demand for a high refractive index due to the thinning of the optical lens and the demand for a high Abbe number are sufficiently satisfied. It is difficult to make it.

In particular, organic materials for forming optical lenses such as projection televisions generally have a higher refractive index for short-wavelength light than long-wavelength light. Therefore, if the Abbe number is small, long-wavelength light (red) is produced. In comparison, there is a problem in that short wavelength light (blue light) is refracted more greatly, and blue loss (a phenomenon in which the screen becomes bluish) occurs on a television screen. In thin rear projection televisions and the like that are becoming mainstream in recent years, the incident angle of light from the light source to the Fresnel lens becomes an acute angle, and short wavelength light is refracted more remarkably. Yes.
Note that if the Abbe number is increased in order to eliminate the problem of blue loss, the refractive index suddenly decreases, making it impossible to achieve a reduction in thickness in a projection television or the like.

JP-A-5-255464 JP-A-2-141702

  An object of the present invention is to provide a radiation-curable composition that provides a cured product that can have a high refractive index and a high Abbe number.

  In order to achieve the above object, the present inventors eagerly searched for a compound capable of simultaneously achieving a high refractive index and a high Abbe number, and obtained a sulfur-containing compound having a specific structure and a compound having an ethylenically unsaturated group. A sulfur-containing ethylenically unsaturated group-containing compound obtained by reaction was found and the present invention was completed.

２．前記エチレン性不飽和基が、（メタ）アクリロイル基である上記１に記載の含硫黄エチレン性不飽和基含有化合物
３．下記式（１−１）〜（１−３）で示される化合物からなる群から選択される上記１又は２に記載の含硫黄エチレン性不飽和基含有化合物。

４．上記１〜３のいずれかに記載の含硫黄エチレン性不飽和基含有化合物を重合させることにより得られる重合体。
５．下記成分（Ａ）及び（Ｂ）：
（Ａ）上記１〜３のいずれか１項に記載の含硫黄エチレン性不飽和基含有化合物
（Ｂ）光重合開始剤
を含有する放射線硬化性組成物。
６．さらに、（Ｃ）脂環式構造及びエチレン性不飽和基を有する成分（Ａ）以外の化合物を含有する上記５に記載の放射線硬化性組成物。
７．さらに、（Ｄ）単独で重合させて得られる硬化物のアッベ数が４０以上である、成分（Ａ）及び（Ｂ）以外のエチレン性不飽和基を有する化合物を含有する上記５又は６に記載の放射線硬化性組成物。
８．光学部材形成用である上記５〜７のいずれかに記載の放射線硬化性組成物。
９．上記５〜８のいずれかに記載の放射線硬化性組成物を硬化させて得られる硬化物。
１０．屈折率（ｎ_Ｄ ^２５）が１．５５５以上であり、かつ、アッベ数が４５以上である上記９に記載の硬化物。
１１．上記９又は１０に記載の硬化物からなる光学部材。 That is, the present invention provides the following novel sulfur-containing ethylenically unsaturated group-containing compound, a radiation-curable composition containing the compound, a cured product obtained by curing the compound, and an optical member.
1. A sulfur-containing ethylenically unsaturated group-containing compound obtained by reacting a sulfur-containing compound represented by the following formula (1) with a compound having an ethylenically unsaturated group.

2. 2. The sulfur-containing ethylenically unsaturated group-containing compound according to 1 above, wherein the ethylenically unsaturated group is a (meth) acryloyl group. The sulfur-containing ethylenically unsaturated group-containing compound according to 1 or 2 above, which is selected from the group consisting of compounds represented by the following formulas (1-1) to (1-3).

4). The polymer obtained by polymerizing the sulfur-containing ethylenically unsaturated group containing compound in any one of said 1-3.
5. The following components (A) and (B):
(A) A radiation curable composition containing the sulfur-containing ethylenically unsaturated group-containing compound (B) photopolymerization initiator according to any one of 1 to 3 above.
6). 6. The radiation curable composition according to 5 above, further comprising (C) a compound other than the component (A) having an alicyclic structure and an ethylenically unsaturated group.
7). Furthermore, (D) The Abbe number of a cured product obtained by polymerizing alone is 40 or more, wherein the compound having an ethylenically unsaturated group other than components (A) and (B) is contained in 5 or 6 above Radiation curable composition.
8). The radiation curable composition according to any one of 5 to 7 above, which is used for forming an optical member.
9. Hardened | cured material obtained by hardening the radiation-curable composition in any one of said 5-8.
10. 10. The cured product as described in 9 above, wherein the refractive index (n _D ²⁵ ) is 1.555 or more and the Abbe number is 45 or more.
11. An optical member comprising the cured product as described in 9 or 10 above.

The novel sulfur-containing ethylenically unsaturated group-containing compound of the present invention has a high refractive index and a high Abbe number, and is a material suitable for optical applications particularly requiring a high refractive index and a high Abbe number. .
The radiation curable composition of the present invention contains the above sulfur-containing ethylenically unsaturated group-containing compound, has excellent coating properties, and can simultaneously achieve a high refractive index and a high Abbe number, and is a cured product suitable for optical applications. give.
Since the optical member of the present invention is formed from a radiation curable composition containing the above sulfur-containing ethylenically unsaturated group-containing compound, it has excellent optical properties that simultaneously satisfy a high refractive index and a high Abbe number. .

  Hereinafter, the novel sulfur-containing ethylenically unsaturated group-containing compound of the present invention, a resin composition produced using the compound, and a cured product will be specifically described.

式（１）で示される含硫黄化合物は、公知化合物であり、公知の方法によって製造することができる。 I. Sulfur-containing ethylenically unsaturated group-containing compound and polymer thereof (I-1) Sulfur-containing ethylenically unsaturated group-containing compound The sulfur-containing ethylenically unsaturated group-containing compound of the present invention is represented by the following formula (1). A compound having a sulfur compound as one of the starting materials and a compound having an ethylenically unsaturated group as the other starting material. Since the sulfur-containing compound represented by the formula (1) has a high sulfur content and an alicyclic moiety, the sulfur-containing ethylenically unsaturated group-containing compound produced using this is polymerized. The coalescence can have a high refractive index and a high Abbe number.

The sulfur-containing compound represented by the formula (1) is a known compound and can be produced by a known method.

Examples of the ethylenically unsaturated group of the other starting material containing the ethylenically unsaturated group-containing compound include a (meth) acryloyl group, a vinyl group, an N-vinyl group, an allyl group, and the like, and a (meth) acryloyl group. It is preferable that
As the ethylenically unsaturated group-containing compound, (meth) acrylic acid, derivatives of (meth) acrylic acid, and the like are preferable, and acrylic acid chloride and (meth) acrylethyl isocyanate are particularly preferable.

As the sulfur-containing ethylenically unsaturated group-containing compound of the present invention, compounds represented by the following formulas (1-1) to (1-3) are preferable.

(I-2) Polymer The polymer of the present invention is obtained by irradiating the sulfur-containing ethylenically unsaturated group-containing compound with radiation.
Here, the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like. A cured product is obtained by irradiating 1000 to 5000 mJ / cm ^{2 of} ultraviolet rays.

The polymer of the present invention is:
The refractive index was 1.58 (wavelength 633 nm), there was no birefringence, and the Abbe number was 50.

II. Radiation curable composition The radiation curable composition of the present invention (hereinafter referred to as the composition of the present invention) may contain the following components (A) to (F). Among these, components (A) and (B) are essential components, and components (C) to (F) are optional components that can be added as necessary.
(A) Sulfur-containing ethylenically unsaturated group-containing compound of the present invention (B) Photopolymerization initiator (C) Compound (D) alone other than component (A) having alicyclic structure and ethylenically unsaturated group Compound (E) having an ethylenically unsaturated group other than components (A) and (B), wherein the Abbe number of the cured product obtained by polymerization is 40 or more, other than components (A), (C) and (D) The compound (F) additive having an ethylenically unsaturated group is described below.

(A) Sulfur-containing ethylenically unsaturated group-containing compound Component (A) in the composition of the present invention is the above-described sulfur-containing ethylenically unsaturated group-containing compound of the present invention. It is a component for simultaneously imparting a high refractive index and a high Abbe number to the resulting cured product. Since the sulfur-containing ethylenically unsaturated group-containing compound is as described above, the description thereof is omitted here.

  In the composition of the present invention, the proportion of component (A) is usually 20 to 95% by mass, preferably 20 to 90% by mass, more preferably 25 to 85% by mass, with the total amount of the composition being 100% by mass. . If the blending ratio of component (A) is less than 20% by mass, sufficient refractive index and Abbe number may not be obtained, and if it exceeds 95% by mass, the elastic modulus of the cured film may be lowered.

(B) Photopolymerization initiator Component (B) used in the composition of the present invention is a photopolymerization initiator. (B) Any photopolymerization initiator may be used as long as it can be decomposed by light irradiation to generate radicals and initiate polymerization. For example, acetophenone, acetophenone benzyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2,2- Dimethoxy-2-phenylacetophenone, xanthone, fluorenone, benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone , Michler's ketone, benzoin propyl ether, benzoin ethyl ether, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-hydroxy- -Methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1- ON, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, and the like.

  Examples of commercially available photopolymerization initiators include Irgacure 184, 369, 651, 500, 819, 907, 784, 2959, CGI-1700, -1750, -1850, CG24-61, Darocur 1116, 1173 (above, Ciba Specialty Chemicals Co., Ltd.), Lucirin TPO, LR8883, LR8970 (above, manufactured by BASF), Ubekrill P36 (manufactured by UCB), and the like.

  In the composition of the present invention, the blending ratio of the component (B) is usually 0.01 to 10% by mass, preferably 0.5 to 7% by mass, with the total amount of the composition being 100% by mass. If the blending ratio of the component (B) is less than 0.01% by mass, the curing rate is unfavorable. On the other hand, when the blending ratio of the component (B) exceeds 10% by mass, the curing characteristics of the composition, the mechanical characteristics and the optical characteristics of the cured product are deteriorated, and handling is difficult.

(C) Compound other than component (A) having alicyclic structure and ethylenically unsaturated group Component (C) is a compound other than component (A) having an alicyclic structure and ethylenically unsaturated group. . The compound of component (C) is preferable because the cured product can exhibit hardness without changing the Abbe number of the cured product obtained from having an alicyclic structure.

Specific examples of the compound of component (C) include, for example, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane, bis ((meth) acryloyloxymethyl) pentacyclo [7 .4.0.1 ^2,5 . 0 ^8,12 . 1 ^7,13 ] pentadecane, bis ((meth) acryloyloxymethyl) bicyclo [2.1.1] heptane, bis ((meth) acryloyloxymethyl) pentacyclo [7.4.0.1 ^2,5 . ^{18 8, 11} . 0 ^7,12 ] pentadecane and the like, and among them, bis ((meth) acryloyloxymethyl) tricyclo [5.2.1.0 ^2,6 ] decane is preferable.

  In the composition of the present invention, the blending ratio of the component (C) is usually 1 to 55% by mass, preferably 1 to 50% by mass, more preferably 3 to 50% by mass, with the total amount of the composition being 100% by mass. . If the blending ratio of component (C) is less than 1% by mass, the Abbe number of the cured product tends to decrease, such being undesirable. On the other hand, when the blending ratio of component (C) exceeds 55% by mass, the blending ratio of the other components to be blended, particularly component (A) decreases, and the refractive index of the cured product tends to decrease. .

(D) A compound having an ethylenically unsaturated group other than components (A) and (B) in which the Abbe number of a cured product obtained by polymerizing alone is 40 or more Component (D) is polymerized alone. It is a compound other than the component (A) and the component (C) having an Abbe number of 40 or more and having an ethylenically unsaturated group. It is preferable to add the component (D) because the coating property can be improved and the Abbe number can be adjusted within a desired numerical range.
Component (D) includes a compound having one ethylenically unsaturated group (hereinafter referred to as “monofunctional monomer”) and a compound having two or more ethylenically unsaturated groups (hereinafter referred to as “polyfunctional monomer”). .) Can be used.

  Specific examples of the monofunctional monomer used as component (D) include N-vinylcaprolactam, N-vinylpyrrolidone, acryloylmorpholine, and the like. Specific examples of the polyfunctional monomer used as component (D) include trimethylolpropane triacrylate, tripropylene glycol diacrylate, dipentaerythritol hexaacrylate, tris (acryloxyethyl) isocyanurate, and tris (2-hydroxyethyl). Examples include isocyanuric acid acrylic ester, nonanediol diacrylate, and tricyclodecane-3,8-diyldimethyldiacrylate.

  As a commercial item of the monofunctional monomer used as a component (D), for example, Aronix M120, M150, M156 (above, manufactured by Toagosei Co., Ltd.), LA, IBXA, 2-MTA, HPA, Biscote # 150, # 155 , # 158, # 190 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), light acrylate BO-A, EC-A, DPM-A, THF-A, HOP-A (above, manufactured by Kyoeisha Chemical Co., Ltd.) , KAYARAD TC110S (manufactured by Nippon Kayaku Co., Ltd.), FA-511A, 512A, 513A (manufactured by Hitachi Chemical Co., Ltd.), VP (manufactured by BASF), ACMO, DMAA (manufactured by Kojin Co., Ltd.) ) And the like.

  As a commercial item of the polyfunctional monomer used as a component (D), for example, New Frontier LC-9A (Daiichi Kogyo Seiyaku Co., Ltd.), Iupimer UV SA1002, SA2007 (above, Mitsubishi Chemical Co., Ltd.), Biscoat # 195, # 230, # 215, # 260, # 335HP, # 295, # 300, # 360, GPT, 3PA (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light Acrylate 4EG-A, 9EG-A, NP-A, DCP-A, BP-4EA, TMP-A, PE-3A, PE-4A, DPE-6A (above, manufactured by Kyoeisha Chemical Co., Ltd.), KAYARAD PET-30, TMPTA, R-604, DPHA , DPCA-20, -30, -60, -120, HX-620, D-310, D-330 (above, Nippon Kayaku Co., Ltd.), Aronic M215, M220, M240, M305, M309, M310, M315, M325, M400 (manufactured by Toagosei Co.), and the like.

  In the composition of the present invention, the blending ratio of the component (D) is usually 1 to 30% by mass, preferably 1 to 20% by mass, more preferably 5 to 20% by mass, with the total amount of the composition being 100% by mass. . The refractive index of hardened | cured material may fall that the compounding ratio of a component (D) is less than 1 mass%. On the other hand, when the blending ratio of the component (D) exceeds 30% by mass, the blending ratio of the component (A) or the component (C) decreases, and the refractive index and Abbe number of the cured product tend to decrease. By setting the blending ratio of the component (D) within the above range, it is possible to obtain a composition that is excellent in coatability and gives a high refractive index and a high Abbe number after curing.

(E) Compounds having an ethylenically unsaturated group other than components (A), (C) and (D) In the composition of the present invention, (E) other than components (A), (C) and (D) A compound having an ethylenically unsaturated group may be added. As such a compound, any of a monofunctional monomer having one ethylenically unsaturated group and a polyfunctional monomer having two or more ethylenically unsaturated groups can be used.

  Examples of the monofunctional monomer used as the component (E) include vinyl monomers such as vinylimidazole and vinylpyridine; benzyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, t-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, N, N-diethyl (meth) Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl building ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, tribromophenol ethoxy Meth) acrylate. Among these, tribromophenol ethoxy (meth) acrylate is preferable.

  Specific examples of the polyfunctional monomer used as the component (E) include di (meth) acrylate of diol which is an adduct of bis (hydroxymethyl) tricyclodecane di (meth) acrylate, bisphenol A polyethylene oxide or propylene oxide. , Di (meth) acrylate of diol which is an adduct of hydrogenated bisphenol A ethylene oxide or propylene oxide, epoxy (meth) acrylate obtained by adding (meth) acrylate to diglycidyl ether of bisphenol A, triethylene glycol divinyl ether And other polyfunctional monomers.

  In the composition of the present invention, the blending ratio of the component (E) is usually 0 to 40% by mass, preferably 0 to 30% by mass, more preferably 10 to 25% by mass, with the total amount of the composition being 100% by mass. . (E) By mix | blending a component, the viscosity of a composition, the refractive index after hardening, etc. can be adjusted in a desired numerical range. When the blending ratio of the component (E) exceeds 40% by mass, the coating property of the resin composition is deteriorated and the mechanical properties of the cured product are deteriorated, which is not preferable.

(G) Additive In the composition of the present invention, other curable oligomers or polymers and various additives can be blended as other optional components as long as the object and effects of the present invention are not impaired. Examples of other curable oligomers or polymers include polyurethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, polyamide (meth) acrylate, siloxane polymer having a (meth) acryloyloxy group, and glycidyl meta. Examples thereof include a reactive polymer obtained by reacting a copolymer of an acrylate with another polymerizable monomer and (meth) acrylic acid.

  Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, silane coupling agents, coating surface improvers, thermal polymerization inhibitors, leveling agents, surfactants, colorants, storage stabilizers, and plasticizers. , Lubricants, mold release agents, solvents, fillers, anti-aging agents, wettability improvers and the like can be blended as necessary. Here, examples of the antioxidant include Irganox 1010, 1035, 1076, 1222 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Antigen P, 3C, FR, GA-80 (manufactured by Sumitomo Chemical Co., Ltd.). Examples of the ultraviolet absorber include Tinuvin P, 234, 320, 326, 327, 328, 329, 213 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Seesorb 102, 103, 110, 501; 202, 712, 704 (above, manufactured by Sipro Kasei Co., Ltd.) and the like. Examples of the light stabilizer include Tinuvin 292, 144, 622LD (above, manufactured by Ciba Specialty Chemicals Co., Ltd.), Sanol LS770 ( Sankyo Co., Ltd.), Sumisorb TM-061 ( As a silane coupling agent, for example, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and a commercially available product. SH6062, 6030 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), KBE903, 603, 403 (above, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Silicone additives such as polyether are listed, and commercially available products include DC-57, DC-190 (above, manufactured by Dow Corning), SH-28PA, SH-29PA, SH-30PA, SH-190 (above, Toray Industries, Inc.).・ Dow Corning Silicone Co., Ltd.), KF351, KF352, KF353, KF3 54 (manufactured by Shin-Etsu Chemical Co., Ltd.), L-700, L-7002, L-7500, FK-024-90 (manufactured by Nihon Unicar Co., Ltd.), and the like.

  The composition of the present invention can contain a photosensitizer in addition to the (B) photopolymerization initiator. Examples of the photosensitizer include triethylamine, diethylamine, N-methyldiethanolamine, ethanolamine, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and isoamyl 4-dimethylaminobenzoate. Etc. As a commercial item, Ubekrill P102, 103, 104, 105 (above, UCB company make) etc. are mentioned, for example.

  The composition of this invention can contain a thermal-polymerization initiator as needed. Preferable examples of the thermal polymerization initiator include peroxides and azo compounds. Specific compound names for the thermal polymerization initiator include benzoyl peroxide, t-butyl-peroxybenzoate, azobisisobutyronitrile, and the like.

  The composition of this invention can be manufactured by mixing each said component by a conventional method. The viscosity of the composition of the present invention thus prepared is usually 200 to 50,000 mPa · s / 25 ° C., preferably 500 to 10,000 mPa · s / 25 ° C. If the viscosity is too high, coating unevenness and undulation will occur when the composition is applied, and it will be difficult to obtain the desired film thickness, and the performance as an optical member (for example, a lens) cannot be fully exhibited. . On the other hand, even if the viscosity is too low, it is difficult to control the film thickness, and a uniform optical member (for example, a lens or the like) having a certain thickness may not be formed.

III. Cured product The cured product of the present invention is obtained by curing the radiation curable composition of the present invention.
In order to cure the composition of the present invention, radiation curing may be performed, or radiation curing and heat curing may be used in combination. Here, the radiation refers to infrared rays, visible rays, ultraviolet rays, X-rays, electron beams, α rays, β rays, γ rays, and the like. Specifically, it is applied on a glass plate using an applicator bar so that the film thickness becomes 200 μm, and is cured by irradiation with ultraviolet rays of 1.0 J / cm ² under nitrogen.

The cured product of the present invention preferably has a refractive index (n _D ²⁵ ) of 1.555 or more, more preferably 1.557 or more.
The cured product of the present invention preferably has an Abbe number of 45 or more, and more preferably 48 or more.
The cured product of the present invention has the high refractive index and high Abbe number and is useful as an optical member.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” and “part” mean “% by mass” and “part by mass”.

<Synthesis of sulfur-containing compounds>
Production Example 1
Synthesis of intermediate 1

  In advance, dicyclopentadiene was thermally decomposed at 190 ° C. to prepare cyclopentadiene. Into a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, scandium triflate (5 mol%) was placed as a Lewis acid catalyst, purged with nitrogen, and dehydrated tetrahydrofuran (hereinafter referred to as THF) was added to 1.4M. Dissolved. Next, it cooled to -20 degreeC, methyl vinyl ketone (1 equivalent) and the cyclopentadiene prepared previously (3 equivalent) were added, and it was made to react by stirring at -20 degreeC for 3 hours. Thereafter, the reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution and extracted with diethyl ether. After the extract was dehydrated with anhydrous magnesium sulfate, diethyl ether was distilled off under reduced pressure. The obtained crude product was purified by distillation under reduced pressure (4.0 Torr, 108 ° C., fraction 55 to 60 ° C.). Yield: 81%.

Production Example 2
Synthesis of intermediate 2

  Into a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, intermediate 1 (1 equivalent) synthesized in Production Example 1 and azoisobutyronitrile (AIBN) (2 mol%) as a radical generator were placed, and the atmosphere was replaced with nitrogen. Then, dehydrated THF was added to dissolve to 4.2 M and dissolved. Next, it heated up to 60 degreeC, 2-mercaptoethanol (1.05 equivalent) was added, and it was made to react by stirring at 60 degreeC for 1 hour. Thereafter, the reaction solution was neutralized with a saturated aqueous sodium hydrogen carbonate solution, washed with distilled water, and extracted with diethyl ether. After the extract was dehydrated with anhydrous magnesium sulfate, diethyl ether was distilled off under reduced pressure. The obtained crude product was purified by silica gel chromatography (developing solvent: diethyl ether / hexane = 2/1). Yield: 69%.

Production Example 3
Synthesis of intermediate 3 (sulfur-containing compound)

  Intermediate 2 (1 equivalent) synthesized in Production Example 2 was placed in a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, purged with nitrogen, and dehydrated THF was added to a concentration of 0.27 M and dissolved. . Then 1,2-ethanoldithiol (3 equivalents) was added. Thereafter, trifluoroboron / diethyl ether complex (40 mol%) was added dropwise. The mixture was stirred at room temperature for 12 hours or more, and the reaction solvent was distilled off under reduced pressure. The obtained crude product was purified by silica gel chromatography (developing solvent: diethyl ether / hexane = 2/1). Yield: 54%.

<Production of sulfur-containing ethylenically unsaturated group-containing compound>
Example 1
2- [2- {5- (2-Methyl-1,3-dithiolan-2-yl) bicyclo [2.2.1] heptyl-2-sulfanyl} ethyloxycarbamoyl] ethyl methacrylate (compound (1-1 ))

Intermediate 3 (1 equivalent) synthesized in Production Example 3 was placed in a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, purged with nitrogen, and dehydrated THF was added to 0.18 M and dissolved. . Next, methacryloyl ethyl isocyanate (manufactured by Showa Denko KK, Karenz MOI 1.1 equivalent) was added. Then, it stirred at 40 degreeC for 1 hour, and the reaction solvent was depressurizingly distilled. The obtained crude product was purified by silica gel chromatography (developing solvent: diethyl ether). Yield: 84%. The IR chart and ¹ H-NMR chart of the obtained compound (1-1) are shown in FIGS. 1 and 2, respectively.

Example 2
2- [2- {5- (2-Methyl-1,3-dithiolan-2-yl) bicyclo [2.2.1] heptyl-2-sulfanyl} ethyloxycarbamoyl] ethyl acrylate (compound (1-2 ))

Intermediate 3 (1 equivalent) synthesized in Production Example 3 was placed in a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, purged with nitrogen, and dehydrated THF was added to 0.18 M and dissolved. . Next, acroylethyl isocyanate (manufactured by Showa Denko KK, Karenz AOI; 1.1 equivalents) was added. Then, it stirred at 40 degreeC for 1 hour, and the reaction solvent was depressurizingly distilled. The resulting crude product was purified by silica gel chromatography (developing solvent: diethyl ether) to obtain compound (1-2). Yield: 90%.
FT-IR (KBr, cm ⁻¹ ): 3430.2, 3040.1, 2340.4, 1720.7, 1635.0, 1592.9, 1565.9, 1492.6, 1442.5, 1361.5 , 1295.1, 1164.4, 856.7

Example 3
Synthesis of 2- [2- {5- (2-methyl-1,3-dithiolan-2-yl) bicyclo [2.2.1] heptyl-2-sulfanyl} ethyloxy] acrylate (compound (1-3))

Intermediate 3 (1 equivalent) synthesized in Production Example 3 was placed in a reaction vessel equipped with a stirrer, a cooler, and a nitrogen introduction tube, purged with nitrogen, and MIBK was added to 0.20 M and dissolved. Next, dimethylaniline (1.1 equivalent) was added and heated to 40 ° C. Acrylic acid chloride (1.1 equivalents) was added dropwise and stirred at 40 ° C. for 8 hours. The reaction solution was neutralized with 1N aqueous ammonia, and the reaction solvent was distilled off under reduced pressure. The resulting crude product was purified by silica gel chromatography (developing solvent: diethyl ether) to obtain compound (1-3). Yield: 72%.
FT-IR (KBr, cm ⁻¹ ): 3427.1, 3034.9, 1722.8, 1635.9, 1593.1, 1566.2, 1493.7, 1441.3, 1364.5, 1294.5 1174.3, 860.1

<Production of polymer of sulfur-containing ethylenically unsaturated group-containing compound>
Example 4 of 2- [2- {5- (2-methyl-1,3-dithiolan-2-yl) bicyclo [2.2.1] heptyl-2-sulfanyl} ethyloxycarbamoyl] ethyl methacrylate polymer Production method

  Into a reaction vessel equipped with a stirrer and a nitrogen introducing tube, the novel sulfur-containing ethylenically unsaturated group-containing compound (1-1) (1 equivalent) synthesized in Example 1 is placed, and the atmosphere is purged with nitrogen, so that DMSO becomes 2M. And dissolved. Next, AIBN (10 mol%) was added and stirred at 65 ° C. for 24 hours. When the obtained viscous solution was reprecipitated in methanol, a white fibrous polymer was obtained. Yield: 84%. The number average molecular weight by GPC was about 29000. The refractive index was 1.58 (wavelength 633 nm) and the Abbe number was 50.

<Production of radiation curable composition>
Example 5
In a reaction vessel equipped with a stirrer, 85 parts by mass of the novel sulfur-containing ethylenically unsaturated group-containing compound (1-1) synthesized in Example 1 and bis (acryloyloxymethyl) tricyclo [5.2.1.0]. ^2,6 ] decane in 15 parts by mass, 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals, Irgacure 184) in 3 parts by mass, thiodiethylenebis [3- (3,5-di-tert-butyl- 4-Hydroxyphenyl) propionate] (Irganox 1035, manufactured by Ciba Specialty Chemicals Co., Ltd.) at a blending ratio of 0.3 part by mass, stirred for 1 hour while controlling the liquid temperature at 50-60 ° C., and uniform radiation curing Sex composition was obtained.

Examples 6-12 and Comparative Example 1
A radiation curable composition was obtained in the same manner as in Example 5 except that the composition shown in Table 1 was used.

<Characteristic evaluation of radiation curable composition and characteristic evaluation of cured product>
The viscosity and coating property of the compositions obtained in Examples 5 to 12 and Comparative Example 1 were evaluated by the following methods. Furthermore, the obtained radiation-curable composition was applied onto a glass plate using an applicator bar so that the film thickness was 200 μm, and 1.0 J / cm ² of ultraviolet light was irradiated under nitrogen to give a test piece. It produced and evaluated the refractive index and the Abbe number by the following method. The results are shown in Table 1.

(1) Viscosity and coating property The radiation curable composition was kept at 25 ° C, and the viscosity was measured using a B-type viscometer according to JIS K-7117.
Regarding the coatability, the case where the viscosity at 25 ° C. exceeds 4,000 (mPa · s) is indicated by “◎”, and the case where the viscosity is 4,000 (mPa · s) or less is indicated by “◯”.

(2) Measurement of refractive index (n _D ²⁵ ) According to JIS K7105, the refractive index at 25 ° C. was measured using an Abbe refractometer manufactured by Atago Co., Ltd.

(3) Measurement of Abbe number It calculated from the refractive index of D line (589nm), F line (486nm), and C line (656nm) calculated | required with the multiwavelength Abbe refractometer of an Atago company.

Abbreviations in Table 1 represent the following.
Irgacure 184: 1-hydroxycyclohexyl phenyl ketone; manufactured by Ciba Specialty Chemicals Inc. Irganox 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]; manufactured by Ciba Specialty Chemicals Co., Ltd.

  From the results in Table 1, a radiation-curable composition excellent in coatability is obtained by using the novel sulfur-containing ethylenically unsaturated group-containing compound represented by formulas (1-1) to (1-3). Furthermore, it can be seen that the cured product has a high Abbe number and a high refractive index.

  The novel sulfur-containing ethylenically unsaturated group-containing compound of the present invention is suitable as a material for producing an optical member that requires a high refractive index and a high Abbe number at the same time. Specifically, examples of the optical member include a coating material of a high refractive index material and a high refractive index material of an antireflection film, an optical waveguide, various lenses, and a sensitivity improving material for an image sensor. In particular, such as lens parts of various lens sheets such as prism lens sheets used for backlights of liquid crystal display devices and lens sheets used for screens of projection televisions (for example, Fresnel lens sheets, lenticular lens sheets, etc.) It is useful as a material for optical members.

3 is IR data of the compound obtained in Example 1. 2 is a ¹ H-NMR chart chart of the compound obtained in Example 1. FIG.

Claims (11)

A sulfur-containing ethylenically unsaturated group-containing compound obtained by reacting a sulfur-containing compound represented by the following formula (1) with a compound having an ethylenically unsaturated group.

  The sulfur-containing ethylenically unsaturated group-containing compound according to claim 1, wherein the ethylenically unsaturated group is a (meth) acryloyl group. The sulfur-containing ethylenically unsaturated group-containing compound according to claim 1 or 2, selected from the group consisting of compounds represented by the following formulas (1-1) to (1-3).

  The polymer obtained by polymerizing the sulfur-containing ethylenically unsaturated group containing compound of any one of Claims 1-3. The following components (A) and (B):
(A) A radiation curable composition containing the sulfur-containing ethylenically unsaturated group-containing compound (B) photopolymerization initiator according to any one of claims 1 to 3.   The radiation curable composition according to claim 5, further comprising (C) a compound other than the component (A) having an alicyclic structure and an ethylenically unsaturated group.   Furthermore, (D) The compound which has an ethylenically unsaturated group other than component (A) and (B) whose Abbe number of the hardened | cured material obtained by superposing | polymerizing independently is 40 or more is contained in Claim 5 or 6 The radiation curable composition as described.   The radiation curable composition according to any one of claims 5 to 7, which is used for forming an optical member.   Hardened | cured material obtained by hardening the radiation-curable composition of any one of Claims 5-8. The cured product according to claim 9, wherein the refractive index (n _D ²⁵ ) is 1.555 or more and the Abbe number is 45 or more. An optical member comprising the cured product according to claim 9 or 10.

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