TW202012456A - Lens composition, lens, lens production method, and display device - Google Patents

Abstract

A lens composition used for forming a lens on an optical path for light transmitted through a color filter of a display device comprising the color filter; a lens in which the lens composition is used; a lens production method; and a display device. The lens composition contains a polymerizable monomer M, a photoinitiator A, and a resin B. When forming a film having a thickness of 2 [mu]m using the lens composition, the maximum value of light absorbance at a wavelength of 400-700 nm of the film is 0.05 or less, and the refractive index of light at a wavelength of 550 nm is 1.5 or more.

Description

Lens composition, lens, lens manufacturing method and display device

The present invention relates to a composition for lenses. More specifically, it relates to a lens composition for forming a lens on the optical path of light passing through the color filter of a display device having a color filter. In addition, the invention relates to a lens, a lens manufacturing method and a display device.

In various display devices, color filters are generally used for colorization of displayed images. For example, Patent Literature 1 describes the following: photosensitivity for color filters using a compound (A) containing a furan group, a compound (B) containing a photopolymerizable functional group, a photopolymerization initiator (C), and a coloring agent Composition to form a color filter, and manufacture an organic electroluminescence display device. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2017-194662

In recent years, it has been desired to further increase the brightness of display devices. The present inventors conducted various studies on further improving the brightness of a display device having a color filter, and found that it is possible to improve the brightness by providing a lens on the optical path of light transmitted through the color filter.

Therefore, an object of the present invention is to provide a lens composition, a lens, a method for manufacturing a lens, and a display device that can increase the brightness of a display device having a color filter.

式中，X¹ 表示O或NH， R¹ 表示氫原子或甲基， L¹ 表示2價的連接基， R¹⁰ 表示取代基， m表示0～2的整數， p表示0以上的整數。 ＜3＞如＜2＞所述之透鏡用組成物，其中樹脂b1還包含來自於烷基（甲基）丙烯酸酯的重複單元。 ＜4＞如＜1＞～＜3＞中任一項所述之透鏡用組成物，其中光聚合起始劑A含有肟化合物。 ＜5＞如＜1＞～＜4＞中任一項所述之透鏡用組成物，其中光聚合起始劑A包含： 在甲醇中的波長365nm的吸光係數為1.0×10³ mL/gcm以上的光聚合起始劑A1；及 在甲醇中的波長365nm的吸光係數為1.0×10² mL/gcm以下，並且波長254nm的吸光係數為1.0×10³ mL/gcm以上的光聚合起始劑A2。 ＜6＞如＜5＞所述之透鏡用組成物，其中光聚合起始劑A1為包含氟原子之肟化合物。 ＜7＞如＜5＞或＜6＞所述之透鏡用組成物，其中光聚合起始劑A2為羥基烷基苯酮化合物。 ＜8＞如＜5＞～＜7＞中任一項所述之透鏡用組成物，其中相對於光聚合起始劑A1的100質量份，含有50～200質量份的光聚合起始劑A2。 ＜9＞如＜5＞～＜8＞中任一項所述之透鏡用組成物，其中在透鏡用組成物的總固體成分中的光聚合起始劑A1和光聚合起始劑A2的合計含量為5～15質量%。 ＜10＞如＜1＞～＜9＞中任一項所述之透鏡用組成物，其中聚合性單體M含有包含3個以上的乙烯性不飽和基之化合物。 ＜11＞如＜1＞～＜10＞中任一項所述之透鏡用組成物，其包含矽烷偶合劑。 ＜12＞如＜1＞～＜11＞中任一項所述之透鏡用組成物，其含有包含呋喃基之化合物。 ＜13＞如＜12＞所述之透鏡用組成物，其中包含呋喃基之化合物為選自由下述式（fur-1）所表示之化合物及包含來自於由下述式（fur-1）所表示之化合物的重複單元之樹脂中之至少1種， [化學式2]

式中，Rf¹ 表示氫原子或甲基，Rf² 表示2價的連接基。 ＜14＞一種透鏡，其由＜1＞～＜13＞中任一項所述之透鏡用組成物獲得。 ＜15＞一種透鏡之製造方法，該方法包括： 在支撐體上塗佈＜1＞～＜13＞中任一項所述之透鏡用組成物來形成組成物層之步驟；及 將組成物層加工成透鏡形狀之步驟。 ＜16＞如＜15＞所述之透鏡之製造方法，其中遍及所有步驟在150℃以下的溫度下進行。 ＜17＞如＜15＞或＜16＞所述之透鏡之製造方法，其中加工成透鏡形狀之步驟包括對組成物層以1J/cm² 以上的曝光量照射波長超過350nm且380nm以下的光之步驟。 ＜18＞如＜15＞或＜16＞所述之透鏡之製造方法，其中加工成透鏡形狀之步驟包括對組成物層照射波長超過350nm且380nm以下的光來進行曝光之後，進一步照射波長254～350nm的光來進行曝光之步驟。 ＜19＞如＜15＞～＜18＞中任一項所述之透鏡之製造方法，其中加工成透鏡形狀之步驟包括將組成物層在100～150℃的溫度下加熱10分鐘以上之步驟。 ＜20＞如＜19＞所述之透鏡之製造方法，其中加熱之步驟在非活性氣體環境下進行。 ＜21＞一種顯示裝置，其具有濾色器和在透射濾色器之光的光徑上所設置之由＜1＞～＜13＞中任一項所述之透鏡用組成物獲得之透鏡。 ＜22＞如＜21＞所述之顯示裝置，其為有機電致發光顯示裝置。 [發明效果]The inventor provides the following. <1> A lens composition for forming a lens on a light path of a display device having a color filter that transmits light of the color filter, wherein the lens composition includes a polymerizable monomer M and a photopolymerization start When the agent A and the resin B use a lens composition to produce a film with a thickness of 2 μm, the maximum absorbance of the film at a wavelength of 400 to 700 nm is 0.05 or less, and the refractive index of light at a wavelength of 550 nm is 1.5 or more. <2> The lens composition according to <1>, wherein the resin B contains a resin b1 containing a repeating unit derived from a compound represented by the following formula (I), [Chemical Formula 1]

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, R ¹⁰ represents a substituent, m represents an integer of 0 to 2, and p represents an integer of 0 or more. <3> The lens composition according to <2>, wherein the resin b1 further contains a repeating unit derived from an alkyl (meth)acrylate. <4> The lens composition according to any one of <1> to <3>, wherein the photopolymerization initiator A contains an oxime compound. <5> The lens composition according to any one of <1> to <4>, wherein the photopolymerization initiator A contains: an absorption coefficient of 1.0×10 ³ mL/gcm or more in methanol at a wavelength of 365 nm Photopolymerization initiator A1; and photopolymerization initiator A2 in methanol with a wavelength of 365 nm and an absorption coefficient of 1.0×10 ² mL/gcm or less and a wavelength of 254 nm with an absorption coefficient of 1.0×10 ³ mL/gcm or more . <6> The lens composition according to <5>, wherein the photopolymerization initiator A1 is an oxime compound containing a fluorine atom. <7> The lens composition according to <5> or <6>, wherein the photopolymerization initiator A2 is a hydroxyalkyl benzophenone compound. <8> The lens composition according to any one of <5> to <7>, which contains 50 to 200 parts by mass of the photopolymerization initiator A2 relative to 100 parts by mass of the photopolymerization initiator A1. . <9> The lens composition according to any one of <5> to <8>, wherein the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the lens composition It is 5 to 15% by mass. <10> The lens composition according to any one of <1> to <9>, wherein the polymerizable monomer M contains a compound containing three or more ethylenic unsaturated groups. <11> The lens composition according to any one of <1> to <10>, which contains a silane coupling agent. <12> The lens composition according to any one of <1> to <11>, which contains a furan group-containing compound. <13> The lens composition according to <12>, wherein the furan-containing compound is selected from compounds represented by the following formula (fur-1) and contains compounds derived from the following formula (fur-1) At least one of the resins of the repeating units of the compound represented, [Chemical Formula 2]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group. <14> A lens obtained from the lens composition according to any one of <1> to <13>. <15> A method for manufacturing a lens, the method comprising: a step of forming a composition layer by coating the lens composition according to any one of <1> to <13> on a support; and applying the composition layer Steps of processing into lens shape. <16> The method for manufacturing a lens according to <15>, wherein all steps are performed at a temperature of 150° C. or less. <17> The method for manufacturing a lens as described in <15> or <16>, wherein the step of processing into a lens shape includes irradiating the composition layer with light having a wavelength of more than 350 nm and less than 380 nm at an exposure of 1 J/cm ² or more step. <18> The method of manufacturing a lens as described in <15> or <16>, wherein the step of processing into a lens shape includes irradiating the composition layer with light having a wavelength of more than 350 nm and less than 380 nm, and then further irradiating a wavelength of 254 to 350nm light to perform the exposure step. <19> The method for manufacturing a lens according to any one of <15> to <18>, wherein the step of processing into a lens shape includes the step of heating the composition layer at a temperature of 100 to 150° C. for 10 minutes or more. <20> The method for manufacturing a lens as described in <19>, wherein the heating step is performed in an inert gas environment. <21> A display device having a color filter and a lens obtained from the lens composition described in any one of <1> to <13> provided on the optical path of light passing through the color filter. <22> The display device according to <21>, which is an organic electroluminescence display device. [Effect of the invention]

According to the present invention, it is possible to provide a lens composition, lens, and method for manufacturing a lens capable of improving the brightness of a display device having a color filter. Furthermore, according to the present invention, a display device with high brightness can be provided.

Hereinafter, the content of the present invention will be described in detail. In the label of the group (atomic group) in this specification, the label not marked with substituted and unsubstituted includes a group (atomic group) without a substituent, and also includes a group (atomic group) with a substituent. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups). Unless otherwise specified, "exposure" in this specification includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams. In addition, as the light used for the exposure, the bright line spectrum of a mercury lamp, excimer laser, and representative actinic rays or radiation such as far ultraviolet, extreme ultraviolet (EUV light), X-ray, and electron beam are generally mentioned. In this specification, the numerical range indicated by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all components of the composition. In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, " "(Meth)allyl" means both or any one of allyl and methallyl, and "(meth)acryl" means both or any of acryl and methacryl One. The term "step" in this specification is not only an independent step, but even if it cannot be clearly distinguished from other steps, as long as the desired effect of the step is achieved, it is also included in the term. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Lens composition> The lens composition of the present invention is used to form a lens on the optical path of light passing through the color filter of a display device having a color filter, and is characterized by, The lens composition includes a polymerizable monomer M, a photopolymerization initiator A and a resin B, When a film with a thickness of 2 μm is manufactured using the lens composition, the maximum absorbance of the film at a wavelength of 400 to 700 nm is 0.05 or less, and the refractive index of light at a wavelength of 550 nm is 1.5 or more.

By using the lens composition of the present invention, the brightness of a display device having a color filter can be further improved.

When the composition of the present invention produces a film having a film thickness of 2 μm, the maximum absorbance of the film at a wavelength of 400 to 700 nm is 0.05 or less, preferably 0.04 or less, and more preferably 0.03 or less. In order to realize the conditions of this kind of absorbance, as the material used in the lens composition, it is preferable to use a material with a small absorbance at a wavelength of 400 to 700 nm, and the maximum value of the absorbance at a wavelength of 400 to 700 nm is 0.05 or less The material is more preferable, and the material with the aforementioned maximum value of 0.03 or less is more preferably used. In addition, when the composition of the present invention produces a film having a thickness of 2 μm, the refractive index of the film at a wavelength of 550 nm is 1.5 or more, preferably 1.52 or more, and more preferably 1.54 or more. The upper limit is preferably 2.0 or less, and more preferably 1.85 or less. The conditions of this kind of refractive index can be realized by including the lens composition with a material having a high refractive index of light at a wavelength of 550 nm. The composition of the present invention satisfies the aforementioned conditions of absorbance and refractive index, whereby the loss of light quantity can be reduced, and as a result, the brightness can be further improved. In addition, the lens composition of the present invention is preferably a pixel having a plurality of colors for a color filter included in a display device, and a lens is formed on an optical path of at least a part of the pixels of the pixels.

Hereinafter, the lens composition of the present invention will be described in detail.

＜＜Polymerizable monomer＞＞ The composition for lenses of the present invention contains a polymerizable monomer. Examples of the polymerizable monomer include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, (meth)allyl group, (meth)acryloyl group and the like. The polymerizable monomer is preferably a compound (radical polymerizable monomer) that can be polymerized by radicals.

The molecular weight of the polymerizable monomer is preferably from 100 to 2000. The upper limit is preferably 1500 or less, and more preferably 1000 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

From the viewpoint of the stability over time of the composition, the ethylenically unsaturated group value of the polymerizable monomer (hereinafter, referred to as C=C value) is preferably 2 to 14 mmol/g. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and further preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable monomer is calculated by dividing the number of ethylenically unsaturated groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

The polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated groups, and more preferably a compound containing 4 or more ethylenically unsaturated groups. The upper limit of the ethylenically unsaturated group is preferably 15 or less, more preferably 10 or less, and further preferably 6 or less. In addition, it is preferable that the polymerizable monomer is a (meth)acrylate compound having three or more functions.

The polymerizable monomer is preferably a compound containing an ethylenically unsaturated group and an alkoxy group. Such a polymerizable monomer has high flexibility and the ethylenically unsaturated group is easy to move. Therefore, the polymerizable monomer easily reacts with each other during exposure, and a lens with excellent adhesion to a support or the like can be formed. In addition, when a hydroxyalkyl benzophenone compound is used as a photopolymerization initiator, it is presumed that the polymerizable monomer is close to the photopolymerization initiator and generates radicals in the vicinity of the polymerizable monomer, which can make the polymerizable monomer more It reacts efficiently, and it is easy to form a lens with more excellent adhesion and solvent resistance.

The number of alkylene oxide groups contained in one molecule of the polymerizable monomer is preferably 3 or more, and more preferably 4 or more. From the viewpoint of the stability over time of the composition, the upper limit is preferably 20 or less.

From the viewpoint of compatibility with other components in the composition, the SP value (Solubility Parameter) of the compound containing an ethylenically unsaturated group and an alkoxy group is preferably 9.0 to 11.0. The upper limit is preferably 10.75 or less, and more preferably 10.5 or less. The lower limit is preferably 9.25 or more, and more preferably 9.5 or more. In addition, in this specification, the SP value uses the calculation value based on the Fedors method.

As the polymerizable monomer, dipentaerythritol triacrylate (available as KAYARAD D-330 as a commercially available product; manufactured by NIPPON KAYAKU CO., Ltd.) and dipentaerythritol tetraacrylate (commercially available) can also be used. The product is KAYARAD D-320; manufactured by NIPPON KAYAKU CO., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercially available product, KAYARAD D-310; manufactured by NIPPON KAYAKU CO., Ltd.), Dipentaerythritol hexa(meth)acrylate (available commercially as KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., Ltd., NK ester A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., Ltd.), And these (meth)acryl acetyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454, SR499 commercially available from SARTOMER Company, Inc.). Furthermore, as the polymerizable monomer, trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide can also be used Alkyl modified tri (meth) acrylate, isocyanuric acid ethylene oxide modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate and other trifunctional (meth) acrylate compounds. Examples of commercially available products of trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Manufactured by Kayaku Co., Ltd.).

The polymerizable monomer may have an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and the carboxyl group is preferred. As a commercially available product of the polymerizable monomer having an acid group, ARONIX M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), etc. may be mentioned.

The preferred acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. As long as the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility in the developer is good, and if it is 40 mgKOH/g or less, it is advantageous in manufacturing or handling.

Compounds having a polymerizable monosystem having a caprolactone structure are also preferred. The polymerizable compound having a caprolactone structure is sold on the market as KAYARAD DPCA series by NIPPON KAYAKU CO., Ltd., for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.

As the polymerizable monomer, the compounds described in Japanese Patent Laid-Open No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, the compound described in Japanese Patent Laid-Open No. 2017-194662, 8UH-1006 , 8UH-1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), Light-Acrylate POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc. are also preferred.

The content of the polymerizable monomer is preferably 10 to 60% by mass in the total solid content of the lens composition. The upper limit is preferably 55% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 15% by mass or more, and more preferably 30% by mass or more.

＜＜Photopolymerization initiator＞＞ The lens composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, a compound having a three-dimensional skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, and a hexaarylbisimidazole compound , Oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoalkyl benzophenone compounds, hydroxyalkyl benzophenone compounds, benzoate Compounds etc. As specific examples of the photopolymerization initiator, for example, refer to paragraphs 0265 to 0268 of Japanese Patent Laid-Open No. 2013-029760, and the description of Japanese Patent No. 6301489, and this content is incorporated in this specification.

Examples of the benzoyl formate compound include methyl benzoyl formate. Examples of commercially available products include DAROCUR-MBF (manufactured by BASF).

Examples of the aminoalkyl benzophenone compounds include those disclosed in Japanese Patent Laid-Open No. 10-291969. In addition, as the aminoalkyl benzophenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all made by BASF) can also be used.

Examples of the acylphosphine compound include the acylphosphine compound described in Japanese Patent No. 4225898. Specific examples include bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide and the like. As the acetylphosphine compound, IRGACURE-819 and DAROCUR-TPO (all manufactured by BASF) can also be used.

式中Rv¹ 表示取代基，Rv² 及Rv³ 分別獨立地表示氫原子或取代基，Rv² 和Rv³ 亦可以彼此鍵結而形成環，m表示0～5的整數。Examples of the hydroxyalkyl benzophenone compound include compounds represented by the following formula (V). Formula (V) [Chemical Formula 3]

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may also be bonded to each other to form a ring, and m represents an integer of 0 to 5.

Examples of the substituent represented by Rv ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear. The alkyl group and alkoxy group represented by Rv ¹ may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group or a group having a hydroxyalkyl benzophenone structure. Examples of the group having a hydroxyalkyl benzophenone structure include a benzene ring bonded to Rv ¹ in formula (V) or a group having a structure in which one hydrogen atom is removed from Rv ¹ .

Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferred. In addition, Rv ² and Rv ³ may be bonded to each other to form a ring (a ring having 4 to 8 carbon atoms is preferable, and an aliphatic ring having 4 to 8 carbon atoms is more preferable). The alkyl group is preferably straight chain or branched, and more preferably straight chain.

As specific examples of the compound represented by the formula (V), the following compounds may be mentioned. [Chemical Formula 4]

As the hydroxyalkyl benzophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: all manufactured by BASF) can also be used.

Examples of the oxime compound include the compounds described in Japanese Patent Laid-Open No. 2001-233842, the compounds described in Japanese Patent Laid-Open No. 2000-080068, the compounds described in Japanese Patent Laid-Open No. 2006-342166, and JCSPerkin Compounds described in II (1979, pp. 1653-1660), compounds described in JCS Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202- 232) The compound described in JP 2000-066385, the compound described in JP 2004-534797, the compound described in JP 2006-342166, The compound described in Japanese Patent Application Publication No. 2017-019766, the compound described in Japanese Patent No. 6065596, the compound described in International Publication No. 2015/152153, and the compound described in International Publication No. 2017/051680 Compounds, compounds described in Japanese Patent Laid-Open No. 2017-198865, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, and the like. Specific examples of the oxime compound include 3-benzyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyimide Butane-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxy Imino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-1-one and the like. Examples of commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Optomer N-1919 (photopolymerization initiator 2 described in ADEKA CORPORATION, Japanese Unexamined Patent Publication No. 2012-014052).

Further, as the oxime compound, the compound described in Japanese Patent Publication No. 2009-519904 in which the oxime is connected to the N position of the carbazole ring, and US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone site can be used The compound described in JP-A No. 2010-015025 and the compound disclosed in US Patent Publication No. 2009-292039, and the ketoxime compound described in International Publication No. 2009/131189 , The compound described in US Patent No. 7556910, which contains a trio and oxime skeleton in the same molecule, has a maximum absorption at 405 nm and is described in Japanese Patent Laid-Open No. 2009-221114 which has good sensitivity to a g-line light source Compounds etc. Preferably, for example, it is possible to refer to paragraphs 0274 to 0306 of Japanese Patent Laid-Open No. 2013-029760, and incorporate the contents into this specification.

The oxime compound is preferably an oxime compound containing a fluorine atom. It is preferable that the oxime compound containing a fluorine atom has a group containing a fluorine atom. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group). As a fluorine-containing group, it is selected from -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R ^F2 , -NHCONR ^F1 R ^F2 , At least one group of -NHCOOR ^F1 , -SO ₂ R ^F1 , -SO ₂ OR ^F1, and -NHSO ₂ R ^F1 is preferred. R ^F1 represents a fluorine-containing alkyl group, and R ^F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group. The fluorine-containing group is preferably -OR ^F1 .

The carbon number of the alkyl group and the fluorine-containing alkyl group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 10, and particularly preferably from 1 to 4. The alkyl group and the fluorine-containing alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. In the fluorine-containing alkyl group, the substitution rate of the fluorine atom is preferably 40 to 100%, more preferably 50 to 100%, and further preferably 60 to 100%. In addition, the substitution rate of a fluorine atom means the ratio (%) of the number of fluorine atoms substituted with respect to the number of all hydrogen atoms which an alkyl group has.

The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and even more preferably 6-10.

The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The condensation number is preferably 2-8, more preferably 2-6, further preferably 3-5, and particularly preferably 3-4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and even more preferably 3 to 20. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and a nitrogen atom is more preferable.

It is preferable that the group containing a fluorine atom has a terminal structure represented by formula (1) or (2). * In the formula represents the connection key. *-CHF ₂ (1) *-CF ₃ (2)

The number of all fluorine atoms in the oxime compound containing fluorine atoms is preferably 3 or more, and more preferably 4-10.

式（OX-1）中，Ar¹ 及Ar² 分別獨立地表示可以具有取代基之芳香族烴環，R¹ 表示具有包含氟原子之基團之芳基，R² 及R³ 分別獨立地表示烷基或芳基。The oxime compound containing a fluorine atom is preferably a compound represented by formula (OX-1). (OX-1) [Chemical Formula 5]

In formula (OX-1), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent, R ¹ represents an aryl group having a group containing a fluorine atom, and R ² and R ³ each independently represent Alkyl or aryl.

Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms of the ring constituting the aromatic hydrocarbon ring is preferably 6-20, more preferably 6-15, and particularly preferably 6-10. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring. Among them, it is preferable that at least one of Ar ¹ and Ar ² is a benzene ring, and it is more preferable that Ar ¹ is a benzene ring. Ar ² is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.

Examples of substituents that Ar ¹ and Ar ² may have include alkyl groups, aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 ,- OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 and -NHSO ₂ R ^X1 and so on. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, and fluorine atom is preferred. The carbon number of the alkyl group as a substituent and the alkyl group represented by R ^X1 and R ^X2 is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. In the alkyl group, part or all of the hydrogen atoms may be substituted with halogen atoms (preferably fluorine atoms). In addition, in the alkyl group, a part or all of the hydrogen atoms may be substituted with the above substituents. The carbon number of the aryl group as a substituent and the aryl group represented by R ^X1 and R ^X2 is preferably 6-20, more preferably 6-15, and even more preferably 6-10. The aryl group may be a single ring or a condensed ring. In addition, in the aryl group, part or all of the hydrogen atom may be substituted with the above-mentioned substituent. The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, and even more preferably 3-12. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, in the heterocyclic group, a part or all of the hydrogen atoms may be substituted with the above substituents.

The aromatic hydrocarbon ring represented by Ar ¹ is preferably unsubstituted. The aromatic hydrocarbon ring represented by Ar ² may be unsubstituted or may have a substituent. Having a substituent is preferable. As a substituent, -COR ^X1 is preferred. R ^X1 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group. The aryl group may have a substituent, or may be unsubstituted. Examples of the substituent include alkyl groups having 1 to 10 carbon atoms.

R ¹ represents an aryl group having a group containing a fluorine atom. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and even more preferably 6-10. The group containing a fluorine atom is preferably an alkyl group containing a fluorine atom (fluorine-containing alkyl group) and a group containing a fluorine atom alkyl group (a fluorine-containing group). The group containing a fluorine atom has the same meaning as the above range, and the preferred range is also the same.

R ² represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described above for the substituents that Ar ¹ and Ar ² may have. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 10, and particularly preferably from 1 to 4. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and even more preferably 6-10.

R ³ represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the substituents described above for the substituents that Ar ¹ and Ar ² may have. The carbon number of the alkyl group represented by R ³ is preferably from 1 to 20, more preferably from 1 to 15, and even more preferably from 1 to 10. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group represented by R ³ is preferably 6-20, more preferably 6-15, and even more preferably 6-10.

Specific examples of the oxime compound having a fluorine atom include the compounds described in Japanese Patent Laid-Open No. 2010-262028, and the compounds 24, 36 to 40 described in Japanese Patent Laid-Open No. 2014-500852, and Japanese Patent Laid-Open 2013 -164471, the compound (C-3) etc. described.

In addition, as the oxime compound, an oxime compound having a fused ring can also be used. As a specific example of the oxime compound having a stilbene ring, the compounds described in Japanese Patent Laid-Open No. 2014-137466 can be cited. Incorporate this content into this manual.

As the oxime compound, an oxime compound having a benzofuran skeleton can also be used. As specific examples, the compounds OE-01 to OE-75 described in International Publication No. 2015/036910 can be cited.

In addition, as the oxime compound, an oxime compound having at least one benzene ring having a carbazole ring as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include the compounds described in International Publication No. 2013/083505.

As the oxime compound, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. As specific examples of the oxime compound having a nitro group, the compounds described in paragraphs 0031 to 0047 of JP-A-2013-114249, paragraphs 0008-0012 and JP0-0079 of JP-A 2014-137466 can be cited. And the compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071.

Specific examples of the oxime compound are shown below, but the present invention is not limited thereto.

[化學式7]

[Chemical Formula 6]

[Chemical Formula 7]

The photopolymerization initiator used in the present invention is preferably a material satisfying the following condition 1. Condition 1: A composition prepared by mixing 1 part by mass of a photopolymerization initiator, 47.5 parts by mass of resin P1 of the following structure, and 51.5 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) using a spin coater: After pre-baking, the film thickness was 2.0 μm. It was applied to the glass substrate, and a 100° C. hot plate was used for 120 seconds of heat treatment (pre-baking) to form a film. The measured film was measured at a wavelength of 400 When the absorbance in the range of -700 nm is used, the maximum value of the absorbance in the aforementioned range is 0.03 or less. Resin P1: propylene glycol monomethyl ether acetate solution of benzyl methacrylate/methacrylic acid (=70/30 [mol ratio]) copolymer (solid content 40% by mass, weight average molecular weight 30000, FUJIKURA KASEI CO. , Manufactured by LTD., Acrybase FF-187)

In the present invention, as the photopolymerization initiator, a photopolymerization initiator A1 having a wavelength of 365 nm in methanol with an absorption coefficient of 1.0×10 ³ mL/gcm or more and a wavelength of 365 nm in methanol are used simultaneously It is preferable that the photopolymerization initiator A2 is 1.0×10 ² mL/gcm or less and the absorption coefficient at a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more. According to this aspect, the composition for the lens can be sufficiently hardened by exposure, and can be produced in a low-temperature process (for example, a temperature of 150° C. or less in all steps, preferably a temperature of 120° C. or less), and has excellent characteristics such as solvent resistance. Of the lens. Therefore, it is particularly effective when manufacturing lenses in low temperature processes. As the photopolymerization initiator A1 and the photopolymerization initiator A2, it is preferable to select and use a compound having the above light absorption coefficient from the above compounds.

上述式中，ε表示吸光係數（mL/gcm），A表示吸光度，c表示光聚合起始劑的濃度（g/mL），l表示光徑長（cm）。Furthermore, in the present invention, the light absorption coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, the measurement solution is prepared by dissolving the photopolymerization initiator in methanol, and it is calculated by measuring the absorbance of the measurement solution. Specifically, the measurement solution was added to a glass dish with a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, and substituted into the following formula to calculate the absorbance at a wavelength of 365 nm and a wavelength of 254 nm. Coefficient (mL/gcm). [Formula 1]

In the above formula, ε represents the absorption coefficient (mL/gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g/mL), and l represents the optical path length (cm).

The absorption coefficient of the photopolymerization initiator A1 at a wavelength of 365 nm in methanol is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ⁴ mL/gcm or more, and 1.1×10 ⁴ mL/gcm or more, 1.2×10 ⁴ ～1.0×10 ⁵ mL/gcm is more preferred, 1.3×10 ⁴ ～5.0×10 ⁴ mL/gcm is even more preferred, 1.5×10 ⁴ ～3.0×10 ⁴ mL/gcm is particularly preferred . In addition, the absorption coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm is preferably 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm, and 1.5×10 ⁴ to 9.5×10 ⁴ mL/gcm is more Preferably, 3.0×10 ⁴ to 8.0×10 ⁴ mL/gcm is more preferable.

As the photopolymerization initiator A1, oxime compounds, aminoalkyl benzophenone compounds, and acetylphosphine compounds are preferred, oxime compounds and acetylphosphine compounds are more preferred, and oxime compounds are further preferred. From the viewpoint of compatibility of other components contained, an oxime compound containing a fluorine atom is particularly preferred. As the oxime compound containing a fluorine atom, the compound represented by the above formula (OX-1) is preferred. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1-[4-(phenylthio)-,2-(o-benzoyl oxime)] (as a commercially available product, For example, IRGACURE-OXE01, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-ethyl Acetyl oxime) (as a commercial product, such as IRGACURE-OXE02, manufactured by BASF), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (as a commercial product, such as IRGACURE- 819, manufactured by BASF), (C-13), (C-14), etc. shown in the specific examples of the above oxime compounds.

The light absorption coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 365 nm is 1.0×10 ² mL/gcm or less, preferably 10 to 1.0×10 ² mL/gcm, and 20 to 1.0×10 ² mL/gcm. Better. In addition, the difference between the absorption coefficient of the light of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm and the absorption coefficient of the light of the photopolymerization initiator A2 in methanol at a wavelength of 365 nm is 9.0×10 ² mL/gcm or more, 1.0 ×10 ³ mL/gcm or more is preferable, 5.0×10 ³ to 3.0×10 ⁴ mL/gcm is more preferable, and 1.0×10 ⁴ to 2.0×10 ⁴ mL/gcm is even more preferable. In addition, the absorption coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ³ to 1.0×10 ⁶ mL/gcm, and 5.0×10 ³ to 1.0×10 ⁵ mL/gcm is better.

As the photopolymerization initiator A2, a hydroxyalkyl benzophenone compound, a benzoate compound, an aminoalkyl benzophenone compound and an acetylphosphine compound are preferred, and a hydroxyalkyl benzophenone compound and a benzophenone The acid ester compound is more preferable, and the hydroxyalkyl benzophenone compound is more preferable. As the hydroxyalkyl benzophenone compound, the compound represented by the above formula (V) is preferred. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-one (as a commercial product, for example, IRGACURE-184, manufactured by BASF), 1-[4-(2-hydroxyethyl Oxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (as a commercially available product, for example, IRGACURE-2959, manufactured by BASF), etc.

As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, the combination of the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkyl benzophenone compound. The photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a combination of compounds represented by the above formula (V). The photopolymerization initiator A1 is an oxime compound containing a fluorine atom and the photopolymerization initiator A2 is The combination of the compounds represented by the above formula (V) is particularly preferred. With this combination, a lens with excellent characteristics such as solvent resistance can be manufactured in a low-temperature process. Furthermore, a lens with less wrinkles or voids can be manufactured.

The content of the photopolymerization initiator is preferably 1 to 20% by mass in the total solid content of the lens composition. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 5% by mass or more. The upper limit is preferably 15% by mass or less, more preferably 14% by mass or less, and further preferably 13% by mass or less. In addition, the lens composition of the present invention preferably contains 5 to 50 parts by mass of a photopolymerization initiator relative to 100 parts by mass of the polymerizable monomer. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. According to this aspect, a pattern with excellent rectangularity can be formed.

In the composition for a lens of the present invention, when the above-mentioned photopolymerization initiator A1 is used as the photopolymerization initiator, the content of the photopolymerization initiator A1 is 1 to 15 in the total solid content of the lens composition Quality% is better. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more. The upper limit is preferably 14% by mass or less, more preferably 12.5% by mass or less, and further preferably 10% by mass or less.

When the photopolymerization initiator A2 is used as the photopolymerization initiator in the lens composition of the present invention, the content of the photopolymerization initiator A2 is 0.5 to 15 in the total solid content of the lens composition Quality% is better. The lower limit is preferably 1% by mass or more, more preferably 1.5% by mass or more, and further preferably 2% by mass or more. The upper limit is preferably 12.5% by mass or less, more preferably 10% by mass or less, and further preferably 7.5% by mass or less.

In the lens composition of the present invention, when the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator, the composition of the lens of the present invention relative to the photopolymerization initiator A1 It is preferable that 100 parts by mass contain 50 to 200 parts by mass of the photopolymerization initiator A2. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. According to this aspect, the lens composition is easily hardened by exposure, and the lens can be manufactured in a low-temperature process (for example, a temperature of 150° C. or less throughout all steps, preferably a temperature of 120° C. or less). Furthermore, a lens with less wrinkles or voids can be manufactured.

In the lens composition of the present invention, when the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator, the photopolymerization initiator in the total solid content of the lens composition The total content of A1 and the photopolymerization initiator A2 is preferably 5 to 15% by mass. The lower limit is preferably 6% by mass or more, more preferably 7% by mass or more, and further preferably 8% by mass or more. The upper limit is preferably 14.5% by mass or less, more preferably 14% by mass or less, and further preferably 13% by mass or less. As long as it is within the above range, the lens composition is easily cured by exposure, and the lens can be manufactured in a low-temperature process (for example, a temperature of 150° C. or less throughout all steps, preferably a temperature of 120° C. or less). Furthermore, a lens with less wrinkles or voids can be manufactured.

＜＜resin＞＞ The lens composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition or the use of a binder. In addition, the resin mainly used to disperse particles and the like in the composition is also referred to as a dispersant. However, this kind of use of the resin is an example, and the resin can be used for purposes other than this kind of use.

The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more.

As the resin, for example, (meth)acrylic resin, (meth)acrylamide resin, epoxy resin, enethiol resin, polycarbonate resin, polyether resin, polyarylate resin, polyphenol resin, poly Ether resin, polystyrene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamidoamide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, silicon Oxyalkyl resin, etc.

In the present invention, as the resin, it is preferable to use a resin having a refractive index of 1.5 or more (hereinafter, also referred to as a high refractive index resin) at a wavelength of 550 nm. The refractive index of the resin at a wavelength of 550 nm is preferably 1.6 or more, more preferably 1.7 or more, and even more preferably 1.8 or more. The upper limit is preferably 4.0 or less, more preferably 3.9 or less, further preferably 3.5 or less, and particularly preferably 3.0 or less. High refractive index resin can be used as a binder or dispersant.

The refractive index of the resin can be measured in the uncured state by the following method. Regarding the specific measurement method, after forming a film composed of only resin on a silicon wafer at a thickness of 300 nm, an ellipsometer (Lambda Ace RE-3300 (product name), Dainippon Screen Mfg. Co., Ltd.) measured the refractive index of the obtained film.

The resin used in the present invention may have an acid group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. This kind of acid group may be only one kind or two or more kinds. Resins with acid groups can also be used as alkali-soluble resins or dispersants.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, further preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferred. For example, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth)acrylic acid, vinyl benzoic acid, partially esterified maleic acid, etc. can be cited. Copolymers of repeating units of monomers, alkali-soluble phenol resins such as novolac-type resins, acidic cellulose derivatives having carboxyl groups on the side chains, polymers with hydroxyl groups and polymers with addition of acid anhydrides. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are preferred. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, and vinyl compounds. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Ester, tolyl (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, ethylene acetate, N-vinylpyrrolidone, polystyrene macromonomer, and polymethyl methacrylate. Molecular monomers, etc. The other monomer copolymerizable with such (meth)acrylic acid may be only one kind, or may be two or more kinds.

The resin having an acid group may have a repeating unit derived from a maleimide compound. Examples of the maleimide compound include N-alkyl maleimide, N-aryl maleimide and the like. Examples of the repeating unit derived from a maleimide compound include a repeating unit represented by the formula (C-mi). [Chemical Formula 8]

In the formula (C-mi), Rmi represents an alkyl group or an aryl group. The carbon number of the alkyl group is preferably 1-20. The alkyl group may be any of linear, branched, and cyclic. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and even more preferably 6-10. Rmi is preferably an aryl group.

The resin having an acid group is derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds are sometimes referred to as "ether dimerization" "." The resin of the repeating unit is also preferred.

[Chemical Formula 9]

式（ED2）中，R表示氫原子或碳數1～30的有機基團。作為式（ED2）的具體例，能夠參閱日本特開2010-168539號公報的記載。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a C 1-25 hydrocarbon group which may have a substituent. [Chemical Formula 10]

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of the formula (ED2), the description in JP 2010-168539A can be referred to.

For specific examples of the ether dimer, refer to paragraph 0317 of Japanese Patent Laid-Open No. 2013-029760, and incorporate this content into this specification.

Examples of the resin containing a repeating unit derived from an ether dimer include resins having the following structures. In the following structural formulas, Me represents a methyl group. [Chemical Formula 11]

The resin used in the present invention may have a polymerizable group. Examples of the polymerizable group include a group having an ethylenic unsaturated bond such as a vinyl group, (meth)allyl group, and (meth)acryloyl group. Examples of commercially available resins having a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer6173 (polycarboxylate acrylate oligomer containing carboxyl group, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS RESIST 106 (all made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all made by Daicel Corporation), Ebecryl3800 (made by DAICEL UCB CO., LTD. ), ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), DP-1305 (manufactured by FUJIFILM Finechemicals Co., Ltd.), etc.

The resin used in the present invention preferably contains a resin b1 containing a repeating unit (hereinafter, also referred to as repeating unit b1-1) derived from the compound represented by formula (I). By using a resin having a repeating unit b1-1, it is easy to form a lens with more excellent transparency. [Chemical Formula 12]

X ¹ represents O or NH, and O is preferred. R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent linking group. Examples of divalent linking groups include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and combination 2 More than one such group. Examples of hydrocarbon groups include alkyl groups and aryl groups. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the type of hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a single ring or a condensed ring. The hydrocarbon group and the heterocyclic group may have a substituent. Examples of the substituent include alkyl groups, aryl groups, hydroxyl groups, and halogen atoms. R ¹⁰ represents a substituent. Examples of the substituent represented by R ¹⁰ include substituent T shown below, and a hydrocarbon group is preferred, and an alkyl group which may have an aryl group as a substituent is more preferred. m represents an integer of 0 to 2, 0 or 1 is preferable, and 0 is more preferable. p represents an integer of 0 or more, 0 to 4 is more preferred, 0 to 3 is more preferred, 0 to 2 is further preferred, 0 or 1 is still more preferred, and 1 is particularly preferred.

(Substituent T) Examples of the substituent T include halogen atom, cyano group, nitro group, hydrocarbon group, heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² ,- NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² . Rt ¹ and Rt ² each independently represent a hydrogen atom, a hydrocarbon group or a heterocyclic group. Rt ¹ and Rt ² may be bonded to form a ring.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Examples of the hydrocarbon group include alkyl, alkenyl, alkynyl and aryl groups. The carbon number of the alkyl group is preferably from 1 to 30, more preferably from 1 to 15, and even more preferably from 1 to 8. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred, and branched is more preferred. The carbon number of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 12, and particularly preferably from 2 to 8. The alkenyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the alkynyl group is preferably 2-30, and more preferably 2-25. The alkynyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and even more preferably 6-12. The heterocyclic group may be a single ring or a condensed ring. The heterocyclic group monocyclic ring or the condensed ring having a condensation number of 2 to 4 is preferred. The number of hetero atoms of the ring constituting the heterocyclic group is preferably 1 to 3. The hetero atom of the ring constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the ring of the heterocyclic group is preferably 3-30, more preferably 3-18, and even more preferably 3-12. The hydrocarbon group and the heterocyclic group may have a substituent, or may be unsubstituted. Examples of the substituent include the substituents described in the above-mentioned substituent T.

The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1). [Chemical Formula 13]

X ¹ represents O or NH, and O is preferred. R ¹ represents a hydrogen atom or a methyl group. R ² , R ³ and R ¹¹ each independently represent a hydrocarbon group. The hydrocarbon group represented by R ² and R ³ is preferably an alkylene group or an aryl group, more preferably an alkylene group. The carbon number of the alkylene group is preferably from 1 to 10, more preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably 2 or 3. The hydrocarbon group represented by R ¹¹ is preferably an alkyl group which may have an aryl group as a substituent, and more preferably an alkyl group which has an aryl group as a substituent. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 5. In addition, when the alkyl group has an aryl group as a substituent, the carbon number of the alkyl group means the carbon number of the alkyl portion. R ¹² represents a substituent. Examples of the substituent represented by R ¹² include the above-mentioned substituent T. n represents an integer of 0 to 15, an integer of 0 to 5 is preferred, an integer of 0 to 4 is more preferred, and an integer of 0 to 3 is even more preferred. m represents an integer of 0 to 2, 0 or 1 is preferable, and 0 is more preferable. p1 represents an integer of 0 or more, 0 to 4 is more preferred, 0 to 3 is more preferred, 0 to 2 is further preferred, 0 to 1 is still more preferred, and 0 is particularly preferred. q1 represents an integer of 1 or more, preferably 1-4, more preferably 1-3, further preferably 1-2, and 1 particularly preferably.

式中，R¹ 表示氫原子或甲基，R²¹ 及R²² 分別獨立地表示伸烷基，n表示0～15的整數。R²¹ 及R²² 所表示之伸烷基的碳數為1～10為較佳，1～5為更佳，1～3為進一步較佳，2或3為特佳。n表示0～15的整數，0～5的整數為較佳，0～4的整數為更佳，0～3的整數為進一步較佳。The compound represented by the formula (I) is preferably a compound represented by the following formula (III). [Chemical Formula 14]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. The carbon number of the alkylene group represented by R ²¹ and R ²² is preferably from 1 to 10, more preferably from 1 to 5, more preferably from 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15, an integer of 0 to 5 is preferred, an integer of 0 to 4 is more preferred, and an integer of 0 to 3 is even more preferred.

Examples of the compound represented by the formula (I) include ethylene oxide or propylene oxide modified (meth)acrylate of cumylphenol. Examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.) and the like.

It is preferable that the resin b1 further contains a repeating unit derived from an alkyl (meth)acrylate (hereinafter, also referred to as repeating unit b1-2). The carbon number of the alkyl portion of the alkyl (meth)acrylate is preferably from 3 to 10, more preferably from 3 to 8, and even more preferably from 3 to 6. Preferred specific examples of the alkyl (meth)acrylate include n-butyl (meth)acrylate and the like.

It is also preferable that the resin b1 further includes a repeating unit having an acid group (hereinafter, also referred to as repeating unit b1-3).

The lens composition of the present invention can contain a resin as a dispersant. Examples of the dispersant include acidic dispersants (acid resins) and basic dispersants (basic resins). Here, the acidic dispersant (acidic resin) means a resin having more acid groups than basic groups. As the acidic dispersant (acid resin), when the total amount of the acid group and the amount of the basic group is set to 100 mol %, a resin having an acid group amount of 70 mol% or more is preferable, and substantially only Resins composed of acid groups are better. The acidic group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, an alkaline dispersant (alkaline resin) means a resin having more basic groups than acid groups. As the basic dispersant (basic resin), when the total amount of the amount of acid groups and the amount of basic groups is set to 100 mol%, a resin having an amount of basic groups exceeding 50 mol% is preferable. The basic group of the basic dispersant is preferably an amine group.

Examples of the dispersant include polymer dispersants [for example, polyamide and its salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly(methyl ) Acrylic acid ester, (meth)acrylic copolymer, formalin naphthalenesulfonate condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkylamine, alkanolamine, etc. The polymer dispersant can be further classified into a linear polymer, a terminal modified polymer, a graft polymer, and a capped polymer according to its structure. The polymer dispersant adsorbs on the surface of particles such as pigments, and plays a role in preventing re-agglomeration. Therefore, as a preferable structure, a terminal modified polymer, a grafted polymer, and an end-capped polymer having a portion anchored to the surface of particles such as pigments can be cited. In addition, the dispersants described in paragraphs 0028 to 0124 of JP 2011-070156 and the dispersants described in JP 2007-277514 are also preferably used.

In the present invention, a blocked copolymer can also be used as a dispersant. The details of the end-capping copolymer can be found in paragraphs 0131 to 0160 of JP-A-2012-137564, and this content is incorporated in this specification. In addition, in the present invention, an oligoimide-based copolymer containing a nitrogen atom in at least one of the main chain and the side chain can also be used as a dispersant. For the oligoimide-based copolymer, refer to the description in paragraphs 0102 to 0174 of JP-A-2012-255128, and incorporate this content into this specification.

Dispersants can also be obtained as commercially available products. Examples of such specific examples include the Disperbyk series (for example, Disperbyk-111, 2001, etc.) manufactured by BYK Chemie GmbH, and the SOLSPERSE series (for example, SOLSPERSE20000, 76500) manufactured by Lubrizol Japan Ltd. Etc.), AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc. etc. In addition, the product described in paragraph 0129 of JP-A-2012-137564 and the product described in paragraph 0235 of JP-A-2017-194662 can also be used as a dispersant.

The content of the resin is preferably 15 to 75% by mass in the total solid content of the lens composition. The upper limit is preferably 65% by mass or less, and more preferably 55% by mass or less. The lower limit is preferably 25% by mass or more, and more preferably 35% by mass or more. In addition, the content of the resin is preferably 25 to 200 parts by mass relative to 100 parts by mass of the polymerizable monomer. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 50 parts by mass or more, and more preferably 75 parts by mass or more. Further, the content of the resin b1 (including the repeating unit derived from the compound represented by formula (III)) in the total amount of resins included in the lens composition of the present invention is preferably 0.1 to 100% by mass, 10 to 100% by mass is better. The upper limit can also be set to 90% by mass or less, 80% by mass or less, and 70% by mass or less. In addition, the content of the resin b1 is preferably 0.1 to 70% by mass in the total solid content of the lens composition. The upper limit is preferably 60% by mass or less, and more preferably 50% by mass or less. The lower limit is preferably 1% by mass or more, and more preferably 5% by mass or more.

<<Furanyl-containing compounds>> The lens composition of the present invention preferably contains a furan group-containing compound (hereinafter, also referred to as furan group-containing compound). According to this aspect, a composition for a lens excellent in low-temperature curability can be produced.

The furan group-containing compound is not particularly limited as long as it contains a furan group (a group in which one hydrogen atom is removed from furan). As for the compound containing a furanyl group, the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used. In addition, Japanese Patent Application Publication No. 2000-233581, Japanese Patent Application Publication No. 1994-271558, Japanese Patent Application Publication No. 1994-293830, Japanese Patent Application Publication No. 1996-239421, Japanese Patent Application Publication No. 1998-508655, Japanese Patent Laid-Open No. 2000-001529, Japanese Patent Laid-Open No. 2003-183348, Japanese Patent Laid-Open No. 2006-193628, Japanese Patent Laid-Open No. 2007-186684, Japanese Patent Laid-Open No. 2010-265377 and Japanese Patent Laid-Open 2011- The compound described in 170069 Gazette.

The furan-containing compound may be a monomer or a polymer. For reasons such as easy availability of lenses with excellent durability, polymers are preferred. In the case of a polymer, the weight average molecular weight is preferably 2,000 to 70,000. The upper limit is preferably 60,000 or less, and more preferably 50,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more. In addition, the polymer type furan group-containing compound is a component of the resin in the lens composition according to the present invention.

式中，Rf¹ 表示氫原子或甲基，Rf² 表示2價的連接基。As the monomer type furan group-containing compound (hereinafter, also referred to as furan group-containing monomer), a compound represented by the following formula (fur-1) may be mentioned. [Chemical Formula 15]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group.

Examples of the divalent linking group represented by Rf ² include alkylene, aryl, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations of these 2 More than one kind of group. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-20, and even more preferably 6-10. The alkylene group and the aryl group may have a substituent. Examples of the substituent include hydroxyl groups.

式中，Rf¹ 表示氫原子或甲基，Rf¹¹ 表示-O-或-NH-，Rf¹² 表示單鍵或2價的連接基。作為Rf¹² 所表示之2價的連接基，可列舉伸烷基、伸芳基、-O-、-CO-、-COO-、-OCO-、-NH-、-S-及組合該等2種以上而成之基團。伸烷基的碳數為1～30為較佳，1～20為更佳，1～15為進一步較佳。伸烷基可以為直鏈、分支、環狀中之任一種。伸芳基的碳數為6～30為較佳，6～20為更佳，6～10為進一步較佳。伸烷基及伸芳基亦可以具有取代基。作為取代基，可列舉羥基等。The furan group-containing monomer is preferably a compound represented by the following formula (fur-1-1). [Chemical Formula 16]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, Rf ¹¹ represents -O- or -NH-, and Rf ¹² represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Rf ¹² include alkylene group, aryl group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. 2 More than one kind of group. The carbon number of the alkylene group is preferably from 1 to 30, more preferably from 1 to 20, and even more preferably from 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-20, and even more preferably 6-10. The alkylene group and the aryl group may have a substituent. Examples of the substituent include hydroxyl groups.

As specific examples of the furan group-containing monomer, compounds having the following structures can be mentioned. In the following structural formulas, Rf ¹ represents a hydrogen atom or a methyl group. [Chemical Formula 17]

As the polymer type furan group-containing compound (hereinafter, also referred to as furan group-containing polymer), a resin containing a furan group-containing repeating unit is preferable, and includes a resin derived from the formula (fur-1) The resin of the repeating unit of the compound is more preferable. The concentration of the furan group in the furan group-containing polymer is preferably 0.5 to 6.0 mmol per 1 g of the furan group containing polymer, and more preferably 1.0 to 4.0 mmol. If the furan group concentration is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a lens excellent in solvent resistance and the like. As long as the furan group concentration is 6.0 mmol or less, preferably 4.0 mmol or less, the lens composition has good stability over time.

The polymer containing a furan group may contain a repeating unit having an acid group and/or a repeating unit having a polymerizable group in addition to the repeating unit having a furan group. Examples of acid groups include carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups. Examples of the polymerizable group include a group having an ethylenic unsaturated bond such as a vinyl group, (meth)allyl group, and (meth)acryloyl group.

When the furan group-containing polymer contains a repeating unit having an acid group, the solubility of the furan group-containing polymer in the lens composition becomes high, so that it is easy to form a lens with more excellent transparency. Furthermore, the reactivity with the polymerizable monomer is increased to further improve the hardenability at a low temperature, and it is easy to form a lens having more excellent solvent resistance. When the polymer containing a furan group contains a repeating unit having an acid group, the acid value is preferably 10 to 200 mgKOH/g, and more preferably 40 to 130 mgKOH/g.

When the polymer containing a furan group contains a repeating unit having a polymerizable group, it is easy to form a lens having more excellent solvent resistance.

The furan group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of Japanese Patent Application Publication No. 2017-194662.

The content of the furan group-containing compound is preferably 0.1 to 70% by mass in the total solid content of the lens composition. The lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and further preferably 7.5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. In addition, when a furan group-containing polymer is used as the furan group-containing compound, the content of the furan group-containing polymer in the resin contained in the lens composition is preferably 0.1 to 100% by mass. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less. Furthermore, when the resin used in the lens composition of the present invention contains the above-mentioned resin b1 and a furan group-containing polymer is used as the furan group-containing compound, the content of the furan group-containing polymer relative to the resin b1 100 parts by mass is preferably 10 to 200 parts by mass. The upper limit is preferably 175 parts by mass or less, and preferably 150 parts by mass or less. The lower limit is preferably 25 parts by mass or more, and preferably 50 parts by mass or more. By using the resin b1 and the furan group-containing polymer at the same time, the effects such as excellent low-temperature curability and transparency can be expected. Furthermore, when the ratio of the two is within the above range, it is easy to obtain a lens having excellent durability.

<<Compounds with epoxy groups>> It is preferable that the lens composition of the present invention further contains a compound having an epoxy group. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferred. It is preferable to have 2 to 100 epoxy groups in one molecule. For example, the upper limit can be set to 10 or less, and can also be set to 5 or less. The epoxy equivalent of the compound having an epoxy group (= molecular weight of the compound having an epoxy group/number of epoxy groups) is preferably 500 g/eq or less, 100 to 400 g/eq is more preferable, and 100 to 300 g/ eq is further preferred. The compound having an epoxy group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, in the case of a polymer with a molecular weight of 1,000 or more, the weight average molecular weight is 1,000 or more). The molecular weight of the compound having an epoxy group (weight average molecular weight in the case of a polymer) is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the molecular weight (weight average molecular weight in the case of a polymer) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

As the compound having an epoxy group, paragraphs 0034 to 0036 of Japanese Patent Laid-Open No. 2013-011869, paragraphs 0147 to 0156 of Japanese Patent Laid-Open No. 2014-043556, and 0085 to Japanese Patent Laid-Open No. 2014-089408 can also be used The compound described in paragraph 0092, the compound described in Japanese Patent Application Laid-Open No. 2017-179172. Incorporate such content into this manual.

When the lens composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group is preferably 0.1 to 40% by mass in the total solid content of the lens composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having an epoxy group may be one kind alone, or two or more kinds may be used simultaneously. When two or more types are used at the same time, the total amount is preferably within the above range.

＜＜White or colorless pigment (white pigment)＞＞ The lens composition of the present invention can contain white or colorless pigments (hereinafter, also referred to as white pigments). When the lens composition of the present invention contains a white pigment, it is easy to form a lens with a high refractive index.

Examples of the white pigment include at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P, and S The particles of elemental oxides are preferably particles containing oxides of at least one element selected from Ti, Zr, Sn, Al and Si. As the oxide, titanium oxide and zirconium oxide are preferred, and titanium oxide is more preferred. Furthermore, examples of titanium oxide include rutile titanium oxide, anatase (Anatase) titanium oxide, and amorphous titanium oxide, and rutile titanium oxide is preferred. In addition, the above-mentioned oxide is preferably surface-treated with a surface-treating agent. Examples of surface treatment agents include inorganic compounds and organic compounds. Both inorganic compounds and organic compounds can be used at the same time. Specific examples of the surface treatment agent include polyol, alumina, aluminum hydroxide, amorphous silica, hydrous silica, alkanolamine, stearic acid, organosiloxane, zirconium oxide, hydrogenated dioxide Methyl silicone oil, silane coupling agent and titanate coupling agent, etc.

The shape of the white pigment is not particularly limited. For example, an isotropic shape (for example, spherical shape, polyhedral shape, etc.), anisotropic shape (for example, needle shape, rod shape, plate shape, etc.), an indefinite shape, and the like can be cited.

The weight average particle diameter of the primary particles of the white pigment is preferably 150 nm or less, more preferably 100 nm or less, and further preferably 80 nm or less. The lower limit value is not particularly set, but it is preferably 1 nm or more. In addition, regarding the weight average particle size of the white pigment, unless otherwise specified, the mixed liquid or dispersion containing the white pigment is diluted to 80 times by using propylene glycol monomethyl ether acetate, and dynamic light scattering is used Method to measure the obtained dilution. For this measurement, the weight average particle diameter obtained by using Microtrac (product name) UPA-EX150 manufactured by Nikkiso Co., Ltd. is assumed.

As a white pigment of specific surface area, 10 ~ 400m ² / g is preferred, 20 ~ 200m ² / g is more preferably, 30 ~ 150m ² / g is further preferred.

The refractive index of the white pigment is preferably 1.6 to 3.0. The lower limit is preferably 1.7 or more, and more preferably 1.8 or more. As an upper limit, 2.9 or less is preferable, and 2.8 or less is more preferable. In addition, the measurement method of the refractive index of a white pigment is based on Japanese Industrial Standards (JIS K 0062:1992).

As the white pigment, a commercially available product can be used. For example, as the titanium oxide, TTO series (TTO-51 (A), TTO-51 (C), TTO-55 (C), etc.), TTO-S, V series (TTO-S-1, TTO-S -2, TTO-V-3, etc.) (above, product name, manufactured by ISHIHARA SANGYO KAISHA, LTD.), MT series (MT-01, MT-05, etc.) (manufactured by TAYCA CORPORATION, product name), etc.

When the composition for lenses of the present invention contains a white pigment, the content of the white pigment is preferably 10 to 60% by mass in the total solid content of the lens composition. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. The lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more. The lens composition of the present invention may contain only one kind of white pigment, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range. Moreover, it is also preferable that the lens composition of the present invention does not substantially contain a white pigment. According to this aspect, it is easy to form a lens with a small surface roughness. The case where the composition for lenses of the present invention does not substantially contain a white pigment means that the content of the white pigment in the total solid content of the lens composition is 0.1% by mass or less, preferably 0.05% by mass or less, and 0.01% by mass % Or less is further preferred, and not contained is particularly preferred.

＜＜Solvent＞＞ The lens composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the lens composition. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph 0223 of International Publication No. 2015/166779, and incorporate the contents into this specification. In addition, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl celulose acetate , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropylamide and 3-butoxy-N , N-dimethylpropylamide, etc. However, the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be reduced due to environmental reasons (for example, it can be set to 50 relative to the total amount of organic solvents) Mass ppm (parts per million) or less can also be set to 10 mass ppm or less, and can also be set to 1 mass ppm or less).

In the present invention, it is preferable to use a solvent with a small metal content. For example, the metal content of the solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, you can also use a quality ppt (parts per trillion) grade of solvents, such high-purity solvents such as provided by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The material of the filter is preferably Teflon, polyethylene or nylon.

The solvent may contain isomers (compounds with the same number of atoms but different structures). In addition, the isomer may contain only one kind or plural kinds.

In the present invention, the content rate of the peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferably substantially free of the peroxide.

The content of the solvent in the lens composition is preferably 40 to 90% by mass. The lower limit is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more. The upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less.

From the viewpoint of environmental regulations, it is preferable that the lens composition of the present invention does not substantially contain environmental regulations. In addition, in the present invention, substantially not containing environmental regulatory substances means that the content of environmental regulatory substances in the lens composition is 50 mass ppm or less, preferably 30 mass ppm or less, and further preferably 10 mass ppm or less. 1 mass ppm or less is particularly preferable. Examples of environmental regulations include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are based on REACH (Registration Evaluation Authorization and Restriction of CHemicals) regulations, PRTR (Pollutant Release and Transfer Register) laws, and VOC (Volatile Organic Compounds: volatile Organic compounds) laws and regulations are registered as environmental laws and regulations, and their usage and disposal methods are strictly controlled. These compounds are sometimes used as solvents in the production of the components used in the lens composition of the present invention and the like, and are sometimes mixed into the lens composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. As a method of reducing environmental regulations substances, a method of heating and depressurizing the inside of the system to be higher than the boiling point of environmental regulations substances, and distilling and removing environmental regulations substances from the system and reducing them. In addition, when distilling a small amount of environmental regulations, it is also useful to azeotrope with a solvent having the same boiling point as the solvent in order to improve efficiency. In addition, when a compound having radical polymerizability is contained, it may be distilled off under reduced pressure after the addition of a polymerization inhibitor, so as to suppress the radical polymerization reaction during the distillation under reduced pressure and cause crosslinking between molecules. These distillation and removal methods can be any of the raw material stage, the stage of the product reacting the raw material (for example, the resin solution after polymerization and the polyfunctional monomer solution), or the stage of the lens composition prepared by mixing these compounds In one stage.

（式（T1）中，n表示2～4的整數，L表示2～4價的連接基。）<<hardening accelerator>> The lens composition of the present invention may be added with a curing accelerator for the purpose of promoting the reaction of the polymerizable monomer or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more thiol groups in the molecule. The polyfunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkyl thiol, and the compound represented by formula (T1) is more preferable. Formula (T1) [Chemical Formula 18]

(In formula (T1), n represents an integer of 2 to 4, and L represents a 2 to 4 valent linking group.)

In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is an alkylene group having 2 to 12 carbon atoms.

In addition, as the hardening accelerator, a hydroxymethyl compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of Japanese Patent Laid-Open No. 2015-034963), amines, phosphonium salts, amidine salts, and amides can also be used Compounds (above, for example, the curing agent described in paragraph 0186 of Japanese Patent Laid-Open No. 2013-041165), alkali generators (for example, ionic compounds described in Japanese Patent Laid-Open No. 2014-055114), cyanic acid Ester compound (for example, the compound described in paragraph 0071 of Japanese Unexamined Patent Publication No. 2012-150180), alkoxysilane compound (for example, an alkoxy group having an epoxy group described in Japanese Unexamined Patent Publication No. 2011-253054 Silane compound), onium salt compounds (for example, the compounds exemplified as the acid generator in paragraph 0216 of Japanese Patent Laid-Open No. 2015-034963, the compounds described in Japanese Patent Laid-Open No. 2009-180949), etc.

When the composition for a lens of the present invention contains a curing accelerator, the content of the curing accelerator is preferably 0.3 to 8.9% by mass in the total solid content of the lens composition, and more preferably 0.8 to 6.4% by mass.

＜＜Silane coupling agent＞＞ The lens composition of the present invention preferably contains a silane coupling agent. By containing a silane coupling agent, it is easy to obtain a lens with excellent adhesion to the support. As the silane coupling agent, a silane compound having at least two functional groups having different reactivity in one molecule is preferred. The silane coupling agent has at least one selected from the group consisting of vinyl group, epoxy group, styryl group, methacryl group, amine group, isocyanurate group, urea group, mercapto group, thioether group and isocyanate group Silane compounds of groups and alkoxy groups are preferred. Specific examples of the silane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602) , N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxysilane ( Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacrylonitrile Oxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) etc. For details of the silane coupling agent, refer to the description in paragraphs 0155 to 0158 of JP-A-2013-254047, and incorporate the contents into this specification. When the composition for a lens of the present invention contains a silane coupling agent, the content of the silane coupling agent in the total solid content of the lens composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, 0.1 Mass% ~ 5 mass% is particularly good. The lens composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

＜＜Polymerization inhibitor＞＞ The lens composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-third butyl-p-cresol, pyrogallol, tertiary butyl catechol, benzoquinone, and 4,4′-sulfur. Bis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosobishydroxylamine salt (Ammonium salt, first cerium salt, etc.) etc. When the composition for lenses of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass in the total solid content of the composition for lenses. The lens composition of the present invention may contain only one kind of polymerization inhibitor, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.

＜＜UV absorber＞＞ The lens composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triphenyl compounds, indole compounds, and the like can be used. Three 𠯤 compounds etc. For details of these, please refer to paragraphs 0052-0072 of JP-A 2012-208374, paragraphs 0317-0334 of JP-A 2013-068814, and paragraphs 0061-0080 of JP-A 2016-162946 The contents of this document are incorporated into this manual. Examples of commercially available products of ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.) and the like. In addition, examples of the benzotriazole compound include the MYUA series manufactured by MIYOSHI & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016). In addition, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. When the composition for lenses of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass in the total solid content of the lens composition, more preferably 0.1 to 5% by mass, 0.1 ~3% by mass is particularly good. In addition, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably in the above range.

＜＜Surfactant＞＞ The lens composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a non-ionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. For the surfactant, refer to paragraphs 0238 to 0245 of International Publication No. 2015/166779, and incorporate this content into this specification.

In the present invention, the surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the lens composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. In addition, it is possible to form a film with less unevenness in thickness.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective from the viewpoint of uniformity of the thickness of the coating film or liquid-saving property, and the solubility in the lens composition is also good.

Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014/017669), etc. The surfactants described in paragraphs 0117 to 0132 of 2011-132503 are incorporated in this specification. Examples of commercially available products of fluorine-based surfactants include Magaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, and MFS. -330 (above, made by DIC CORPORATION), Fluorad FC430, FC431, FC171 (above, made by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.), etc.

In addition, as the fluorine-based surfactant, an acrylic compound can be preferably used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom. When heated, a part of the functional group containing a fluorine atom is broken and the fluorine atom is volatilized. . Examples of such fluorine-based surfactants include Magaface DS series manufactured by DIC CORPORATION (Chemical Industry Daily, February 22, 2016) (Nikkei Industry News, February 23, 2016), and, for example, Magaface DS-21.

In addition, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkyl ether group and a hydrophilic vinyl ether compound. Such a fluorine-based surfactant can refer to the description in Japanese Patent Laid-Open No. 2016-216602, and this content is incorporated in this specification.

關於上述的化合物的重量平均分子量，較佳為3000～50000，例如為14000。上述的化合物中，表示重複單元的比例之%為莫耳%。As the fluorine-based surfactant, a blocked polymer can also be used. For example, the compound described in JP 2011-089090 can be cited. As the fluorine-based surfactant, a fluorine-containing polymer compound can be preferably used. The fluorine-containing polymer compound contains: repeating units derived from a (meth)acrylate compound having a fluorine atom; and from having more than 2 ( It is preferably 5 or more) repeating units of the (meth)acrylate compound of the alkoxy group (preferably the ethoxy group and the propylene group). As the fluorine-based surfactant used in the present invention, the following compounds are also exemplified. [Chemical Formula 19]

The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above-mentioned compounds,% representing the ratio of repeating units is mole %.

In addition, as the fluorine-based surfactant, a fluoropolymer having an ethylenically unsaturated bond group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Laid-Open No. 2010-164965, for example, Magaface RS-101, RS-102, RS-718K, RS- manufactured by DIC CORPORATION 72-K etc. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

Examples of nonionic surfactants include glycerin, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerin propoxylates, glycerin ethoxylates) Etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate Ester, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904 , 150R1 (manufactured by BASF), SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Corporation), PIONIN D-6112, D-6112-W, D-6315 (Manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Examples of silicone surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, BYK Chemie GmbH), etc.

The content of the surfactant in the total solid content of the lens composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In two or more cases, the total amount is preferably within the above range.

＜＜Other additives＞＞ Various additives such as fillers, adhesion promoters, antioxidants, and anti-agglomerating agents can be blended into the lens composition of the present invention as needed. Examples of such additives include those described in paragraphs 0155 to 0156 of Japanese Patent Laid-Open No. 2004-295116, and the contents are incorporated in this specification. In addition, as the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, a compound described in paragraph 0044 of Japanese Patent Laid-Open No. 2011-090147), and a sulfide compound can be used. Examples of commercially available products include Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330 manufactured by ADEKA CORPORATION Wait). In addition, as the antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600, the antioxidant described in International Publication No. 2017/164024, and Japanese Patent No. 6268967 0023- The antioxidant described in paragraph 0048. Only one type of antioxidant may be used, or two or more types may be used. In addition, the lens composition of the present invention may contain a latent antioxidant as needed. As a latent antioxidant, a compound in which a part functioning as an antioxidant is protected by a protecting group, and the protecting group is heated at 100 to 250°C or at 80 to 200°C in the presence of an acid/base catalyst A compound that is heated to be detached and functions as an antioxidant. As specific examples of the latent antioxidant, the compounds described in International Publication No. WO2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Publication No. 2017-008219 can be cited. Examples of commercially available products include ADEKAARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Furthermore, the lens composition of the present invention can contain the sensitizer or light stabilizer described in paragraph 0078 of Japanese Patent Laid-Open No. 2004-295116, and the heat described in paragraph 0081 of Japanese Patent Laid-Open No. 2004-295116 Polymerization inhibitor.

It is preferable that the lens composition of the present invention does not substantially contain color colorants and black colorants. The case where the composition for lenses of the present invention does not substantially contain a color colorant and a black colorant means that the total content of the color colorant and black colorant is 0.1% by mass or less in the total solid content of the lens composition, 0.05 Mass% or less is preferable, 0.01 mass% or less is even more preferable, and no content is particularly preferable. In addition, the color colorant mentioned here does not contain the said white pigment.

The viscosity (25°C) of the lens composition of the present invention is preferably from 1.5 to 10 mPa･s. The lower limit is preferably 2.0 mPa･s or more, and more preferably 2.5 mPa･s or more. The upper limit is preferably 9.5 mPa･s or less, and more preferably 9.0 mPa･s or less. As long as the viscosity is within the above range, the coatability is excellent.

The solid content concentration of the lens composition of the present invention is preferably 15 to 50% by mass. The lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more. The upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less. As long as the solid content concentration is within the above range, it is easy to produce a lens with wrinkles or voids suppressed.

Regarding the lens composition of the present invention, the content of the free metal that is not bonded or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. good. According to this aspect, it is possible to expect the improvement of the spectroscopic characteristics accompanying the stabilization of the pigment dispersion (agglomeration inhibition), the improvement of the dispersibility, the stabilization of the curable component, or the change in the conductivity accompanying the elution of metal atoms/metal ions. The effect of the suppression, the improvement of display characteristics and so on. In addition, Japanese Patent Laid-Open No. 2012-153796, Japanese Patent Laid-Open No. 2000-345085, Japanese Patent Laid-Open No. 2005-200560, Japanese Patent Laid-Open No. 08-043620, Japanese Patent Laid-Open No. 2004-145078, Japanese Patent Application Publication No. 2014-119487, Japanese Patent Application Publication No. 2010-083997, Japanese Patent Application Publication 2017-090930, Japanese Patent Application Publication 2018-025612, Japanese Patent Application Publication 2018-025797, Japanese Patent Application 2017- Effects described in 155228, JP-A-2018-036521, etc. Examples of the above-mentioned free metal include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi, etc. In addition, regarding the lens composition of the present invention, the content of free halogen that is not bonded or coordinated with the pigment or the like is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less, and does not substantially contain It is especially good. Examples of methods for reducing free metals or halogens in the composition include methods such as washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resin.

It is also preferable that the composition for lenses of the present invention does not contain terephthalate.

<Storage container> The container for the lens composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of preventing impurities from being mixed into the raw material or the lens composition, it is preferable to use a multi-layer bottle composed of 6 kinds of 6-layer resins or a bottle with 6 kinds of resins having a 7-layer structure. Examples of such containers include those described in Japanese Patent Laid-Open No. 2015-123351.

<Manufacturing method of lens composition> The lens composition of the present invention can be produced by mixing the aforementioned components. When manufacturing a composition for a lens, all components can be dissolved and/or dispersed in a solvent at the same time to manufacture the composition for a lens, or each component can be appropriately set to two or more solutions or dispersions as needed. At the time (at the time of coating), these are mixed to produce a lens composition.

In addition, when manufacturing a composition for a lens, a process of dispersing particles such as pigments may be included. In the process of dispersing the pigment, examples of the mechanical force for dispersing the pigment include compression, pressing, impact, shearing, and cavitation. Specific examples of such processes include bead mills, sand mills, roller mills, ball mills, paint shakers, microfluidizers, high-speed impellers, and sand mills. Flow jet mixer, high-pressure wet micronization, ultrasonic dispersion, etc. In addition, in the pulverization of the pigment in the sand mixer (bead mill), it is preferable to perform the treatment under the condition that the pulverization efficiency is improved by using beads having a small diameter and increasing the filling rate of the beads. In addition, it is preferable to remove coarse particles by filtration, centrifugal separation, etc. after the pulverization treatment. In addition, the process and the dispersing machine for dispersing the pigment can use "Dispersion Technology Encyclopedia, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Suspension (solid/liquid dispersion system) as the center Practical comprehensive data set of decentralized technology and industrial applications, issued by the Publishing Department of the Management Development Center, October 10, 1978, and the process and decentralized machine described in paragraph 0022 of Japanese Patent Laid-Open No. 2015-157893. In addition, in the process of dispersing the pigment, the particles can be refined by a salt milling step. For materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in Japanese Patent Laid-Open Nos. 2015-194521 and 2012-046629 can be referred to.

When manufacturing a composition for a lens, it is preferable to filter the composition for a lens with a filter for the purpose of removing foreign substances or reducing defects. The filter can be used without particular limitation as long as it is a filter that has always been used for filtering purposes. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) Filters of materials such as density and ultra-high molecular weight polyene resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be more reliably removed. For the pore size value of the filter, refer to the nominal value of the filter manufacturer. As the filter, various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon micro squirrel Co., Ltd.) and KITZMICROFILTER CORPORATION can be used.

In addition, it is also preferable to use a fibrous filter material as a filter. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD.

When using filters, you can also combine different filters (for example, the first filter and the second filter, etc.). At this time, the filtering by each filter may be performed only once, or may be performed twice or more. Furthermore, filters with different pore sizes can be combined within the above range. In addition, the filtration by the first filter is performed only on the dispersion liquid, and after the other components are mixed, the filtration can also be performed by the second filter.

<Lens> The lens of the present invention is a lens obtained from the above-mentioned lens composition of the present invention. The maximum absorbance of the lens of the present invention at a wavelength of 400 to 700 nm is preferably 0.05 or less, more preferably 0.04 or less, and even more preferably 0.03 or less. In addition, the lens of the present invention preferably has a light transmittance of 90% or more at a wavelength of 400 to 700 nm, more preferably 91.5% or more, and further preferably 93% or more. In addition, the lens of the present invention preferably has a refractive index of 1.5 or more for light having a wavelength of 550 nm, more preferably 1.52 or more, and further preferably 1.54 or more. The upper limit is preferably 2.0 or less, and more preferably 1.85 or less.

As the lens shape, various shapes derived from the design of the optical system can be adopted, and for example, a convex shape, a concave shape, etc. may be mentioned. For example, by setting it to a concave shape (concave lens), it is easy to improve the light condensing property.

The radius of curvature of the lens is preferably within a range that exhibits the desired effect, and is not particularly limited.

The thickness of the lens is preferably 0.5 to 3.0 μm. The upper limit is preferably 2.5 μm or less, and more preferably 2.0 μm or less. The lower limit is preferably 0.7 μm or more, and more preferably 0.9 μm or more. Here, the thickness of the lens refers to the thickness of the thickest part of the lens. For example, in the case of a lenticular lens, it means the distance from the vertex of one convex surface to the vertex of the other convex surface.

The lens of the present invention is provided on a display device having a color filter and used for transmitting the light path of the color filter. The lens of the present invention may be disposed on the side of incident light incident on the color filter, or may be disposed on the side of incident light emitted from the color filter. When provided on the side of the incident light incident on the color filter, the amount of light condensed on the color filter can be increased. In addition, when it is provided on the light emitting side emitted from the color filter, the amount of light condensed on the display can be increased. In addition, the lens of the present invention may directly contact the color filter, or another layer such as an adhesion layer or a planarization layer may be provided between the lens of the present invention and the color filter. In addition, the lens of the present invention can also be arranged and used as described in International Publication No. 2018/135189.

Examples of the display device using the lens of the present invention include organic electroluminescence display devices and liquid crystal display devices. Organic electroluminescence display devices are preferred.

<Manufacturing method of lens> Next, the method of manufacturing the lens of the present invention will be described. The method for manufacturing a lens of the present invention includes the steps of coating the above-mentioned lens composition of the present invention on a support to form a composition layer, and processing the composition layer into a lens shape.

In the method of manufacturing a lens of the present invention, it is preferable to perform at all the steps at a temperature of 150° C. or lower, more preferably at a temperature of 120° C. or lower, and further preferably at a temperature of 100° C. or lower. By manufacturing the lens in this way, it is possible to suppress heating shrinkage of the film and easily form a lens with less wrinkles or less voids. Furthermore, it is possible to reduce the damage to the support by heat. In particular, organic light-emitting layers such as organic electroluminescent elements tend to have low heat resistance, and hardening treatment is performed at a low temperature of 150° C. or lower (preferably 120° C. or lower), thereby reducing heat damage to the organic light-emitting layer .

(Steps to form the composition layer) Next, each step will be described. In the step of forming a composition layer, the composition for a lens of the present invention is used to form a composition layer on a support. Examples of the support include glass substrates, polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamidoimide substrates, and polyimide substrates. An organic light emitting layer can be formed on these substrates. In addition, a color filter may be further formed on the organic light-emitting layer. In addition, the substrate or the color filter may be provided with an undercoat layer in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface.

As a coating method of the lens composition, a known method can be used. For example, drop method (drop cast); slit coating method; spray coating method; roll coating method; spin coating method (spin coating method); cast coating method; slit spin coating method; pre Wet method (for example, the method described in Japanese Patent Laid-Open No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), nozzle jetting, etc. discharge system printing, flexographic printing, screen printing , Gravure printing, reverse offset printing, metal mask printing and other printing methods; transfer method using molds, etc.; nano imprint method. The application method using inkjet is not particularly limited, and for example, "Extended･Usable inkjet-Infinite possibilities visible in patents -, issued February 2005, SBRESEARCH CO., LTD." The method shown (especially 115 pages to 133 pages) or, JP 2003-262716, JP 2003-185831, JP 2003-261827, JP 2012-126830, The method described in Japanese Unexamined Patent Publication No. 2006-169325. In addition, regarding the application method of the curable composition, the descriptions in International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in this specification.

The composition layer formed on the support can also be dried (pre-baked). In the case of pre-baking, the pre-baking temperature is preferably 100°C or lower, more preferably 90°C or lower, further preferably 80°C or lower, and particularly preferably 70°C or lower. The lower limit can be set to 40° C. or higher, for example. The pre-baking time is preferably 10 to 3600 seconds. The pre-baking can be performed using a hot plate, an oven, or the like.

(Steps of processing into lens shape) As a method of processing the composition layer into a lens shape, a conventionally known processing method can be used. For example, it can be manufactured using a transfer method, an imprint method, a heat sagging method, or the like. Among them, the transfer method is preferable from the viewpoint of easy control of the lens shape and the like.

In the transfer method, the composition layer formed on the support can be hardened to form a hardened material layer, a photoresist layer is formed on the hardened material layer, and the photoresist layer pattern is formed into a lens shape, and The patterned photoresist layer is used as a mask to dry-etch the hardened material layer, and the lens shape is transferred onto the hardened material layer for manufacturing. In addition, as for the manufacturing method of the lens using the transfer method, Japanese Patent Application Publication No. 2006-073605, Japanese Patent Application Publication No. 2006-190903, Japanese Patent Application Publication No. 2008-281414, Japanese Patent Application Publication No. 2014-029524 can also be used. The methods described in the Japanese Patent Gazette, etc. are incorporated into this specification.

In the imprint method, it is possible to press a mold having a pattern on a composition layer formed on a support body to sandwich the composition layer between the mold and the support body, in a state where the composition layer is sandwiched between the mold and the support body After exposing and hardening the composition layer, the mold is peeled off from the support to manufacture.

In the heat sinking method, the composition layer formed on the support is hardened to form a hardened material layer, and the hardened material layer is heated to thermally sink the surface of the hardened material layer, whereby the hardened material layer can be processed Into a lens shape.

In the step of processing into a lens shape, the step of exposing the composition layer is preferable. This makes it possible to harden the composition layer of the exposed portion. Exposure is used as a hardening treatment of the composition layer. Regarding the exposure, the composition layer is preferably irradiated with radiation. Examples of radiation include g-rays and i-rays. In addition, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc. KrF line (wavelength 248 nm) is preferred. In addition, a long-wavelength light source of 300 nm or more can also be used.

In addition, during exposure, light may be continuously irradiated for exposure, or may be irradiated in a pulse manner for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light is irradiated repeatedly and stopped to stop exposure in a short time (for example, below a millisecond level). In the case of pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, and can be set to 1 femtosecond (fs) or more, and can also be set to 10 femtoseconds or more. The frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and further preferably 10 kHz or less. The maximum instantaneous illuminance is preferably 50000000W/m ² or more, more preferably 100000000W/m ² or more, and further preferably 200000000W/m ² or more. Furthermore, the upper limit of the maximum instantaneous illuminance is preferably 1000000000W/m ² or less, more preferably 800000000W/m ² or less, and further preferably 500000000W/m ² or less. Furthermore, the pulse width refers to the time that the light in the pulse period is irradiated. Also, frequency refers to the number of pulse cycles per second. Also, the maximum instantaneous illuminance refers to the average illuminance during the time irradiated by the light in the pulse period. In addition, the pulse period means a period in which one cycle of irradiation and stop of light in pulse exposure is made.

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ^{2, and more} preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected. In addition to being performed in the atmosphere, for example, it can be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (eg, 15% by volume, 5% by volume, or substantially oxygen-free) Exposure can also be performed in a high oxygen environment with an oxygen concentration greater than 21% by volume (eg 22% by volume, 30% by volume or 50% by volume). In addition, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m ² to 100,000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² , and 35000 W/m ² ). The oxygen concentration and the exposure illuminance can be appropriately combined. For example, the oxygen concentration can be 10% by volume and the illuminance is 10,000 W/m ² , the oxygen concentration is 35% by volume and the illuminance is 20,000 W/m ^2, or the like.

In the exposure process of the composition layer, the composition layer may be exposed in a pattern. For example, by using a step exposure machine, a scanning exposure machine, or the like, and exposing the composition layer through a mask having a predetermined mask pattern, it can be exposed in a pattern. With this, the composition layer of the exposed portion can be selectively hardened. Furthermore, by developing and removing unexposed portions of the composition layer, a pattern can be formed. Regarding development, the unexposed portion of the composition layer can be removed using a developer. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal property, the following steps may be repeated several times, that is, the developer solution is shaken every 60 seconds and the developer solution is further supplied again. Examples of the developing solution include organic solvents and alkaline developing solutions. As the alkaline developing solution, an alkaline aqueous solution obtained by diluting the alkaline agent with pure water is preferred. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diethylene glycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, Organic basic compounds such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, Inorganic basic compounds such as sodium metasilicate. Regarding the alkali agent, a compound with a large molecular weight is preferable in terms of environment and safety. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferred. From the viewpoint of convenience in transportation and storage, the developer can also be temporarily made into a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and it can be set in the range of 1.5 to 100 times, for example. Moreover, it is also preferable to wash (rinse) with pure water after development. In addition, regarding the rinsing, it is preferable to rotate the support body on which the composition layer after development is formed, and supply the rinsing liquid to the composition layer after development. Furthermore, it is also preferable to move the nozzle that discharges the rinse liquid from the center of the support to the peripheral edge of the support. At this time, when moving from the center portion of the support body of the nozzle to the peripheral portion, it is possible to move the nozzle while gradually reducing the moving speed of the nozzle. By performing rinsing in this way, the in-plane deviation of rinsing can be suppressed. In addition, the same effect can be obtained by moving the nozzle from the center portion of the support body to the peripheral edge portion and gradually reducing the rotation speed of the support body.

The heat treatment (post-baking) may be carried out after exposure (in the case of development, after development and drying). The heating temperature is preferably 100 to 150°C, and more preferably 100 to 120°C. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, 300 minutes or less is preferable. It is also preferable to perform post-baking in an inert gas environment. According to this aspect, it is possible to perform thermal polymerization at a very high efficiency without being affected by oxygen, even when the lens is manufactured at a temperature of 150° C. or less (preferably 120° C. or less) throughout all steps. A lens with excellent characteristics such as solvent resistance. Examples of the inert gas include nitrogen, argon, and helium, and nitrogen is preferred. The oxygen concentration during post-baking is preferably 100 ppm or less.

In the present invention, the step of processing into a lens shape includes the step of irradiating the composition layer with light having a wavelength of more than 350 nm and less than 380 nm at an exposure amount of 1 J/cm ² or more. By performing exposure in this way, the composition layer can be sufficiently hardened, and even if the lens is manufactured at a temperature of 150° C. or less throughout all steps, a lens with excellent characteristics such as solvent resistance can be manufactured.

In the present invention, the step of processing into a lens shape includes irradiating the composition layer with light having a wavelength exceeding 350 nm and 380 nm or less (hereinafter, also referred to as exposure 1), and further irradiating light with a wavelength of 254 to 350 nm to perform exposure ( Hereinafter, the step also referred to as exposure 2) is also preferred. With this aspect, the composition layer can be sufficiently hardened, and even when the lens is manufactured at a temperature of 150° C. or less throughout all steps, a lens with excellent characteristics such as solvent resistance can be manufactured.

When forming a pattern, the composition layer is irradiated with light having a wavelength exceeding 350 nm and 380 nm or less to be exposed in a pattern (exposure 1), the composition layer after exposure 1 is developed, and the composition layer after development is irradiated with a wavelength of 254 to Exposure with 350 nm light (exposure 2) is preferred. By exposing the composition layer in two stages before development and after development, the composition can be properly hardened by the first exposure (exposure before development), and the whole composition can be utilized by the next exposure (exposure after development) Almost completely hardened. As a result, the composition can be sufficiently cured under low-temperature conditions, and a pattern excellent in solvent resistance, adhesion, and rectangularity can be formed.

The light used in exposure 1 is light with a wavelength exceeding 350 nm and less than 380 nm, light with a wavelength of 355 to 370 nm is preferred, and i-line is more preferred. The irradiation amount (exposure amount) is, for example, preferably 30 to 1500 mJ/cm ² , and more preferably 50 to 1000 mJ/cm ² . The oxygen concentration at the time of exposure can be appropriately selected.

The light used in exposure 2 is light with a wavelength of 254 to 350 nm, and light with a wavelength of 254 nm is more preferable. The exposure 2 can be performed using, for example, an ultraviolet photoresist curing device. For example, the ultraviolet photoresist curing device may irradiate light with a wavelength of 254 to 350 nm and other light (for example, i-rays). The difference between the wavelength of light used in exposure 1 and the wavelength of light used in exposure 2 is preferably 200 nm or less, and more preferably 100 to 150 nm. The exposure amount (exposure amount) in exposure ² is preferably 30 to 4000 mJ/cm ² , and more preferably 50 to 3500 mJ/cm ² . The oxygen concentration at the time of exposure can be appropriately selected.

<Display device> The display device of the present invention includes the lens and color filter of the present invention described above. Furthermore, in the display device of the present invention, the lens is provided on the optical path of the light transmitted through the color filter. The color filter may include a filter having one or more colored pixels such as red pixels, blue pixels, green pixels, cyan pixels, magenta pixels, and yellow pixels. Specific examples of the color filter include a filter having at least red pixels, blue pixels, and green pixels, or a filter having at least cyan pixels, magenta pixels, and yellow pixels. The color filter can be manufactured using a coloring composition containing color colorants. Regarding the display device of the present invention, the color filter included in the display device has pixels of a plurality of colors, and it is preferable to form the lens of the present invention on the optical path of at least a part of the pixels of the pixels. The color filter may have a structure in which each colored pixel is filled in a space partitioned by a partition into, for example, a lattice shape. In this case, the partition wall preferably has a low refractive index with respect to each colored pixel. In addition, the partition wall may be formed with the structure described in US2018/0040656. As a display device, a liquid crystal display device, an organic electroluminescence display device, etc. are mentioned. The definition of the display device and the details of each image display device are described in, for example, "Electronic Display Equipment (Showa Sasaki, Kogyo Chosakai Publishing Co., Ltd. issued in 1990)", "Display Equipment (Ibuki Shunzhang, Sangyo-Tosho Publishing Co. Ltd., issued in 1989)", etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Editor Uchida Ryuo, Kogyo Chosakai Publishing Co., Ltd., issued in 1994)." The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "new generation liquid crystal display technology".

The organic electroluminescence display device may be a light source composed of white organic electroluminescence elements. As a white organic electroluminescent element, a tandem structure is preferred. The series structure of organic electroluminescent elements is described in Japanese Patent Application Laid-Open No. 2003-045676, oversight by Mikami Akira, "Forefront of organic EL technology development-high brightness, high precision, long life, and technical know-how -" , Technical Information Association, 326-328 pages, 2008, etc. Regarding the spectrum of the white light emitted by the organic EL element, it is better to have a strong maximum emission peak in the blue region (430 nm-485 nm), green region (530 nm-580 nm), and yellow region (580 nm-620 nm). In addition to these luminescence peaks, it is better to further have a very large luminescence peak in the red region (650 nm-700 nm). [Example]

The present invention will be specifically described below with examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Preparation of pigment dispersion> (Pigment dispersion T1) Using the Ultra Apex Mill (product name) manufactured by Kotobuki Industries Co., Ltd. as a circulation type dispersing device (bead mill), the mixed liquid of the following composition A was subjected to dispersion treatment as follows to prepare a pigment dispersion liquid T1.

･丙二醇單甲醚乙酸酯（PGMEA）……71.1質量份(Composition A) ･White pigment (using aluminum hydroxide (Al(OH) ₃ ), amorphous silicon dioxide (SiO ₂ ) and stearic acid (C ₁₇ H ₃₅ COOH) surface treatment agent for titanium dioxide Particle surface-treated particles (containing 75% by mass or more of titanium dioxide, less than 15% by mass of aluminum hydroxide, less than 5% by mass of amorphous silicon dioxide, and less than 10% by mass of stearic acid) 、Average primary particle size 40nm)……22.8 parts by mass ･dispersant (resin of the following structure, acid value = 50mgKOH/g, weight average molecular weight = 10,000, the value appended to the main chain is mole ratio, appended to the side chain The value is the number of repeating units)...6.1 parts by mass [Chemical formula 20]

･Propylene glycol monomethyl ether acetate (PGMEA)……71.1 parts by mass

The dispersing device was operated under the following conditions. ･Bead diameter: 0.05mm diameter ･Bead filling rate: 75% by volume ･Circumferential speed: 8m/sec ･Pump supply: 10Kg/hour ･Cooling water: tap water ･Inner volume of circular path of bead mill: 0.15L ･Dispersed mixed liquid volume: 0.44kg

･矽烷偶合劑1（KBM-602、Shin-Etsu Chemical Co., Ltd.製）……0.175質量份 ･PGMEA……28.25質量份<Preparation of Lens Composition> (Example 1) After mixing and stirring the raw materials shown below, a nylon filter (manufactured by NIHON PALL LTD.) with a pore size of 0.45 μm was used for filtration to prepare a lens composition. ･Photopolymerization initiator A1 (Initiator 1)... 1.75 parts by mass ･Photopolymerization initiator A2 (Initiator 4)... 1.41 parts by mass ･Resin (40 mass% PGMEA solution of Resin 1)... 39.54 parts by mass･polymerizable monomer M1……28.84 parts by mass･polymerization inhibitor 1 (p-methoxyphenol)……0.008 parts by mass･surfactant 1 (compound of the following structure, Mw=14000, indicating repeating unit The value of% of the ratio is mole %)...0.021 parts by mass [Chemical formula 21]

･Silane coupling agent 1 (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.)……0.175 parts by mass･PGMEA……28.25 parts by mass

(Examples 2-15, 17-33, Comparative Example 1) In addition to changing the type and content of the photopolymerization initiator, the type of resin, the type of polymerizable monomer, the type of solvent, and the total solid content of the lens composition as described in the following table, The lens composition was prepared in the same manner as in Example 1. Furthermore, the total solid content of the lens composition was adjusted by changing the blending amount of the solvent.

(Example 16) After mixing and stirring the raw materials shown below, it was filtered with a nylon filter (manufactured by NIHON PALL LTD.) with a pore size of 0.45 μm to prepare a lens composition. ･Pigment dispersion T1……69.29 parts by mass･Photopolymerization initiator A1 (Initiator 1)……1.75 parts by mass･Photopolymerization initiator A2(Initiator 4)……1.41 parts by mass･Resin (resin 1 40% by mass PGMEA solution)... 9.29 parts by mass ･polymerizable monomer M1… 14.52 parts by mass ･polymerization inhibitor 1 …0.008 parts by mass ･surfactant 1 …0.021 parts by mass ･silane coupling agent 1… …17.5 parts by mass･PGMEA……3.57 parts by mass [Table 1]

The numerical value described in the content column of the above table is a value of the content (mass %) of the photopolymerization initiator A1 or the photopolymerization initiator A2 in the total solid content of the lens composition.

(Photopolymerization initiator) ･Initiator 1: IRGACURE-OXE01 (manufactured by BASF, the compound of the following structure, the absorption coefficient at a wavelength of 365 nm in methanol is 6969mL/gcm. It is measured by the following method The maximum absorbance of the starting agent coating film is 0.01.) ･Initiator 2: IRGACURE-OXE02 (made by BASF Corporation, the compound of the following structure, the absorption coefficient at a wavelength of 365 nm in methanol is 7749 mL/gcm. The maximum absorbance of the initiator-coated film measured by the following method is 0.01.) ･Initiator 3: The compound of the following structure (absorption coefficient of light with a wavelength of 365 nm in methanol is 18900 mL/gcm. Use The maximum absorbance of the initiator-coated film measured by the following method is 0.02.) ･Initiator 4: IRGACURE-2959 (manufactured by BASF, compound of the following structure, absorbance at a wavelength of 365 nm in methanol The coefficient is 48.93mL/gcm, and the absorption coefficient at a wavelength of 254nm is 3.0×10 ⁴ mL/gcm. The maximum absorbance of the starter coating film measured by the following method is 0.005.) ･Initiator 5: IRGACURE-184 (manufactured by BASF, the compound of the following structure, the absorption coefficient in methanol at a wavelength of 365nm is 88.64mL/gcm, and the absorption coefficient at a wavelength of 254nm is 3.3×10 ⁴ mL/gcm. Use the following method The maximum absorbance of the measured starter coating film is 0.004.) ･Initiator 6: compound of the following structure (absorption coefficient of light with a wavelength of 365 nm in methanol is 13200 mL/gcm. Use the following method The maximum absorbance of the measured starter coating film is 0.13.) [Chemical Formula 22]

M2：ARONIX M-309（TOAGOSEI CO., LTD.製、三羥甲基丙烷三丙烯酸酯） M3：ARONIX M-310（TOAGOSEI CO., LTD.製、三羥甲基丙烷聚氧丙烯改質三丙烯酸酯） M4：ARONIX M-350（TOAGOSEI CO., LTD.製、三羥甲基丙烷聚氧乙烯改質三丙烯酸酯） M5：ARONIX M-408（TOAGOSEI CO., LTD.製、二三羥甲基丙烷四丙烯酸酯）(Polymerizable monomer) M1: Compound of the following structure [Chemical Formula 23]

M2: ARONIX M-309 (manufactured by TOAGOSEI CO., LTD., trimethylolpropane triacrylate) M3: ARONIX M-310 (manufactured by TOAGOSEI CO., LTD., trimethylolpropane polyoxypropylene modified three Acrylate) M4: ARONIX M-350 (manufactured by TOAGOSEI CO., LTD., trimethylolpropane polyoxyethylene modified triacrylate) M5: ARONIX M-408 (manufactured by TOAGOSEI CO., LTD., ditrihydroxy) Methyl propane tetraacrylate)

(Resin) Resin 1: Resin of the following structure (Mw=11000, acid value=31.5mgKOH/g, the value appended to the main chain is the molar ratio.) [Chemical Formula 24]

Resin 2: Resin synthesized by the following method 70.0 parts by mass of cyclohexanone was put into a separable 4-neck flask equipped with a thermometer, cooling tube, nitrogen introduction tube, dropping tube and stirring device, and the temperature was raised to 80°C. After replacing the flask with nitrogen, the drop tube After 2 hours, 13.3 parts by mass of n-butyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, 4.3 parts by mass of methacrylic acid, and cumylphenol ethylene oxide modified acrylate (TOAGOSEI CO. , LTD., ARONIX M110) 7.4 parts by mass and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts by mass. After the dropwise addition, the reaction was further continued for 3 hours to obtain a 30% by mass solution of Resin 2 (Mw=26000).

Resin 3: Resin synthesized by the following method 90.0 parts by mass of propylene glycol monomethyl ether acetate was added to a reaction vessel equipped with a stirrer, thermometer, dropping device, return flow cooler, and gas introduction tube, and heated to 60°C while injecting nitrogen gas into the vessel, and the same temperature was passed for 2 hours 50.0 parts by mass of furfuryl methacrylate, 26.7 parts by mass of 2-methacryl oxyethyl succinic acid, 23.3 parts by mass of hydroxyethyl 2-methacrylate, 2,2'-azobis (2,4 -Dimethylvaleronitrile) 2.5 parts by mass of the mixture was polymerized. After completion of the dropwise addition, after further reacting at 60° C. for 1 hour, 0.5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) was added and dissolved in propylene glycol monomethyl ether acetate 10.0 parts by mass After obtaining the portion, the copolymer was continuously stirred at the same temperature for 3 hours. After cooling to room temperature, a 20% by mass solution of resin 3 (Mw=52000) was obtained by dilution with propylene glycol monomethyl ether acetate.

Resin 4: Resin of the following structure (Mw=30000, the value appended to the main chain is the molar ratio.) [Chemical Formula 25]

Resin 5: resin synthesized by the following method 90.0 parts by mass of propylene glycol monomethyl ether acetate was added to a reaction vessel equipped with a stirrer, thermometer, dropping device, return flow cooler, and gas introduction tube, and heated to 60°C while injecting nitrogen gas into the vessel, and the same temperature was passed for 2 hours A mixture of 35.0 parts by mass of glycidyl methacrylate, 45.0 parts by mass of methyl methacrylate, and 2.5 parts by mass of 2,2'-azobisisobutyronitrile was added to perform a polymerization reaction. After the end of the dropwise addition, after further reacting at 60°C for 1 hour, add 0.5 parts by mass of 2,2'-azobisisobutyronitrile to 10.0 parts by mass of propylene glycol monomethyl ether acetate, and then add the same The stirring was continued for 3 hours at the temperature to obtain the copolymer. Next, dry air was injected into the reaction vessel, 10.0 parts by mass of acrylic acid, 30.2 parts by mass of propylene glycol monomethyl ether acetate, 1.30 parts by mass of dimethylbenzylamino group, and 0.26 parts by mass of methoquinone were heated to 100 The stirring was continued for 20 hours at ℃, and the acid value was measured to confirm that the target product was produced. Further, 10.0 parts by mass of tetrahydrophthalic anhydride and 27.7 parts by mass of propylene glycol monomethyl ether acetate were continuously added to the reaction vessel, and after stirring at 60°C for 3 hours, after cooling to room temperature, propylene glycol monomethyl ether acetate was used. By dilution, a 20% by mass solution of resin 5 (Mw=12000) was obtained.

(Solvent) PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether

[Measurement of absorbance of starter coating film] Starter composition 1 was prepared by mixing 1 part by mass of initiator 1, 47.5 parts by mass of resin and 51.5 parts by mass of PGMEA. Resin P1: propylene glycol monomethyl ether acetate solution of benzyl methacrylate/methacrylic acid (=70/30 [mol ratio]) copolymer (solid content 40% by mass, weight average molecular weight 30000, FUJIKURA KASEI CO. , Manufactured by LTD., Acrybase FF-187)

The starter compositions 2 to 6 were prepared in the same manner as the starter composition 1 except that the starters 2 to 6 were used instead of the starter 1.

Using a spin coater, each starter composition was applied to a glass substrate so that the film thickness after pre-baking became 2.0 μm, and a 120-second heating process was performed using a 100°C hot plate (pre-baking) grilled). Regarding the obtained cured film, the absorbance of light in the wavelength range of 400 to 700 nm was measured with a spectrophotometer (reference: glass substrate) of ultraviolet-visible-near infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation).

<Evaluation> (Absorbance and refractive index) Using a spin coater, each lens composition was applied on a glass substrate so that the film thickness after pre-baking became 2.0 μm, and a 120° C. hot plate was used for 120 Heat treatment in seconds (pre-bake). Next, the i-ray was irradiated with an exposure amount of 100 mJ/cm ² using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.). Next, using an ultraviolet photoresist curing device (UMA-802-HC-552; manufactured by USHIO INC.), exposure was performed at an exposure amount of 3000 mJ/cm ² to produce a cured film. Regarding the obtained cured film, the absorbance of light in the wavelength range of 400 to 700 nm was measured with a spectrophotometer (reference: glass substrate) of ultraviolet-visible-near infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation). The smaller the absorbance, the better the visible transparency. The evaluation criteria of absorbance are as follows. AA: The maximum value of absorbance over the entire wavelength range of 400 to 700 nm is less than 0.03. A: The maximum value of absorbance in the entire range of wavelengths from 400 to 700 nm is 0.03 or more and less than 0.04. B: The maximum value of absorbance in the entire range of wavelengths from 400 to 700 nm is 0.04 or more and less than 0.05. C: The maximum value of absorbance in the entire range of wavelengths from 400 to 700 nm is 0.05 or more. Further, regarding the obtained cured film, the refractive index of light at a wavelength of 550 nm was measured using an ellipsometer manufactured by JA Woollam Japan Co., Inc.

(Solvent resistance) Regarding the obtained cured film, after dropping N-methylpyrrolidone (NMP), it was left for 200 seconds and rinsed with running water for 10 seconds to perform a solvent resistance test. The thickness of the film before and after the solvent resistance test was measured, and the residual film ratio was measured to evaluate the solvent resistance. The closer the residual film ratio is to 1, the better the solvent resistance. Residual film rate = thickness of cured film before and after solvent resistance test / thickness of cured film before solvent resistance test AA: The residual film ratio is 0.95 or more and 1.0 or less. A: The residual film ratio is 0.90 or more and less than 0.95. B: The residual film ratio is 0.85 or more and less than 0.90. C: The residual film rate is less than 0.85.

(Rectangularity) By spin coating, each lens composition was applied on a glass substrate so that the film thickness after pre-baking became 2.0 μm, and then a 120°C hot plate was used for heat treatment for 120 seconds. To form the composition layer. Next, using an i-line stepper exposure device, the i-line was exposed with an exposure amount of 100 mJ/cm ² through a mask formed with an island-shaped pattern of 10 μm square. Thereafter, a 0.3% by mass aqueous solution of tetramethylammonium hydroxide was used for liquid-covered development at 23° C. for 60 seconds, followed by a rinse treatment. Next, a pattern was formed by exposing (post-exposure) light with a wavelength of 254 to 350 nm at an exposure amount of 3000 mJ/cm ² . Using a length measuring SEM (scanning electron microscope), the width of the pattern formed on the glass substrate and the length of the diagonal line of the pattern were observed from directly above the glass substrate. The rectangularity was evaluated on the following criteria. The closer the value of the diagonal length of the pattern/(width of the pattern×2 ^0.5 ) to 1.0, the better the rectangularity. AA: The length of the diagonal of the pattern/(width of the pattern×2 ^0.5 ) is more than 0.95 and 1.0 or less. A: The length of the diagonal of the pattern/(width of the pattern×2 ^0.5 ) exceeds 0.90 and 0.95 or less. B: The length of the diagonal of the pattern/(width of the pattern×2 ^0.5 ) exceeds 0.80 and 0.90 or less. C: The length of the diagonal of the pattern/(width of the pattern×2 ^0.5 ) is 0.80 or less.

<Wrinkle on lens surface> Using a spin coating method, the lens composition is applied to 8 inches (20.32 cm) sprayed with hexamethyldisilazane so that the film thickness after pre-baking becomes 2.0 μm. On the silicon wafer, a 100°C hot plate was used for 120 seconds of heat treatment to form a composition layer. Next, using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.), i-rays were irradiated with an exposure amount of 100 mJ/cm ² through an island-shaped pattern mask of 100 μm square. After that, the silicon wafer on which the exposed composition layer was formed was placed on a horizontal rotary table of a rotary/spray developing machine (DW-30 type; manufactured by Chemitronics Co., Ltd.) using CD-2000 (FUJIFILM Electronic The 40% dilution of Materials Co., Ltd. was subjected to liquid-covered development at 23°C for 180 seconds. Next, the silicon wafer was fixed on a horizontal rotating table by a vacuum chuck method, the silicon wafer was rotated at 50 rpm by a rotating device, and pure water was sprayed from a spray nozzle from above the center of rotation to perform After rinsing, spin drying was performed. Next, a pattern was formed by exposure (post-exposure) using an ultraviolet photoresist curing device (UMA-802-HC-552; manufactured by USHIO INC.) at an exposure amount of 3000 mJ/cm ² . Next, a positive type photoresist (HPR-204ESZ-9-5mPa･s, manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to the obtained pattern with a dry film thickness of 0.5 μm, and heated The board was heated at 90°C for 1 minute. Then, the light transmittance of the central part of each lens is 0%. After adjusting the transmittance to a halftone mask that increases as the light transmittance increases toward the peripheral part, an i-line stepper exposure device FPA-3000i5+ is used (Manufactured by Canon Inc.) The i-ray was irradiated with an exposure of 300 mJ/cm ² . Next, using an alkaline developer (HPRD-429E, manufactured by FUJIFILM Electronic Materials Co., Ltd.), after performing liquid-covered development at room temperature for 60 seconds, it was further carried out by rotary spray using pure water Rinse for 20 seconds. Thereafter, after further washing with pure water, the substrate was dried by high-speed rotation, and further heated by a hot plate at 100° C. for 15 minutes to form a lens-shaped photoresist pattern. Using a dry etching device (manufactured by Hitachi High-Technologies Corporation: U-621), the substrate obtained as above was subjected to dry etching treatment under the following conditions, and processed into a shape that can be used as a microlens to produce a lens.

(Lens processing conditions) ･RF (radio frequency: RF) power: 800W ･Antenna bias: 100W ･Wafer bias: 500W ･Internal pressure: 0.5Pa ･Substrate temperature: 50°C ･ Mixed gas type and flow rate: CF ₄ /C ₄ F ₆ /O ₂ /Ar=175/25/50/200ml/min･Etching speed of photoresist: 140nm/min

The surface of the obtained lens was observed with an optical microscope (500 times), and the surface wrinkle was observed and evaluated according to the evaluation criteria shown below. AA: Wrinkle was not confirmed at all on the surface. A: Almost no wrinkles were observed on the surface. B: Wrinkle was slightly confirmed on the surface. C: Obvious wrinkling was observed.

[Table 2]

As shown in the above table, Examples 1 to 33 have excellent absorbance and refractive index characteristics. In particular, the evaluation of the lens surface wrinkles of Examples 1 to 16, 19, 20, and 22 to 33 was good. Furthermore, the evaluations of solvent resistance and rectangularity are both B or more. As a result of forming the lenses of Examples 1 to 33 on the surface of the color filter of the display device with the color filter and mounting it on the display device, the brightness was better than that of the display device without the lenses of Examples 1 to 33. In particular, the brightness of the display device in which the lenses of Examples 1 to 16, 19, 20, and 22 to 33 were mounted was particularly good. On the other hand, it was observed that the brightness of the display device equipped with the lens of Comparative Example 1 was lower than that of the display device without the lens.

When evaluating the wrinkle on the lens surface, the lens was manufactured by the same method and the result of the wrinkle on the lens surface was observed by the same method except that the heating plate was heated and cured at 230°C for 15 minutes instead of post-exposure. The amount of generation of wrinkles is greater than when a lens is manufactured by performing post-exposure.

Using a spin coater, the lens composition of Example 12 or Example 33 was applied on a glass substrate so that the film thickness after pre-baking became 2.0 μm, and a hot plate at 100° C. was used for 120 seconds. Heat treatment (pre-baking). Next, an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.) was used to irradiate i-line with an exposure of 3000 mJ/cm ² to produce a cured film. The solvent resistance of the obtained cured film was evaluated by the same method as described above, and the solvent resistance was all AA evaluation.

Using a spin coater, the lens composition of Example 12 or Example 33 was applied on a glass substrate so that the film thickness after pre-baking became 2.0 μm, and a hot plate at 100° C. was used for 120 seconds. Heat treatment (pre-baking). Next, i-rays were irradiated with an exposure amount of 100 mJ/cm ² using an i-line stepper exposure device FPA-3000i5+ (manufactured by Canon Inc.). Next, a 120° C. hot plate was used for heat treatment for 900 seconds to produce a cured film. The solvent resistance of the obtained cured film was evaluated by the same method as described above, and the solvent resistance was all evaluated as A.

Even if the lens composition of each embodiment is used to form a concave lens, the same effect as that of each embodiment can be obtained.

no

no

no.

Claims (22)

A lens composition for forming a lens on an optical path of a display device having a color filter that transmits light of the color filter, wherein The lens composition includes a polymerizable monomer M, a photopolymerization initiator A and a resin B, When a film with a thickness of 2 μm is manufactured using the lens composition, the maximum absorbance of the film at a wavelength of 400 nm to 700 nm is 0.05 or less, and the refractive index of light at a wavelength of 550 nm is 1.5 or more. The composition for a lens as described in item 1 of the patent application, wherein the resin B contains a resin b1 containing a repeating unit derived from a compound represented by the following formula (I),

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, R ¹⁰ represents a substituent, m represents an integer of 0 to 2, and p represents an integer of 0 or more. The lens composition as described in item 2 of the patent application scope, in which The resin b1 also contains a repeating unit derived from alkyl (meth)acrylate. The lens composition as described in item 1 or item 2 of the patent application scope, in which The photopolymerization initiator A contains an oxime compound. The lens composition according to item 1 or item 2 of the patent application scope, wherein the photopolymerization initiator A comprises: photopolymerization with an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol The initiator A1 and the photopolymerization initiator A2 having an absorption coefficient of 1.0×10 ² mL/gcm or less at a wavelength of 365 nm in methanol and an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 254 nm. The lens composition as described in item 5 of the patent application scope, in which The photopolymerization initiator A1 is an oxime compound containing fluorine atoms. The lens composition as described in item 5 of the patent application scope, in which The photopolymerization initiator A2 is a hydroxyalkyl benzophenone compound. The lens composition as described in item 5 of the patent application scope, in which It contains 50 to 200 parts by mass of the photopolymerization initiator A2 relative to 100 parts by mass of the photopolymerization initiator A1. The lens composition as described in item 5 of the patent application scope, in which The total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the lens composition is 5 to 15% by mass. The lens composition as described in item 1 or item 2 of the patent application scope, in which The polymerizable monomer M contains a compound containing three or more ethylenic unsaturated groups. The lens composition as described in item 1 or 2 of the patent application scope, which contains a silane coupling agent. The lens composition as described in item 1 or 2 of the patent application scope contains a furan-containing compound. The lens composition as described in item 12 of the patent application scope, wherein the compound containing the furan group is selected from compounds represented by the following formula (fur-1) and contains compounds derived from the following formula (fur-1) At least one of the resins of the repeating units of the compound represented,

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group. A lens obtained from the lens composition described in any one of claims 1 to 13. A method for manufacturing a lens, the method includes: The step of applying the lens composition according to any one of claims 1 to 13 on the support to form a composition layer; and The step of processing the composition layer into a lens shape. The method of manufacturing a lens as described in item 15 of the patent application scope, in which All steps are carried out at a temperature below 150°C. The method for manufacturing a lens as described in item 15 or 16 of the patent application, wherein the step of processing into the shape of the lens includes irradiating the composition layer with a wavelength of more than 350 nm and less than 380 nm at an exposure of 1 J/cm ² or more The steps of light. The method of manufacturing a lens as described in item 15 or 16 of the patent application scope, in which The step of processing into a lens shape includes the step of irradiating the composition layer with light having a wavelength exceeding 350 nm and 380 nm or less, and further irradiating light with a wavelength of 254 nm to 350 nm to perform exposure. The method of manufacturing a lens as described in item 15 or 16 of the patent application scope, in which The step of processing into a lens shape includes the step of heating the composition layer at a temperature of 100°C to 150°C for 10 minutes or more. The method of manufacturing a lens as described in item 19 of the patent application scope, in which This heating step is performed in an inert gas environment. A display device having a color filter and a lens obtained from the lens composition described in any one of claims 1 to 13 provided on the optical path of light passing through the color filter. The display device as described in Item 21 of the patent application scope is an organic electroluminescence display device.