TW202122237A - Resin lens manufacturing method using developing solution and rinsing solution, and rinsing solution - Google Patents

Resin lens manufacturing method using developing solution and rinsing solution, and rinsing solution Download PDF

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TW202122237A
TW202122237A TW109134267A TW109134267A TW202122237A TW 202122237 A TW202122237 A TW 202122237A TW 109134267 A TW109134267 A TW 109134267A TW 109134267 A TW109134267 A TW 109134267A TW 202122237 A TW202122237 A TW 202122237A
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aforementioned
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resin composition
photosensitive resin
rinsing
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TWI837425B (en
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鈴木朋哉
安達
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日商日產化學股份有限公司
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/02—Surface shaping of articles, e.g. embossing; Apparatus therefor by mechanical means, e.g. pressing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/426—Stripping or agents therefor using liquids only containing organic halogen compounds; containing organic sulfonic acids or salts thereof; containing sulfoxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Mechanical Engineering (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

To provide a resin lens manufacturing method using a developing solution and a rinsing solution that employ specific organic solvents. A resin lens manufacturing method comprising: a step for coating a support on which a pattern having an opening is formed with a negative type photosensitive resin composition; an imprinting step for bringing the negative type photosensitive resin composition and a mold having a reverse pattern of a target lens shape and a light-blocking film into contact with each other; a photocuring step for forming a photocured portion in the opening by exposing the negative type photosensitive resin composition through the mold; a mold releasing step for separating the photocured portion and the mold; a developing step for removing an uncured portion of the negative type photosensitive resin composition using a developing solution containing [gamma]-butyrolactone to expose the photocured portion and form a photocured product; a rinsing step for performing rinsing treatment using a rinsing solution containing a specific compound; a drying step for removing the rinsing solution; and a step for exposing the whole surface of the photocured product.

Description

使用顯影液及沖洗液之樹脂製透鏡的製造方法，以及該沖洗液Manufacturing method of resin lens using developer and washing liquid, and the washing liquid

本發明關於一種樹脂製透鏡之製造方法，其係使用了採用特定有機溶劑的顯影液及沖洗液。本發明進一步關於前述沖洗液。The present invention relates to a method for manufacturing a resin lens, which uses a developing solution and a rinse solution using a specific organic solvent. The present invention further relates to the aforementioned flushing liquid.

具有相機模組等的受光元件的電子裝置中，為了提升集光效率及修正光路而裝載了微透鏡及模組透鏡等的光學透鏡。另外，近年來，在LiDAR(Light Detection and Ranging)感測器及TOF(Time of Flight)感測器等的感測裝置中，以高性能化及提升精密度為目的也嘗試裝載光學透鏡。為了使光線折射、聚焦或散射，開發出了具有各種表面形狀的光學透鏡。光學透鏡依照其表面形狀可分類成球面狀透鏡、非球面狀透鏡、柱面透鏡、環形透鏡、菲涅爾透鏡、折射率分佈透鏡及繞射透鏡。另外，光學透鏡的材質可大致區別成玻璃與樹脂。近年來，用在智慧型手機及平板終端裝置等的行動終端裝置的樹脂製透鏡的需求正在增加。In electronic devices with light-receiving elements such as camera modules, optical lenses such as microlenses and module lenses are installed in order to improve the light collection efficiency and correct the optical path. In addition, in recent years, in sensing devices such as LiDAR (Light Detection and Ranging) sensors and TOF (Time of Flight) sensors, attempts have been made to mount optical lenses for the purpose of improving performance and improving precision. In order to refract, focus or scatter light, optical lenses with various surface shapes have been developed. Optical lenses can be classified into spherical lenses, aspheric lenses, cylindrical lenses, ring lenses, Fresnel lenses, refractive index distribution lenses, and diffractive lenses according to their surface shapes. In addition, the material of the optical lens can be roughly divided into glass and resin. In recent years, the demand for resin lenses used in mobile terminal devices such as smartphones and tablet terminal devices is increasing.

光學透鏡的成型方法可依照光學透鏡的材質適當地選擇。在樹脂製透鏡方面，已知有使用金屬模具(mold)的晶圓等級成型及利用光蝕刻的成型方法。晶圓等級成型是在玻璃基板等的支持體上同時形成多個微細的透鏡圖案的方法。在利用光蝕刻的成型方法的情況，一般是使用光硬化性樹脂組成物等的感光性樹脂組成物，使該感光性樹脂組成物曝光後，為了除去不需要的感光性樹脂組成物而經過利用顯影液的顯影步驟及利用沖洗液的沖洗步驟，圖案化成為目標的透鏡形狀。The molding method of the optical lens can be appropriately selected according to the material of the optical lens. Regarding resin lenses, wafer-level molding using a mold and molding methods using photolithography are known. Wafer-level molding is a method of simultaneously forming a plurality of fine lens patterns on a support such as a glass substrate. In the case of a molding method using photoetching, a photosensitive resin composition such as a photocurable resin composition is generally used. After the photosensitive resin composition is exposed, it is used to remove unnecessary photosensitive resin composition. The developing step of the developer solution and the rinsing step using the rinse solution are patterned into the target lens shape.

感光性樹脂組成物，依照該組成物中所含有的化合物的化學構造的種類，可大致區別成感光後的部分變得可溶於顯影液的正型；及感光後的部分變得不溶於顯影液的負型。負型感光性樹脂組成物，可列舉例如組成物中含有具有丙烯醯基或甲基丙烯醯基(以下在本說明書中簡稱為(甲基)丙烯醯基)的化合物的光自由基硬化型。負型感光性樹脂組成物，在使用有機溶劑的顯影步驟中，與正型感光性樹脂組成物相比，會有顯影時的溶解性對比較低的情形。According to the type of chemical structure of the compound contained in the photosensitive resin composition, it can be roughly distinguished into a positive type in which the part after exposure becomes soluble in the developing solution; and the part after exposure becomes insoluble in development Liquid negative type. The negative photosensitive resin composition includes, for example, a photo-radical curable type containing a compound having an acrylic group or a methacryl group (hereinafter referred to as a (meth)acryl group) in the composition. The negative photosensitive resin composition may have lower solubility contrast during development than the positive photosensitive resin composition in the development step using an organic solvent.

另一方面，由感光性樹脂組成物所形成的膜的膜厚是重要的因子，可依照目標用途來選擇膜厚。在光學透鏡用途的情況，通常100μm以上的膜厚是必要的，然而一般被報告出來的感光性樹脂組成物的阻劑組成物，所形成的膜的膜厚未達100μm。並無法確認有藉由包含使用有機溶劑的顯影步驟的圖案化來形成膜厚100μm以上的厚膜(透鏡圖案)的報告例。On the other hand, the film thickness of the film formed of the photosensitive resin composition is an important factor, and the film thickness can be selected according to the intended use. In the case of optical lens applications, a film thickness of 100 μm or more is usually necessary. However, it is generally reported that a resist composition of a photosensitive resin composition has a film thickness of less than 100 μm. It has not been confirmed that there is a report example in which a thick film (lens pattern) having a film thickness of 100 μm or more is formed by patterning including a development step using an organic solvent.

感光性樹脂組成物，依照目標用途，有文獻報告出各種組成物。構成感光性樹脂組成物的成分可大致區別成有機化合物與無機化合物。前述有機化合物的例子，可列舉具有(甲基)丙烯醯基的化合物，前述無機化合物的例子，可列舉氧化物微粒子。專利文獻1所記載的光硬化性組成物，是以製作光學透鏡為目的，含有經過表面修飾的二氧化矽粒子作為氧化物微粒子。For photosensitive resin compositions, various compositions have been reported in the literature according to the intended use. The components constituting the photosensitive resin composition can be roughly divided into organic compounds and inorganic compounds. Examples of the aforementioned organic compounds include compounds having a (meth)acryloyl group, and examples of the aforementioned inorganic compounds include oxide fine particles. The photocurable composition described in Patent Document 1 is for the purpose of producing an optical lens and contains surface-modified silicon dioxide particles as oxide fine particles.

然而在專利文獻1中並未揭示藉由包含使用有機溶劑的顯影步驟的圖案化來形成膜厚100μm以上的厚膜(透鏡圖案)時的課題。 [先前技術文獻] [專利文獻]However, Patent Document 1 does not disclose a problem when a thick film (lens pattern) having a film thickness of 100 μm or more is formed by patterning including a development step using an organic solvent. [Prior Technical Literature] [Patent Literature]

[專利文獻1] 國際公開第2019/142601號[Patent Document 1] International Publication No. 2019/142601

[發明所欲解決的課題][The problem to be solved by the invention]

到目前，本發明的發明人等仔細檢討了含有具有至少一個(甲基)丙烯醯基的化合物、經過表面修飾的二氧化矽粒子及光自由基聚合起始劑的負型感光性樹脂組成物藉由使用有機溶劑的顯影步驟來形成膜厚為100μm以上的厚膜(透鏡圖案)的圖案化。在前述形成膜厚為100μm以上的厚膜(透鏡圖案)的圖案化的情況，為了促進選擇性地除去未曝光部中不需要的負型感光性樹脂組成物，對該負型感光性樹脂組成物溶解性高的顯影液是適合的。So far, the inventors of the present invention have carefully reviewed a negative photosensitive resin composition containing a compound having at least one (meth)acryloyl group, surface-modified silica particles, and a photoradical polymerization initiator. The patterning of a thick film (lens pattern) having a film thickness of 100 μm or more is formed by a development step using an organic solvent. In the case of patterning of a thick film (lens pattern) with a film thickness of 100 μm or more, in order to promote the selective removal of unnecessary negative photosensitive resin composition in the unexposed area, the negative photosensitive resin composition Developers with high substance solubility are suitable.

然而逐漸知道了對前述負型感光性樹脂組成物溶解性高的顯影液會顯著滲入該負型感光性樹脂組成物的曝光部，因為光硬化後圖案的膨潤及收縮，該圖案的麓部會有發生龜裂的情形。在前述圖案的麓部發生的龜裂，在用來將該圖案裝載至電子裝置的步驟(以下稱為後製程)時，可能會成為該圖案由玻璃基板等的支持體剝離的原因，而為不佳。為了讓此龜裂不發生，若選擇對於負型感光性樹脂組成物溶解性低的顯影液，則無法將未曝光部的負型感光性樹脂組成物完全除去，會殘留成為殘渣。此殘渣在前述後製程時會由基板脫離，會成為顆粒產生的原因，故為不佳。However, it is gradually known that the developer with high solubility to the negative photosensitive resin composition will significantly penetrate into the exposed part of the negative photosensitive resin composition, and the swelling and shrinkage of the pattern after photocuring will cause the bottom of the pattern to be affected. There are cases of cracking. The cracks that occur at the foot of the aforementioned pattern may cause the pattern to peel off from a support such as a glass substrate when it is used to load the pattern into an electronic device (hereinafter referred to as a post process). Bad. In order to prevent such cracks from occurring, if a developer with low solubility for the negative photosensitive resin composition is selected, the negative photosensitive resin composition in the unexposed area cannot be completely removed, and it will remain as a residue. This residue will be detached from the substrate during the aforementioned post-processing process, and will be a cause of particle generation, so it is not good.

前述負型感光性樹脂組成物，藉由隔著光罩來曝光，會被分成感光部分的光硬化部及未感光部分(未曝光部)的未硬化部。前述光硬化部與前述未硬化部，對顯影液的溶解性會產生顯著差異，因此藉由以該顯影液來顯影，該未硬化部會選擇性地溶解。結果可由前述光硬化部形成所希望的圖案。前述所希望的圖案為光硬化物。在前述光硬化部，(甲基)丙烯醯基會以任意比例形成有機物三維交聯構造，經過表面修飾的二氧化矽粒子會在被保持在該有機物三維交聯構造中的狀態。在使用有機溶劑作為顯影液的顯影步驟中，該有機溶劑若與前述光硬化部接觸，則會滲入該光硬化部。藉由前述有機溶劑的滲入，前述有機物三維交聯構造會因為該有機溶劑的親和性而發生一定程度的膨潤。另一方面，前述經過表面修飾的二氧化矽粒子幾乎不會膨潤，因此在該經過表面修飾的二氧化矽粒子與前述有機物三維交聯構造的界面膨潤量有差異，會發生由形變所造成的應力。在此狀態下，有機溶劑由前述光硬化部中被釋放出來時，若該有機溶劑的釋放速度快，則應力的緩和趕不上前述光硬化部的形狀變化(收縮)，為了讓殘留應力發散，該光硬化部會發生龜裂。尤其於形狀急峻的圖案的麓部應力容易累積，在該圖案的麓部容易發生龜裂。The aforementioned negative photosensitive resin composition is exposed through a photomask to be divided into a light-cured part of the photosensitive part and an uncured part of the non-photosensitive part (unexposed part). The photo-hardened portion and the unhardened portion have a significant difference in solubility to the developer. Therefore, by developing with the developer, the unhardened portion is selectively dissolved. As a result, a desired pattern can be formed by the aforementioned photohardening part. The aforementioned desired pattern is a photocured material. In the aforementioned photohardening part, the (meth)acryloyl group will form an organic three-dimensional cross-linked structure at an arbitrary ratio, and the surface-modified silica particles will be kept in the organic three-dimensional cross-linked structure. In the development step using an organic solvent as a developer, if the organic solvent comes into contact with the photo-curing part, it will penetrate into the photo-curing part. Through the penetration of the organic solvent, the three-dimensional cross-linked structure of the organic substance will swell to a certain extent due to the affinity of the organic solvent. On the other hand, the aforementioned surface-modified silica particles hardly swell, so there is a difference in the amount of swelling at the interface between the surface-modified silica particles and the aforementioned three-dimensional cross-linked structure of organic substances, which may be caused by deformation. stress. In this state, when the organic solvent is released from the photo-curing part, if the release rate of the organic solvent is fast, the stress relaxation cannot keep up with the shape change (shrinkage) of the photo-curing part. Cracks may occur in the light hardened part. In particular, stress is likely to accumulate at the foot of a pattern with a sharp shape, and cracks are likely to occur at the foot of the pattern.

前述負型感光性樹脂組成物，在藉由使用有機溶劑的顯影步驟來形成膜厚為100μm以上的厚膜(透鏡圖案)的圖案化之中的課題，是抑制圖案的麓部發生龜裂與前述未硬化部產生殘渣的兩者。The problem of the negative photosensitive resin composition in the patterning of forming a thick film (lens pattern) with a film thickness of 100 μm or more by a development step using an organic solvent is to suppress the occurrence of cracks and cracks at the foot of the pattern. Both of the above-mentioned unhardened parts generate residues.

本發明是基於前述狀況而完成，其所欲解決的課題在於，以提供一種選定適合於負型感光性樹脂組成物的顯影液及沖洗液，且不會發生圖案製作後的麓部龜裂及殘渣之圖案的製造方法為目的。 [用於解決課題的手段]The present invention has been completed based on the foregoing situation, and the problem to be solved is to provide a developer and rinse solution suitable for the negative photosensitive resin composition, without causing foot cracks and cracks after pattern production. The manufacturing method of the pattern of the residue is the purpose. [Means used to solve the problem]

本發明的第一態樣為一種樹脂製透鏡之製造方法，其係具有： 在形成具有開口部的圖案的支持體上塗佈負型感光性樹脂組成物之步驟； 使前述負型感光性樹脂組成物與具有目標透鏡形狀的反轉圖案及遮光膜的模具接觸之壓印步驟； 在前述壓印步驟之後，透過前述模具使前述負型感光性樹脂組成物曝光，在前述開口部形成光硬化部之光硬化步驟； 使前述光硬化部與前述模具分離之脫模步驟； 在前述脫模步驟之後，使用含有γ-丁內酯的顯影液除去前述負型感光性樹脂組成物的未硬化部，使前述光硬化部露出，形成光硬化物之顯影步驟； 在前述顯影步驟之後，使用含有選自由乳酸酯、碳原子數1至5之直鏈或支鏈醇、具有至少一個甲基或乙基作為取代基之環己烷衍生物及碳原子數4至8之氫氟碳化物所構成的群中的化合物的沖洗液進行沖洗處理之沖洗步驟； 除去前述沖洗液之乾燥步驟；及 在前述乾燥步驟之後，使前述光硬化物的全面曝光之步驟。The first aspect of the present invention is a method of manufacturing a resin lens, which has: A step of coating a negative photosensitive resin composition on a support formed with a pattern having openings; Imprinting step of bringing the negative photosensitive resin composition into contact with a mold having a reversal pattern of the target lens shape and a light-shielding film; After the embossing step, the negative photosensitive resin composition is exposed through the mold to form a photo-curing step in the opening; The demolding step of separating the aforementioned light hardening part from the aforementioned mold; After the demolding step, a developing solution containing γ-butyrolactone is used to remove the uncured portion of the negative photosensitive resin composition to expose the photo-cured portion to form a photo-cured product; After the aforementioned development step, a cyclohexane derivative containing a lactic acid ester, a linear or branched alcohol having 1 to 5 carbon atoms, a substituent having at least one methyl or ethyl group, and a carbon atom number of 4 are used. The rinsing liquid of the compound in the group consisting of up to 8 hydrofluorocarbons undergoes the rinsing step of the rinsing process; The drying step of removing the aforementioned rinse liquid; and After the drying step, a step of exposing the entire surface of the photocured material.

在前述光硬化步驟之後，前述脫模步驟之前、中途或後，可進一步具有將前述光硬化部加熱的步驟。After the photocuring step, before, during or after the demolding step, there may be a step of heating the photocuring part.

在使前述光硬化物的全面曝光的步驟之後，可進一步具有將該光硬化物加熱之後烘步驟。After the step of exposing the entire surface of the aforementioned photocured product, there may be a further step of heating the photocured product and then baking.

在使前述光硬化物的全面曝光的步驟之後，可進一步具有在該光硬化物的表面形成抗反射膜的步驟。After the step of exposing the entire surface of the aforementioned photocured product, there may be a step of forming an anti-reflection film on the surface of the photocured product.

在前述乾燥步驟之後，使前述光硬化物的全面曝光的步驟之前，可進一步具有前述顯影步驟、前述沖洗步驟及前述乾燥步驟。After the drying step, and before the step of exposing the entire surface of the photocured material, the development step, the rinsing step, and the drying step may be further included.

前述顯影液或前述沖洗液，可進一步含有具有環狀構造且可具有醚鍵"-O-"之碳原子數5或6之醇。該碳原子數5或6之醇為例如四氫呋喃甲醇或環己醇。The developer or the rinse liquid may further contain an alcohol having a cyclic structure and an ether bond "-O-" with carbon atoms of 5 or 6. The alcohol having 5 or 6 carbon atoms is, for example, tetrahydrofuranmethanol or cyclohexanol.

前述沖洗液，含有例如具有至少一個甲基或乙基作為取代基的環己烷衍生物及前述碳原子數5或6之醇，相對於該環己烷衍生物及該碳原子數5或6之醇的合計100質量%，含有該環己烷衍生物至少50質量%。The aforementioned rinse solution contains, for example, a cyclohexane derivative having at least one methyl or ethyl group as a substituent and the aforementioned alcohol with 5 or 6 carbon atoms, relative to the cyclohexane derivative and the 5 or 6 carbon atoms The total amount of alcohol is 100% by mass, and the cyclohexane derivative contains at least 50% by mass.

前述負型感光性樹脂組成物，例如含有一分子中具有至少一個(甲基)丙烯醯基的化合物、經過表面修飾的二氧化矽粒子及光自由基聚合起始劑。The aforementioned negative photosensitive resin composition contains, for example, a compound having at least one (meth)acryloyl group in one molecule, surface-modified silica particles, and a photo-radical polymerization initiator.

本發明的第二態樣為一種使用於樹脂製透鏡的製造之沖洗液，其含有具有至少一個甲基或乙基作為取代基的環己烷衍生物及具有環狀構造且可具有醚鍵"-O-"之碳原子數5或6之醇。The second aspect of the present invention is a rinsing liquid used in the manufacture of resin lenses, which contains a cyclohexane derivative having at least one methyl or ethyl group as a substituent and a cyclic structure and may have an ether bond." -O-" is an alcohol with 5 or 6 carbon atoms.

前述環己烷衍生物為例如甲基環己烷，前述碳原子數5或6之醇為例如四氫呋喃甲醇或環己醇。The cyclohexane derivative is, for example, methylcyclohexane, and the alcohol having 5 or 6 carbon atoms is, for example, tetrahydrofuranmethanol or cyclohexanol.

前述沖洗液，例如相對於前述環己烷衍生物及前述碳原子數5或6之醇的合計100質量%，含有該環己烷衍生物至少50質量%。 [發明之效果]The rinse solution contains, for example, at least 50% by mass of the cyclohexane derivative with respect to 100% by mass of the total of the cyclohexane derivative and the alcohol having 5 or 6 carbon atoms. [Effects of Invention]

在前述負型感光性樹脂組成物的未硬化部，於具有至少一個(甲基)丙烯醯基的化合物中，經過表面修飾的二氧化矽粒子會呈分散的狀態。在使用有機溶劑作為顯影液的顯影步驟中，該有機溶劑若與前述未硬化部接觸，則會溶解前述具有至少一個(甲基)丙烯醯基的化合物，並與前述經過表面修飾的二氧化矽粒子一起被除去。若選擇對於前述具有至少一個(甲基)丙烯醯基的化合物溶解性高的顯影液，則殘渣不易殘留在藉由前述顯影步驟除去的前述未硬化部，若選擇對於該化合物溶解性低的顯影液，則殘渣容易殘留於應藉由前述顯影步驟除去的前述未硬化部。所以，本發明藉由選擇具有與負型感光性樹脂組成物適當的親和性，且由前述光硬化部中釋放速度慢的顯影液，即使是形成膜厚100μm以上的厚膜(透鏡圖案)的圖案化，也可抑制圖案的麓部發生龜裂，還可抑制前述未硬化部的殘渣。In the uncured portion of the negative photosensitive resin composition, the surface-modified silica particles are dispersed in the compound having at least one (meth)acrylic group. In the development step using an organic solvent as a developer, if the organic solvent comes into contact with the aforementioned unhardened part, it will dissolve the aforementioned compound having at least one (meth)acrylic acid group and interact with the aforementioned surface-modified silica The particles are removed together. If a developer with high solubility for the aforementioned compound having at least one (meth)acryloyl group is selected, the residue will not easily remain in the unhardened portion removed by the aforementioned development step. If a developer with low solubility for the compound is selected If it is liquid, the residue is likely to remain in the unhardened portion that should be removed by the development step. Therefore, in the present invention, by selecting a developer that has appropriate affinity with the negative photosensitive resin composition and has a slow release rate from the aforementioned photohardening part, even if a thick film (lens pattern) with a film thickness of 100 μm or more is formed Patterning can also suppress the occurrence of cracks at the foot of the pattern, and can also suppress the residue of the aforementioned unhardened portion.

本發明使用的顯影液中所含有的γ-丁內酯是脂環式構造，因此具有對有機化合物的高親和性，另一方面與水也可混合，而表現出特異的溶解性，因此會發生特異性地滲入感光後的光硬化部。此外，γ-丁內酯因為具有200℃以上的高沸點，由前述光硬化部中釋放的速度慢，因此可緩和前述形變所造成的應力。所以，藉由使用含有γ-丁內酯的顯影液，可抑制圖案的麓部發生的龜裂。The γ-butyrolactone contained in the developer used in the present invention has an alicyclic structure and therefore has a high affinity for organic compounds. On the other hand, it can be mixed with water and exhibits specific solubility. Occurs specifically to penetrate into the light-hardened area after exposure. In addition, since γ-butyrolactone has a high boiling point of 200°C or higher, the rate of release from the aforementioned photohardened portion is slow, and therefore, the stress caused by the aforementioned deformation can be alleviated. Therefore, by using a developer containing γ-butyrolactone, the occurrence of cracks at the foot of the pattern can be suppressed.

本發明的沖洗液不會對前述負型感光性樹脂組成物造成傷害，而且具有將前述含有γ-丁內酯的顯影液洗掉的功能。亦即，本發明的沖洗液，對前述負型感光性樹脂組成物的親和性低，且具有與前述含有γ-丁內酯的顯影液混合的機能。另外，本發明的沖洗液，在前述顯影步驟之後殘留前述經過表面修飾的二氧化矽粒子及在前述顯影步驟之後殘留前述一分子中具有至少一個(甲基)丙烯醯基的化合物的情況，該化合物也能夠與前述含有γ-丁內酯的顯影液一起洗掉。前述負型感光性樹脂組成物，藉由利用含有γ-丁內酯的顯影液進行的顯影步驟，在前述光硬化部中會含有一定量的含有γ-丁內酯的顯影液。然後，藉由使用本發明的沖洗液，可由前述光硬化部中徐緩除去含有γ-丁內酯的顯影液。此外，本發明的沖洗液具有較高的揮發性，因此可減少殘存於所形成的圖案中及該圖案的周邊的該沖洗液。The rinsing liquid of the present invention does not cause damage to the negative photosensitive resin composition, and has a function of washing off the developer containing γ-butyrolactone. That is, the rinse solution of the present invention has a low affinity for the negative photosensitive resin composition and has a function of mixing with the developer containing γ-butyrolactone. In addition, in the rinse solution of the present invention, the surface-modified silicon dioxide particles remain after the development step and the compound having at least one (meth)acryloyl group in one molecule remains after the development step. The compound can also be washed away with the aforementioned developer containing γ-butyrolactone. In the negative photosensitive resin composition, a certain amount of a developer containing γ-butyrolactone is contained in the photohardening part through a development step performed with a developer containing γ-butyrolactone. Then, by using the rinsing liquid of the present invention, the developer containing γ-butyrolactone can be gradually removed from the photohardening part. In addition, the rinsing liquid of the present invention has high volatility, so it can reduce the rinsing liquid remaining in the formed pattern and the periphery of the pattern.

＜塗佈步驟＞＜Coating Step＞

以下針對本發明說明細節。 本發明的樹脂製透鏡之製造方法，具有在形成具有開口部的圖案的支持體上塗佈負型感光性樹脂組成物的步驟。前述具有開口部的圖案，是使負型感光性樹脂組成物或正型感光性樹脂組成物圖案化而形成，該圖案的形狀為例如格子狀。前述支持體，可列舉例如以氧化矽膜被覆的矽等的半導體基板、以氮化矽膜或氮氧化矽膜被覆的矽等的半導體基板、氮化矽基板、石英基板、玻璃基板(包含無鹼玻璃、低鹼玻璃、結晶化玻璃)、形成有ITO膜的玻璃基板。於其上藉由點膠機、旋轉台等的適當塗佈方法來塗佈前述負型感光性樹脂組成物。前述負型感光性樹脂組成物，含有一分子中具有至少一個(甲基)丙烯醯基的化合物、經過表面修飾的二氧化矽粒子、光自由基聚合起始劑及任意的其他添加劑，可列舉例如前述專利文獻1所記載的壓印用光硬化性組成物。The details of the present invention will be described below. The manufacturing method of the resin lens of this invention has the process of apply|coating a negative photosensitive resin composition on the support body which forms the pattern with an opening part. The aforementioned pattern having openings is formed by patterning a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, and the shape of the pattern is, for example, a lattice shape. The aforementioned support includes, for example, a semiconductor substrate such as silicon coated with a silicon oxide film, a semiconductor substrate such as silicon coated with a silicon nitride film or a silicon oxynitride film, a silicon nitride substrate, a quartz substrate, and a glass substrate (including Alkali glass, low-alkali glass, crystallized glass), a glass substrate on which an ITO film is formed. The negative photosensitive resin composition is coated thereon by an appropriate coating method such as a dispenser or a rotating table. The aforementioned negative photosensitive resin composition contains a compound having at least one (meth)acryloyl group in one molecule, surface-modified silica particles, a photo-radical polymerization initiator, and any other additives, including For example, the photocurable composition for imprint described in Patent Document 1 mentioned above.

＜壓印步驟＞ 本發明的樹脂製透鏡之製造方法，具有使前述負型感光性樹脂組成物與具有目標透鏡形狀的反轉圖案及遮光膜的模具接觸之壓印步驟。此處，在前述目標透鏡形狀為凹透鏡的情況，前述反轉圖案為凸透鏡圖案。前述模具的材料，只要是可讓後述光硬化步驟所使用的紫外線等的光線透過的材料，則不受限定，可列舉例如聚甲基甲基丙烯酸酯等的(甲基)丙烯酸樹脂、環烯烴聚合物(COP)樹脂、石英、硼矽酸玻璃及氟化鈣。在前述模具的材料為樹脂的情況，可為非感光性樹脂、感光性樹脂任一者。前述感光性樹脂可列舉例如國際公開第2019/031359號所揭示的壓印用複製模具材料。另外，前述遮光膜的材料，只要不會讓在後述光硬化步驟所使用的紫外線等的光線透過，則不受限定，可列舉例如鋁、鉻、鎳、鈷、鈦、鉭、鎢及鉬。前述模具，為了後述的脫模步驟，希望藉由塗佈脫模劑並且乾燥來作脫模處理然後才使用。前述脫模劑能夠以市售品的形式取得，可列舉例如Novec(註冊商標)1700、Novec(註冊商標)1710、Novec(註冊商標)1720(以上為3M Japan股份有限公司製)、Fluoro Surf(註冊商標)FG-5084、Fluoro Surf(註冊商標)FG-5093(以上為Fluoro Technology股份有限公司製)、DURASURF(註冊商標)DP-500、DURASURF(註冊商標)DP-200、DURASURF(註冊商標)DS-5400、DURASURF(註冊商標)DH-100、DURASURF(註冊商標)DH-405TH、DURASURF(註冊商標)DH-610、DURASURF(註冊商標)DS-5800、DURASURF(註冊商標)DS-5935(以上為HARVES股份有限公司製)、POLYFLON(註冊商標)PTFETC-7105GN、POLYFLON(註冊商標)PTFETC-7109BK、POLYFLON(註冊商標)PTFETC-7113LB、POLYFLON(註冊商標)PTFETC-7400CR、POLYFLON(註冊商標)PTFETC-7405GN、POLYFLON(註冊商標)PTFETC-7408GY、POLYFLON(註冊商標)PTFETC-7409BK、POLYFLON(註冊商標)PTFETC-7609M1、POLYFLON PTFETC-7808GY、POLYFLON PTFETC-7809BK、POLYFLON(註冊商標)PTFETD-7139BD、OPTOOL(註冊商標)DAC-HP、OPTOOL(註冊商標)DSX-E、OPTOACE(註冊商標)WP-140、DAIFREE(註冊商標)GW-4000、DAIFREE(註冊商標)GW-4010、DAIFREE(註冊商標)GW-4500、DAIFREE(註冊商標)GW-4510、DAIFREE(註冊商標)GW-8000、DAIFREE(註冊商標)GW-8500、DAIFREE(註冊商標)MS-175、DAIFREE(註冊商標)GF-700、DAIFREE(註冊商標)GF-750、DAIFREE(註冊商標)MS-600、DAIFREE(註冊商標)GA-3000、DAIFREE(註冊商標)GA-9700、DAIFREE(註冊商標)GA-9750(以上為DAIKIN工業股份有限公司製)、MEGAFAC(註冊商標)F-553、MEGAFAC(註冊商標)F-555、MEGAFAC(註冊商標)F-558、MEGAFAC(註冊商標)F-561(以上為DIC股份有限公司製)及SFE-DP02H、SNF-DP20H、SFE-B002H、SNF-B200A、SCV-X008、SFE-X008、SNF-X800、SR-4000A、S-680、S-685、MRF-6441-AL、MRF-6711-AL、MRF-6758-AL、MRF-6811-AL、MR EF-6521-AL(以上為AGC SEIMI CHEMICAL股份有限公司製)。前述脫模劑除了上述市售品以外，還可列舉例如國際公開第2019/031312號所揭示的模具用脫模劑。<Imprinting steps> The method of manufacturing a resin lens of the present invention has an imprint step of bringing the negative photosensitive resin composition into contact with a mold having a reversal pattern of the target lens shape and a light-shielding film. Here, when the target lens shape is a concave lens, the inversion pattern is a convex lens pattern. The material of the aforementioned mold is not limited as long as it can transmit light such as ultraviolet rays used in the photocuring step described later, and examples include (meth)acrylic resins such as polymethmethacrylate and cycloolefins. Polymer (COP) resin, quartz, borosilicate glass and calcium fluoride. When the material of the aforementioned mold is a resin, it may be either a non-photosensitive resin or a photosensitive resin. Examples of the photosensitive resin include the copy mold material for imprint disclosed in International Publication No. 2019/031359. In addition, the material of the aforementioned light-shielding film is not limited as long as it does not transmit light such as ultraviolet rays used in the photocuring step described later, and examples include aluminum, chromium, nickel, cobalt, titanium, tantalum, tungsten, and molybdenum. For the aforementioned mold, it is desirable to apply a mold release agent and dry it for mold release treatment before using it for the demolding step described later. The aforementioned release agent can be obtained in the form of a commercially available product, and examples thereof include Novec (registered trademark) 1700, Novec (registered trademark) 1710, Novec (registered trademark) 1720 (above 3M Japan Co., Ltd.), Fluoro Surf ( Registered trademark) FG-5084, Fluoro Surf (registered trademark) FG-5093 (the above are manufactured by Fluoro Technology Co., Ltd.), Durasurf (registered trademark) DP-500, Durasurf (registered trademark) DP-200, Durasurf (registered trademark) DS-5400, Durasurf (registered trademark) DH-100, Durasurf (registered trademark) DH-405TH, Durasurf (registered trademark) DH-610, Durasurf (registered trademark) DS-5800, Durasurf (registered trademark) DS-5935 (above Manufactured by HARVES Co., Ltd., POLYFLON (registered trademark) PTFETC-7105GN, POLYFLON (registered trademark) PTFETC-7109BK, POLYFLON (registered trademark) PTFETC-7113LB, POLYFLON (registered trademark) PTFETC-7400CR, POLYFLON (registered trademark) PTFETC -7405GN, POLYFLON (registered trademark) PTFETC-7408GY, POLYFLON (registered trademark) PTFETC-7409BK, POLYFLON (registered trademark) PTFETC-7609M1, POLYFLON PTFETC-7808GY, POLYFLON PTFETC-7809BK, POLYFLON (registered trademark) PTFETD-7139BD, OPTOOL (Registered trademark) DAC-HP, OPTOOL (registered trademark) DSX-E, OPTOACE (registered trademark) WP-140, DAIFREE (registered trademark) GW-4000, DAIFREE (registered trademark) GW-4010, DAIFREE (registered trademark) GW -4500, DAIFREE (registered trademark) GW-4510, DAIFREE (registered trademark) GW-8000, DAIFREE (registered trademark) GW-8500, DAIFREE (registered trademark) MS-175, DAIFREE (registered trademark) GF-700, DAIFREE ( Registered trademark) GF-750, DAIFREE (registered trademark) MS-600, DAIFREE (registered trademark) GA-3000, DAIFREE (registered trademark) GA-9700, DAIFREE (registered trademark) GA-9750 (the above are DAIKIN Industrial Co., Ltd. Division), MEGAFAC (registered trademark) F-553, MEGAFAC (registered trademark) F-555, MEGAFAC (registered trademark) F-558, MEGAFAC (registered trademark) F-561 (the above are manufactured by DIC Co., Ltd.) and SFE -DP02H, SNF-DP20H, SFE-B002H, SNF-B200A, SCV-X008, SFE-X008, SNF-X800, SR-4000A, S-680, S-685, MRF-6441-AL, MRF-6711-AL , MRF-6758-AL, MRF-6811-AL, MR EF-6521-AL (the above are manufactured by AGC SEIMI CHEMICAL Co., Ltd.). In addition to the above-mentioned commercially available products, the mold release agent may include, for example, mold release agents disclosed in International Publication No. 2019/031312.

＜光硬化步驟＞ 本發明的樹脂製透鏡之製造方法，具有在前述壓印步驟之後，透過前述模具使前述負型感光性樹脂組成物曝光，在前述開口部形成光硬化部之光硬化步驟。對前述負型感光性樹脂組成物曝光所使用的光線，只要可形成前述光硬化部，則並未受到特別限定，可使用例如波長436nm的g射線、波長405nm的h射線、波長365nm的i射線、ghi射線(寬帶域)及波長248nm的KrF準分子雷射。前述光硬化部的膜厚通常為1μm至2000μm，宜為100μm至1000μm，較佳為300μm至700μm。前述模具是由可讓紫外線等的光線透過的材料製作，且具有不讓該紫外線等的光線透過的遮光膜，因此在本步驟中可作為光罩來使用。＜Light curing step＞ The method for manufacturing a resin lens of the present invention includes a photocuring step of exposing the negative photosensitive resin composition through the mold after the imprinting step, and forming a photocuring portion in the opening. The light used for exposing the negative photosensitive resin composition is not particularly limited as long as it can form the photocurable portion. For example, g-rays with a wavelength of 436nm, h-rays with a wavelength of 405nm, and i-rays with a wavelength of 365nm can be used. , Ghi ray (broadband) and KrF excimer laser with a wavelength of 248nm. The film thickness of the aforementioned photohardening part is usually 1 μm to 2000 μm, preferably 100 μm to 1000 μm, and preferably 300 μm to 700 μm. The aforementioned mold is made of a material that can transmit light such as ultraviolet rays, and has a light-shielding film that does not transmit light such as ultraviolet rays, so it can be used as a mask in this step.

＜脫模步驟＞ 本發明的樹脂製透鏡之製造方法，具有使前述光硬化部與前述模具分離之脫模步驟。脫模方法，只要前述光硬化部沒有損傷及變形，可由前述模具完全分離，則並未受到特別限定。前述模具，藉由塗佈前述脫模劑並乾燥的脫模處理，前述光硬化部與該模具的分離會變得容易。在前述光硬化步驟之後，本脫模步驟之前、中途或後，亦可進一步具有將前述光硬化部加熱的步驟，此情況下，該光硬化部的加熱條件，可由例如加熱溫度80℃至100℃及加熱時間30秒至60分鐘的範圍適當地選擇。＜Demoulding step＞ The manufacturing method of the resin lens of this invention has the mold release process which separates the said photohardening part from the said mold. The demolding method is not particularly limited as long as the photo-cured part is not damaged or deformed and can be completely separated from the mold. In the mold, the photohardening part can be easily separated from the mold by a mold release process in which the mold release agent is applied and dried. After the photo-curing step, before, during or after the demolding step, there may be a step of heating the photo-curing part. In this case, the heating condition of the photo-curing part can be, for example, a heating temperature of 80°C to 100°C. The temperature range and heating time of 30 seconds to 60 minutes are appropriately selected.

＜顯影步驟＞ 本發明的樹脂製透鏡之製造方法，具有在前述脫模步驟之後，使用含有γ-丁內酯的顯影液除去前述負型感光性樹脂組成物的未硬化部，使前述光硬化部露出，形成光硬化物之顯影步驟。顯影方法只要不損及本發明效果，則並未受到特別限定，可列舉例如浸漬法、覆液法、噴霧法、動態分配法及靜態分配法。顯影的條件，可由例如顯影溫度5℃至50℃、顯影時間l0秒至300秒的範圍適當地選擇。<Development step> The method of manufacturing a resin lens of the present invention includes, after the demolding step, using a developer containing γ-butyrolactone to remove the uncured portion of the negative photosensitive resin composition to expose the photocured portion to form The development step of light hardening material. The development method is not particularly limited as long as it does not impair the effects of the present invention, and examples thereof include a dipping method, a liquid coating method, a spray method, a dynamic distribution method, and a static distribution method. The conditions of the development can be appropriately selected from, for example, a development temperature of 5°C to 50°C and a development time of 10 seconds to 300 seconds.

前述含有γ-丁內酯的顯影液，可進一步含有具有環狀構造且可具有醚鍵之碳原子數5或6之醇。前述碳原子數5或6之醇，可列舉例如四氫呋喃甲醇、3-呋喃甲醇、5-羥甲基-2-糠醛、5-(羥甲基)呋喃-2-羧酸、環戊醇、2-環己烯-1-醇、1-環丙基乙醇、環丁烷甲醇、環戊烷甲醇、3-乙基-3-氧雜環丁烷基甲醇、4-羥基-2-(羥甲基)-2-環戊烯-1-酮、1-甲基環戊醇、3-甲基-3-氧雜環丁烷基甲醇、四氫吡喃-4-甲醇及環己醇。此外，γ-丁內酯與前述碳原子數5或6之醇的混合比，以定為γ-丁內酯/前述碳原子數5或6之醇=10質量%至90質量%/90質量%至10質量%為佳。The aforementioned developer containing γ-butyrolactone may further contain an alcohol having 5 or 6 carbon atoms which has a cyclic structure and may have an ether bond. The aforementioned alcohols with 5 or 6 carbon atoms include, for example, tetrahydrofuranmethanol, 3-furanmethanol, 5-hydroxymethyl-2-furaldehyde, 5-(hydroxymethyl)furan-2-carboxylic acid, cyclopentanol, 2 -Cyclohexen-1-ol, 1-cyclopropyl ethanol, cyclobutane methanol, cyclopentane methanol, 3-ethyl-3-oxetanyl methanol, 4-hydroxy-2-(hydroxymethyl Yl)-2-cyclopenten-1-one, 1-methylcyclopentanol, 3-methyl-3-oxetanylmethanol, tetrahydropyran-4-methanol and cyclohexanol. In addition, the mixing ratio of γ-butyrolactone and the aforementioned alcohol with 5 or 6 carbon atoms is defined as γ-butyrolactone/the aforementioned alcohol with 5 or 6 carbon atoms = 10% by mass to 90% by mass/90% by mass % To 10% by mass is preferable.

＜沖洗步驟＞ 本發明的樹脂製透鏡之製造方法，具有在前述顯影步驟之後，使用含有選自由乳酸酯、碳原子數1至5之直鏈或支鏈醇、具有至少一個甲基或乙基作為取代基的環己烷衍生物及碳原子數4至8之氫氟碳化物所構成的群中的化合物的沖洗液進行沖洗處理之沖洗步驟。沖洗方法只要不損及本發明效果，則並未受到特別限定，可列舉例如浸漬法、覆液法、噴霧法、動態分配法及靜態分配法。沖洗的條件，可由沖洗溫度5℃至50℃、沖洗時間10秒至300秒的範圍適當地選擇。＜Rinse step＞ The method for producing a resin lens of the present invention includes, after the aforementioned development step, the use of a linear or branched alcohol selected from the group consisting of lactic acid ester, a carbon number of 1 to 5, and at least one methyl or ethyl group as a substituent The rinsing solution of the compound in the group consisting of cyclohexane derivatives and carbon atoms of 4 to 8 hydrofluorocarbons is subjected to a rinsing step of rinsing treatment. The rinsing method is not particularly limited as long as it does not impair the effect of the present invention, and examples thereof include a dipping method, a liquid coating method, a spray method, a dynamic distribution method, and a static distribution method. The conditions of the rinsing can be appropriately selected from the range of the rinsing temperature of 5°C to 50°C and the rinsing time of 10 seconds to 300 seconds.

前述乳酸酯，可列舉例如乳酸甲酯、乳酸乙酯、乳酸丙酯、乳酸異丙酯、乳酸丁酯、乳酸異丁酯、乳酸戊酯及乳酸己酯。前述碳原子數1至5之直鏈或支鏈醇，可列舉例如甲醇、乙醇、1-丙醇、異丙醇、1-丁醇、2-丁醇、第三丁醇、異丁醇、1-戊醇、2-戊醇、3-戊醇、2-甲基-1-丁醇、3-甲基-2-丁醇、第三戊基醇及異戊基醇。前述具有至少一個甲基或乙基作為取代基的環己烷衍生物，可列舉例如甲基環己烷、乙基環己烷、1,2-二甲基環己烷、1,3-二甲基環己烷及1,4-二甲基環己烷。前述碳原子數4至8之氫氟碳化物，可列舉例如Vertrel(註冊商標)XF、Vertrel(註冊商標)XF-UP、Vertrel(註冊商標)XF-Seiect、Vertrel(註冊商標)XE、Vertrel(註冊商標)XE10(以上為三井･科慕氟產品股份有限公司製)及Novec(註冊商標)7000、Novec(註冊商標)7100、Novec(註冊商標)7200、Novec(註冊商標)7300(以上為3M Japan股份有限公司製)。Examples of the aforementioned lactate include methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, isobutyl lactate, pentyl lactate, and hexyl lactate. The aforementioned linear or branched alcohols having 1 to 5 carbon atoms include, for example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, tertiary butanol, isobutanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-2-butanol, tertiary amyl alcohol and isoamyl alcohol. The aforementioned cyclohexane derivatives having at least one methyl or ethyl group as a substituent include, for example, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, and 1,3-dimethylcyclohexane. Methylcyclohexane and 1,4-dimethylcyclohexane. The aforementioned hydrofluorocarbons having 4 to 8 carbon atoms include, for example, Vertrel (registered trademark) XF, Vertrel (registered trademark) XF-UP, Vertrel (registered trademark) XF-Seiect, Vertrel (registered trademark) XE, Vertrel ( Registered trademark) XE10 (above made by Mitsui & Chemours Fluorine Products Co., Ltd.) and Novec (registered trademark) 7000, Novec (registered trademark) 7100, Novec (registered trademark) 7200, Novec (registered trademark) 7300 (above 3M) Japan Co., Ltd. system).

前述沖洗液中，與前述含有γ-丁內酯的顯影液同樣地，亦可進一步含有具有環狀構造且可具有醚鍵之碳原子數5或6之醇。前述碳原子數5或6之醇的例子如前述。前述沖洗液可單獨使用一種或將兩種以上組合使用。在前述沖洗液含有前述環己烷衍生物及前述碳原子數5或6之醇的情況，相對於這些成分的合計100質量%，含有該環己烷衍生物至少50質量%為佳。In the aforementioned rinse solution, similarly to the aforementioned developer containing γ-butyrolactone, it may further contain an alcohol having 5 or 6 carbon atoms which has a cyclic structure and may have an ether bond. Examples of the aforementioned alcohols having 5 or 6 carbon atoms are as described above. The aforementioned rinsing liquid can be used alone or in combination of two or more. When the rinse solution contains the cyclohexane derivative and the alcohol having 5 or 6 carbon atoms, it is preferable that the cyclohexane derivative contains at least 50% by mass relative to 100% by mass of the total of these components.

[界面活性劑] 在本發明的樹脂製透鏡之製造方法所使用的顯影液及沖洗液中，為了提升對前述光硬化部的潤濕性，使顯影及沖洗有效率地進行，亦可進一步含有界面活性劑。前述界面活性劑可列舉例如聚環氧乙烷月桂基醚、聚環氧乙烷硬脂醯基醚、聚環氧乙烷鯨蠟基醚、聚環氧乙烷油醚等的聚環氧乙烷烷醚類、聚環氧乙烷辛基苯醚、聚環氧乙烷壬基苯醚等的環氧乙烷烷基芳香基醚類、聚環氧乙烷･聚氧丙烯嵌段共聚物類、去水山梨醇單月桂酸酯、去水山梨醇單棕櫚酸酯、去水山梨醇單硬脂酸酯、去水山梨醇單油酸酯、去水山梨醇三油酸酯、去水山梨醇三硬脂酸酯等的去水山梨醇脂肪酸酯類、聚環氧乙烷去水山梨醇單月桂酸酯、聚環氧乙烷去水山梨醇單棕櫚酸酯、聚環氧乙烷去水山梨醇單硬脂酸酯、聚環氧乙烷去水山梨醇三油酸酯、聚環氧乙烷去水山梨醇三硬脂酸酯等的聚環氧乙烷去水山梨醇脂肪酸酯類等的非離子系界面活性劑、F TOP(註冊商標)EF301、F TOP(註冊商標)EF303、F TOP(註冊商標)EF352(以上為三菱材料電子化成股份有限公司製)、MEGAFAC(註冊商標)F-171、MEGAFAC(註冊商標)F-173、MEGAFAC(註冊商標)R-30、MEGAFAC(註冊商標)R-40、MEGAFAC(註冊商標)R-40-LM、MEGAFAC(註冊商標)R-41(以上為DIC股份有限公司製)、Fluorad FC430、Fluorad FC431(以上為3M Japan股份有限公司製)、Asahiguard(註冊商標)AG710、Surflon(註冊商標)S-382、Surflon(註冊商標)SC101、Surflon(註冊商標)SC102、Surflon(註冊商標)SC103、Surflon(註冊商標)SC104、Surflon(註冊商標)SC105、Surflon(註冊商標)SC106(以上為AGC股份有限公司製)、BYK-302、BYK-307、BYK-322、BYK-323、BYK-331、BYK-333、BYK-377、BYK-378(以上為BYK-Chemie Japan股份有限公司製)、FTX-206D、FTX-212D、FTX-218、FTX-220D、FTX-230D、FTX-240D、FTX-212P、FTX-220P、FTX-228P、FTX-240G、DFX-18等Ftergent系列(NEOS股份有限公司製)等的氟系界面活性劑及有機矽氧烷聚合物KP341(信越化學工業股份有限公司製)。[Surfactant] The developer and rinsing liquid used in the method of manufacturing a resin lens of the present invention may further contain a surfactant in order to improve the wettability of the photocurable portion and to efficiently perform development and rinsing. The aforementioned surfactants include, for example, polyethylene oxide such as polyethylene oxide lauryl ether, polyethylene oxide stearyl ether, polyethylene oxide cetyl ether, and polyethylene oxide oleyl ether. Alkyl ethers, polyethylene oxide octyl phenyl ether, polyethylene oxide nonyl phenyl ether and other ethylene oxide alkyl aromatic ethers, polyethylene oxide and polyoxypropylene block copolymers Class, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, dehydrated Sorbitan fatty acid esters such as sorbitol tristearate, polyethylene oxide sorbitan monolaurate, polyethylene oxide sorbitan monopalmitate, polyethylene oxide Polyethylene oxide sorbitan fatty acid such as sorbitan monostearate, polyethylene oxide sorbitan trioleate, polyethylene oxide sorbitan tristearate, etc. Non-ionic surfactants such as esters, F TOP (registered trademark) EF301, F TOP (registered trademark) EF303, F TOP (registered trademark) EF352 (the above are manufactured by Mitsubishi Materials Electronics Co., Ltd.), MEGAFAC (registered) Trademark) F-171, MEGAFAC (registered trademark) F-173, MEGAFAC (registered trademark) R-30, MEGAFAC (registered trademark) R-40, MEGAFAC (registered trademark) R-40-LM, MEGAFAC (registered trademark) R -41 (The above is made by DIC Co., Ltd.), Fluorad FC430, Fluorad FC431 (the above is made by 3M Japan Co., Ltd.), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, Surflon (registered trademark) SC101 , Surflon (registered trademark) SC102, Surflon (registered trademark) SC103, Surflon (registered trademark) SC104, Surflon (registered trademark) SC105, Surflon (registered trademark) SC106 (the above are manufactured by AGC Co., Ltd.), BYK-302, BYK -307, BYK-322, BYK-323, BYK-331, BYK-333, BYK-377, BYK-378 (the above are manufactured by BYK-Chemie Japan Co., Ltd.), FTX-206D, FTX-212D, FTX-218 , FTX-220D, FTX-230D, FTX-240D, FTX-212P, FTX-220P, FTX-228P, FTX-240G, DFX-18 and other Ftergent series (manufactured by NEOS Co., Ltd.) and other fluorine-based surfactants and Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

前述界面活性劑可單獨使用一種或將兩種以上組合使用。另外，在使用前述界面活性劑的情況，其在前述顯影液或沖洗液中的含量，相對於該顯影液或沖洗液的總質量為0.001質量%至5質量%，宜為0.01質量%至3質量%，較佳為0.05質量%至1質量%。The aforementioned surfactants can be used singly or in combination of two or more. In addition, in the case of using the aforementioned surfactant, its content in the aforementioned developer or rinse solution is 0.001% to 5% by mass, preferably 0.01% to 3% by mass relative to the total mass of the developer or rinse solution. % By mass, preferably 0.05% by mass to 1% by mass.

[其他添加劑] 在本發明的樹脂製透鏡之製造方法所使用的負型感光性樹脂組成物、顯影液及沖洗液，在不損及本發明效果的前提之下，可因應必要含有抗氧化劑作為其他添加劑。前述抗氧化劑能夠以市售品的形式取得，可列舉例如IRGANOX(註冊商標)245、IRGANOX(註冊商標)1010、IRGANOX(註冊商標)1035、IRGANOX(註冊商標)1076、IRGANOX(註冊商標)1135、IRGAFOS(註冊商標)168(以上為BASF Japan股份有限公司製)、SUMILIZER(註冊商標)GA-80、SUMILIZER(註冊商標)GP、SUMILIZER(註冊商標)MDP-S、SUMILIZER(註冊商標)BBM-S、SUMILIZER(註冊商標)WX-R(以上為住友化學股份有限公司製)及ADEKASTAB(註冊商標)AO-20、ADEKASTAB(註冊商標)AO-30、ADEKASTAB(註冊商標)AO-40、ADEKASTAB(註冊商標)AO-50、ADEKASTAB(註冊商標)AO-60、ADEKASTAB(註冊商標)AO-80、ADEKASTAB(註冊商標)AO-330、ADEKASTAB(註冊商標)PEP-36、ADEKASTAB(註冊商標)PEP-8、ADEKASTAB(註冊商標)HP-18、ADEKASTAB(註冊商標)HP-10、ADEKASTAB(註冊商標)2112、ADEKASTAB(註冊商標)2112RG、ADEKASTAB(註冊商標)1178、ADEKASTAB(註冊商標)1500、ADEKASTAB(註冊商標)C、ADEKASTAB(註冊商標)135A、ADEKASTAB(註冊商標)3010、ADEKASTAB(註冊商標)TPP(以上為ADEKA股份有限公司製)。[Other additives] The negative photosensitive resin composition, developer, and rinsing solution used in the method of manufacturing a resin lens of the present invention may contain antioxidants as other additives as necessary without impairing the effects of the present invention. The aforementioned antioxidants can be obtained in the form of commercially available products, for example, IRGANOX (registered trademark) 245, IRGANOX (registered trademark) 1010, IRGANOX (registered trademark) 1035, IRGANOX (registered trademark) 1076, IRGANOX (registered trademark) 1135, IRGAFOS (registered trademark) 168 (the above are made by BASF Japan Co., Ltd.), SUMILIZER (registered trademark) GA-80, SUMILIZER (registered trademark) GP, SUMILIZER (registered trademark) MDP-S, SUMILIZER (registered trademark) BBM-S , SUMILIZER (registered trademark) WX-R (manufactured by Sumitomo Chemical Co., Ltd.) and ADEKASTAB (registered trademark) AO-20, ADEKASTAB (registered trademark) AO-30, ADEKASTAB (registered trademark) AO-40, ADEKASTAB (registered Trademark) AO-50, ADEKASTAB (registered trademark) AO-60, ADEKASTAB (registered trademark) AO-80, ADEKASTAB (registered trademark) AO-330, ADEKASTAB (registered trademark) PEP-36, ADEKASTAB (registered trademark) PEP-8 , ADEKASTAB (registered trademark) HP-18, ADEKASTAB (registered trademark) HP-10, ADEKASTAB (registered trademark) 2112, ADEKASTAB (registered trademark) 2112RG, ADEKASTAB (registered trademark) 1178, ADEKASTAB (registered trademark) 1500, ADEKASTAB (registered) Trademark) C, ADEKASTAB (registered trademark) 135A, ADEKASTAB (registered trademark) 3010, ADEKASTAB (registered trademark) TPP (the above are manufactured by ADEKA Co., Ltd.).

＜乾燥步驟＞ 本發明的樹脂製透鏡之製造方法，具有除去前述沖洗液之乾燥步驟。藉由旋轉台、塗佈機等的可旋轉乾燥的裝置，使前述支持體旋轉，可實施本步驟。乾燥條件並未受到特別限定，可由例如轉速200rpm至3000rpm、10秒至10分鐘的範圍適當地選擇。＜Drying step＞ The manufacturing method of the resin lens of this invention has the drying process which removes the said rinse liquid. This step can be implemented by rotating the aforementioned support by means of a rotary drying device such as a rotary table and a coating machine. The drying conditions are not particularly limited, and can be appropriately selected, for example, in the range of 200 rpm to 3000 rpm and 10 seconds to 10 minutes.

本發明的樹脂製透鏡之製造方法中，在前述乾燥步驟之後，後述全面曝光步驟之前，可進一步具有前述顯影步驟、前述沖洗步驟及前述乾燥步驟。藉由重覆前述顯影步驟、前述沖洗步驟及前述乾燥步驟，雖然樹脂製透鏡的生產性會因為步驟數的增加而降低，然而可將並未完全除去的前述未硬化部的殘渣完全除去。In the method of manufacturing a resin lens of the present invention, after the drying step and before the full exposure step described below, the development step, the rinsing step, and the drying step may be further provided. By repeating the aforementioned development step, the aforementioned washing step, and the aforementioned drying step, although the productivity of the resin lens decreases due to the increase in the number of steps, the residue of the uncured portion that has not been completely removed can be completely removed.

＜全面曝光步驟＞ 本發明的樹脂製透鏡之製造方法，具有在前述乾燥步驟之後，使前述光硬化物的全面曝光的步驟。本步驟所使用的光線可使用在前述光硬化步驟中所可使用的g射線、h射線、i射線及KrF準分子雷射。此外，在本步驟之前並且在前述乾燥步驟之後，或者在本步驟之後，亦可對於前述光硬化物使用熱板等的加熱手段進行後烘步驟。後烘的條件，可由例如加熱溫度80℃至100℃、加熱時間30秒至60分鐘的範圍適當地選擇。藉由進行前述後烘，在前述顯影液及沖洗液殘留於前述光硬化物的情況，可使該顯影液及沖洗液由該光硬化物完全釋放出來，同時可使該光硬化物的著色脫色。＜Full exposure steps＞ The method of manufacturing a resin lens of the present invention includes a step of exposing the entire surface of the photocured material after the drying step. The light used in this step can use g-rays, h-rays, i-rays, and KrF excimer lasers that can be used in the aforementioned photohardening step. In addition, before this step and after the aforementioned drying step, or after this step, a heating means such as a hot plate may be used to perform a post-baking step on the aforementioned photocured material. The conditions of the post-baking can be appropriately selected, for example, in the range of a heating temperature of 80°C to 100°C and a heating time of 30 seconds to 60 minutes. By performing the post-bake, in the case where the developer and rinsing liquid remain on the photohardened material, the developer and rinsing liquid can be completely released from the photohardened material, and at the same time, the coloring and decolorization of the photohardened material .

＜抗反射膜形成步驟＞ 在使前述光硬化物的全面曝光的步驟之後，進行前述後烘步驟的情況，在該後烘步驟之後可進一步具有在該光硬化物表面形成抗反射膜的步驟。前述抗反射膜是為了抑制入射至前述光硬化物的光線的反射、提升透過率而形成於該光硬化物的表面。前述抗反射膜的形成方法可列舉例如真空蒸鍍法、濺鍍法、CVD法、霧化法、旋轉塗佈法、浸漬塗佈法及噴霧塗佈法。另外，前述抗反射膜可列舉氟化鎂、二氧化矽等的無機膜及聚矽氧烷等的有機膜。 [實施例]<Steps for forming anti-reflective film> After the step of exposing the entire surface of the photocured object, in the case of performing the post-baking step, after the post-baking step, there may be a step of forming an anti-reflection film on the surface of the photocured object. The anti-reflection film is formed on the surface of the photo-cured object in order to suppress the reflection of the light incident on the photo-cured object and increase the transmittance. Examples of the method for forming the anti-reflection film include a vacuum evaporation method, a sputtering method, a CVD method, an atomization method, a spin coating method, a dip coating method, and a spray coating method. In addition, examples of the anti-reflection film include inorganic films such as magnesium fluoride and silicon dioxide, and organic films such as polysiloxane. [Example]

以下列舉實施例更具體地說明本發明，然而本發明並不受下述實施例限定。此外，在下述實施例及比較例中，試樣調製及物性分析所使用的裝置及條件如以下所述。The following examples are given to explain the present invention more specifically, but the present invention is not limited by the following examples. In addition, in the following Examples and Comparative Examples, the apparatus and conditions used for sample preparation and physical property analysis are as follows.

(1)攪拌脫泡機 裝置：Thinky股份有限公司製 自轉･公轉攪拌機除泡練太郎(註冊商標)ARE-310 (2)UV曝光 裝置1：CCS股份有限公司製 批次式UV-LED照射裝置(波長365nm) 裝置2：岩崎電氣股份有限公司製 UV-LED照射裝置LHPUV365/2501 (3)顯影裝置 裝置：Actes京三股份有限公司製 小型顯影裝置ADE-3000S (4)光學顯微鏡(麓部龜裂及殘渣的觀察) 裝置：Olympus股份有限公司製 光學顯微鏡MX61A 條件：明視野、對物10倍(1) Stirring and deaerator Device: manufactured by Thinky Co., Ltd. Rotation and revolution mixer defoaming Rintaro (registered trademark) ARE-310 (2) UV exposure Device 1: CCS Co., Ltd. batch UV-LED irradiation device (wavelength 365nm) Device 2: UV-LED irradiation device LHPUV365/2501 manufactured by Iwasaki Electric Co., Ltd. (3) Developing device Device: Actes Kyosan Co., Ltd. Small developing device ADE-3000S (4) Optical microscope (observation of cracks and residues at the foot) Device: Olympus Co., Ltd. Optical microscope MX61A Conditions: bright field of view, 10 times the object

在以下所記載的各製造例及負型感光性樹脂組成物的調製時所使用的化合物的供應商如以下所述。 UA-4200：新中村化學工業股份有限公司製 商品名：NK Oligo UA-4200 V#260：大阪有機化學工業股份有限公司製 商品名：VISCOAT #260 SA1303P：Advanced Softmaterials股份有限公司製 商品名：SeRM(註冊商標)super polymer SA1303P APG-100：新中村化學工業股份有限公司製 商品名：NK Ester APG-100 4HBA：東京化成工業股份有限公司製 化合物名：丙烯酸4-羥丁酯 I184：IGM Resins製 商品名：OMNIRAD(註冊商標)184(舊IRGACURE(註冊商標)184） I245：BASF Japan股份有限公司製 商品名：IRGANOX(註冊商標)245 AO-503：ADEKA股份有限公司製 商品名：ADEKASTAB(註冊商標)AO-503PEPT：SC有機化學股份有限公司製 商品名：PEPTThe suppliers of the compounds used in the preparation of the respective production examples and the negative photosensitive resin composition described below are as follows. UA-4200: manufactured by Shinnakamura Chemical Industry Co., Ltd. Trade name: NK Oligo UA-4200 V#260: Produced by Osaka Organic Chemical Industry Co., Ltd. Trade name: VISCOAT #260 SA1303P: manufactured by Advanced Softmaterials Co., Ltd. Trade name: SerM (registered trademark) super polymer SA1303P APG-100: manufactured by Shinnakamura Chemical Industry Co., Ltd. Trade name: NK Ester APG-100 4HBA: manufactured by Tokyo Chemical Industry Co., Ltd. Compound name: 4-hydroxybutyl acrylate I184: Produced by IGM Resins Trade name: OMNIRAD (registered trademark) 184 (old IRGACURE (registered trademark) 184) I245: manufactured by BASF Japan Co., Ltd. Trade name: IRGANOX (registered trademark) 245 AO-503: manufactured by ADEKA Co., Ltd. Trade name: ADEKASTAB (registered trademark) AO-503 PEPT: manufactured by SC Organic Chemical Co., Ltd. Trade name: PEPT

[製造例1] 秤量一分子中具有兩個(甲基)丙烯醯基的胺甲酸乙酯(甲基)丙烯酸酯化合物UA-4200 40.9g置於500mL茄型燒瓶中，以甲醇50.0g使其溶解。然後加入經過具有(甲基)丙烯醯基的官能基表面修飾且一次粒徑為20nm至25nm的二氧化矽粒子(固體成分40質量%的甲醇分散液)125g，加以攪拌使其均勻化。然後，使用蒸發器，在60℃、減壓度133.3Pa以下的條件下將甲醇餾除，得到經過具有(甲基)丙烯醯基的官能基表面修飾的二氧化矽粒子的UA-4200分散液(該經過表面修飾的二氧化矽粒子的含量為55質量%)。[Manufacturing Example 1] 40.9 g of urethane (meth)acrylate compound UA-4200 having two (meth)acrylic acid groups in one molecule was weighed, placed in a 500 mL eggplant-shaped flask, and dissolved in 50.0 g of methanol. Then, 125 g of silica particles (a methanol dispersion with a solid content of 40% by mass) having a surface modification of a functional group having a (meth)acryloyl group and having a primary particle size of 20 nm to 25 nm were added, and stirred to homogenize. Then, using an evaporator, the methanol was distilled off at 60°C and a reduced pressure of 133.3 Pa or less to obtain a UA-4200 dispersion of silica particles surface-modified with (meth)acrylic functional groups. (The content of the surface-modified silica particles is 55% by mass).

[製造例2] 秤量一分子中具有兩個(甲基)丙烯醯基的二官能(甲基)丙烯酸酯化合物V#260 20.0g置於500mL茄型燒瓶中。然後加入聚輪烷 SA1303P(在由環糊精所形成的環狀分子的側鏈具有丙烯醯基的聚輪烷、固體成分50質量%的甲基乙基酮分散液)40.0g，加以攪拌使其均勻化。然後，使用蒸發器，在50℃、減壓度133.3Pa以下的條件下將甲基乙基酮餾除，得到聚輪烷的V#260溶液(該聚輪烷的含量為50質量%)。[Manufacturing Example 2] Weigh 20.0 g of the difunctional (meth)acrylate compound V#260 with two (meth)acrylic acid groups in one molecule and place it in a 500 mL eggplant-shaped flask. Then, 40.0 g of polyrotaxane SA1303P (polyrotaxane having an acryl group on the side chain of a cyclic molecule formed of cyclodextrin, a dispersion of methyl ethyl ketone with a solid content of 50% by mass) was added, and stirred to make Its homogenization. Then, using an evaporator, methyl ethyl ketone was distilled off under conditions of 50° C. and a reduced pressure of 133.3 Pa or less to obtain a V#260 solution of polyrotaxane (the polyrotaxane content is 50% by mass).

[負型感光性樹脂組成物的調製] 將作為經過具有(甲基)丙烯醯基的官能基表面修飾的二氧化矽粒子之製造例1所得到的前述UA-4200分散液的固體成分20.9g、一分子中具有兩個(甲基)丙烯醯基的二官能(甲基)丙烯酸酯化合物V#260 14.8g及APG-100 2.5g、一分子中具有兩個(甲基)丙烯醯基的胺甲酸乙酯(甲基)丙烯酸酯化合物UA-4200 1.3g、一分子中具有一個(甲基)丙烯醯基的單官能(甲基)丙烯酸酯化合物4HBA 1.0g、作為聚輪烷之製造例2所得到的前述V#260溶液的固體成分7.0g、作為光自由基聚合起始劑的I184 0.5g，以及作為抗氧化劑的I245 0.35g及AO-503 0.25g摻合。然後，將摻合物在50℃下振動15小時混合之後，添加多官能硫醇化合物PEPT 2.5g，使用攪拌脫泡機，攪拌脫泡2分鐘，調製出負型感光性樹脂組成物。[Preparation of negative photosensitive resin composition] The solid content of the aforementioned UA-4200 dispersion obtained in Production Example 1 of the silicon dioxide particles surface-modified with a functional group having a (meth)acryloyl group was 20.9 g, and there were two (methyl) groups in one molecule. Acrylic difunctional (meth)acrylate compound V#260 14.8g and APG-100 2.5g, a urethane (meth)acrylate compound having two (meth)acrylic groups in one molecule UA-4200 1.3g, 4HBA 1.0g, a monofunctional (meth)acrylate compound having one (meth)acryloyl group in one molecule, as a solid of the aforementioned V#260 solution obtained in Production Example 2 of polyrotaxane Ingredients: 7.0 g, 0.5 g of I184 as a photo-radical polymerization initiator, 0.35 g of I245 as an antioxidant, and 0.25 g of AO-503 are blended. Then, after shaking and mixing the blend at 50°C for 15 hours, 2.5 g of a polyfunctional thiol compound PEPT was added, and a stirring and degassing machine was used to stir and degas for 2 minutes to prepare a negative photosensitive resin composition.

＜實施例1~7及比較例1~3＞ 在藉由塗佈Novec(註冊商標)1720(3M Japan股份有限公司製)並且乾燥來作脫模處理後的光罩基板(開口部1cm見方)上滴入適量的前述負型感光性樹脂組成物。然後，隔著500μm厚的聚矽氧橡膠製間隔物，以無鹼玻璃基板(10cm見方、0.7mm厚)夾住前述脫模處理後的光罩基板上的前述負型感光性樹脂組成物。前述無鹼玻璃基板是塗佈將信越化學工業股份有限公司製接著助劑(製品名：KBM-5803)以丙二醇單甲醚醋酸酯稀釋成10質量%後的溶液並且乾燥而作密著處理的基板。對該夾住的負型感光性樹脂組成物，使用前述岩崎電氣股份有限公司製的UV-LED照射裝置，隔著前述脫模處理後的光罩基板，以140mW/cm2 進行UV曝光3.2秒鐘，形成光硬化部。<Examples 1 to 7 and Comparative Examples 1 to 3> After coating Novec (registered trademark) 1720 (manufactured by 3M Japan Co., Ltd.) and drying, the mask substrate (opening 1 cm square) An appropriate amount of the negative photosensitive resin composition described above was dropped. Then, the negative photosensitive resin composition on the mask substrate after the mold release treatment was sandwiched by an alkali-free glass substrate (10 cm square, 0.7 mm thick) with a spacer made of silicone rubber having a thickness of 500 μm. The aforementioned alkali-free glass substrate is coated with an adhesive agent manufactured by Shin-Etsu Chemical Co., Ltd. (product name: KBM-5803) diluted with propylene glycol monomethyl ether acetate to a solution of 10% by mass, and dried for adhesion treatment Substrate. Using the aforementioned Iwasaki Electric Co., Ltd. UV-LED irradiation device, the sandwiched negative photosensitive resin composition was subjected to UV exposure at 140 mW/cm 2 for 3.2 seconds through the mask substrate after the mold release treatment. Bell, forming a light hardening part.

將前述光硬化部密著的無鹼玻璃基板由前述脫模處理後的光罩基板剝離之後，使用前述顯影裝置，以轉速200rpm使前述無鹼玻璃基板旋轉，同時將下述表1的實施例1~7及比較例1~3所記載的顯影液(23℃)以200mL/分鐘的流量噴霧吐出10秒鐘，進行顯影。然後，使用前述顯影裝置，以轉速300rpm使前述無鹼玻璃基板旋轉，同時將下述表1的實施例1~7及比較例1~3所記載的沖洗液(23℃)以200mL/分鐘的流量噴霧吐出20秒鐘，進行沖洗。然後，使用前述顯影裝置，以3000rpm使前述無鹼玻璃基板旋轉30秒鐘，進行乾燥。然後，使用前述顯影裝置，依照與上述方法同樣的方法再度進行顯影/沖洗/乾燥。接下來，在23℃的溫度條件下靜置2小時，然後使用前述CCS股份有限公司製的UV-LED裝置，以50mW/cm2 進行UV曝光111秒鐘，進一步以100℃的熱板加熱10分鐘。結果，在前述密著處理後的無鹼玻璃基板上製作出1cm見方、厚度0.5mm的光硬化物。所製作出的1cm見方、厚度0.5mm的光硬化物的頂面如表1所示般，為平面形狀。After peeling the alkali-free glass substrate adhered to the photohardening part from the mask substrate after the release process, the alkali-free glass substrate was rotated at a rotation speed of 200 rpm using the developing device, and the examples in Table 1 below were used to rotate the alkali-free glass substrate The developer (23°C) described in 1 to 7 and Comparative Examples 1 to 3 was sprayed and discharged at a flow rate of 200 mL/min for 10 seconds to perform development. Then, using the aforementioned developing device, the aforementioned alkali-free glass substrate was rotated at a rotation speed of 300 rpm, and the rinse solution (23°C) described in Examples 1 to 7 and Comparative Examples 1 to 3 in the following Table 1 was adjusted at 200 mL/min. The flow spray is spit out for 20 seconds to rinse. Then, using the aforementioned developing device, the aforementioned alkali-free glass substrate was rotated at 3000 rpm for 30 seconds and dried. Then, using the aforementioned developing device, developing/rinsing/drying is performed again in the same way as the above-mentioned method. Next, let it stand for 2 hours at a temperature of 23°C, and then use the aforementioned UV-LED device manufactured by CCS Co., Ltd. to perform UV exposure at 50mW/cm 2 for 111 seconds, and further heat it with a hot plate at 100°C for 10 minute. As a result, on the alkali-free glass substrate after the adhesion treatment, a photocured product having a square of 1 cm and a thickness of 0.5 mm was produced. As shown in Table 1, the top surface of the photocured material having a square of 1 cm and a thickness of 0.5 mm was a flat surface.

＜實施例8＞ 除了將前述脫模處理後的光罩基板變更為脫模處理後的附遮光膜的樹脂製模具(約100μm厚的反轉透鏡形狀)，並將前述500μm厚的聚矽氧橡膠製間隔物變更為600μm厚的聚矽氧橡膠製間隔物，顯影液及沖洗液變更為下述表1的實施例8所記載的顯影液及沖洗液以外，以與前述1cm見方、厚度0.5mm的光硬化物的製作方法同樣的方法製作出具有透鏡形狀的光硬化物。所製作出的具有透鏡形狀的光硬化物的頂面如表1所示般，為曲面形狀。前述附遮光膜的樹脂製模具的脫模處理方法，與前述光罩基板的脫模處理方法同樣。<Example 8> In addition to changing the mask substrate after the release process to a resin mold with a light-shielding film after the release process (approximately 100μm thick inverted lens shape), and the aforementioned 500μm thick silicone rubber spacer A spacer made of silicone rubber with a thickness of 600μm. The developer and rinse solution were changed to the developer and rinse solution described in Example 8 of Table 1 below, and the same as the above-mentioned 1cm square and 0.5mm thick photo-cured material. The production method of the same method to produce a lens-shaped photo-cured object. As shown in Table 1, the top surface of the produced photocured material having a lens shape was curved. The mold release processing method of the said resin mold with a light-shielding film is the same as the mold release processing method of the said mask board|substrate.

[麓部龜裂評估] 對於前述頂面為平面形狀的光硬化物及前述頂面為曲面形狀的光硬化物，分別以前述光學顯微鏡來觀察該光硬化物的麓部。將在前述光硬化物的麓部確認有龜裂的情況判定為"×"，將該光硬化物的麓部沒有觀察到龜裂的情況判定為"○"，將其結果揭示於下述表2。[Assessment of foot cracks] Regarding the photo-cured object with a flat top surface and the photo-cured object with a curved top surface, the foot of the photo-cured object was observed with the optical microscope. The case where cracks were confirmed at the foot of the photocured material was judged as "×", and the case where no cracks were observed at the foot of the photocured material was judged as "○", and the results are disclosed in the following table 2.

[殘渣評估] 以前述光學顯微鏡觀察在前述密著處理後的無鹼玻璃基板上所製作出的光硬化物的周邊。將在前述光硬化物的周邊確認有殘渣的情況判定為"×"，將該光硬化物的周邊沒有觀察到殘渣的情況判定為"○"，將其結果一起揭示於下述表2。[Residual Evaluation] The periphery of the photocured material produced on the alkali-free glass substrate after the adhesion treatment was observed with the optical microscope. The case where residues were confirmed around the photo-cured material was judged as "×", and the case where no residues were observed around the photo-cured material was judged as "○", and the results are shown in Table 2 below.

Figure 02_image001
Figure 02_image001

在上述表1中，GBL表示γ-丁內酯，THFA表示四氫呋喃甲醇，IPE表示二異丙基醚，EL表示乳酸乙酯，EtOH表示乙醇，MCH表示甲基環己烷，Vertrel XF表示Vertrel(註冊商標)XF(三井･科慕氟產品股份有限公司製)。在顯影液或沖洗液為混合溶劑的情況，將其混合比率以質量比來表示。In Table 1, GBL means γ-butyrolactone, THFA means tetrahydrofuran methanol, IPE means diisopropyl ether, EL means ethyl lactate, EtOH means ethanol, MCH means methylcyclohexane, Vertrel XF means Vertrel( Registered trademark) XF (manufactured by Mitsui & Chemours Fluorine Products Co., Ltd.). When the developer or rinsing liquid is a mixed solvent, the mixing ratio is expressed as a mass ratio.

Figure 02_image003
Figure 02_image003

由上述表2所示的結果可知，藉由將實施例1至實施例8所記載的顯影液及沖洗液適用於透鏡製造時的顯影步驟及沖洗步驟，可抑制所製作出的光硬化物的麓部的龜裂，且可抑制殘渣。From the results shown in Table 2 above, it can be seen that by applying the developer and rinsing solution described in Examples 1 to 8 to the development step and the rinsing step during lens manufacturing, it is possible to suppress the deterioration of the produced photocured material. Cracks at the foot and can suppress residues.

Claims (12)

一種樹脂製透鏡之製造方法，其係具有： 在形成具有開口部的圖案的支持體上塗佈負型感光性樹脂組成物之步驟； 使前述負型感光性樹脂組成物與具有目標透鏡形狀的反轉圖案及遮光膜的模具接觸之壓印步驟； 在前述壓印步驟之後，透過前述模具使前述負型感光性樹脂組成物曝光，在前述開口部形成光硬化部之光硬化步驟； 使前述光硬化部與前述模具分離之脫模步驟； 在前述脫模步驟之後，使用含有γ-丁內酯的顯影液除去前述負型感光性樹脂組成物的未硬化部，使前述光硬化部露出，形成光硬化物之顯影步驟； 在前述顯影步驟之後，使用含有選自由乳酸酯、碳原子數1至5之直鏈或支鏈醇、具有至少一個甲基或乙基作為取代基之環己烷衍生物及碳原子數4至8之氫氟碳化物所構成的群中的化合物的沖洗液進行沖洗處理之沖洗步驟； 除去前述沖洗液之乾燥步驟；及 在前述乾燥步驟之後，使前述光硬化物的全面曝光之步驟。A method for manufacturing a resin lens, which has: A step of coating a negative photosensitive resin composition on a support formed with a pattern having openings; Imprinting step of bringing the negative photosensitive resin composition into contact with a mold having a reversal pattern of the target lens shape and a light-shielding film; After the embossing step, the negative photosensitive resin composition is exposed through the mold to form a photo-curing step in the opening; The demolding step of separating the aforementioned light hardening part from the aforementioned mold; After the demolding step, a developing solution containing γ-butyrolactone is used to remove the uncured portion of the negative photosensitive resin composition to expose the photo-cured portion to form a photo-cured product; After the aforementioned development step, a cyclohexane derivative containing a lactic acid ester, a linear or branched alcohol having 1 to 5 carbon atoms, a substituent having at least one methyl or ethyl group, and a carbon atom number of 4 are used. The rinsing liquid of the compound in the group consisting of up to 8 hydrofluorocarbons undergoes the rinsing step of the rinsing process; The drying step of removing the aforementioned rinse liquid; and After the drying step, a step of exposing the entire surface of the photocured material. 如請求項1之樹脂製透鏡之製造方法，其中在前述光硬化步驟之後、前述脫模步驟之前、中途或後，進一步具有將前述光硬化部加熱的步驟。The method for manufacturing a resin lens according to claim 1, wherein after the photocuring step, before, during or after the demolding step, there is further a step of heating the photocuring part. 如請求項1或2之樹脂製透鏡之製造方法，其中在使前述光硬化物的全面曝光之步驟之後，進一步具有將該光硬化物加熱之後烘步驟。The method of manufacturing a resin lens according to claim 1 or 2, wherein after the step of exposing the entire surface of the photocured material, the photocured material is heated and then baked. 如請求項1至3中任一項之樹脂製透鏡之製造方法，其中在使前述光硬化物的全面曝光之步驟之後，進一步具有在該光硬化物的表面形成抗反射膜之步驟。The method for manufacturing a resin lens according to any one of claims 1 to 3, wherein after the step of exposing the entire surface of the photocured material, there is a step of forming an anti-reflection film on the surface of the photocured material. 如請求項1至4中任一項之樹脂製透鏡之製造方法，其中在前述乾燥步驟之後，使前述光硬化物的全面曝光之步驟之前，進一步具有前述顯影步驟、前述沖洗步驟及前述乾燥步驟。The method for manufacturing a resin lens according to any one of claims 1 to 4, wherein after the drying step, before the step of fully exposing the photocured material, the development step, the rinsing step, and the drying step are further provided . 如請求項1至5中任一項之樹脂製透鏡之製造方法，其中前述顯影液或前述沖洗液進一步含有具有環狀構造且可具有醚鍵之碳原子數5或6之醇。The method for manufacturing a resin lens according to any one of claims 1 to 5, wherein the developer or the rinse solution further contains an alcohol having a cyclic structure and a carbon number of 5 or 6 which may have an ether bond. 如請求項6之樹脂製透鏡之製造方法，其中前述碳原子數5或6之醇為四氫呋喃甲醇或環己醇。The method for manufacturing a resin lens according to claim 6, wherein the alcohol having 5 or 6 carbon atoms is tetrahydrofuran methanol or cyclohexanol. 如請求項6或7之樹脂製透鏡之製造方法，其中前述沖洗液含有具有至少一個甲基或乙基作為取代基之環己烷衍生物及前述碳原子數5或6之醇，相對於該環己烷衍生物及該碳原子數5或6之醇的合計100質量%，含有該環己烷衍生物至少50質量%。The method for producing a resin lens according to claim 6 or 7, wherein the rinse solution contains a cyclohexane derivative having at least one methyl or ethyl group as a substituent and the alcohol with 5 or 6 carbon atoms, relative to the A total of 100% by mass of the cyclohexane derivative and the alcohol having 5 or 6 carbon atoms contains at least 50% by mass of the cyclohexane derivative. 如請求項1至8中任一項之樹脂製透鏡之製造方法，其中前述負型感光性樹脂組成物含有一分子中具有至少一個(甲基)丙烯醯基的化合物、經過表面修飾的二氧化矽粒子及光自由基聚合起始劑。The method for manufacturing a resin lens according to any one of claims 1 to 8, wherein the negative photosensitive resin composition contains a compound having at least one (meth)acryloyl group in one molecule, and a surface-modified dioxide Silicon particles and light radical polymerization initiator. 一種使用於樹脂製透鏡的製造之沖洗液，其含有前述具有至少一個甲基或乙基作為取代基之環己烷衍生物及具有環狀構造且可具有醚鍵之碳原子數5或6之醇。A rinsing solution used in the manufacture of resin lenses, which contains the aforementioned cyclohexane derivative with at least one methyl or ethyl group as a substituent and a cyclic structure with 5 or 6 carbon atoms that may have an ether bond alcohol. 如請求項10之沖洗液，其中前述環己烷衍生物為甲基環己烷，前述碳原子數5或6之醇為四氫呋喃甲醇或環己醇。Such as the rinse solution of claim 10, wherein the aforementioned cyclohexane derivative is methylcyclohexane, and the aforementioned alcohol with 5 or 6 carbon atoms is tetrahydrofuran methanol or cyclohexanol. 如請求項10或11之沖洗液，其中相對於前述環己烷衍生物及前述碳原子數5或6之醇的合計100質量%，含有該環己烷衍生物至少50質量%。The rinsing liquid of claim 10 or 11, which contains at least 50% by mass of the cyclohexane derivative with respect to 100% by mass of the total of the aforementioned cyclohexane derivative and the aforementioned alcohol with 5 or 6 carbon atoms.
TW109134267A 2019-11-15 2020-09-30 Method for manufacturing a resin lens using a developer and a rinse solution, and the rinse solution TWI837425B (en)

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