JP2013043983A - Photocurable resin composition, wafer-level lens, and method for producing the lens - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded body being excellent in optical characteristics and process adaptability, having only small release force from a mold, and being excellent in glass adhesiveness.SOLUTION: There is provided the photocurable resin composition including: (A) a resin having an alicyclic hydrocarbon group; (B) a compound having an alicyclic hydrocarbon group and a polymerizable group; (C) a compound generating a radical or an acid by irradiation of an active ray or a radioactive ray; and (D) a surfactant, and there are provided a lens, in particular, a wafer-level lens, formed by using the photocurable resin composition, and a method for producing the lens and the wafer-level lens.

Description

  The present invention relates to a photocurable resin composition, a lens produced using the photocurable resin composition, and a wafer level lens. The present invention also relates to a method for manufacturing a lens and a wafer level lens.

  In recent years, portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units. Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor or a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, and a lens that forms a subject image on the solid-state imaging device. ing.

  With the downsizing / thinning of portable terminals and the widespread use of portable terminals, further reduction in size / thinning is required for imaging units mounted on the portable terminals, and productivity is required. In response to such a request, a lens substrate on which a plurality of lenses are formed and a sensor substrate on which a plurality of solid-state image sensors are formed are combined in an integrated manner, and then each lens substrate includes a lens and a solid-state image sensor. In addition, a method of mass-producing an imaging unit by cutting a sensor substrate is known. As another manufacturing method, for example, only a lens is produced on a glass wafer, cut into an appropriate size for use in combination with individual sensors, and imaged in combination with an image sensor that has been separated into pieces. A method of manufacturing a unit, a method in which only a resin is used, a plurality of lenses are formed with a mold, these are combined on a sensor substrate and cut, and a lens is cut into a size to be combined with an individual sensor, and separated in advance. It is possible to adopt a method of manufacturing an imaging unit by combining with an image sensor.

  Here, in order to manufacture an optical component such as a lens, a photocurable resin composition is employed as an alternative to a glass lens. Such a photocurable resin composition is poured into a mold or the like and cured to be molded. In particular, a photocurable resin composition that contains a polymer having a polymerizable group called a prepolymer to reduce curing shrinkage has been studied. As such a photocurable resin composition, the thing of patent document 1 and 2 is known. Patent Document 1 discloses a technique for reducing volume shrinkage during curing and forming a fine shape with high accuracy by photopolymerizing a composition containing an alicyclic hydrocarbon skeleton and a radical polymerizable monomer. . The curable resin composition described in Patent Document 1 has small shrinkage due to curing, good releasability, excellent scratch resistance, and excellent long-term stability at 60 ° C. On the other hand, Patent Document 2 describes a curable resin composition containing adamantyl acrylate.

JP 2003-286316 A JP 2006-213851 A

Here, the compositions described in Patent Documents 1 and 2 have poor process suitability at the time of lens production, and are difficult to use for the production of lenses, particularly wafer level lenses. One of the causes is that the compositions described in Patent Documents 1 and 2 have high viscosity. Moreover, in patent document 2, it is mention | raise | lifted that the transparency of the lens obtained is inferior.
On the other hand, in the lens field, there is a demand for a curable resin composition that can produce a lens that has a small peel force from a mold and excellent adhesion to glass. The object of the present invention is to provide a photocurable resin composition that solves such problems. Furthermore, a lens having a high refraction and a high Abbe number has a high technical difficulty.

  As a result of investigation by the inventors of the present application under the above problems, as a resin that is a main component of the photocurable resin composition, a resin having an aliphatic cyclic hydrocarbon group is used, and as a polymerizable compound component, It has been found that the above-mentioned problems can be solved by employing an aliphatic cyclic hydrocarbon group and further using a surfactant in combination. Specifically, it was achieved by the following means <1>, preferably <2> to <14>.

〔一般式（１）中、Ｒ¹は、水素原子または置換基を表し、Ｌ¹は二価の連結基または単結合を表し、環αは単環式または多環式の環を表す。〕
＜９＞前記（Ａ）樹脂が、さらに、下記一般式（３）で表される繰返単位を含む、＜８＞に記載の光硬化性樹脂組成物。

〔一般式（３）中、Ｒ³〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、Ｌ³は二価の連結基または単結合を表す。〕
＜１０＞ウエハレベルレンズ用である、＜１＞〜＜９＞のいずれか１項に記載の光硬化性樹脂組成物。
＜１１＞＜１＞〜＜１０＞のいずれか１項に記載の光硬化性樹脂組成物を用いて形成された、レンズ。
＜１２＞＜１＞〜＜１０＞のいずれか１項に記載の光硬化性樹脂組成物を用いて形成された、ウエハレベルレンズ。
＜１３＞＜１＞〜＜１０＞のいずれか１項に記載の光硬化性樹脂組成物を硬化することを含む、レンズの製造方法。
＜１４＞＜１＞〜＜１０＞のいずれか１項に記載の光硬化性樹脂組成物を硬化することを含む、ウエハレベルレンズの製造方法。 <1> (A) a resin having an aliphatic cyclic hydrocarbon group,
(B) a compound having an aliphatic cyclic hydrocarbon group and having a polymerizable group,
(C) A photocurable resin composition comprising a compound that generates radicals or acids upon irradiation with actinic rays or radiation, and (D) a surfactant.
<2> The photocurable resin composition according to <1>, wherein the polymerizable group of the (B) compound is a (meth) acryloyl group and / or an epoxy group.
<3> (D) The photocurable resin composition according to <1> or <2>, wherein the surfactant contains a silicon atom and / or a fluorine atom.
<4> The photocurability according to any one of <1> to <3>, wherein the ratio (mass ratio) of the (A) resin and the (B) compound is 1: 1.9 to 1: 4. Resin composition.
<5> (A) The photocurable resin according to any one of <1> to <4>, wherein the resin includes a repeating unit containing an aliphatic cyclic hydrocarbon group and a repeating unit containing a polymerizable group. Composition.
<6> The photocurable resin composition according to any one of <1> to <5>, wherein the aliphatic cyclic hydrocarbon group included in the (A) resin is a hydrocarbon group having 6 or more carbon atoms.
<7> (A) The resin has at least one polymerizable group selected from acryloyl group, methacryloyl group, vinyl group, allyl group, isocyanate group, and epoxy group, <1> to <6> The photocurable resin composition according to any one of the above.
<8> The photocurable resin composition according to any one of <1> to <7>, wherein the (A) resin has a repeating unit represented by the following general formula (1): .

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]
<9> The photocurable resin composition according to <8>, wherein the (A) resin further includes a repeating unit represented by the following general formula (3).

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ]
<10> The photocurable resin composition according to any one of <1> to <9>, which is used for a wafer level lens.
<11> A lens formed using the photocurable resin composition according to any one of <1> to <10>.
<12> A wafer level lens formed using the photocurable resin composition according to any one of <1> to <10>.
<13> A method for producing a lens, comprising curing the photocurable resin composition according to any one of <1> to <10>.
<14> A method for producing a wafer level lens, comprising curing the photocurable resin composition according to any one of <1> to <10>.

  According to the present invention, it has become possible to provide a curable resin composition capable of providing a molded article having good optical properties and process suitability, a small peeling force from a mold, and good glass adhesion.

It is a top view which shows an example of a structure of a wafer level lens. FIG. 2 is a cross-sectional view taken along line AA of the configuration of the wafer level lens shown in FIG. 1. It is a figure which shows the state which is supplying the molding material used as a lens to a board | substrate. 4A to 4C are diagrams showing a procedure for forming a lens on a substrate with a mold. It is a figure which shows the other structural example of a wafer level lens.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The photocurable composition of the present invention includes (A) a resin having an aliphatic cyclic hydrocarbon group, (B) a compound having an aliphatic cyclic hydrocarbon group and having a polymerizable group, (C) an actinic ray or radiation. A compound that generates a radical or an acid upon irradiation, and (D) a surfactant.
Hereinafter, the detail of the photocurable resin composition of this invention is demonstrated.

〔一般式（１）中、Ｒ¹は、水素原子または置換基を表し、Ｌ¹は二価の連結基または単結合を表し、環αは単環式または多環式の環を表す。〕
一般式（１）中、Ｒ¹は、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましい。
一般式（１）中、Ｌ¹は、−ＣＯ−、−Ｏ−、−ＣＨ₂−およびこれらの組み合わせからなる基から選択される二価の連結基、または、単結合であることが好ましく、−ＣＯ−、−Ｏ−、−ＣＨ₂−およびこれらの組み合わせからなる基から選択される二価の連結基がより好ましい。Ｌ¹は、主鎖に結合する側が、−Ｃ（＝Ｏ）−Ｏ−であることが好ましい。
一般式（１）中、αは、炭素数６〜２０の炭素原子を骨格とする環状構造であることが好ましく、下記群（１）から選択される構造を骨格とする環状構造であることがより好ましい。
群（１）

上記環状構造は、置換基を有していてもよいし、置換基を有していなくてもよい。置換基を有している場合、アルキル基が好ましく、炭素数１〜３のアルキル基がより好ましく、メチル基がさらに好ましい。

〔一般式（２）中、環βは単環式または多環式の環を表す。〕
一般式（２）中、βは、炭素数６〜２０の炭素原子を骨格とする環状構造であり、下記群（２）から選択される構造を骨格とする環状構造であることがより好ましい。

上記環状構造は、置換基を有していてもよいし、置換基を有していなくてもよい。置換基を有している場合、アルキル基、アリル基、オキソ基、ヒドロキシ基、シアノ基、ハロゲン原子が挙げられ、これらはさらにこれら基によって置換されていてもよい。置換基は、炭素原子、水素原子、酸素原子および窒素原子のいずれか１種以上から構成されることが好ましい。上記置換基は、炭素原子、酸素原子および窒素原子の合計原子数が、１〜１０個であることが好ましく、１〜５個であることがより好ましい。 [Resin (A)]
The resin (A) used in the present invention has an aliphatic cyclic hydrocarbon group.
The aliphatic cyclic hydrocarbon group has a main chain composed of carbon atoms, and has an alicyclic structure in the main chain or side chain.
The resin (A) preferably further has a polymerizable group. As a preferable aspect of the resin (A) of the present invention, a repeating unit having a main chain composed of carbon atoms and having an alicyclic structure in the main chain or a side chain, and a repeating unit having a polymerizable group ( Preferably, there is an embodiment having a repeating unit having a polymerizable group in the side chain, and a more preferred embodiment has a main chain composed of carbon atoms and an alicyclic structure in the main chain or side chain. The aspect which has a repeating unit which has the repeating unit which has a repeating unit which has a principal chain which has a carbon atom, and has a polymeric group in a side chain is mentioned.
Here, (A) resin has at least one kind of repeating unit of the repeating unit represented by the following general formula (1) and the repeating unit represented by the following general formula (2). Is preferred.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ]
In general formula (1), R ¹ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group.
In general formula (1), L ¹ is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —CH ₂ — and combinations thereof, or a single bond, More preferred are divalent linking groups selected from the group consisting of —CO—, —O—, —CH ₂ —, and combinations thereof. L ¹ is preferably —C (═O) —O— on the side bonded to the main chain.
In the general formula (1), α is preferably a cyclic structure having a carbon atom having 6 to 20 carbon atoms as a skeleton, and a cyclic structure having a structure selected from the following group (1) as the skeleton. More preferred.
Group (1)

The cyclic structure may have a substituent or may not have a substituent. When it has a substituent, an alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is further more preferable.

[In general formula (2), ring β represents a monocyclic or polycyclic ring. ]
In General Formula (2), β is a cyclic structure having a carbon atom having 6 to 20 carbon atoms as a skeleton, and more preferably a cyclic structure having a structure selected from the following group (2) as a skeleton.

The cyclic structure may have a substituent or may not have a substituent. When it has a substituent, an alkyl group, an allyl group, an oxo group, a hydroxy group, a cyano group, and a halogen atom are exemplified, and these may be further substituted with these groups. The substituent is preferably composed of at least one of a carbon atom, a hydrogen atom, an oxygen atom and a nitrogen atom. The total number of carbon atoms, oxygen atoms, and nitrogen atoms in the substituent is preferably 1 to 10, and more preferably 1 to 5.

  Of the general formulas (1) and (2), the general formula (1) is preferable.

〔一般式（３）中、Ｒ³〜Ｒ⁶はそれぞれ独立に水素原子または置換基を表し、Ｌ³は二価の連結基または単結合を表す。〕
Ｒ³は、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましい。
Ｒ⁴およびＲ⁵は、それぞれ、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましく、水素原子が特に好ましい。
Ｒ⁶は、水素原子またはアルキル基が好ましく、水素原子または炭素数１〜４のアルキル基がより好ましく、水素原子またはメチル基がさらに好ましい。
Ｌ³は、−ＣＯ−、−Ｏ−、−ＣＨ₂−およびこれらの組み合わせからなる基から選択される二価の連結基であることが好ましい。Ｌ³は、−Ｃ（＝Ｏ）−Ｏ−で表される構造を有することがより好ましい。 As the polymerizable group of the resin (A) in the present invention, an acryloyl group, a methacryloyl group (in this specification, an acryloyl group and a methacryloyl group may be collectively referred to as “(meth) acryloyl group”), a vinyl group An allyl group, an isocyanate group and an epoxy group are exemplified, a (meth) acryloyl group, an epoxy group and a vinyl group are more preferred, a (meth) acryloyl group and a vinyl group are more preferred, and a vinyl group is particularly preferred.
In the present invention, it is particularly preferable to include a repeating unit represented by the following general formula (3).

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ]
R ³ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
R ⁴ and R ⁵ are each preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, still more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.
R ⁶ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.
L ³ is preferably a divalent linking group selected from the group consisting of —CO—, —O—, —CH ₂ —, and combinations thereof. L ³ more preferably has a structure represented by —C (═O) —O—.

  (A) Resin can be normally synthesize | combined by a well-known method using the photocurable resin composition containing a polymerizable monomer. For example, polymerization may be performed by radical polymerization, or polymerization may be performed by ionic polymerization or ring-opening polymerization.

  As the repeating units represented by the general formula (1), the general formula (2), and the general formula (3), only one type may be used, or two or more types may be used in combination.

  Specific examples of the polymerizable compound that can form the repeating unit represented by the general formula (1) by polymerization are shown below in A1, and the repeating unit represented by the general formula (2) is Specific examples of the polymerizable compound that can be formed are shown in A2 below, and specific examples of the polymerizable compound that can form the repeating unit represented by the general formula (3) are shown as A3 below. The monomers that can be employed in the invention are not limited to these specific examples.

<Copolymerizable monomer>
(A) resin used by this invention is represented by the repeating unit represented by General formula (1), the repeating unit represented by General formula (2), or General formula (3) by superposing | polymerizing. You may manufacture by copolymerizing another monomer with the monomer which can form a repeating unit. As such other monomers, those described in Polymer Handbook 2nd ed., J. Brandrup, Wiley lnterscience (1975) Chapter 2 Page 1 to 483 can be used.

  Specifically, for example, styrene derivatives, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylcarbazole, acrylic acid, methacrylic acid, acrylic esters, methacrylic esters, acrylamides, methacrylamides, dialkyl itaconates And compounds having one addition polymerizable unsaturated bond selected from dialkyl esters or monoalkyl esters of fumaric acid.

  Examples of the styrene derivative include styrene, 2,4,6-tribromostyrene, 2-phenylstyrene, 4-chlorostyrene and the like.

  Examples of the acrylic esters include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, trimethylolpropane monoacrylate, and benzyl acrylate. , Benzyl methacrylate, methoxybenzyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, and the like.

  Examples of the methacrylic acid esters include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, tert-butyl methacrylate, chloroethyl methacrylate, 2-hydroxyethyl methacrylate, trimethylolpropane monomethacrylate, benzyl methacrylate, and methoxy. Examples include benzyl methacrylate, furfuryl methacrylate, and tetrahydrofurfuryl methacrylate.

  Examples of the acrylamides include acrylamide, N-alkylacrylamide (alkyl group having 1 to 3 carbon atoms, such as methyl group, ethyl group, propyl group), N, N-dialkylacrylamide (alkyl group having 1 carbon atom). ~ 6), N-hydroxyethyl-N-methylacrylamide, N-2-acetamidoethyl-N-acetylacrylamide and the like.

  Examples of the methacrylamides include methacrylamide, N-alkyl methacrylamide (alkyl groups having 1 to 3 carbon atoms, such as methyl, ethyl, propyl), N, N-dialkyl methacrylamide (as alkyl groups). Are those having 1 to 6 carbon atoms), N-hydroxyethyl-N-methylmethacrylamide, N-2-acetamidoethyl-N-acetylmethacrylamide and the like.

  Examples of the dialkyl itaconates include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate. Examples of the dialkyl esters or monoalkyl esters of the fumaric acid include dibutyl fumarate.

  In addition, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile, maleilonitrile and the like can also be mentioned.

  In the resin (A), the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) is represented by the general formula (3) as 5 to 100% by mass. It is preferable that the repeating unit is composed of 0 to 95% by weight and 5% by mass or less of the repeating unit derived from another polymerizable monomer. Furthermore, it is preferable that the repeating unit represented by General formula (1) and / or the repeating unit represented by General formula (2) is 5-95 mass%, and is 30-90 mass%. Is more preferable, and it is still more preferable that it is 40-80 mass%. On the other hand, the polymerizable monomer that can form the repeating unit represented by the general formula (3) is preferably 5 to 95% by mass, more preferably 10 to 70% by mass, and still more preferably. Is 20-60 mass%.

  The molecular weight of the resin (A) is preferably 40,000 or less in terms of viscosity, and more preferably 3,000 to 25,000 from the viewpoint of volume shrinkage.

  The molecular weight dispersion (Pd) of the resin (A) is preferably (1.0 to 6.0), and more preferably 1.0 to 3.5.

  The resin (A) is preferably included in the photocurable resin composition of the present invention in a range of 5 to 60% by mass, more preferably in a range of 7 to 50% by mass, and 10 to 40%. More preferably, it is contained in the range of mass%.

[Polymerizable compound (B)]
The polymerizable compound (B) used in the present invention is characterized by having a polymerizable group with an aliphatic cyclic hydrocarbon group. However, the polymerizable compound (B) is intended to exclude those corresponding to the above-mentioned “(A) resin having an aliphatic cyclic hydrocarbon group and having a weight average molecular weight of 40,000 or less”. 000 or less, preferably a monomer or oligomer.

  The polymerizable group is preferably an acryloyl group, a methacryloyl group, a propenyl group, a vinyl group, an allyl group, an isocyanate group, or an epoxy group, and is preferably cured by at least one of a (meth) acryloyl group and an epoxy group. From the viewpoint of sex. One polymerizable group may be included in one molecule, but two or more polymerizable groups may be included.

The alicyclic structure having 6 to 16 carbon atoms is more preferable, and the alicyclic structure having 6 to 10 carbon atoms is further preferable.
The polymerizable group and the alicyclic structure are bonded directly or via a linking group, and are selected from a group that is bonded directly or is composed of —CO—, —O—, —CH ₂ —, and a combination thereof. More preferably, they are bonded via a divalent linking group.
The molecular weight of the polymerizable compound (B) is preferably 100 to 700, more preferably 130 to 600, and still more preferably 150 to 400.
Although the specific example of a polymeric compound (B) is shown below, it is not limited to these structures.

  These two or more polymerizable compounds (B) may be used alone or in combination of two or more in the photocurable resin composition. In the present invention, it is preferable to use a polymerizable compound having a (meth) acrylate group and a polymerizable compound having an epoxy group in combination.

  The two or more polymerizable compounds (B) are preferably included in the range of 20 to 90% by mass in the photocurable resin composition of the present invention, and may be included in the range of 25 to 80% by mass. More preferably, it is contained in the range of 30 to 70% by mass.

  The ratio of the resin (A) to the polymerizable compound (B) is preferably 1: 1.9 to 1: 4 from the viewpoint of viscosity, and preferably 1: 2.3 to 1: 3.5. From the viewpoint of volumetric shrinkage, it is more preferable.

[(C) Compound that generates radical or acid upon irradiation with actinic ray or radiation]
The compound that generates radicals upon irradiation with actinic rays or radiation according to the present invention (hereinafter also referred to as “(photo) polymerization initiator”) is known as, for example, a radical polymerization initiator without departing from the gist of the present invention. It can be selected from known compounds.
As the polymerization initiator, for example, a photopolymerization initiator having photosensitivity to visible light from the ultraviolet region is preferable, and an activator that generates an active radical by generating some action with a photoexcited sensitizer. Alternatively, an initiator that initiates cationic polymerization according to the type of monomer may be used.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As an aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, compounds described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source of 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the carbazole N position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, ADEKA The compounds described in JP 2010-15025 A and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, the ketoxime compounds described in International Publication No. 2009-131189, triazine skeleton and oxime Even if a compound described in US Pat. No. 7,556,910 containing a skeleton in the same molecule, a compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-ray light source, etc. Good.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A are particularly preferable in terms of high light absorption and high sensitivity.
In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be suitably used. .

Most preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-267979 and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, the oxime photopolymerization initiator is preferably a compound represented by the following formula (1). The N—O bond of the oxime may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .

（式（１）中、Ｒ及びＢは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表す。）
前記Ｒで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
前記一価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、１以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基又はアリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。

(In formula (1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.)
The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group. Moreover, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, and specifically, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group. , Dodecyl group, okdadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1- Naphthoylmethyl group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2- Methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, and , 3 Nitorofenashiru group can be exemplified.

The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, specifically, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, or a 9-anthryl group. 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m- and p-tolyl group, Xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, tarnaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, ASEAN Trirenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, ter Nthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an ovalenyl group.

The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, specifically, an acetyl group, a propanoyl group, a butanoyl group, a trifluoroacetyl group, a pentanoyl group, a benzoyl group, 1-naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2 -Methoxybenzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and And 4-methoxybenzoyl group.

The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, or a hexyloxy group. Examples thereof include a carbonyl group, an octyloxycarbonyl group, a decyloxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

Specific examples of the aryloxycarbonyl group which may have a substituent include phenoxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanyl. Phenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxy Carbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl , 4-fluorophenyl oxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group which may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathiyl Nyl, 2H-pyrrolyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolizinyl, isoindolyl, 3H-indolyl, indolyl, 1H-indazolyl, purinyl 4H-quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl Group Midinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolidinyl group Examples include a group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxanthryl group.

  Specific examples of the alkylthiocarbonyl group which may have a substituent include a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, and an octadecylthiocarbonyl group. Examples thereof include a group and a trifluoromethylthiocarbonyl group.

  Specific examples of the arylthiocarbonyl group which may have a substituent include a 1-naphthylthiocarbonyl group, a 2-naphthylthiocarbonyl group, a 4-methylsulfanylphenylthiocarbonyl group, and a 4-phenylsulfanylphenylthiocarbonyl group. 4-dimethylaminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3 -Chlorophenylthiocarbonyl group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenyl Two thiocarbonyl group, and a and a 4-methoxyphenylthiocarbonyl group.

  The monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Of these, the structures shown below are particularly preferred.
In the following structure, Y, X, and n have the same meanings as Y, X, and n in formula (2) described later, and preferred examples are also the same.

Examples of the divalent organic group represented by A include an alkylene group having 1 to 12 carbon atoms, a cyclohexylene group, and an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent. Examples of the substituent include the same substituents as those introduced into the substituted aryl group mentioned above as specific examples of the aryl group which may have a substituent.
Among these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  In the formula (1), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following formula (2).

（式（２）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａ及びＹは各々独立に二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）
式（２）におけるＲ、Ａ、及びＡｒは、前記式（１）におけるＲ、Ａ、及びＡｒと同義であり、好ましい例も同様である。

(In formula (2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n represents 0-5. (It is an integer.)
R, A, and Ar in formula (2) have the same meanings as R, A, and Ar in formula (1), and preferred examples are also the same.

  Examples of the monovalent substituent represented by X include an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic group, and a halogen atom. These groups may have one or more substituents. Examples of the substituent include the above-described substituents. Moreover, the substituent mentioned above may be further substituted by another substituent.

Among these, X is preferably an alkyl group from the viewpoints of solvent solubility and improvement in absorption efficiency in the long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

Examples of the divalent organic group represented by Y include the structures shown below. In the groups shown below, “” represents the bonding position between Y and an adjacent carbon atom in the formula (2).

  Among these, from the viewpoint of increasing sensitivity, the following structures are preferable.

（式（３）中、Ｒ及びＸは各々独立に一価の置換基を表し、Ａは二価の有機基を表し、Ａｒはアリール基を表し、ｎは０〜５の整数である。）
式（３）におけるＲ、Ｘ、Ａ、Ａｒ、及び、ｎは、前記式（２）におけるＲ、Ｘ、Ａ、Ａｒ、及び、ｎとそれぞれ同義であり、好ましい例も同様である。 Furthermore, the oxime compound is preferably a compound represented by the following formula (3).

(In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is an integer of 0 to 5.)
R, X, A, Ar, and n in Formula (3) have the same meanings as R, X, A, Ar, and n in Formula (2), respectively, and preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds that can be suitably used are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has high absorbance at 365 nm and 455 nm.

The molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
A known method can be used for the molar extinction coefficient of the compound. Specifically, for example, 0.01 g of an ultraviolet-visible spectrophotometer (Varian Inc., Carry-5 spctrophotometer) is used with an ethyl acetate solvent. It is preferable to measure at a concentration of / L.

You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
The content of the photopolymerization initiator in the radiation-sensitive composition (the total content in the case of two or more) is 0.1 with respect to the total amount (total mass) of the composition from the viewpoint of volume shrinkage. The range of -15 mass% is preferable, More preferably, it is the range of 0.5-10 mass%, Most preferably, it is the range of 0.5-8 mass%. Within this range, good sensitivity and pattern formability can be obtained.

The polymerizable composition may contain a sensitizer for the purpose of improving the radical generation efficiency of the photopolymerization initiator and increasing the photosensitive wavelength. As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-described (C) photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer used in the polymerizable composition include compounds described in paragraph numbers [0101] to [0154] of JP-A-2008-32803.
The content of the sensitizer in the polymerizable composition is preferably 0% by mass to 20% by mass in terms of solid content, and preferably 0% by mass to 0% by mass, from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. 15 mass% is more preferable.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

The compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as “acid generator”) is not particularly limited as long as it is a known compound, but preferably the following general formulas (ZI), (ZII), And a compound represented by (ZIII).

In the general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, there can be mentioned an alkylene group (e.g., butylene, pentylene).
Z ⁻ represents a non-nucleophilic anion (an anion having an extremely low ability to cause a nucleophilic reaction).

Examples of Z ⁻ include a sulfonate anion (an aliphatic sulfonate anion, an aromatic sulfonate anion, a camphor sulfonate anion, etc.), a carboxylate anion (an aliphatic carboxylate anion, an aromatic carboxylate anion, an aralkyl carboxylate anion). Etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group having 1 to 30 carbon atoms and a carbon number. 3-30 cycloalkyl groups are mentioned.
The aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms such as a phenyl group, a tolyl group, and a naphthyl group.

  The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specific examples thereof include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7), an alkylthio group (preferably 1 to 15 carbon atoms), an alkylsulfonyl group (preferably 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably 2 to 15 carbon atoms), an aryloxysulfonyl group (preferably carbon) Number 6-20), alkylaryloxysulfonyl group (preferably C7-20), cycloalkylary Examples thereof include an oxysulfonyl group (preferably having 10 to 20 carbon atoms), an alkyloxyalkyloxy group (preferably having 5 to 20 carbon atoms), a cycloalkylalkyloxyalkyloxy group (preferably having 8 to 20 carbon atoms), and the like. . About the aryl group and ring structure which each group has, an alkyl group (preferably C1-C15) can further be mentioned as a substituent.

The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 6 to 12 carbon atoms, such as benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, naphthylbutyl group, and the like.
Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, cycloalkylaryloxysulfonyl groups, and the like. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
Examples of other Z ⁻ include fluorinated phosphorus, fluorinated boron, and fluorinated antimony.

Z ⁻ includes an aliphatic sulfonate anion substituted with at least α-position of sulfonic acid with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group substituted with a fluorine atom. Bis (alkylsulfonyl) imide anions and tris (alkylsulfonyl) methide anions in which the alkyl group is substituted with a fluorine atom are preferred. The non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonate anion (more preferably 4 to 8 carbon atoms), a benzenesulfonate anion having a fluorine atom, still more preferably a nonafluorobutanesulfonate anion, or perfluorooctane. A sulfonate anion, a pentafluorobenzenesulfonate anion, and a 3,5-bis (trifluoromethyl) benzenesulfonate anion.
From the viewpoint of acid strength, the pKa of the generated acid is preferably −1 or less in order to improve sensitivity.

_Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include an aryl group (preferably having 6 to 15 carbon atoms), a linear or branched alkyl group (preferably having 1 to 10 carbon atoms), and a cycloalkyl group (having 3 carbon atoms). ~ 15 are preferred).

Of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , at least one is preferably an aryl group, more preferably all three are aryl groups. As the aryl group, in addition to a phenyl group, a naphthyl group, and the like, a heteroaryl group such as an indole residue and a pyrrole residue can be used. These aryl groups may further have a substituent. Examples of the substituent include halogen atoms such as nitro groups and fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms). ), An aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 2 carbon atoms). 7) and the like, but are not limited thereto.

Two selected from R ₂₀₁ , R ₂₀₂ and R ₂₀₃ may be bonded via a single bond or a linking group. Examples of the linking group include an alkylene group (preferably having 1 to 3 carbon atoms), —O—, —S—, —CO—, —SO ₂ — and the like, but are not limited thereto.

Preferred structures when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group include paragraphs 0047 and 0048 of JP-A-2004-233661, paragraphs 0040 to 0046 of JP-A-2003-35948, US2003 Compounds exemplified as formulas (I-1) to (I-70) in the specification of / 0224288A1, and formulas (IA-1) to (IA-54), formula (IB-1) in the specification of US2003 / 0077540A1 ) To (IB-24), and the like.

In particular, when at least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is not an aryl group, the following embodiment (1) or (2) is particularly preferable.

(1) At least one of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ has a structure represented by Ar—CO—X—, and the remaining group is a linear or branched alkyl group or a cycloalkyl group. If. At this time, when there are two remaining groups, two linear or branched alkyl groups or cycloalkyl groups may be bonded to each other to form a ring structure.

Here, Ar represents an aryl group which may have a substituent, and specifically, is the same as the aryl group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ . A phenyl group which may have a substituent is preferable.

  X represents an alkylene group which may have a substituent. Specifically, it is an alkylene group having 1 to 6 carbon atoms. Preferably it is a C1-C3 linear or branched alkylene group.

The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. Moreover, when the remaining groups are two, it is preferable that they are bonded to each other to form a ring structure (preferably a 5- to 7-membered ring).

(2) one or two of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are an aryl group which may have a substituent, and the remaining group is a linear or branched alkyl group or a cycloalkyl group; If there is.

At this time, as the aryl group include, the same as the aryl group of R _201, R ₂₀₂ and R _203, a phenyl group or a naphthyl group is preferable. The aryl group preferably has any one of a hydroxyl group, an alkoxy group, and an alkyl group as a substituent. More preferably, it is a C1-C12 alkoxy group as a substituent, More preferably, it is a C1-C6 alkoxy group.

  The remaining linear or branched alkyl group or cycloalkyl group preferably has 1 to 6 carbon atoms. These atomic groups may further have a substituent. When the remaining groups are two, the two may be bonded to each other to form a ring structure.

In general formulas (ZII) and (ZIII),
R ₂₀₄ to R ₂₀₇ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ are the same as the aryl group described as the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the aforementioned compound (ZI).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of the substituent include those that the aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ in the above-described compound (ZI) may have.

Z ⁻ represents a non-nucleophilic anion, and examples thereof include the same as the non-nucleophilic anion of Z ^{− in} formula (ZI).
Examples of the acid generator further include compounds represented by the following general formulas (ZIV), (ZV), and (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents an aryl group.
R ₂₀₈ , R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group or an aryl group.
A represents an alkylene group, an alkenylene group or an arylene group.
Among acid generators, particularly preferred examples are given below.

An acid generator can be used individually by 1 type or in combination of 2 or more types.
The content of the acid generator in the composition is preferably 0.1 to 20% by mass, more preferably 0.1 to 15% by mass, and still more preferably 0.1 to 20% by mass, based on the total solid content of the composition. 10% by mass.

Surfactant (D)
The photocurable resin composition of the present invention contains a surfactant. Surfactants include various surfactants such as fluorine-containing surfactants containing fluorine atoms, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants containing silicon atoms. A surfactant containing a silicon atom and / or a fluorine atom is preferable. The addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.005% by mass to 1.0% by mass with respect to the total mass of the photocurable resin composition. is there. Only one type of surfactant may be used, or two or more types may be combined.
In particular, the blending amount of the surfactant containing a fluorine atom is preferably 4% by weight or less of the solid content of the photocurable composition from the viewpoint of glass adhesion. The lower limit is not particularly defined, but can be, for example, (0.1) wt% or more.
The compounding quantity of the surfactant containing a silicon atom can be made into 0.5-10 mass% of solid content of a photocurable composition, for example, and it may be sufficient from a viewpoint of peeling force reduction, so that there is much addition amount. However, 0.5-5 mass% is preferable from a viewpoint of shape collapse and distortion.
However, this is not the case when a surfactant containing a silicon atom and a fluorine atom is used.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.).

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in a photocurable resin composition. .

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Sol Perth 20000 (manufactured by Nippon Lubrizol Corporation), and the like.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

Additive (E)
In addition, the curable resin composition of the present invention may contain additives such as a polymerization inhibitor and a dissolution regulator.
In the curable resin composition of the present invention, the components other than the above (A) to (D) are preferably 15% by mass or less.

Polymerization inhibitor The composition of the present invention may contain a polymerization inhibitor. Only one type of polymerization inhibitor may be used, or two or more types may be included. Polymerization inhibitors include phenolic hydroxyl group-containing compounds, quinones, N-oxide compounds, piperidine-1-oxyl free radical compounds, pyrrolidine-1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, And compounds selected from the group consisting of anilines, pyridines, aliphatic tertiary amines, and cationic dyes.

  Specifically, haloquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, resorcinol, catechol, t-butylcatechol, hydroquinone monoalkyl ether (for example, hydroquinone monomethyl ether, hydroquinone monobutyl ether), Benzoquinone, 4,4-thiobis (3-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2,6,6-tetramethylpiperidine and its Derivatives, di-t-butyl nitroxide, 2,2,6,6-tetramethylpiperidine-N-oxide and derivatives thereof, piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 4-o So-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6 6-tetramethylpiperidine 1-oxyl free radical, 4-maleimido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl Free radical, 3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical, N-nitrosophenylhydroxylamine cerium salt, N-nitrosophenylhydroxylamine aluminum salt, crystal violet, methyl violet, Ethyl violet, and Victoria Pure Blue BOH, N, N-diethylaniline, 4-methylaniline, 2,6-dimethylpyridine, 4-hydroxypyridine, tributylamine, trioctylamine, caryophyllene, and the like.

  As content in the composition of a polymerization inhibitor, 0.1-15 mass% is preferable with respect to the total amount (total mass) of a composition from a viewpoint of volume shrinkage, and 0.5-10 mass% is preferable. More preferably, 1-10 mass% is further more preferable.

Solvent The composition of the present invention may contain a solvent. The content is preferably 10% by mass or less, and more preferably 5% by mass or less from the viewpoint of reducing bubbles in the molded body.
However, it is preferable that the photocurable resin composition of the present invention does not substantially contain a solvent. “Substantially free” means, for example, that the content of the solvent is 1% by mass or less of the photocurable resin composition.

  The curable resin composition of the present invention can have a viscosity of 0.1 to 25 Pa · s, further 0.3 to 15 Pa · s, and further 0.3 to 7 Pa · s. It can be. In the curable resin composition of the present invention, high optical characteristics and low volume shrinkage can be maintained even with such a low viscosity.

In the photocurable resin composition of the present invention, the volume shrinkage when cured is preferably 10% or less, more preferably 5% or less, and further preferably 3% or less.
In the curable resin composition, it is technically difficult to achieve both high refraction and a high Abbe number. Specifically, it is difficult to achieve a refractive index of 1.5 or more and an Abbe number of 50 or more.
In conventional lens forming compositions, inorganic fine particles have been added to increase the refractive index and Abbe number. In the present invention, such inorganic fine particles are substantially not added (for example, And 1% by mass or less of the composition), a high refractive index and Abbe number can be achieved.
In the curable resin composition of the present invention, the haze after being cured is preferably 5% or less, and more preferably 3% or less.
The glass transition temperature when the photocurable resin composition of the present invention is cured is preferably 200 ° C. or higher, and particularly preferably 260 ° C. or higher.

<Optical parts>
The cured product of the curable resin composition of the present invention includes, for example, various display devices (liquid crystal display, plasma display, etc.), various projector devices (OHP, liquid crystal projector, etc.), optical fiber communication devices (optical waveguide, optical amplifier, etc.), It can also be preferably used as an optical component of a camera or a video camera.

  The optical component using the cured product of the present invention is particularly suitable for a lens.

<Wafer level lens>
Next, the wafer level lens of the present invention will be described. FIG. 1 is a plan view showing an example of the configuration of a wafer level lens. FIG. 2 is a cross-sectional view of the wafer level lens shown in FIG.
As shown in FIG. 2, the wafer level lens includes a substrate 10 and a plurality of lenses 12 arranged on the substrate 10. The plurality of lenses 12 are arranged one-dimensionally or two-dimensionally with respect to the substrate 10. Further, a light shielding film 14 that prevents light transmission from a portion other than the lens may be provided between the plurality of lenses 12.
In the present embodiment, a configuration in which a plurality of lenses 12 are two-dimensionally arranged with respect to the substrate 10 as illustrated in FIG. 1 will be described as an example. The lens 12 and the substrate 10 are made of a cured product of the photocurable resin composition of the present invention, and are molded integrally on the substrate 10 or formed as separate structures and fixed on the substrate. It has been The photocurable resin composition of the present invention is preferably used when the lens 12 and the substrate 10 are integrally formed.
The size of the wafer level lens of the present invention is not particularly defined, and can be, for example, 6 to 12 inches. However, the curable resin composition of the present invention is preferable in that a good wafer level lens can be produced even when the size is 8 inches or more. In particular, it can be more preferably applied to 8 to 12 inch size ones. The wafer level lens is likely to warp when the size is increased, but when the curable resin composition of the present invention is used, a good wafer level lens can be produced even when the size is 8 inches or more.
Here, although an example was given, the wafer level lens of the present invention is not limited to this mode, and can take various modes such as a multi-layer structure and a lens module separated by dicing.

<Method for producing molded body>
As a method for producing a molded article such as an optical component using the photocurable resin composition of the present invention, a known method can be widely adopted. For example, the photocurable resin composition of the present invention can be filled in a mold, and cured by irradiation with active energy and / or heating. In the present invention, it is particularly preferable to use both active energy irradiation and heating. By adopting such means, the amount of cure shrinkage in the molding die (preferably the molding die) is suppressed, so that the shape transferability of the molding die is excellent, and the molding gap (clearance) is improved. Can be suppressed.

<Formation of wafer level lens>
Next, an example of a method for forming a wafer level lens will be described. FIG. 3 is a view showing a state where the photocurable resin composition of the present invention (described as M in FIG. 3), which is a molding material, is supplied to a substrate. As shown in FIG. 3, the molding material M is dropped onto the portion of the substrate 10 where the lens is to be molded using the dispenser 50. Here, an amount of the molding material M corresponding to one lens 12 is supplied to one part to be supplied.

  After the molding material M is supplied to the substrate 10, as shown in FIG. 4A, a mold 60 for molding a lens is disposed. The mold 60 is provided with recesses 62 for transferring the shape of the lens 12 according to the desired number of lenses 12.

  As shown in FIG. 4B, the mold 60 is pressed against the molding material M on the substrate 10, and the molding material M is deformed following the shape of the recess. When the mold 60 is pressed against the molding material M and the molding material M is a thermosetting resin or an ultraviolet curable resin, the molding material M is cured by irradiating heat or ultraviolet rays from the outside of the mold. .

  After the molding material M is cured, the substrate 10 and the lens 12 are released from the mold 60 as shown in FIG. 4C.

  FIG. 5 is a diagram showing another configuration example of the wafer level lens. The wafer level lens in FIG. 5 has a configuration (monolithic type) in which the substrate 10 and the lens 12 are molded simultaneously. In this example, a plurality of concave lenses 12 are formed on one surface (upper surface in the drawing) of the substrate 10, and a convex lens 20 is formed on the other surface (lower surface in the drawing). A plurality of are formed. Also in the present embodiment, the patterned light-shielding film 14 may be formed in a region excluding the lens surface 12a of the substrate 10, that is, the surface of the substrate 10 and the surface of the lens edge portion 12b.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Synthesis Example (A) of the resin Synthesis Example reflux condenser, 1L three-necked flask equipped with a gas introduction cock, tricyclo [5,2,1,0 ^2,6] dec-8-yl methacrylate (manufactured by Hitachi Chemical Co., Ltd. FA-513M, corresponding to Exemplified Compound A1-1) 45.0 g, allyl methacrylate (made by Wako Pure Chemical Industries, Ltd., corresponding to Exemplified Compound A3-1), 5.0 g, and ethyl acetate 50.0 g were added. After substituting with nitrogen twice, 0.6 g of W-65 (trade name) manufactured by Wako Pure Chemical Industries, Ltd. was added as a polymerization initiator, and after further substituting with nitrogen twice, the mixture was heated at 65 ° C. under a nitrogen stream for 6 hours. Thereafter, the reaction solution was poured into 2 L of methanol, and the precipitated white solid was collected by suction filtration. The polymer P-1 was obtained by drying under reduced pressure at 70 ° C. for 5 hours and distilling off the solvent (yield 60%, weight average molecular weight (Mw) 40,000, molecular weight dispersion (Pd) 2.43). .
For the other exemplified polymers, the types or blending ratios of the raw material monomer components (a) and (b) were changed as follows, and others were performed in the same manner to obtain a polymer.

Ｐ−１〜Ｐ−６

Ｐ−７

Ｐ−８

Ｐ−９

Ｐ−１０

Ｐ−１１

Ｐ−１２

P-1 to P-6

P-7

P-8

P-9

P-10

P-11

P-12

(Preparation of materials)
The polymer prepared above was placed in a glass bottle and stirred overnight with a high viscosity stirrer. The obtained liquid was filtered with a disk filter having a pore size of 5 μm to obtain (Le-1) to (Le-14). The numbers in the table below are ratios (% by weight) of the respective components.

(B-1) Dimethylol-tricyclodecane diacrylate (manufactured by Kyoeisha Chemical)
(B-2) 1-adamantyl methacrylate (manufactured by Osaka Organic Chemical Industry)
(B-3) 3,4-epoxycyclohexenylmethyl-3, '4'-epoxycyclohexene carboxylate (Daicel Chemical Industries, Celoxide 2021)
(B-4) tert-butyl methacrylate (B-5) 1,3-bis (isocyanatomethyl) cyclohexane (Takenate 600, manufactured by Mitsui Chemicals)
(B-6) Cyclohexyl methacrylate

(C-1) IRGACURE184 (manufactured by BASF)
(C-2) WPI-113 (manufactured by WAKO)

(D-1) KF-6012 (manufactured by Shin-Etsu Chemical)
(D-2) KF-6015 (manufactured by Shin-Etsu Chemical)
(D-3) FTX-230G (manufactured by Neos Corporation)
(D-4) FTX-209F (manufactured by Neos Corporation)

(E-1) p-methoxyphenol (manufactured by Tokyo Chemical Industry, M0122)
(E-2) β-caryophyllene (Tokyo Chemical Industry Co., Ltd., C0796)
(E-3) Hydroquinone (E-4) Tributylamine

(Evaluation method)
(1) Refractive index measurement The liquid was poured on the glass substrate hydrophobized, and it was set as the film form of thickness 1mm. Then, after exposing to 4000 mJ / cm ² with a high pressure mercury lamp HB-50101BY manufactured by Ushio and heating in an N ₂ atmosphere at 180 ° C. for 2 hours, the glass substrate was removed to obtain a cured film having a thickness of 1 mm. The obtained film was subjected to light having a wavelength of 589 nm using an Abbe refractometer (Atago Co., Ltd., DR-M4).

(2) Abbe number (νD) measurement Using the cured film prepared by the above refractive index measurement, the Abbe refractometer (manufactured by Atago Co., Ltd., DR-M4) uses a refractive index of each of the wavelengths 486 nm, 589 nm, and 656 nm. The refractive index at a wavelength of 486 nm is n _F , the refractive index at a wavelength of 589 nm is n _D , and the refractive index at a wavelength of 656 nm is n _C. A higher Abbe number is preferred.

(3) Viscosity measurement The prepared liquid was subjected to shear viscosity measurement with a rheometer (manufactured by Anton Paar, Physica MCR301), and the viscosity was calculated.

(4) Peeling force measurement A 2 cm × 2 cm polydimethylsiloxane mold was set in an air pressurization type UV imprint apparatus (manufactured by MEPJ) with a peeling force measurement function, and about 1 μL of the adjusted liquid was applied thereon. A glass wafer was placed thereon, and the space between the mold and the glass wafer was 200 μm. Thereafter, after exposure for 100 seconds, the mold was removed. At this time, the maximum force (N) applied to the mold was defined as a measurement area (cm ² ) and a peeling force (N / cm ² ).

(5) Glass adhesion The prepared liquid was applied on a 7 cm × 7 cm glass substrate with a spin coater at 1000 rpm. This substrate was exposed to 4000 mJ / cm ² with a Ushio high-pressure mercury lamp HB-50101BY. A JIS standard cross cellophane tape peeling test was performed on the obtained coating film.
Judgment criteria are as follows, and the smaller the number, the better the glass adhesion.
(1) After peeling off the tape, the film remains completely.
(2) After peeling off the tape, 70% of the grid remains.
(3) After peeling off the tape, all the film is peeled off.

The results are shown in the table below.

  As is clear from the above table, it is clear that the composition of the present invention can achieve both refractive index, Abbe number, viscosity, peeling force, and glass adhesion.

10 substrate 12 lens (wafer level lens)
14 Patterned light shielding film

Claims (14)

(A) a resin having an aliphatic cyclic hydrocarbon group,
(B) a compound having an aliphatic cyclic hydrocarbon group and having a polymerizable group,
(C) A photocurable resin composition comprising a compound that generates radicals or acids upon irradiation with actinic rays or radiation, and (D) a surfactant. (B) The photocurable resin composition of Claim 1 whose polymeric group which a compound has is a (meth) acryloyl group and / or an epoxy group. (D) The photocurable resin composition of Claim 1 or 2 in which surfactant contains a silicon atom and / or a fluorine atom. The photocurable resin composition of any one of Claims 1-3 whose ratio (mass ratio) of (A) resin and (B) compound is 1: 1.9-1: 4. (A) The photocurable resin composition of any one of Claims 1-4 in which the resin contains the repeating unit containing a repeating unit containing an aliphatic cyclic hydrocarbon group and a polymeric group. (A) The photocurable resin composition of any one of Claims 1-5 whose aliphatic cyclic hydrocarbon group which resin has is a C6 or more hydrocarbon group. The resin (A) has at least one polymerizable group selected from acryloyl group, methacryloyl group, vinyl group, allyl group, isocyanate group, and epoxy group. The photocurable resin composition described in 1. (A) Resin has a repeating unit represented by following General formula (1), The photocurable resin composition of any one of Claims 1-7 characterized by the above-mentioned.

[In General Formula (1), R ¹ represents a hydrogen atom or a substituent, L ¹ represents a divalent linking group or a single bond, and ring α represents a monocyclic or polycyclic ring. ] The photocurable resin composition according to claim 8, wherein the (A) resin further includes a repeating unit represented by the following general formula (3).

[In General Formula (3), R ^{3 to} R ⁶ each independently represents a hydrogen atom or a substituent, and L ³ represents a divalent linking group or a single bond. ] The photocurable resin composition according to any one of claims 1 to 9, which is used for a wafer level lens. The lens formed using the photocurable resin composition of any one of Claims 1-10. The wafer level lens formed using the photocurable resin composition of any one of Claims 1-10. The manufacturing method of a lens including hardening the photocurable resin composition of any one of Claims 1-10. The manufacturing method of a wafer level lens including hardening the photocurable resin composition of any one of Claims 1-10.

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