Photosensitive composition, pattern film and method for producing same, display device, optical material, and solid-state imaging element

Abstract

Disclosed is a photosensitive composition which contains the components (A) and (B) described below. (A): One or more Si-containing compounds selected from among (A1) and (A2) described below (A1): An Si-containing compound that has a structural unit a1 having an alkali-soluble group and a polymerizable group, and a structural unit a2 having a polymerizable group or a structural unit a3 having an alkali-soluble group (A2): An Si-containing compound that has a structural unit a2 having a polymerizable group and a structural unit a3 having an alkali-soluble group (B): Photopolymerization initiator

Description

Photosensitive composition, patterned film and method for producing the same, as well as display device, optical material and solid-state imaging device

[0001] The present invention relates to a photosensitive composition, a patterned film and a method for producing the same, as well as a display device, an optical material, and a solid-state imaging device.

[0002] Low refractive index films are formed on optical components as optically functional films such as anti-reflection films, reflective films, semi-transmissive semi-reflective films, visible light-reflecting and infrared-transmitting films, infrared light-reflecting and visible light-transmitting films, blue reflective films, green reflective films or red reflective films, bright line cut filters, color correction films, etc. Furthermore, optically functional films containing low refractive index films are needed not only for optical components with flat surfaces, but also for the surfaces of microstructures of optical components such as optical pickup lenses, compact camera lenses, aspherical lenses, lens films for improving brightness in LCD backlights, diffusion films, and Fresnel lenses, lenticular lenses, or microlenses used in the screens of video projection televisions.

[0003] Conventionally, as a photosensitive composition capable of forming a low refractive index film, for example, a photosensitive composition containing hollow or porous particles, a photopolymerization initiator, and a Si-containing compound having a specific structural unit has been proposed (Patent Document 1).

[0004] JP 2012-32673 A

[0005] However, since it is difficult to uniformly disperse particles in the photosensitive composition, nozzles are prone to clogging and the particles are prone to settling over time. Furthermore, since a low refractive index is achieved by using particles to form voids in the film, it is essential that the photosensitive composition contain particles. On the other hand, photosensitive compositions that do not contain particles may be repelled by the substrate when applied to the substrate (hereinafter also referred to as "cissing"), making it difficult to form a uniform coating film. Given these circumstances, there is a need for a photosensitive composition that can form a cured film with a low refractive index without causing cissing on the substrate. An object of the present invention is to provide a photosensitive composition that suppresses cissing on the substrate, has good coatability, and can form a cured film with a low refractive index. Another object of the present invention is to provide a patterned film using the photosensitive composition, a method for producing the same, and an optical material and a solid-state imaging device using the patterned film.

[0006] The present inventors have found that by incorporating a photopolymerization initiator together with a Si-containing compound having a specific structural unit, repelling on a substrate is suppressed, the coating properties are good, and a cured film with a low refractive index can be formed without the need for particles.

[0007] That is, the present invention provides the following [1] to

[10] . [1] A photosensitive composition containing the following components (A) and (B): (A) one or more Si-containing compounds selected from the following (A1) and (A2): (A1) an Si-containing compound containing a structural unit a1 having an alkali-soluble group and a polymerizable group, and a structural unit a2 having a polymerizable group, or a structural unit a3 having an alkali-soluble group; (A2) an Si-containing compound containing a structural unit a2 having a polymerizable group, and a structural unit a3 having an alkali-soluble group; (B) a photopolymerization initiator. [2] The photosensitive composition according to the above [1], wherein the structural unit a1 is a structural unit represented by the following formula (1) or a structural unit represented by the following formula (2):

[0008]

[0009] [In formulas (1) to (4), R A represents a monovalent group having an alkali-soluble group and a radically polymerizable group. B represents a monovalent group having a radical polymerizable group. C represents a monovalent group having an alkali-soluble group. 1 , R 21 and R 31 R each independently represents a monovalent organic group (excluding alkali-soluble groups and radically polymerizable groups). 2 , R 12 , R 22 and R 32 each independently represents a divalent linking group.

[0010] [3] The photosensitive composition according to [1] or [2] above, wherein the Si-containing compound further contains a structural unit represented by the following formula (5) as the structural unit a4:

[0011]

[0012] [In formula (5), R 41 each independently represents a monovalent organic group (excluding an alkali-soluble group and a radically polymerizable group). 42 represents a divalent linking group.

[0013] [4] The photosensitive composition according to any one of [1] to [3] above, wherein the weight-average molecular weight of the Si-containing compound is 5,000 to 50,000. [5] The photosensitive composition according to any one of [1] to [4] above, further comprising a polymerizable compound having a radically polymerizable group as component (C). [6] A method for producing a patterned film, comprising: applying the photosensitive composition according to any one of [1] to [5] above onto a substrate to form a photosensitive film; exposing the photosensitive film; and developing the exposed photosensitive film with an alkaline developer to obtain a patterned film. [7] A patterned film produced by the method for producing a patterned film according to [6] above. [8] A display device having the patterned film according to [7] above. [9] An optical material comprising the patterned film according to [7] above as a low refractive index layer, in combination with a high refractive index layer having a refractive index higher than that of the low refractive index layer.

[10] A solid-state imaging device having the patterned film according to [7] above.

[0014] The photosensitive composition of the present invention has good coating properties with suppressed cissing on a substrate, and can inexpensively form a cured film with a low refractive index without requiring particles. Therefore, the photosensitive composition of the present invention is useful for forming a low refractive index film, and can be applied to various optical components as an optically functional film such as an antireflection film.

[0015] The present invention will be described in detail below with reference to preferred embodiments. In this specification, a numerical range indicated using "to" means that the numerical values ​​before and after "to" are included as the lower and upper limits. A "structural unit" refers to a unit that mainly constitutes the main chain structure, and at least two or more units are contained in the main chain structure.

[0016] In this specification, the term "hydrocarbon group" encompasses chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. The term "chain hydrocarbon group" refers to a linear hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure in the main chain and is composed solely of a chain structure. However, the group may be saturated or unsaturated. The term "alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. However, the group does not necessarily have to be composed solely of an alicyclic hydrocarbon structure, and may also contain a chain structure as part of the ring structure. The term "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, the group does not necessarily have to be composed solely of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of the ring structure. The ring structures of the alicyclic hydrocarbon group and aromatic hydrocarbon group may have a substituent group composed of a hydrocarbon structure.

[0017] In this specification, "(meth)acrylic" is intended to encompass "acrylic" and "methacrylic." "(meth)acryloyl group" is intended to encompass "acryloyl group" and "methacryloyl group."

[0018] [Photosensitive Composition] The photosensitive composition of the present invention contains the following components (A) and (B). <Component (A)> Component (A) is one or more Si-containing compounds selected from the following (A1) and (A2). Component (A) having such a configuration improves wettability to the substrate and reduces the occurrence of cissing, making it easier to form a uniform coating film. (A1) Si-containing compound containing a structural unit a1 having an alkali-soluble group and a polymerizable group, and a structural unit a2 having a polymerizable group, or a structural unit a3 having an alkali-soluble group. (A2) Si-containing compound containing a structural unit a2 having a polymerizable group and a structural unit a3 having an alkali-soluble group.

[0019] The alkali-soluble group is not particularly limited as long as it is soluble in an alkaline aqueous solution, and examples thereof include an acid group and a maleimide group. In this specification, "alkali-soluble" means soluble in an alkaline aqueous solution such as a 2.38% by mass aqueous solution of tetramethylammonium hydroxide. Furthermore, "acid group" refers to a proton-dissociating group having an acid dissociation constant (pKa) of 12 or less. Specific examples of alkali-soluble groups include a carboxy group, a phenolic hydroxyl group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, and a phosphonic acid group. In this specification, a "phenolic hydroxyl group" refers to a hydroxyl group directly bonded to an aromatic ring (e.g., a benzene ring, a naphthalene ring, an anthracene ring, etc.). One or more alkali-soluble groups can be present in one structural unit.

[0020] Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group. One or more polymerizable groups may be contained in one structural unit. Among these, a radically polymerizable group is preferred as the polymerizable group, since it is easier to obtain the effects of the present invention.

[0021] The radical polymerizable group is preferably, for example, an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, an α-methylvinyl group, a vinyloxy group, an allyl group, a styryl group, an α-methylstyryl group, a maleimide group, a (meth)acrylic group, a (meth)acryloxy group, and a (meth)acrylamide group. Of these, the radical polymerizable group is preferably, from the viewpoint of reactivity, a (meth)acryloxy group or a styryl group.

[0022] The alkali-soluble group and the polymerizable group may have a divalent hydrocarbon group, in which case the alkali-soluble group and the polymerizable group may be present at the end or on a side chain of the divalent hydrocarbon group.

[0023] Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. The divalent aliphatic hydrocarbon group may be either a straight chain or a branched chain, and examples thereof include an alkanediyl group. The divalent aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 2 to 6 carbon atoms. Specific examples include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, a propane-2,2-diyl group, a butane-1,2-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,5-diyl group, a hexane-1,6-diyl group, a 2-methylpropane-1,2-diyl group, and a 2,2-dimethylpropane-1,3-diyl group. Examples of divalent alicyclic hydrocarbon groups include cycloalkanediyl groups. The divalent alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Specific examples include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group. The divalent aromatic hydrocarbon group may be a monocyclic aromatic hydrocarbon group or a polycyclic aromatic hydrocarbon group, and an arylene group is an example. The divalent aromatic hydrocarbon group preferably has 6 to 14 carbon atoms. Specific examples include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, and an anthrylene group.

[0024] The divalent hydrocarbon group may have a substituent within the scope of the present invention. The position and number of the substituent are optional, and when two or more substituents are present, the substituents may be the same or different. Examples of the substituent include a halo group, a hydroxy group, a cyano group, a formyl group, a nitro group, an amino group, a dialkylamino group, a diarylamino group, an alkoxy group, an alkoxycarbonyl group, an alkylthio group, an arylthio group, and a trialkylsilyl group. The divalent hydrocarbon group may also have a linking group between the C-C bonds. Examples of the linking group include -O-, -S-, -SO2-, -CO-, -COO-, -OCO-, and -CONR X - (R X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NR X - (R X has the same meaning as above), and the linking group may have one or more. The linking group may be attached at any position.

[0025] The structural unit a1 is not particularly limited as long as it has an alkali-soluble group and a polymerizable group, but for example, a structural unit represented by the following formula (1) or a structural unit represented by the following formula (2) is preferred, and the structural unit represented by the following formula (1) is more preferred. The structural unit a2 is not particularly limited as long as it has a polymerizable group, but for example, a structural unit represented by the following formula (3) is preferred. The structural unit a3 is not particularly limited as long as it has an alkali-soluble group, but a structural unit represented by the following formula (4) is preferred. The Si-containing compound in the present invention is preferably linear because it is easy to achieve a low refractive index, and preferably contains 80 mol % or more, more preferably 90 mol % or more, and even more preferably 95 mol % or more of structural units constituting a linear chain such as those shown in formulas (1) to (4), assuming that all structural units constituting the Si-containing compound are 100 mol %.

[0026]

[0027] [In formulas (1) to (4), R A represents a monovalent group having an alkali-soluble group and a radically polymerizable group. Brepresents a monovalent group having a radical polymerizable group. C represents a monovalent group having an alkali-soluble group. 1 , R 21 and R 31 R each independently represents a monovalent organic group (excluding alkali-soluble groups and radically polymerizable groups). 2 , R 12 , R 22 and R 32 each independently represents a divalent linking group.

[0028] R A R is preferably an alkanediyl group, a cycloalkanediyl group, or a combination thereof, which has an alkali-soluble group and a radically polymerizable group, and more preferably an alkanediyl group, a cycloalkanediyl group, or a combination thereof, which has a carboxy group and a (meth)acryloyl group. B As R, an alkanediyl group, a cycloalkanediyl group, or a combination thereof having a radical polymerizable group is preferred, and an alkanediyl group having a (meth)acryloyl group is more preferred. C is preferably an alkanediyl group, a cycloalkanediyl group, or a combination thereof, each having an alkali-soluble group, and more preferably an alkanediyl group having a carboxy group. The alkanediyl group and the cycloalkanediyl group may have a linking group between the C-C bonds. Examples of the linking group include the same as those mentioned above. Among these, -O-, -CO-, -COO-, -OCO-, -CONR X - (R X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NR X - (R Xare as defined above) are preferred. The linking group may be one or more, and the bonding position is optional. The alkanediyl group and the cycloalkanediyl group may have a substituent. Examples of the substituent include the same as those described above. Among them, a halo group, a hydroxy group, a cyano group, an amino group, a dialkylamino group, a diarylamino group, an alkoxy group, and an alkoxycarbonyl group are preferred. The linking group may be two or more, and the bonding position is optional.

[0029] R 1 , R 21 and R 31 Examples of the monovalent organic group in the above formula (1) include monovalent hydrocarbon groups. The monovalent hydrocarbon group may be any of a monovalent saturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. The monovalent saturated aliphatic hydrocarbon group may be either linear or branched. The monovalent hydrocarbon group may have a substituent within the scope of the present invention. The position and number of the substituents are optional, and when two or more substituents are present, the substituents may be the same or different. Examples of the substituent include those similar to those described above. Among these, halo groups, hydroxy groups, cyano groups, amino groups, dialkylamino groups, diarylamino groups, alkoxy groups, and alkoxycarbonyl groups are preferred. Two or more substituents may be present, and the substitution positions are optional. The monovalent hydrocarbon group may have a linking group between the C-C bond. Examples of the linking group include those similar to those described above. Among these, -O-, -CO-, -COO-, -OCO-, -CONR X - (R X represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), —NR X - (R X has the same meaning as above). The compound may have one or more linking groups, and the bonding position is optional.

[0030] Examples of the monovalent saturated aliphatic hydrocarbon group include an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a 1-methyldecyl group, a dodecyl group, a 1-methylundecyl group, a 1-ethyldecyl group, a tridecyl group, a tetradecyl group, a tert-dodecyl group, a pentadecyl group, a 1-heptyloctyl group, a hexadecyl group, and an octadecyl group.

[0031] Examples of the monovalent saturated alicyclic hydrocarbon group include a cycloalkyl group, a condensed polycyclic hydrocarbon group, a bridged ring hydrocarbon group, a spiro hydrocarbon group, and a cyclic terpene hydrocarbon group. Among these, a cycloalkyl group is preferred. The number of carbon atoms in the monovalent saturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 12. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a t-butylcyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Specific examples of the condensed polycyclic hydrocarbon group include a tricyclodecanyl group, a decahydro-2-naphthyl group, and an adamantyl group. Specific examples of the bridged ring hydrocarbon group include tricyclo[5.2.1.0] 2,6 Examples of the spiro hydrocarbon group include monovalent groups obtained by removing one hydrogen atom from spiro[3,4]heptane and spiro[3,4]octane, and examples of the cyclic terpene hydrocarbon group include monovalent groups obtained by removing one hydrogen atom from p-menthane, thujane, carane, etc.

[0032] Examples of the monovalent aromatic hydrocarbon group include an aryl group and an aralkyl group. The number of carbon atoms in the monovalent aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. Specific examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenylene group, an azulenyl group, and a 9-fluorenyl group. Specific examples of the aralkyl group include a benzyl group, a phenethyl group, and a trityl group.

[0033] Among them, R 1 , R 21 and R 31 As R, an alkyl group is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is even more preferable. 32 Examples of the divalent linking group according to the formula (1) include the same groups as those mentioned above. Among them, —O— is preferred in that it is easier to enjoy the effects of the present invention.

[0034] R 2 , R 12 , R 22 , R 32 Examples of the divalent linking group according to the formula (1) include the same groups as those mentioned above. Among them, —O— is preferred in that it is easier to enjoy the effects of the present invention.

[0035] Component (A) may further contain a structural unit represented by the following formula (5) as structural unit a4.

[0036]

[0037] [In formula (5), R 41 Each of X independently represents a monovalent organic group (excluding alkali-soluble groups and radically polymerizable groups). 42 represents a divalent linking group.

[0038] R 41Examples of the monovalent organic group according to the formula (1) include a monovalent hydrocarbon group. The monovalent hydrocarbon group may be any of a monovalent saturated aliphatic hydrocarbon group, a monovalent saturated alicyclic hydrocarbon group, and a monovalent aromatic hydrocarbon group. The monovalent saturated aliphatic hydrocarbon group may be either linear or branched. Specific embodiments of the monovalent hydrocarbon group, the monovalent saturated aliphatic hydrocarbon group, the monovalent saturated alicyclic hydrocarbon group, and the monovalent aromatic hydrocarbon group are shown in R 1 , R 21 and R 31 This is as explained for the monovalent organic group according to the formula (I).

[0039] Among them, R 41 As R, an alkyl group is preferable, an alkyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is even more preferable. 42 Examples of the divalent linking group according to the formula (1) include the same groups as those mentioned above. Among them, —O— is preferred in that it is easier to enjoy the effects of the present invention.

[0040] From the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving lithography properties and chemical resistance, component (A) is preferably a Si-containing compound represented by any of formulas (6) to (8) below, more preferably a Si-containing compound represented by formula (6) or (8) below, and even more preferably a Si-containing compound represented by formula (6) below. Note that the Si-containing compounds represented by formulas (6) and (7) below have structural units a1, a2, and a4, and the Si-containing compound represented by formula (8) below has structural units a2, a3, and a4.

[0041]

[0042] In a preferred embodiment of component (A), the proportions of each structural unit in the Si-containing compound are as follows. By setting these proportions, wettability to the substrate is further improved, and cissing is prevented, making it easier to obtain a uniform coating film. In the Si-containing compound represented by formula (6) or (7) above, the proportion of structural unit a1 is preferably 1 to 40 mol %, more preferably 3 to 30 mol %, and even more preferably 5 to 25 mol %, based on all structural units. The proportion of structural unit a2 is preferably 1 to 40 mol %, more preferably 3 to 30 mol %, and even more preferably 5 to 25 mol %, based on all structural units. The proportion of structural unit a4 is the remainder. In the Si-containing compound represented by the formula (8), the proportion of the structural unit a2 is preferably 1 to 40 mol %, more preferably 3 to 30 mol %, and even more preferably 5 to 25 mol %, based on all structural units, and the proportion of the structural unit a3 is preferably 1 to 30 mol %, more preferably 3 to 30 mol %, and even more preferably 5 to 25 mol %, based on all structural units. The proportion of the structural unit a4 is the remainder.

[0043] Component (A) can be produced by any suitable method, including, for example, the following methods. Typical synthesis conditions can be used for the reaction conditions. (1) A side-chain (alicyclic) epoxy-modified silicone is reacted with a carboxylic acid having a radically polymerizable group to introduce the radically polymerizable group, and then some of the resulting hydroxyl groups are reacted with an acid anhydride to introduce carboxy groups. (2) Some of the carbinol groups of the side-chain carbinol-modified silicone are reacted with an isocyanate compound having a radically polymerizable group to introduce the radically polymerizable group, and then the remaining carbinol groups are reacted with an acid anhydride to introduce carboxy groups. (3) A side-chain hydrogen-modified silicone is reacted with an acid anhydride having a radically polymerizable group to introduce an acid anhydride group, and then the acid anhydride group is ring-opened to introduce a carboxy group, and then some of the carboxy groups are reacted with a cyclic ether compound having a radically polymerizable group to introduce the radically polymerizable group.

[0044] Commercially available modified silicones can be used. For example, side-chain (alicyclic) epoxy-modified silicones include X-22-343, KF-101, KF-1001, X-22-2200, X-22-2046, KF-102, X-22-4741, KF-1002, and KF-1005 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Side-chain carbinol-modified silicones include X-22-4039 and X-22-4015 (all manufactured by Shin-Etsu Chemical Co., Ltd.). Side-chain hydrogen-modified silicones include KF-99 and KF-9901 (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0045] Examples of the carboxylic acid having a radical polymerizable group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, and fumaric acid.

[0046] Examples of acid anhydrides include succinic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, phthalic anhydride, and trimellitic anhydride.

[0047] Examples of the isocyanate compound having a radical polymerizable group include 2-isocyanatoethyl methacrylate (Karenz MOI, manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (Karenz AOI, manufactured by Showa Denko K.K.), and 1,1-(bisacryloyloxyethyl)ethyl isocyanate (Karenz BEI, manufactured by Showa Denko K.K.).

[0048] Examples of acid anhydrides having a radical polymerizable group include allylsuccinic anhydride, 2-buten-1-ylsuccinic anhydride, 2-hexen-1-ylsuccinic anhydride, 2-octenylsuccinic anhydride, decenylsuccinic anhydride, and hexadecenylsuccinic anhydride.

[0049] Examples of cyclic ether compounds having a radical polymerizable group include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl methacrylate, (oxetan-3-yl)methyl acrylate, (oxetan-3-yl)methyl methacrylate, (3-methyloxetan-3-yl)methyl acrylate, (3-methyloxetan-3-yl)methyl methacrylate, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether can be mentioned.

[0050] Component (A) preferably has a weight average molecular weight (Mw) of 5,000 to 50,000, more preferably 6,000 to 40,000, and even more preferably 7,000 to 30,000, as measured by gel permeation chromatography (hereinafter also referred to as "GPC") in terms of polystyrene.

[0051] When component (A) has a carboxy group as the alkali-soluble group, the carboxylic acid equivalent is preferably 400 to 2000 g / mol, more preferably 700 to 1600 g / mol, and even more preferably 800 to 1200 g / mol.

[0052] When component (A) has a (meth)acrylic group or a (meth)acryloxy group as the radically polymerizable group, the (meth)acrylic equivalent is preferably 200 to 1800 g / mol, more preferably 300 to 1500 g / mol, and even more preferably 400 to 1200 g / mol.

[0053] <Component (B)> Component (B) contains a photopolymerization initiator. This can impart radiation sensitivity to the photosensitive composition. Component (B) is a compound that generates active species that can initiate polymerization of radically polymerizable groups when exposed to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beams, or X-rays.

[0054] Component (B) is not particularly limited and can be appropriately selected from known photopolymerization initiators. Examples include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyloxime-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polynuclear quinone-based compounds, diazo-based compounds, imidosulfonate-based compounds, and onium salt-based compounds. Component (B) can be used alone or in combination.

[0055] Among these, component (B) is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

[0056] Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

[0057] Examples of acetophenone compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, and 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholinophenyl)butan-1-one.

[0058] Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, and 2,2'-bis(2,4,6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

[0059] When a biimidazole compound is used as component (B), it is preferable to use a hydrogen donor in combination, as this can improve sensitivity. The term "hydrogen donor" as used herein refers to a compound capable of donating a hydrogen atom to a radical generated from the biimidazole compound upon exposure. Examples of hydrogen donors include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; and amine hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. In the present invention, one or more hydrogen donors can be used; however, it is preferable to use a combination of one or more mercaptan hydrogen donors and one or more amine hydrogen donors, as this can further improve sensitivity.

[0060] Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(5-methylfuran-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, Examples of the triazine compounds having a halomethyl group include 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, and 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

[0061] Examples of O-acyloxime compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime), and ethanone, 1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazol-3-yl]-, 1-(O-acetyloxime). As commercially available O-acyloxime compounds, NCI-831, NCI-930 (both manufactured by ADEKA Corporation) and the like can also be used.

[0062] In the present invention, when a photopolymerization initiator other than a biimidazole compound, such as an acetophenone compound, is used, a sensitizer can also be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

[0063] The content of component (B) is preferably 1 to 50 parts by mass, more preferably 3 to 35 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of component (A), from the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving the lithography properties and chemical resistance.

[0064] <Component (C)> The photosensitive composition of the present invention can contain, as component (C), a polymerizable compound having a radically polymerizable group. Examples of the radically polymerizable group include ethylenically unsaturated groups. Specific examples of the ethylenically unsaturated group are as described above. Of these, a (meth)acryloxy group is preferred. As component (C), a polyfunctional (meth)acrylate is preferred from the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving lithography properties and chemical resistance. One or more types of component (C) can be used.

[0065] Examples of polyfunctional (meth)acrylates include polyfunctional (meth)acrylates which are reaction products of aliphatic polyhydroxy compounds and (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, alkylene oxide-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates which are reaction products of hydroxyl group-containing (meth)acrylates and polyfunctional isocyanates, and carboxyl group-containing polyfunctional (meth)acrylates which are reaction products of hydroxyl group-containing (meth)acrylates and acid anhydrides.

[0066] Examples of aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; and trivalent or higher aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and glycerol dimethacrylate. Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include dibasic acid anhydrides such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and tetrabasic acid dianhydrides such as pyromellitic anhydride, biphenyltetracarboxylic dianhydride, and benzophenonetetracarboxylic dianhydride.

[0067] Examples of caprolactone-modified polyfunctional (meth)acrylates include the compounds described in paragraphs

[0015] to

[0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth)acrylate include bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, isocyanuric acid tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, trimethylolpropane tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, pentaerythritol tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, pentaerythritol tetra(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, dipentaerythritol penta(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, and dipentaerythritol hexa(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide.

[0068] Among these, from the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving lithography properties and chemical resistance, component (C) is preferably one or more selected from polyfunctional (meth)acrylates which are reaction products of trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional urethane (meth)acrylates, and polyfunctional (meth)acrylates having a carboxyl group, and more preferably one or more selected from trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, a reaction product of pentaerythritol triacrylate with succinic anhydride, and a reaction product of dipentaerythritol pentaacrylate with succinic anhydride.

[0069] From the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving the lithography properties and chemical resistance, the content of component (C) is preferably 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of component (A).

[0070] <Component (D)> The photosensitive composition of the present invention can contain a solvent as component (D). Component (D) can be appropriately selected and used as long as it disperses or dissolves components (A) and (B) and other components constituting the photosensitive composition, does not react with these components, and has appropriate volatility. An organic solvent is usually used as component (D). One or more types of component (D) can be used.

[0071] Examples of the organic solvent include (poly)alkylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;

[0072] Alkyl lactate esters such as methyl lactate and ethyl lactate; (cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, and cyclohexanol; keto alcohols such as diacetone alcohol;

[0073] (Poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

[0074] Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, etc.; alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate, etc.; other esters such as ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate, etc.; aromatic hydrocarbons such as toluene, xylene, etc.; Examples include amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0075] Among these, from the viewpoints of further suppressing cissing on the substrate and further improving coatability, (poly)alkylene glycol monoalkyl ether acetates are preferred as component (D), with ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate being more preferred, and with one or more selected from propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and dipropylene glycol monomethyl ether acetate being even more preferred.

[0076] From the viewpoints of further suppressing cissing on the substrate, further reducing the refractive index of the cured film, and improving lithography properties and chemical resistance, the content of component (D) is an amount such that the solids concentration of the photosensitive composition is preferably 5 to 50 mass %, more preferably 10 to 45 mass %, and even more preferably 15 to 40 mass %. Here, in this specification, the term "solids concentration" refers to the proportion of the total mass of components other than the solvent in the photosensitive composition of the present invention to the total mass of the composition.

[0077] <Other Components> In addition to the components (A) to (D) described above, the photosensitive composition of the present invention may further contain other components (hereinafter also referred to as "other components"). Examples of other components include adhesion aids, surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), polymerization inhibitors, chain transfer agents, sensitizers, crosslinking agents, antioxidants, thermal radical generators, thermal acid generators, acid diffusion controllers, UV absorbers, thickeners, development accelerators, acid multipliers, plasticizers, and suspending agents. The content of these components can be appropriately selected depending on the type of component, as long as the effects of the present invention are not impaired.

[0078] [Patterned Film and Manufacturing Method Thereof] The patterned film of the present invention is manufactured using the photosensitive composition of the present invention described above, and can be manufactured, for example, by a method including the following (Step 1) to (Step 3): (Step 1) a step of applying the photosensitive composition of the present invention onto a substrate to form a photosensitive film; (Step 2) a step of exposing the photosensitive film; and (Step 3) a development step of developing the exposed photosensitive film with an alkaline developer to obtain a patterned film.

[0079] Each step will be described in detail below. (Step 1) Step 1 is a step of forming a photosensitive film by applying a photosensitive composition onto a substrate. Examples of the substrate include semiconductor substrates, glass substrates, silicon substrates, and substrates formed by providing various metal films on the surfaces of semiconductor plates, glass plates, and silicon plates. The shape of the substrate is not particularly limited. It may be flat, or may have a shape formed by providing recesses (holes) in a flat plate like a silicon wafer. In the case of a substrate having recesses and further having a copper film on the surface, a copper film may be provided at the bottom of the recesses, like a TSV structure.

[0080] Examples of methods that can be used to apply the photosensitive composition include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, spin coating is particularly preferred. In the case of spin coating, the rotation speed is typically 250 to 3,000 rpm, preferably 270 to 2,000 rpm, and the rotation time is typically 1 to 300 seconds, preferably 5 to 200 seconds. After spin coating the photosensitive composition, the resulting coating film is dried by heating at typically 50 to 180°C, preferably 60 to 150°C, and more preferably 70 to 110°C, for approximately 1 to 30 minutes, thereby forming a photosensitive film.

[0081] The thickness of the photosensitive film is usually 0.1 to 100 μm, preferably 0.3 to 50 μm, more preferably 0.5 to 20 μm, and even more preferably 0.5 to 10 μm.

[0082] (Step 2) Step 2 is a step of exposing the photosensitive film. The exposure is usually carried out by exposing the photosensitive film through a desired photomask using, for example, a contact aligner, a stepper, or a scanner. As the exposure light, light with a wavelength of 200 to 500 nm (e.g., i-line (365 nm)) is used. The exposure dose varies depending on the type and amount of components in the photosensitive film, the thickness of the coating film, etc., but when i-line is used as the exposure light, it is usually 1 to 10,000 mJ / cm. 2 is.

[0083] Heat treatment can also be carried out after exposure. The conditions for the heat treatment after exposure can be appropriately selected depending on the types and amounts of components in the photosensitive film, the thickness of the coating film, etc., but are usually carried out at 70 to 180°C for 1 to 60 minutes.

[0084] (Step 3) Step 3 is a step of developing the exposed photosensitive film with an alkaline developer. This results in a patterned film. Examples of the developer that can be used include aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene, and 1,5-diazabicyclo[4.3.0]-5-nonane. Alternatively, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the above-mentioned aqueous alkali solution can also be used as the developer.

[0085] The development time varies depending on the type and blending ratio of each component in the photosensitive film, the thickness of the coating film, etc., but is usually 30 to 600 seconds. Examples of the development method include the puddle method, dipping method, puddle method, spray method, and shower development method, and any of these methods is acceptable. The pattern may be washed with running water, etc. Thereafter, it may be air-dried using an air gun, or dried under heat using a hot plate or oven, etc.

[0086] The patterned film of the present invention can be formed on a solid substrate such as an optical member to form an optically functional film such as a layer that improves light extraction efficiency, an anti-reflection film, a reflective film, a semi-transmissive / semi-reflective film, a visible light-reflecting / infrared light-transmitting film, an infrared light-reflecting / visible light-transmitting film, a blue reflective film, a green reflective film or a red reflective film, a bright line cut filter, or a color tone correction film.

[0087] The solid substrate may be flat or have other shapes. The shape may be a microstructure having geometrical optical properties. Examples of the microstructure include an optical pickup lens, a compact camera lens, an aspherical lens, a lenticular lens sheet, a Fresnel lens sheet, a prism sheet, a microlens array sheet, an on-chip microlens array sheet, a light guide sheet, a diffusion sheet, a hologram sheet, a solar cell, etc.

[0088] Furthermore, the patterned film of the present invention conforms well to microstructures having geometrical optical properties, such as optical functional components such as brightness-enhancing lens films and diffusion films for liquid crystal backlights, Fresnel lenses, lenticular lenses, and microlenses used in video projection television screens, etc. As a result, the patterned film of the present invention can function as an optically functional film without impairing the geometrical optical properties of the microstructures.

[0089] Specific examples of the microstructure include lenses for optical pickups, lenses for small cameras, aspherical lenses, lenticular lenses, Fresnel lenses, prisms, microlens arrays, light-guiding microstructures, light-diffusing microstructures, and microstructures for obtaining holograms.

[0090] The refractive index of the patterned film of the present invention is usually less than 1.5. In this specification, the "refractive index" is measured at 25°C using light with a wavelength of 589 nm.

[0091] [Optical Materials, Display Devices] The optical material of the present invention is a low-refractive index layer formed by the patterned film of the present invention, combined with a high-refractive index layer having a higher refractive index than the low-refractive index layer, and can be suitably used as an optical material for optical devices. For example, to explain this more specifically based on a display device, by combining a low-refractive index layer formed by the patterned film of the present invention with a high-refractive index layer on the image display surface of the display device, the light reflected on the surface of the low-refractive index layer and the light reflected at the interface between the low-refractive index layer and the high-refractive index layer can be interfered with by light to reduce reflectivity and suppress reflection of external light. Furthermore, by forming a display device having a colored layer laminated on one side of a transparent substrate and a low-refractive index layer and a high-refractive index layer laminated on the other side of the transparent substrate, the difference in refractive index between the low-refractive index layer and the high-refractive index layer can be utilized to enhance light collection and light extraction efficiency, thereby significantly improving brightness. The low-refractive index layer and the high-refractive index layer may be provided on a sealing layer laminated on the other side of the transparent substrate. Examples of display devices include liquid crystal display devices and organic electroluminescence (EL) display devices.

[0092] The low refractive index layer and the high refractive index layer constituting the optical material may be a single layer or multiple layers. The optical material may be a laminate in which a low refractive index layer and a high refractive index layer are stacked vertically, or may have a structure in which a low refractive index layer and a high refractive index layer are arranged adjacent to each other in parallel. When a low refractive index layer and a high refractive index layer are stacked, the stacking order is not particularly limited, and may be the low refractive index layer followed by the high refractive index layer, or the high refractive index layer followed by the low refractive index layer. The optical material may have two or more such stacked structures. When a low refractive index layer and a high refractive index layer are arranged adjacent to each other in parallel, the low refractive index layer and the high refractive index layer may be arranged in parallel by repeating two or more times. The interface between the low refractive index layer and the high refractive index layer may be flat or uneven.

[0093] The refractive index of the low refractive index layer is preferably lower than that of the transparent substrate, and is usually 1.5 or less.The refractive index of the high refractive index layer is not particularly limited as long as it is higher than that of the low refractive index layer, but from the viewpoint of improving light extraction efficiency and further improving brightness, the refractive index is preferably 0.05 or more higher than that of the low refractive index layer, more preferably 0.1 or more higher, and even more preferably 0.15 or more higher.In addition, the material constituting the high refractive index layer can be appropriately selected from commonly used materials as long as the refractive index is within the above-mentioned value.

[0094] [Solid-state imaging device] The solid-state imaging device of the present invention includes the patterned film of the present invention. For example, a low refractive index film composed of the above-described patterned film can be applied to an anti-reflection film, an intermediate film, or a partition wall of a color filter. The solid-state imaging device is composed of, for example, a light-receiving element (photodiode), a lower planarization film, a color filter, an upper planarization film, a microlens, etc., provided on a silicon substrate. The color filter is composed of red (R), green (G), and blue (B) color filter pixel portions.

[0095] The planarization film is formed to cover the upper surface of the color filter and planarizes the color filter surface. The microlenses are condensing lenses arranged with their convex surfaces facing up, and are provided above the planarization film and above the light-receiving elements. That is, the microlenses, color filter pixel sections, and light-receiving elements are arranged in series along the direction of light incidence, resulting in a structure that efficiently guides external light to each light-receiving element. The light-receiving elements and microlenses can be selected from those that are commonly used. The pattern film formed from the photosensitive composition of the present invention may be applied to the surface of the pixel sections as an anti-reflection film, or may be used as a planarization film located below the pixel sections.

[0096] For example, in the method for producing a patterned film described above, such a solid-state imaging device can be produced by using a substrate (e.g., a silicon substrate) on which an imaging device (light-receiving device) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) is provided. The patterned film may be formed on the imaging device-forming side (front surface) of the solid-state imaging device substrate, or on the non-imaging device-forming side (rear surface). A light-shielding film may be provided between each imaging device in the solid-state imaging device substrate or on the rear surface of the solid-state imaging device substrate. Furthermore, if necessary, a primer layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, or flatten the substrate surface.

[0097] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the examples and comparative examples, "parts" and "%" are by mass unless otherwise specified.

[0098] [Weight-average molecular weight (Mw)] Mw was measured by gel permeation chromatography (GPC) under the following conditions: Apparatus: Showa Denko "GPC-101" Column: Showa Denko "GPC-KF-801", "GPC-KF-802", "GPC-KF-803", and "GPC-KF-804" connected together Mobile phase: Tetrahydrofuran Column temperature: 40°C Flow rate: 1.0 mL / min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Detector: Differential refractometer Standard material: Monodisperse polystyrene

[0099] The abbreviations of the compounds and solvents used in the following synthesis examples and comparative synthesis examples are as follows: PGMEA: propylene glycol monomethyl ether acetate

[0100] Side chain epoxy-modified dimethyl silicone (P-1): "KF-101" manufactured by Shin-Etsu Chemical Co., Ltd., where R represents an alkanediyl group.

[0101]

[0102] Side chain epoxy-modified dimethyl silicone (P-2): "X-22-343" manufactured by Shin-Etsu Chemical Co., Ltd., where R represents an alkanediyl group.

[0103]

[0104] Side chain carbinol-modified dimethyl silicone (P-3): "X-22-4039" manufactured by Shin-Etsu Chemical Co., Ltd., where R represents an alkanediyl group.

[0105]

[0106] Side chain hydrogen-modified dimethyl silicone (P-4): "HF-9901" manufactured by Shin-Etsu Chemical Co., Ltd.

[0107]

[0108] Both ends epoxy-modified dimethyl silicone (P-5): "KF-105" manufactured by Shin-Etsu Chemical Co., Ltd., where R represents an alkanediyl group.

[0109]

[0110] Synthesis Example 1 21.0 g of side-chain epoxy-modified dimethylsilicone (P-1), 4.3 g of acrylic acid, 0.05 g of 4-methoxyphenol, and 24.1 g of PGMEA were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube and stirred, and then 0.2 g of dimethylbenzylamine was added and reacted for 6 hours at 110° C. To the resulting reaction solution, 31.2 g of PGMEA and 2.4 g of succinic anhydride were further added, and the mixture was reacted for 6 hours at 60° C. to obtain a solution of linear polysiloxane (P-1-1) containing structural units a1, a2, and a4.

[0111]

[0112] Synthesis Example 2 21.0 g of side-chain epoxy-modified dimethylsilicone (P-1), 4.3 g of acrylic acid, 0.05 g of 4-methoxyphenol, and 24.1 g of PGMEA were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube and stirred, and then 0.2 g of dimethylbenzylamine was added and reacted for 6 hours at 110° C. To the resulting reaction solution, 32.4 g of PGMEA and 3.6 g of succinic anhydride were further added, and the mixture was reacted for 6 hours at 60° C. to obtain a solution of linear polysiloxane (P-1-2) containing structural units a1, a2, and a4.

[0113]

[0114] Synthesis Example 3 21.0 g of side-chain epoxy-modified dimethylsilicone (P-1), 4.3 g of acrylic acid, 0.05 g of 4-methoxyphenol, and 24.1 g of PGMEA were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube and stirred, and then 0.2 g of dimethylbenzylamine was added and reacted for 6 hours at 110° C. To the resulting reaction solution, 32.4 g of PGMEA and 4.7 g of 1,2-cyclohexanedicarboxylic anhydride were further added, and the mixture was reacted for 6 hours at 60° C. to obtain a solution of linear polysiloxane (P-1-3) containing structural units a1, a2, and a4.

[0115]

[0116] Synthesis Example 4 A solution of a linear polysiloxane (P-2-1) containing structural units a1, a2, and a4 was obtained by the same synthesis method as in Synthesis Example 1, except that P-2 was used as the side-chain epoxy-modified dimethyl silicone.

[0117]

[0118] Synthesis Example 5 38.2 g of side-chain carbinol-modified dimethyl silicone (P-3), 0.03 g of dibutyltin dilaurate, and 40.3 g of PGMEA were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube and stirred, and then 4.1 g of Karenz AOI manufactured by Resonac Co., Ltd. was added and reacted for 3 hours at 60° C. To the resulting reaction solution, 47.1 g of PGMEA, 0.2 g of dimethylbenzylamine, and 2.9 g of succinic anhydride were further added, and the mixture was reacted for 6 hours at 60° C. to obtain a solution of linear polysiloxane (P-3-1) containing structural units a2, a3, and a4.

[0119]

[0120] Comparative Synthesis Example 1 Under a nitrogen atmosphere, 9.6 g of allylsuccinic anhydride and 16 g of dehydrated toluene were placed in a 200 mL three-neck flask, and while stirring with a magnetic stirrer, 0.03 g of hexachloroplatinic (IV) acid hexahydrate was added. The mixture was then heated to 70°C, and a toluene solution of 11.2 g of side-chain hydrogen-modified dimethyl silicone (P-4) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 110°C for 3 hours. Water was further added and the mixture was heated to reflux at 100°C for 6 hours to open the acid anhydride ring. Subsequently, the resulting reaction solution was substituted with PGMEA to achieve a solids concentration of 50%. Furthermore, 0.5 g of dimethylbenzylamine, 0.05 g of 4-methoxyphenol, and 12.0 g of 3,4-epoxycyclohexylmethyl acrylate were added to the obtained resin solution, and the mixture was reacted at 110°C for 6 hours to obtain a solution of linear polysiloxane (P-4-1) containing structural units a1 and a4.

[0121]

[0122] Comparative Synthesis Example 2 29.4 g of the epoxy-terminated dimethylsilicone (P-6), 4.3 g of acrylic acid, 0.05 g of 4-methoxyphenol, and 34.1 g of PGMEA were added to a 200 mL three-neck flask equipped with a thermometer and a nitrogen inlet tube and stirred, followed by addition of 0.3 g of dimethylbenzylamine, and the mixture was reacted for 6 hours at 110° C. To the resulting reaction solution, 34.0 g of PGMEA and 7.0 g of succinic anhydride were further added, and the mixture was reacted for 6 hours at 60° C., yielding a solution of the structural unit a4 and a linear polysiloxane (P-5-1) having a carboxy group and a (meth)acryloyl group at its terminals.

[0123]

[0124] Table 1 shows the carboxylic acid equivalent, (meth)acrylic equivalent, and weight average molecular weight (Mw) of the Si-containing compounds synthesized in Synthesis Examples 1 to 5 and Comparative Synthesis Examples 1 and 2.

[0125]

[0126] The components used in the preparation of the photosensitive compositions in the examples and comparative examples are as follows: (A) Si-containing compound (polysiloxane) (1) Linear polysiloxanes containing structural units a1, a2, and a4 synthesized in Synthesis Examples 1 to 4 above: (P-1-1), (P-1-2), (P-1-3), and (P-2-1) (2) Linear polysiloxanes containing structural units a2, a3, and a4 synthesized in Synthesis Example 5 above: (P-3-1) (3) Linear polysiloxanes containing structural units a1 and a4 synthesized in Comparative Synthesis Example 1 above: (P-4-1) (4) Linear polysiloxanes having structural units a4 and terminal carboxyl and (meth)acryloyl groups synthesized in Comparative Synthesis Example 2 above: (P-5-1) (5) Resin having a cresol novolac main chain with a carboxy group and a (meth)acryloyl group on the side chain: CCR-1358H (manufactured by Nippon Kayaku Co., Ltd.)

[0127] (B) Photopolymerization initiator (B-1): Oxime-based radical photopolymerization initiator ("NCI-930" manufactured by ADEKA Corporation) (B-2): "Irgacure (registered trademark) Oxe01" manufactured by BASF Japan Corporation

[0128] (C) Polymerizable Compounds (C-1): Dipentaerythritol hexaacrylate (C-2): Propylene oxide-modified trimethylolpropane polypropylene glycol triacrylate

[0129] Example 1 Preparation of Photosensitive Composition 100 parts by mass of (A) Si-containing compound (P-1-1) in terms of resin solids, 5 parts by mass of (B) photopolymerization initiator (B-1), 30 parts by mass of (C-1) as a (C) polymerizable compound, 3 parts by mass of 3-methacryloxypropyltrimethoxysilane as an adhesion aid, and 0.15 parts by mass of a surfactant ("DOWSIL 8019 Additive" from Dow Corning Toray Co., Ltd.) were mixed. The mixture was then diluted with PGMEA to a total solids concentration of 30% by mass, and then filtered through a membrane filter with a pore size of 0.2 μm to prepare a photosensitive composition.

[0130] Examples 2 to 8, Comparative Examples 1 to 3 Preparation of Photosensitive Compositions Photosensitive compositions were prepared in the same manner as in Example 1, using the types and amounts of the components shown in Table 2.

[0131]

[0132] (Evaluation of Coatability) For the photosensitive compositions of Examples 1 to 8 and Comparative Examples 1 to 3, a solution of each composition was spin-coated onto a silicon substrate to a film thickness of 3.0 μm, and then pre-baked using a hot plate at 85° C. for 2 minutes to form a coating film. The coating film was observed using a sodium lamp and evaluated according to the following criteria.

[0133] (Evaluation criteria) ◯: A uniform coating film was formed on the substrate without any cissing. △: Minor cissing (liquid return) was observed on the edge of the substrate. ×: Capping was observed over the entire surface of the substrate.

[0134] (Evaluation of lithography properties) The coating film used in the evaluation of coating properties was scanned using a projection scanner (DSC-200, manufactured by SUSS MicroTec) through a 10 μm×10 μm square hole pattern mask (illuminance=500 mW, NA=0.10, λ=ghi line, 80 mJ / cm 2) was used. Thereafter, development was carried out at 25°C for 1 minute using an aqueous solution of tetramethylammonium hydroxide (concentration 2.38%). Thereafter, the substrate was washed with running water and dried to form a pattern on the substrate. Next, an exposure machine (TME-400PRJ, manufactured by TOPCON) was used to expose the substrate to 500 mJ / cm with ghi mixed rays. 2 The insulating film (patterned thin film) obtained by the above method was observed with a scanning electron microscope (SEM) for the bottom dimensions of the holes, and evaluated according to the following criteria.

[0135] (Evaluation criteria) ◯: Bottom dimension is 8 μm or more △: Bottom dimension is less than 8 μm, 5 μm or more ×: Unresolved

[0136] (Evaluation of Chemical Resistance) A cured film was formed for each composition in the same manner as in the evaluation of lithography properties, except that bare glass was used and the entire surface was exposed to light. The obtained substrate was immersed in PGMEA for 3 minutes, and the remaining film ratio of the insulating film before and after immersion was calculated using the following formula and evaluated according to the following criteria.

[0137] Residual film rate (%) = insulating film thickness after immersion / insulating film thickness before immersion × 100

[0138] (Evaluation criteria) ◯: Residual film rate is 95% or more △: Residual film rate is less than 95%, 90% or more ×: Residual film rate is less than 90%

[0139] (Evaluation of Refractive Index) A cured film was formed for each composition in the same manner as in the evaluation of chemical resistance. The refractive index of the resulting cured film was measured at 589 nm using a spectroscopic ellipsometer (SE2000, manufactured by SEMILAB).

[0140]

[0141] As shown in Table 3, the photosensitive compositions of Examples 1 to 8 suppressed repelling on the substrate and had good coatability, and the pattern films formed from these photosensitive compositions not only had good lithography properties and chemical resistance, but also had refractive indices that could be reduced to less than 1.5, which was not possible without the inclusion of conventional particles.

Claims

1. A photosensitive composition containing the following components (A) and (B): (A) one or more Si-containing compounds selected from the following (A1) and (A2): (A1) a Si-containing compound containing a structural unit a1 having an alkali-soluble group and a polymerizable group, and a structural unit a2 having a polymerizable group, or a structural unit a3 having an alkali-soluble group; (A2) a Si-containing compound containing a structural unit a2 having a polymerizable group, and a structural unit a3 having an alkali-soluble group; (B) a photopolymerization initiator.

2. The photosensitive composition according to claim 1, wherein the structural unit a1 is a structural unit represented by the following formula (1) or a structural unit represented by the following formula (2), the structural unit a2 is a structural unit represented by the following formula (3), and the structural unit a3 is a structural unit represented by the following formula (4). [In formulas (1) to (4), R A R represents a monovalent group having an alkali-soluble group and a radically polymerizable group. B R represents a monovalent group having a radical polymerizable group. C R represents a monovalent group having an alkali-soluble group. 1 , R 21 and R 31 R each independently represents a monovalent organic group (excluding an alkali-soluble group and a radically polymerizable group). 2 , R 12 , R 22 and R 32 each independently represents a divalent linking group.

3. The photosensitive composition according to claim 1, wherein the Si-containing compound further contains a structural unit represented by the following formula (5) as the structural unit a4: [In formula (5), R 41 Each of X independently represents a monovalent organic group (excluding an alkali-soluble group and a radically polymerizable group). 42 represents a divalent linking group.

4. The photosensitive composition according to claim 1, wherein the weight average molecular weight of the Si-containing compound is from 5,000 to 50,000.

5. The photosensitive composition according to claim 1, further comprising a polymerizable compound having a radically polymerizable group as component (C).

6. A method for producing a patterned film, comprising the steps of: applying the photosensitive composition according to any one of claims 1 to 5 onto a substrate to form a photosensitive film; exposing the photosensitive film to light; and developing the exposed photosensitive film with an alkaline developer to obtain a patterned film.

7. A patterned film produced by the method for producing a patterned film according to claim 6.

8. A display device having the patterned film according to claim 7.

9. An optical material comprising the pattern film according to claim 7 as a low refractive index layer in combination with a high refractive index layer having a refractive index higher than that of the low refractive index layer.

10. A solid-state imaging device having the pattern film according to claim 7.

Images