JP2013054341A - Photosensitive composition, microlens array and stereoscopic image display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive composition for forming a member such as a spacer of a microlens array comprising a liquid crystal layer held between substrates, and to provide a microlens array and a stereoscopic image display device.SOLUTION: The photosensitive composition is prepared by using (A) an alkali-soluble resin, (B) a polyfunctional monomer, (C) a photosensitive polymerization initiator and (D) an organic solvent. A microlens array 1 is constituted by holding a liquid crystal layer 4 having a thickness of 20 μm to 100 μm between a pair of substrates 2, 3 having an interdigital electrode 6 and a common electrode 5 formed thereon, and forming a spacer 7 of the above photosensitive composition. A stereoscopic image display device 100 is constituted with the microlens array 1 having the spacer 7 and an image display unit 102 that can switch and display between a planar image and a stereoscopic image.

Description

  The present invention relates to a photosensitive composition, a microlens array, and a stereoscopic image display device. In particular, a photosensitive composition used for forming a microlens array suitable for switching between a planar image and a stereoscopic image, a microlens array suitable for switching between a planar image and a stereoscopic image, and a planar image including the microlens array The present invention relates to a stereoscopic image display device that can switch between and display a stereoscopic image.

In recent years, in the field of image display devices using a flat display panel, development of a stereoscopic image display device capable of displaying a stereoscopic image has been promoted as an effort for higher functionality.
A number of methods have been proposed for a technique for constructing a stereoscopic image on a stereoscopic image display device. They can be classified into a method in which an observer needs dedicated glasses when observing a stereoscopic image and a method in which dedicated glasses are not required.

  As a method for displaying a stereoscopic image (three-dimensional image) without using dedicated glasses, a lenticular method, a parallax method, and the like are known.

  FIG. 7 is a schematic perspective view illustrating the structure of the lenticular lens.

In the lenticular method, a lenticular lens 200 illustrated in FIG. 7 is used.
In displaying a stereoscopic image by the lenticular method, parallax right-eye images and left-eye images are alternately arranged in stripes on the image display unit of the stereoscopic image display device. The lenticular lens 200 is configured by arranging elongated and fine convex lenses on the surface so as to correspond to the right-eye image and the left-eye image arranged in the stripe shape. Then, the lenticular lens 200 is arranged in front of the image display unit so that only the right eye image is observed in the observer's right eye and only the left eye image is observed in the left eye. provide.

  In a stereoscopic image display device, there is a case where display of a planar image (two-dimensional image) is required depending on usage conditions or the like. In such a case, in the stereoscopic image display device using the lenticular method, the right-eye image and the left-eye image can be dealt with by using the same image without parallax, but the right-eye image and the left-eye image are the same image. If so, the resolution of the image display unit is halved. And the brightness | luminance of the planar image on an image display part falls because of the lenticular lens arrange | positioned between a stereo image display apparatus and an observer.

  In order to avoid such problems of the lenticular method using the conventional lenticular lens, it functions as a lenticular lens when displaying a stereoscopic image, and loses the function of the lenticular lens when displaying a flat image, and is simply a transparent body (non-lens transparent) A microlens array configured to function as a body has been proposed (see, for example, Patent Documents 1 and 2). In Patent Document 1, a liquid crystal panel is constituted by a pair of substrates having electrodes formed on opposite surfaces and a liquid crystal layer having refractive index anisotropy sandwiched between the substrates, and the liquid crystal panel is used as a microlens array. The technique used is disclosed. In the microlens array described in Patent Document 1, the liquid crystal is aligned in a desired state by ON / OFF of the applied voltage, and the refractive index of the liquid crystal layer can be adjusted. When a voltage is applied, the lens exhibits a lenticular lens function, and when a voltage is not applied, it functions as a non-lens transparent body. In the lenticular stereoscopic image display using such a microlens array, the above-described problems of resolution reduction and luminance reduction can be avoided.

  In such a microlens array technology using liquid crystal, a high-quality stereoscopic image is displayed, and thus the function as a lenticular lens needs to be exhibited uniformly in a plane. Therefore, it is required to realize liquid crystal alignment control with high accuracy by ON / OFF of the applied voltage. In order to realize high-precision alignment control of the liquid crystal, it is necessary to control the thickness of the liquid crystal layer sandwiched between the pair of substrates with high accuracy in a plane. Therefore, in a lenticular microlens array suitable for switching between a flat image and a three-dimensional image, which is configured by sandwiching a liquid crystal layer between a pair of substrates, the thickness of the liquid crystal layer can be uniformly controlled in a plane with high accuracy. The technology to do is demanded.

JP 2000-102038 A Japanese Patent No. 4602369

  The present invention has been made based on the above findings. That is, an object of the present invention is a microlens array which is configured by sandwiching a liquid crystal layer between a pair of substrates and is suitable for switching between a planar image and a stereoscopic image while maintaining the thickness of the liquid crystal layer uniformly in the plane. It is providing the photosensitive composition suitable for formation of.

  Another object of the present invention is a microlens array that is configured by sandwiching a liquid crystal layer between a pair of substrates and is suitable for switching between a planar image and a stereoscopic image while maintaining the thickness of the liquid crystal layer uniformly in the plane. Is to provide.

  Still another object of the present invention is a microlens that is configured by sandwiching a liquid crystal layer between a pair of substrates, and is suitable for switching between a planar image and a stereoscopic image while maintaining the thickness of the liquid crystal layer uniformly in the plane. To provide a stereoscopic image display device configured using an array.

  Other objects and advantages of the present invention will become apparent from the following description.

A first aspect of the present invention is a photosensitive composition containing an alkali-soluble resin,
The present invention relates to a photosensitive composition, which is used for forming a member disposed between substrates of a microlens array configured by sandwiching a liquid crystal layer having a thickness of 20 μm to 100 μm between a pair of substrates.

In the first aspect of the present invention,
(A) an alkali-soluble resin,
It is preferable to contain (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator.

  In the first aspect of the present invention, the (A) alkali-soluble resin is preferably a polymer having a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group.

  1st aspect of this invention WHEREIN: It is preferable that (B) polyfunctional monomer contains the compound which has an epoxy group.

In the first aspect of the present invention,
(A-II) It is preferable to contain a resin whose solubility in alkali is increased by the action of an acid, and (B-II) a compound that generates an acid upon irradiation with actinic rays or radiation.

  In the first aspect of the present invention, (A-II) a resin whose solubility in alkali is increased by the action of an acid is a resin comprising a copolymer containing a structural unit having a specific structure represented by the following formula (11) It is preferable to contain.

（式（１１）中、Ｒ^１０１は水素原子またメチル基、Ｒ^１０２は低級アルキル基を示し、Ｘはそれが結合している炭素原子と共に炭素数５〜２０の炭化水素環を形成する。）

(In formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.)

  1st aspect of this invention WHEREIN: It is preferable that the expansion / contraction rate at the time of the member arrange | positioned between board | substrates at 200 degreeC heating is 5% or less.

According to a second aspect of the present invention, there are provided a first substrate and a second substrate which are disposed to face each other, a liquid crystal layer sandwiched between the first substrate and the second substrate, and a liquid crystal side of the first substrate. A comb electrode having a plurality of electrode elements arranged in parallel to each other, and a common electrode provided on the liquid crystal side surface of the second substrate, between the comb electrode and the common electrode A microlens array that acts as a lens by driving a liquid crystal layer by applying a voltage to
Having a member between the first substrate and the second substrate;
The member relates to a microlens array formed from a photosensitive composition containing an alkali-soluble resin.

  In the second aspect of the present invention, it is preferable that an alignment film for parallel alignment is provided on a surface in contact with the liquid crystal layer of each of the first substrate and the second substrate.

In the second aspect of the present invention, the photosensitive composition comprises:
(A) an alkali-soluble resin,
It is preferable to contain (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator.

  In the second aspect of the present invention, the (A) alkali-soluble resin is preferably a polymer having a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group.

  2nd aspect of this invention WHEREIN: It is preferable that (B) polyfunctional monomer contains the compound which has an epoxy group.

In the second aspect of the present invention, the photosensitive composition comprises:
(A-II) It is preferable to contain a resin whose solubility in alkali is increased by the action of an acid, and (B-II) a compound that generates an acid upon irradiation with actinic rays or radiation.

  In the second aspect of the present invention, (A-II) a resin whose solubility in alkali is increased by the action of an acid is a resin comprising a copolymer containing a structural unit having a specific structure represented by the following formula (11) It is preferable to contain.

（式（１１）中、Ｒ^１０１は水素原子またメチル基、Ｒ^１０２は低級アルキル基を示し、Ｘはそれが結合している炭素原子と共に炭素数５〜２０の炭化水素環を形成する。）

(In formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.)

  In the second aspect of the present invention, the liquid crystal layer is preferably configured to contain a liquid crystal having positive dielectric anisotropy.

  In the second aspect of the present invention, the thickness of the liquid crystal layer sandwiched between the substrates is preferably 20 μm to 100 μm.

  In the second aspect of the present invention, the member between the first substrate and the second substrate preferably has an expansion / contraction ratio of 5% or less when heated at 200 ° C.

A third aspect of the present invention is a microlens array according to the second aspect of the present invention,
The present invention relates to a stereoscopic image display device having an image display unit that switches between a planar image and a stereoscopic image for display.

  In the third aspect of the present invention, the image display unit is preferably a liquid crystal display type, EL display type or plasma display type image display unit.

  According to the first aspect of the present invention, it is suitable for switching between a flat image and a three-dimensional image, and is suitable for forming a microlens array that uniformly functions in a plane as a lenticular lens when displaying a three-dimensional image. A composition is provided.

  In addition, according to the second aspect of the present invention, there is provided a microlens array that is suitable for switching between a planar image and a stereoscopic image, and that uniformly functions in a plane as a lenticular lens when displaying a stereoscopic image.

  Furthermore, according to the third aspect of the present invention, the microlens array is suitable for switching between a planar image and a stereoscopic image, and is configured by using a microlens array that uniformly functions in a plane as a lenticular lens when displaying a stereoscopic image. A stereoscopic image display device is provided.

It is sectional drawing which illustrates typically the structure of the microlens array of embodiment of this invention. It is a top view explaining the structure of the micro lens array of embodiment of this invention typically. It is a figure which illustrates typically the orientation state of the liquid crystal of the micro lens array of embodiment of this invention formed by voltage application. It is sectional drawing which illustrates typically the structure of the microlens array which is another example of embodiment of this invention. It is sectional drawing which illustrates typically the structure of the three-dimensional image display apparatus of embodiment of this invention. It is sectional drawing which illustrates typically the structure of the three-dimensional image display apparatus of embodiment of this invention which has the micro lens array to which the voltage was applied. It is a typical perspective view explaining the structure of a lenticular lens.

  The microlens array of the present invention is a microlens array suitable for a stereoscopic image display apparatus using a lenticular method. And it is comprised so that it may respond | correspond to the case where a planar image and a stereoscopic image are switched and displayed with a stereoscopic image display apparatus.

  The microlens array of the present invention includes a pair of substrates on which electrodes are formed on opposite surfaces, and a liquid crystal layer having refractive index anisotropy sandwiched therebetween. The microlens array of the present invention is used in a stereoscopic image display device and functions as a substantially transparent body when displaying a planar image. On the other hand, when a stereoscopic image is displayed, the liquid crystal layer between the substrates is driven by applying a voltage, and the lens functions by controlling the spatial alignment state of the liquid crystal. That is, the microlens array of the present invention functions as a lenticular lens by applying a voltage.

  In the microlens array of the present invention, in order to provide a high-quality three-dimensional image, it is necessary to uniformly exhibit the function as a lenticular lens in a plane. When the microlens array of the present invention functions as a lenticular lens by driving liquid crystal between substrates, it is required to control the spatial alignment state of the liquid crystal layer with high accuracy by applying a voltage. Therefore, it is necessary to control the thickness of the liquid crystal layer sandwiched between the pair of substrates with high accuracy in a plane.

  A liquid crystal display element is known as an element that is configured by sandwiching a liquid crystal layer between a pair of substrates and requires high precision in controlling the thickness of the liquid crystal layer, although it is in a different technical field. In the field of such a liquid crystal display element, for example, as described in Japanese Patent Application Laid-Open No. 2008-281594, a technique using a columnar spacer is known. That is, in order to control the thickness of the liquid crystal layer sandwiched between a pair of substrates with high accuracy, columnar spacers (hereinafter simply referred to as spacers unless otherwise specified) are provided between the substrates. A technique for keeping the distance between the substrates constant is known. For the formation of the spacer, a photolithography technique is usually used. In this technique, a photosensitive composition is applied on a substrate with a predetermined film thickness so as to have a thickness corresponding to the thickness of a target liquid crystal layer. Then, after exposure with ultraviolet rays through a predetermined mask, development and patterning are performed to form dot or stripe spacers having a height corresponding to the thickness of the liquid crystal layer.

  Therefore, the present inventors have intensively studied and provide a microlens array having a novel structure in which a member having a desired structure such as a spacer is provided between a pair of substrates sandwiching a liquid crystal layer. The member disposed between the pair of substrates of the microlens array functions as a support member for realizing the control of the thickness of the liquid crystal layer sandwiched between the substrates with high accuracy. That is, in a microlens array composed of a pair of substrates each having an electrode formed on each of opposing surfaces and a liquid crystal layer having refractive index anisotropy sandwiched between the substrates, the substrate is patterned by patterning using photolithography technology. The above-described members are arranged between them, and they function as support members to form a microlens array having a novel structure.

  A problem in providing a microlens array having such a new structure is that the spacer technology that has been effective in liquid crystal display elements cannot be applied to the microlens array as it is. For example, there is a problem related to the thickness of the liquid crystal layer sandwiched between the substrates described below, and a new technique is required to cope with the problem in order to enable application to a microlens array.

  Although there are some differences in liquid crystal display elements depending on the liquid crystal display mode, the thickness of a liquid crystal layer is about 1 μm to 10 μm for a recent liquid crystal TV. Therefore, in the liquid crystal display element, a spacer having a height of 10 μm or less corresponding to the thickness of the liquid crystal layer has been used.

  On the other hand, in the microlens array of the present invention in which the liquid crystal layer is sandwiched between a pair of substrates, the thickness of the liquid crystal layer is set in order to realize the desired liquid crystal alignment state and control the in-plane refractive index distribution. It is necessary to make it thicker than a conventional liquid crystal display element. For example, a thickness of 10 μm or more is required, preferably a thickness of 20 μm to 100 μm. And in order to implement | achieve the orientation state of a desired liquid crystal with high precision, it is more preferable that the thickness of a liquid-crystal layer shall be 30 micrometers-70 micrometers. Therefore, in the microlens array of the present invention, when it is intended to control the thickness of the liquid crystal layer sandwiched between the pair of substrates, it is necessary to cope with such a thick liquid crystal layer. That is, in the microlens array of the present invention, when the thickness of the liquid crystal layer between the substrates is controlled by the same spacer as the liquid crystal display element, it corresponds to a thick liquid crystal layer that is not used in the conventional liquid crystal display element. It is necessary to form a spacer having the above height.

  In the formation of the spacer of the liquid crystal display element, as described above, the photosensitive composition is a main component. Also in the microlens array of the present invention, the use of photolithography technology is effective for forming a member disposed between a pair of substrates that sandwich a liquid crystal layer, and a photosensitive composition is an important component. Become. However, in the case of the microlens array of the present invention, there is a strict requirement regarding the thickness of the liquid crystal layer described above. Therefore, in the microlens array of the present invention, in order to provide a member having a desired structure between a pair of substrates sandwiching a liquid crystal layer, a conventional photosensitive composition for a liquid crystal display element cannot be used as it is.

  Therefore, in the formation of the microlens array of the present invention, it is possible to form a coating film with a thicker film than in the past, realizing patterning with excellent resolution, and as a result, a member having a desired height and shape The photosensitive composition which can form is required. Furthermore, since the formed member maintains the distance between the substrates and maintains the thickness of the liquid crystal layer, it needs strength as a support member. In addition, these members placed between the substrates of the microlens array are slightly expanded and contracted by heating after the formation, and the height and shape of the members vary depending on the heating process when forming other components of the microlens array. It is required to have a characteristic that is difficult to occur.

  As described above, in order to provide a microlens array having a novel structure in which a member having a desired structure is disposed between a pair of substrates sandwiching a liquid crystal layer, it is suitable for forming a member disposed between the substrates. A photosensitive composition is required. The members arranged between the substrates include a columnar spacer structure in which the cross-sectional structure in the direction parallel to the substrate surface is in the form of dots or stripes, as well as a liquid crystal layer sandwiched between the substrates. It is desirable to realize a desired structure such as a partition wall structure provided between the substrates and control the thickness of the liquid crystal layer sandwiched between the substrates with high accuracy. Therefore, the photosensitive composition is preferably such that the structure of the member formed between the substrates can be the above-described spacer structure or partition structure by patterning using a photolithography technique.

  As a result of intensive studies, the present inventors have found a photosensitive composition that can meet the above requirements. That is, the photosensitive composition of the present embodiment suitable for forming a member having a desired structure, which is disposed between a pair of substrates of a microlens array and controls the thickness of a liquid crystal layer sandwiched between the substrates with high accuracy. I came to find something. Then, using the photosensitive composition of the present embodiment, a microlens of the present embodiment is formed by forming a member disposed between the substrates of the microlens array having a liquid crystal layer sandwiched between a pair of substrates. It has been found that an array can be formed and that the stereoscopic image display apparatus of the present embodiment can be configured using the array.

  In the following, a member having a structure such as a columnar spacer structure or a partition wall structure that is erected between the above-described substrates and disposed between a pair of substrates that sandwich the liquid crystal layer of the microlens array of the present embodiment ( Hereinafter, unless otherwise specified, the photosensitive composition of the present embodiment suitable for forming a member such as a spacer will be described.

[1] Photosensitive composition The photosensitive composition of this embodiment suitable for forming the members of the microlens array of this embodiment can form a coating film with a thick film exceeding 10 μm, for example, and has excellent resolution. Patterning is realized. Then, a member having a desired height and shape can be formed as a pattern. As described above, the formed member partitions the liquid crystal layer sandwiched between the substrates in addition to the columnar spacer structure in which the cross-sectional structure in the direction parallel to the substrate surface is in the form of dots or stripes. A desired structure such as a partition structure standing between the substrates can be selected. The member such as the spacer functions as a support member and has a strength necessary for maintaining the thickness of the liquid crystal layer while maintaining the distance between the substrates. Furthermore, a member such as a spacer composed of the photosensitive composition of the present embodiment has a characteristic that the expansion and contraction due to heating is slight, and the height and shape are not easily changed by heating.

  The photosensitive composition of this embodiment comprises the following components (A) to (C). And it is preferable to contain (D) component: an organic solvent.

(A) component: alkali-soluble resin (B) component: polyfunctional monomer (C) component: photosensitive polymerization initiator (D) component: organic solvent

[1-1] Component (A): Alkali-soluble resin The alkali-soluble resin of the component (A) is not particularly limited as long as it is a resin having alkali developability, and various resins can be selected.
And the photosensitive composition of this embodiment is a polymer which has structural unit (a1) which has a phenolic hydroxyl group, and structural unit (a2) which has an alicyclic hydrocarbon group as alkali-soluble resin of (A) component. Selection of (polymer (A)) is preferred.

When the polymer (A) is selected as the alkali-soluble resin of the component (A), the photosensitive composition of the present embodiment has a function of deactivating active species due to phenolic hydroxyl groups and a coating with alicyclic hydrocarbon groups. The film is configured with attention paid to the function of increasing the transparency of the film to light and the improvement of heat resistance by the synergistic effect of the phenolic hydroxyl group and the alicyclic hydrocarbon group.
That is, since the polymer (A) has the structural unit (a2) having an alicyclic hydrocarbon group, the light transmittance of the coating film can be increased, and the exposure of the coating film near the substrate and the surface is exposed. The amount increases. However, since the coating film having the polymer (A) having the structural unit (a1) having a phenolic hydroxyl group has a function of deactivating active species, the activity is proportional to the amount of generated active species. The seed is deactivated. For this reason, the active species generated more in the vicinity of the surface of the coating film and in the vicinity of the substrate of the coating film are deactivated by the exposure. As a result, the amount of active species is uniform in the thickness direction of the coating film, and as a result, a member having a desired structure, that is, a member such as a spacer is formed.

  Furthermore, it is known that the polymer having a structural unit having a phenolic hydroxyl group and the polymer having an alicyclic hydrocarbon group are each excellent in heat resistance, but in the present embodiment, these two kinds of By setting it as the polymer (A) which has a structural unit, it becomes the thing excellent in heat resistance. For the reasons described above, the photosensitive member for forming a member of the present embodiment contains a polymer (A) having a structural unit (a1) having a phenolic hydroxyl group and a structural unit (a2) having an alicyclic hydrocarbon group. A member such as a spacer obtained from the composition is a member such as a spacer that can maintain a desired shape during heating. Hereinafter, the polymer (A) contained in the photosensitive composition of the present embodiment will be described in more detail.

  When the content of the structural unit (a1) having a phenolic hydroxyl group contained in the polymer (A) is 100 parts by mass, the structural unit (a2) having an alicyclic hydrocarbon group contained in the polymer (A) The content of is preferably 25 parts by mass to 8000 parts by mass, more preferably 60 parts by mass to 6500 parts by mass, and still more preferably 90 parts by mass to 5500 parts by mass. This content is preferably in the range of 25 parts by mass to 8000 parts by mass because a member such as a spacer that can maintain a desired shape during heating can be formed.

  The weight average molecular weight (Mw) in terms of polystyrene determined by gel permeation column chromatography of the polymer (A) is the type of monomer used to obtain the polymer (A), the polymerization formulation, and the glass transition of the polymer (A). Although it is appropriately selected depending on the temperature, it is usually Mw = 5000 to 20000, preferably Mw = 8000 to 12000.

  Although the content rate of the polymer (A) used for the photosensitive composition of this embodiment is suitably selected by the height of members, such as a spacer formed, and the coating method, Preferably, it is contained in the photosensitive composition. When all the components are 100% by mass, they are 30% by mass to 90% by mass.

  When all the components of the photosensitive composition of this Embodiment except a solvent (D) are 100 mass%, Preferably the content rate of a polymer (A) is 30 mass%-90 mass%. This is because by using the polymer (A) as a main component of a member such as a spacer, a member such as a spacer that can maintain a desired shape during heating can be formed.

<Structural unit (a1) having phenolic hydroxyl group>
The “phenolic hydroxyl group” refers to a hydroxyl group directly bonded to an aromatic ring such as a benzene ring or a naphthalene ring. The “structural unit” indicates a polymer structure in which one monomer is used for each monomer used in forming the polymer. This “structural unit having a phenolic hydroxyl group” is polymerized by using a monomer having a phenolic hydroxyl group (a1 ′) or a monomer having a group that can be converted to a phenolic hydroxyl group. Then, the structural unit (a1) which has a phenolic hydroxyl group can be introduce | transduced into the structure of a polymer (A) by converting into a phenolic hydroxyl group.

  The content ratio of the structural unit (a1) having a phenolic hydroxyl group is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% when the total structural unit in the polymer (A) is 100% by mass. It is 10 mass%, More preferably, it is 10 mass%-20 mass%. When the content rate of the structural unit (a1) which has a phenolic hydroxyl group is 1 mass%-40 mass%, the photosensitive composition of this embodiment excellent in the resolution can be obtained.

  Examples of a method for introducing the “structural unit (a1) having a phenolic hydroxyl group” obtained by polymerization using a monomer (a1 ′) having a phenolic hydroxyl group into the polymer (A) include phenol and naphthol. A method of introducing a phenol and a condensing agent such as an aldehyde by condensation polymerization, radical polymerization or cationic polymerization of a monomer having a polymerizable group such as a (meth) acryl group or vinyl group and a phenolic hydroxyl group And the like. Among these, a vinyl group and a phenolic hydroxyl group are easy to copolymerize with a monomer having an alicyclic hydrocarbon group, which will be described later, and easily form a member such as a spacer that can maintain a desired shape during heating. A method of introducing a monomer having a radical polymerization by radical polymerization is preferred.

  Examples of the monomer having a vinyl group and a phenolic hydroxyl group include p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p-hydroxystyrene, α-methyl-m-hydroxystyrene, Examples thereof include monomers represented by the following formula (1) such as α-methyl-o-hydroxystyrene.

（式（１）中、Ｒ^１は水素原子またはメチル基を示す。）

(In formula (1), R ¹ represents a hydrogen atom or a methyl group.)

  When radical polymerization is performed using the monomer represented by the above formula (1), the polymer has a structural unit represented by the following formula (2).

（式（２）中、Ｒ^２は水素原子またはメチル基を示す。）

(In formula (2), R ² represents a hydrogen atom or a methyl group.)

  One type of monomer represented by the above formula (1) may be used, or two or more types may be used. The radical polymerization method can be obtained by a conventional method such as the method described in JP2009-192613A or JP2009-163080A.

<Structural unit (a2) having alicyclic hydrocarbon group>
The “alicyclic hydrocarbon group” refers to a group composed of only carbon and hydrogen and having a cyclic structure (including a polycyclic structure), except for an aromatic group. The “structural unit” indicates a polymer structure in which one monomer is used for each monomer used in forming the polymer. This “structural unit having a phenolic hydroxyl group” is obtained by polymerizing using a monomer (a2 ′) having an alicyclic hydrocarbon group to thereby superimpose the structural unit (a2) having an alicyclic hydrocarbon group. It can be introduced into the coalescence (A).

  The content ratio of the structural unit (a2) having an alicyclic hydrocarbon group is preferably 10% by mass to 80% by mass from the viewpoint of transmittance when the total structural unit in the polymer (A) is 100% by mass. %, More preferably 30% by mass to 50% by mass.

  As a method for introducing the “structural unit (a2) having an alicyclic hydrocarbon group” obtained by polymerization using a monomer (a2 ′) having an alicyclic hydrocarbon group into the polymer (A). And a method of introducing a monomer having a polymerizable group such as a (meth) acryl group or a vinyl group and an alicyclic hydrocarbon group by radical polymerization or cationic polymerization. Among these, from the point which is easy to obtain the copolymer with the monomer which has the above-mentioned phenolic hydroxyl group, and the point which tends to form members, such as a spacer which can maintain a desired shape at the time of a heating, (meth) acryl group and A method of introducing a monomer having an alicyclic hydrocarbon group by radical polymerization is preferred.

  Examples of the monomer having the (meth) acryl group and the alicyclic hydrocarbon group described in JP-A-2008-233346, JP-A-2009-192613, and JP-A-2009-163080. And monomers shown in the following formula (3).

（式（３）中、Ｒ^３は水素原子またはメチル基を示す。Ｒ^４は炭素数７〜３０の炭素原子および水素原子のみからなる脂環式炭化水素基である。）

(In formula (3), R ³ represents a hydrogen atom or a methyl group. R ⁴ is an alicyclic hydrocarbon group consisting of only a C 7-30 carbon atom and a hydrogen atom.)

Examples of the monomer having the structure represented by the above formula (3) include tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane. -8-yloxyethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl acrylate, Examples thereof include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, isobornyl acrylate, and tetrahydrofurfuryl methacrylate. Among these, since it is easy to form a member such as a spacer that can maintain a desired shape during heating, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate and isobornyl acrylate are selected. preferable.

  When radical polymerization is performed using the monomer represented by the above formula (3), the polymer has a structural unit represented by the following formula (4).

（式（４）中、Ｒ^５は水素原子またはメチル基を示す。Ｒ^６は炭素数７〜３０の炭素原子および水素原子のみからなる脂環式炭化水素基である。）

(In formula (4), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ is an alicyclic hydrocarbon group consisting of only a C 7-30 carbon atom and a hydrogen atom.)

  As for the monomer represented by the above formula (3), only one type may be used, or two or more types may be used. By using two or more types in combination, a monomer that is difficult to radically polymerize is contained in the polymer. Can be introduced. The radical polymerization method can be obtained by a conventional method such as the method described in JP2009-192613A or JP2009-163080A.

<Other structural unit (a3)>
The polymer (A), which is a component of the photosensitive composition of the present embodiment, contains other structural units (a3) within a range that does not impair the effect of being able to form a member such as a spacer that can maintain a desired shape during heating. Can be contained. The other structural unit (a3) includes a structural unit having a polyalkylene glycol group used for the purpose of improving adhesion to the substrate, and a carboxyl group for the purpose of adjusting the solubility of the polymer (A) in the developer. And a structural unit having

  The structural unit having the polyalkylene glycol group is not particularly limited as long as it has a polyalkylene glycol group, but the monomer having a phenolic hydroxyl group represented by the above formula (1) or the above formula (3) When the monomer having the alicyclic hydrocarbon group shown is used, the monomer having a polymerizable group and a polyalkylene glycol group is preferably radically polymerized and introduced into the polymer (A).

  Examples of the monomer having a polymerizable group and a polyalkylene glycol group described above include monomers described in JP-A-2008-273820 and JP-A-2009-192613, and a monomer represented by the following formula (5). The body can be mentioned.

（式（５）中、Ｒ^７は水素原子又はメチル基を示す。Ｒ^８はメチレン基または炭素数２〜４のアルキレン基を示す。Ｒ^９は炭素数６〜１２の直鎖状、環状もしくは芳香族の炭化水素基、またはこれらの基の少なくとも１つの水素原子が炭化水素基に置換された置換炭化水素基を示す。ｍは１〜１０の整数を示す。）

(In Formula (5), R ⁷ represents a hydrogen atom or a methyl group. R ⁸ represents a methylene group or an alkylene group having 2 to 4 carbon atoms. R ⁹ is a straight chain, cyclic or 6 to 12 carbon atoms. An aromatic hydrocarbon group, or a substituted hydrocarbon group in which at least one hydrogen atom of these groups is substituted with a hydrocarbon group, m represents an integer of 1 to 10.)

  As the monomer having the structure represented by the above formula (5), phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxydipropylene glycol (meth) acrylate, Phenoxytripropylene glycol (meth) acrylate, Phenoxytetrapropylene glycol (meth) acrylate, Lauroxydiethylene glycol (meth) acrylate, Lauroxytriethylene glycol (meth) acrylate, Lauroxytetraethylene glycol (meth) acrylate, Lauroxydipropylene glycol (Meth) acrylate, Lauroxytripropylene glycol (Meth) acrylate, Lauroxytetrap Propylene glycol (meth) acrylate.

  When radical polymerization is performed using the monomer represented by the above formula (5), a structural unit represented by the following formula (6) can be obtained.

（式（６）中、Ｒ^１０は水素原子またはメチル基を示す。Ｒ^１１はメチレン基または炭素数２〜４のアルキレン基を示す。Ｒ^１２は炭素数６〜１２の直鎖状、環状もしくは芳香族の炭化水素基、またはこれらの基の少なくとも１つの水素原子が炭化水素基に置換された置換炭化水素基を示す。ｎは１〜１０の整数を示す。）

(In the formula (6), R ¹⁰ represents a hydrogen atom or a methyl group. R ¹¹ represents a methylene group or an alkylene group having 2 to 4 carbon atoms. R ¹² represents a linear, cyclic or cyclic group having 6 to 12 carbon atoms. An aromatic hydrocarbon group or a substituted hydrocarbon group in which at least one hydrogen atom of these groups is substituted with a hydrocarbon group, n represents an integer of 1 to 10.)

  The structural unit having a carboxyl group is not particularly limited as long as it has a carboxyl group, but a monomer having a phenolic hydroxyl group represented by the above formula (1) or an alicyclic group represented by the above formula (3). When using a monomer having a hydrocarbon group, the monomer having a polymerizable group and a carboxyl group is usually radically polymerized and introduced into the polymer.

  Examples of the monomer having a polymerizable group and a carboxyl group include methacrylic acid and acrylic acid.

  As other structural unit (a3), in addition to the structural unit having a polyalkylene glycol group and the structural unit having a carboxyl group, those described in JP2009-192613A, JP2009-163080A, and the like. It may have a structural unit derived from a monomer.

[1-2] Component (B): Multifunctional monomer The polyfunctional monomer (polyfunctional monomer (B)) of the component (B) is at least two polymerizable monomers. It is a monomer having a saturated bonding group. The polyfunctional monomer (B) is a component that can act on the active species generated from the photosensitive polymerization initiator of the component (C) by the action of light to initiate polymerization and form a three-dimensionally crosslinked structure. And a component capable of forming a crosslinked structure by heat such as epoxy group. Thereby, in the coating film obtained from the photosensitive composition of this Embodiment, the location where light was applied becomes difficult to melt | dissolve with respect to a developing solution.

  The content of the polyfunctional monomer (B) used in the photosensitive composition of the present embodiment is appropriately selected depending on the sensitivity and resolution in the method for forming a member such as a spacer of the microlens array of the present embodiment. When the content of the polymer (A) described above is 100 parts by mass, the content of the polyfunctional monomer (B) is preferably used within the range of 1 part by mass to 100 parts by mass.

  Examples of the polyfunctional monomer (B) include polyfunctional monomers described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol; di (meth) acrylates of polyalkylene glycol such as polyethylene glycol and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, di Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as pentaerythritol and their dicarboxylic acid-modified products; oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, and spirane resin Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone; - (meth) acryloyloxyethyl] phosphate, and the like can be mentioned.

  Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( Meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred because they can form a member such as a spacer that can maintain a desired shape during heating.

  Examples of the compound having two or more 3,4-epoxycyclohexyl groups in one molecule as the polyfunctional monomer (B) include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexane. Carboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy -6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ', 4'-epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diene Epoxide, ethylene glycol di (3,4-epoxy Black hexyl) ether, ethylenebis (3,4-epoxycyclohexane carboxylate), lactone-modified 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexane carboxylate and the like.

As a compound having two or more glycidyl groups in one molecule, for example,
Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, Diglycidyl ethers of bisphenol compounds such as brominated bisphenol F diglycidyl ether and brominated bisphenol S diglycidyl ether;
Polyhydric alcohols such as 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether Glycidyl ether;
Polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
Phenol novolac type epoxy resin;
Cresol novolac type epoxy resin;
Polyphenol type epoxy resin;
Cycloaliphatic epoxy resin;
Diglycidyl esters of aliphatic long-chain dibasic acids;
Glycidyl esters of higher fatty acids;
Examples include epoxidized soybean oil and epoxidized linseed oil.

As these commercial products, for example,
As bisphenol A type epoxy resin, Epicoat 1001, 1002, 1003, 1004, 1007, 1009, 1010, 828 (Japan Epoxy Resin Co., Ltd.) and the like;
As bisphenol F type epoxy resin, Epicoat 807 (Japan Epoxy Resin Co., Ltd.) and the like;
As a phenol novolac type epoxy resin, Epicoat 152, 154, 157S65 (above, Japan Epoxy Resin Co., Ltd.), EPPN (registered trademark) 201, 202 (above, Nippon Kayaku Co., Ltd.), etc .;
As cresol novolac type epoxy resin, EOCN (registered trademark) 102, 103S, 104S, 1020, 1025, 1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Japan Epoxy Resin Co., Ltd.), etc .;
As polyphenol type epoxy resin, Epicoat 1032H60, XY-4000 (above, Japan Epoxy Resin Co., Ltd.) and the like;
Cyclic aliphatic epoxy resins include CY-175, 177, 179, Araldite CY-182, 192, 184 (above, Ciba Specialty Chemicals), ERL-4234, 4299, 4221, 4206. (Above, U.C.C), Shodyne 509 (Showa Denko), Epicron 200, 400 (above, Dainippon Ink), Epicoat 871, 872 (above, Japan Epoxy Resin), ED- 5661, 5562 (above, Celanese Coating), etc .;
Examples of the aliphatic polyglycidyl ether include Epolite 100MF (Kyoeisha Chemical Company), Epiol (registered trademark) TMP (Nippon Yushi Co., Ltd.) and the like.
Among these, selection of a phenol novolac type epoxy resin and a polyphenol type epoxy resin is preferable.

[1-3] Component (C): Photosensitive polymerization initiator The photosensitive polymerization initiator of component (C) is a semiconductor laser, a metal halide lamp, a high-pressure mercury lamp (g-line, h-line, i-line, etc.), excimer laser. It is a compound that can generate active species capable of initiating polymerization by the above-mentioned polyfunctional monomer (B) by exposure light such as extreme ultraviolet rays and electron beams.

  The content of the photosensitive polymerization initiator (C) used in the photosensitive composition of the present embodiment is appropriately selected depending on the sensitivity and resolution with respect to exposure light in the method for forming a member such as a spacer of the microlens array of the present embodiment. However, when the content of the polymer (A) described above is 100 parts by mass, the content of the photosensitive polymerization initiator (C) is preferably used in the range of 1 part by mass to 50 parts by mass. .

  Examples of the photosensitive polymerization initiator (C) include photosensitive polymerization initiators described in JP-A-2006-285035 and JP-A-2009-192613. Specifically, oxime ester compounds, acylphosphine oxide compounds, biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, triazines Compound, O-acyloxime type compound and the like. These may use only 1 type and may use 2 or more types together. In particular, as the photosensitive polymerization initiator (C) in the present invention, when using a high pressure mercury lamp containing g-line, h-line and i-line as exposure light, it is possible to form a member such as a spacer having a good shape with high sensitivity. Therefore, a combination of an acylphosphine oxide compound and an acetophenone compound is preferable.

  Examples of oxime ester compounds include 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- (2-methylbenzoyl). -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

  Acylphosphine oxide compounds include bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dioxy). Chlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2-naphthylphosphine oxide, bis (2, 6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,4-dimethoxyphenylphosphine oxide , Screw (2,6-dic Rubenzoyl) -decylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,4,6-trimethyl) Benzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3, 4,5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxy Phenylphosphine oxide, bis (2-mes 1-naphthoyl) -2-naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide Bis (2-methoxy-1-naphthoyl) -4-ethoxyphenylphosphine oxide, bis (2-chloro-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2 4,4-trimethylpentylphosphine oxide and the like.

  Examples of acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, -(4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 4- (2-hydroxy Ethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2- Examples include dimethoxy-1,2-diphenylethane-1-one.

[1-4] Component (D): Organic Solvent The photosensitive composition of the present embodiment preferably contains an organic solvent as the component (D).
The organic solvent of component (D) is a compound that can uniformly dissolve components other than the organic solvent (D) contained in the photosensitive composition of the present embodiment and does not react with these other components. If it is, it will not be limited.

  Content of the organic solvent (D) contained in the photosensitive composition of this embodiment can be suitably determined according to the height etc. of members, such as a coating method and a spacer.

  Examples of the organic solvent (D) include alcohols such as ethylene glycol; cyclic ethers such as tetrahydrofuran; alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl ether; alkyl ether acetates of polyhydric alcohols such as propylene glycol monomethyl ether acetate. Aromatic hydrocarbons such as toluene; ketones such as methyl ethyl ketone; esters such as ethyl acetate; These organic solvents may use only 1 type and may use 2 or more types together.

  Also, N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzylethyl ether, dihexyl ether, acetonylacetone , Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc. High boiling organic solvents can also be used.

[1-5] Other components In the photosensitive composition of the present embodiment, a thermal polymerization inhibitor, a surfactant, an adhesion aid, a solubility modifier, a viscosity modifier, and the like may be used as necessary. it can.

  The thermal polymerization inhibitor means that the photosensitive polymerization initiator (C) generates active species by heat and acts on the polyfunctional monomer (B) during storage of the photosensitive composition of the present embodiment. It is a component used for preventing. Examples of the thermal polymerization inhibitor include pyrogallol, benzoquinone, hydroquinone, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone and the like.

  The surfactant is a component used for improving the coating property, defoaming property, and leveling property when the photosensitive composition of the present embodiment is applied to the substrate. As a surfactant, for example, commercially available FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218, FTX-220D, FTX-222D (manufactured by Neos Co., Ltd.), BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC- 170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (above, Asahi Glass) Manufactured by Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, Toray Dow Corning Silicone) Co., Ltd.)), and the like.

  The adhesion assistant is a component used for improving the adhesion between a member such as a spacer and the substrate. As the adhesion assistant, a functional silane coupling agent is preferable. In addition, a functional silane coupling agent means the silane coupling agent which has reactive substituents, such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group. Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.

  A solubility regulator is a component used in order to adjust the solubility with respect to the developing solution of the coating film obtained from the photosensitive composition of this embodiment. As the solubility adjuster, when developing with an inorganic developer such as sodium hydroxide or potassium hydroxide, a low molecular carboxylic acid or a low molecular phenol compound is preferable. Low molecular carboxylic acids include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, iso-butyric acid, n-valeric acid, iso-valeric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3 Hydroxy such as hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid Monocarboxylic acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, malonic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2 , 4-cyclohexanetricarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, Polycarboxylic acids such as polytetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexa Hydrophthalic acid, methyltetrahydrophthalic anhydride, hymic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trianhydride There are acid anhydrides such as merit acid, anhydrous benzophenone tetracarboxylic acid, ethylene glycol bis trimellitic anhydride, and glycerin tris anhydrous trimellitate.

A low molecular weight phenol compound is a compound having a phenolic hydroxyl group and a molecular weight of 1000 or less. JP-A-3-200251, JP-A-3-200252, JP-A-3-200263, JP-A-3-200254. JP-A-4-1650, JP-A-4-11260, JP-A-4-12356, JP-A-4-12357, and the like. For example, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, tris (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, tris (4-hydroxyphenyl) ) Ethane, 1,3-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 1,4-bis [1- (4-hydroxyphenyl) -1-methylethyl] benzene, 4,6 -Bis [1- (4-hydroxyphenyl) -1-methylethyl] -1,3-dihydroxybenzene, 1,1-bis (4-hydroxyphenyl) -1- [4- [1- (4-hydroxyphenyl) ) -1-methylethyl] phenyl] ethane, 1,1,2,2-tetra (4-hydroxyphenyl) ethane and the like.
As the solubility modifier, one kind may be used alone, or two or more kinds may be mixed and used. In order to obtain a member such as a good spacer, a low molecular carboxylic acid and a low molecular phenol compound are used. It is preferable to use both.

  The viscosity modifier is used for the purpose of improving the coating property by adjusting the viscosity of the photosensitive composition of the present embodiment. Examples of the viscosity modifier include benite and silica gel.

[1-6] Preparation of Photosensitive Composition The photosensitive composition of the present embodiment is prepared by uniformly mixing the above-described components (A) to (D) and other components optionally added. The The photosensitive composition of this embodiment is used in a solution state in which other components are dissolved in the appropriate organic solvent (D) described above, for example. For example, a photosensitive composition in a solution state can be prepared by mixing the components (A) to (C) and other components optionally added together with the organic solvent (D) at a predetermined ratio. it can.

  When the photosensitive composition of the present embodiment is prepared as a solution, components other than the organic solvent (D) in the solution (ie, components (A) to (C) and other components optionally added) (Total amount) can be arbitrarily set according to the purpose of use, the value of the desired film thickness, and the like.

  Next, as the photosensitive composition of the embodiment, a so-called positive photosensitive composition can be used. That is, the photosensitive composition which is another example of this embodiment can also be positive-type photosensitive.

  Another example of the photosensitive composition of the embodiment of the present invention is configured to contain an alkali-soluble resin in the same manner as the photosensitive resin of the present embodiment described above. Another example of the photosensitive composition according to the embodiment of the present invention is as follows: (A-II) component: resin whose solubility in alkali is increased by the action of an acid, and (B-II) component: actinic ray or radiation. It is preferably configured to contain a compound that generates an acid upon irradiation. Hereinafter, the main component is demonstrated about another example of the photosensitive composition of embodiment of this invention.

[1-7] (A-II) Resin whose solubility in alkali is increased by the action of acid (A-II) The solubility in alkali is increased by the action of acid (A-II) used in the photosensitive composition of the embodiment of the present invention. Resin (hereinafter referred to as (A-II) component) is (a-ii-1) the following formula (11):

（式（１１）中、Ｒ^１０１は水素原子またメチル基、Ｒ^１０２は低級アルキル基を示し、Ｘはそれが結合している炭素原子と共に炭素数５〜２０の炭化水素環を形成する。）で示される特定構造を有する構成単位（以下、（ａ−ｉｉ−１）単位という。）を含む共重合体からなる樹脂を含有する。

(In formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.) The resin which consists of a copolymer containing the structural unit (henceforth (a-ii-1) unit) which has the specific structure shown by these is contained.

(A-ii-1) Unit:
The (a-ii-1) unit is a structural unit represented by the above formula (11).
In the above formula (11), R ¹⁰¹ is a hydrogen atom or a methyl group.
The lower alkyl group represented by R ¹⁰² may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, various pentyl groups, etc. Among these, from the viewpoint of realizing high contrast ratio photosensitivity and good resolution, depth of focus, etc., the number of carbon atoms is 2. A lower alkyl group of ˜4 is preferred.

X forms a monocyclic or polycyclic hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.
Examples of the monocyclic hydrocarbon ring include cyclopentane, cyclohexane, cycloheptane, cyclooctane and the like.

  Examples of the polycyclic hydrocarbon ring include a bicyclic hydrocarbon ring, a tricyclic hydrocarbon ring, and a tetracyclic hydrocarbon ring. Specific examples thereof include polycyclic hydrocarbon rings such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

  As the hydrocarbon ring having 5 to 20 carbon atoms formed by X together with the carbon atom to which X is bonded, a cyclohexane ring and an adamantane ring are particularly preferable among the above.

  Preferred examples of the structural unit represented by the above formula (11) include 1-ethylcyclopentyl (meth) acrylate, 1-propylcyclopentyl (meth) acrylate, 1-butylcyclopentyl (meth) acrylate, 1 -Ethylcyclohexylmeth) acrylate, 1-propylcyclohexylmeth) acrylate, 1-butylcyclohexylmeth) acrylate and the like can be mentioned.

  As the (a-ii-1) unit, one type of structural units represented by the above formula (11) may be used, but two or more types of structural units having different structures may be used.

  Further, the component (A-II) is a resin comprising a copolymer containing the above-described (a-ii-1) unit and (a-ii-2) a structural unit derived from a polymerizable compound having an ether bond. It is preferable that By including the (a-ii-2) structural unit (hereinafter referred to as the (a-ii-2) unit), the adhesion to the substrate during development is improved.

(A-ii-2) Unit:
The (a-ii-2) unit is a structural unit derived from a polymerizable compound having an ether bond.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol ( Illustrative radical polymerizable compounds such as (meth) acrylic acid derivatives having ether bonds and ester bonds such as (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate Preferably, it is 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, or methoxytriethylene glycol (meth) acrylate. These compounds can be used alone or in combination of two or more.

  Furthermore, the component (A-II) can contain other polymerizable compounds as monomers for the purpose of appropriately controlling physical and chemical properties. Here, the “other polymerizable compound” means a polymerizable compound constituting other than the above-mentioned (a-ii-1) unit and (a-ii-2) unit. Examples of such polymerizable compounds include known radically polymerizable compounds and anionic polymerizable compounds. For example, monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid and 2-methacryloyloxyethyl Radical polymerizable compounds such as methacrylic acid derivatives having carboxyl groups and ester bonds such as phthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc. (Meth) acrylic acid alkyl esters; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meth) acrylic acid aryl esters such as dil (meth) acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, Vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; Vinyl group-containing aliphatic compounds such as vinyl acetate; Conjugated diolefins such as butadiene and isoprene; Nitrile groups such as acrylonitrile and methacrylonitrile Containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide.

  The content of the (a-ii-1) unit in the component (A-2) is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. If it exceeds 90% by mass, the sensitivity tends to decrease, and if it is less than 10% by mass, the residual film ratio tends to decrease.

  The content of the (a-ii-2) unit in the component (A-2) is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. If it exceeds 90% by mass, the remaining film ratio tends to decrease, and if it is less than 10% by mass, the adhesion to the substrate during development tends to deteriorate.

  Further, the polystyrene-reduced mass average molecular weight (hereinafter referred to as mass average molecular weight) of the component (A-II) is preferably 10,000 to 600,000, more preferably 50,000 to 600,000, and further preferably 230000 to 550,000. .

  The component (A-II) is preferably a resin having a dispersity of 1.05 or more.

  The blending amount of the component (A-II), when containing other alkali-soluble resin as the component (C-II) described later, is a total mass of 100 masses of the component (A-II) and the component (C-II). Parts by weight to 5 parts by weight to 95 parts by weight, preferably 10 parts by weight to 90 parts by weight. Since the sensitivity tends to be improved by setting it to 5 parts by mass or more and 95 parts by mass or less, it is preferable.

[1-8] (B-II) Compound that generates acid upon irradiation with actinic rays or radiation (B-II) Used in another example of the photosensitive composition of the present embodiment. Generates acid upon irradiation with actinic rays or radiation. The compound to be used (hereinafter referred to as the component (B-II)) is an acid generator and is not particularly limited as long as it is a compound that generates an acid directly or indirectly by light.

  Specifically, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (2-furyl) ethenyl]- s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-Ethyl-2-furyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-propyl-2-furyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,5-dimethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,5-diethoxyphenyl) ) Ethenyl] -s-tria 2,4-bis (trichloromethyl) -6- [2- (3,5-dipropoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3 -Methoxy-5-ethoxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- [2- (3-methoxy-5-propoxyphenyl) ethenyl] -s-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (3,4-methylenedioxyphenyl) ethenyl] -s-triazine, 2,4-bis (trichloromethyl) -6- (3,4-methylenedioxyphenyl) ) -S-triazine, 2,4-bis-trichloromethyl-6- (3-bromo-4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromide) -4methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4methoxy) styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6- (3- Bromo-4methoxy) styrylphenyl-s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [ 2- (5-methyl-2-furyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,5-dimethoxyphenyl) ethenyl] -4, 6 -Bis (trichloromethyl) -1,3,5-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -1,3,5-triazine, 2 -(3,4-methylenedioxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, tris (1,3-dibromopropyl) -1,3,5-triazine, tris ( Halogen-containing triazine compounds such as 2,3-dibromopropyl) -1,3,5-triazine and halogen-containing triazine compounds represented by the following formula (12) such as tris (2,3-dibromopropyl) isocyanurate;

（式（１２）中、Ｒ^１０３〜Ｒ^１０５は、それぞれ同一であっても異なってもよく、それぞれハロゲン化アルキル基を示す。）

(In formula (12), R ^{103 to} R ¹⁰⁵ may be the same or different, and each represents a halogenated alkyl group.)

α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2 -Chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, a compound represented by the following formula (13);

(In the formula (13), R ¹⁰⁶ represents a monovalent to trivalent organic group, R ¹⁰⁷ represents a substituted, unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group or aromatic compound group, and n is 1 It represents a natural number of ˜3, wherein the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to the aromatic compound, for example, an aromatic hydrocarbon such as a phenyl group or a naphthyl group. Group, a heterocyclic group such as a furyl group, a thienyl group, etc. These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. R ¹⁰⁷ is particularly preferably an alkyl group having 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group, in particular, R ¹⁰⁶ is an aromatic compound group, and R ¹⁰⁷ is a lower alkyl group. The compound of the formula (13) is preferred. In The acid generator represented, when n = 1, R ¹⁰⁶ is a phenyl group, methylphenyl group, be any of the methoxyphenyl group, the compound by R ¹⁰⁷ is a methyl group, specifically alpha-( Examples include methylsulfonyloxyimino) -1-phenylacetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methoxyphenyl) acetonitrile. (When n = 2, the acid generator represented by the above formula (13) specifically includes an acid generator represented by the following chemical formula.)

  Bissulfonyldiazomethanes such as bis (p-toluenesulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane; p-toluenesulfone Nitrobenzyl derivatives such as 2-nitrobenzyl acid, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, dinitrobenzyl carbonate; pyrogallol trimesylate , Pyrgallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysk Sulfonic acid esters such as N-imide, N-phenylsulfonyloxymaleimide and N-methylsulfonyloxyphthalimide; trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; diphenyliodonium hexafluorophosphate, (4-methoxy Phenyl) phenyliodonium trifluoromethanesulfonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, (p-tert-butylphenyl) Onium salts such as diphenylsulfonium trifluoromethanesulfonate; Over DOO, benzoin tosylate such as α- methyl benzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, benzyl carbonate and the like.

  Among the above, as the component (B-II), the following formula (14):

（式（１４）中、Ｒは置換もしくは無置換の、例えば、炭素数１〜８のアルキル基またはアリール基である。）

(In the formula (14), R represents a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms or an aryl group.)

A compound having at least two oxime sulfonate groups represented by the formula (15):

（式（１５）中、Ａは二価の、例えば、置換または未置換の炭素数１〜８のアルキレン基または芳香族性化合物基であり、Ｒは置換もしくは無置換の、例えば、炭素数１〜８のアルキル基またはアリール基である。）

(In the formula (15), A is a divalent, for example, substituted or unsubstituted alkylene group having 1 to 8 carbon atoms or an aromatic compound group, and R is a substituted or unsubstituted, for example, 1 carbon atom. -8 alkyl group or aryl group.)

The compound represented by these is preferable. Here, the aromatic compound group refers to a group of a compound exhibiting physical and chemical properties peculiar to the aromatic compound, for example, an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, a furyl group, a thienyl group. And heterocyclic groups such as groups. These may have one or more suitable substituents on the ring, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. Further, a compound in which A in the above formula (15) is a phenylene group and R is, for example, a lower alkyl group having 1 to 4 carbon atoms is more preferable.

  This (B-II) component may be used independently and may be used in combination of 2 or more type.

  The blending amount is 0.1 parts by mass to 20 parts by mass, preferably 0.2 parts by mass to 10 parts by mass with respect to 100 parts by mass as a total mass of the components (A-II) (and (C-II)). Part. By setting it to 0.1 parts by mass or more, sufficient sensitivity can be obtained, and by setting it to 20 parts by mass or less, solubility in a solvent is good, a uniform solution is obtained, and storage stability tends to be improved. There is.

[1-9] (C-II) Other Alkali-Soluble Resin Another example of the photosensitive composition of the embodiment of the present invention preferably contains (C-II) another alkali-soluble resin. (C-II) Another alkali-soluble resin used in another example of the photosensitive composition according to the embodiment of the present invention is a resin composed of a copolymer containing the structural unit represented by the above formula (11). This is a resin to be removed (hereinafter referred to as (C-II) component). As the component (C-II), an arbitrary one can be appropriately selected from known alkali-soluble resins in conventional chemically amplified resists. Among these, it is particularly selected from (c-ii-1) novolak resin, (c-ii-2) a copolymer having a hydroxystyrene structural unit and a styrene structural unit, and (c-ii-3) an acrylic resin. It is preferable to contain at least one kind of resin, and (c-ii-1) a novolak resin and / or (c-ii-2) a copolymer of a hydroxystyrene structural unit and a styrene structural unit. It is preferable. By doing so, it becomes easy to control the coating property and developing speed of the photosensitive composition.

(C-ii-1) Novolac resin:
The novolak resin as component (c-ii-1) is obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst. It is done.

In this case, the phenols used include, for example, phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3 , 4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglicinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, etc. Et It is.
Examples of aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

The catalyst for the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like are used as the acid catalyst.
In particular, a novolak resin using only m-cresol as a phenol is preferable because the development profile is particularly good.

(C-ii-2) Copolymer having hydroxystyrene structural unit and styrene structural unit:
The component (c-ii-2) used in the present embodiment is a copolymer having at least a hydroxystyrene structural unit and a styrene structural unit. That is, a copolymer comprising a hydroxystyrene constituent unit and a styrene constituent unit, or a copolymer comprising a hydroxystyrene constituent unit, a styrene constituent unit and other constituent units.

Examples of the hydroxystyrene structural unit include hydroxystyrene structural units such as hydroxystyrene such as p-hydroxystyrene, and α-alkylhydroxystyrene such as α-methylhydroxystyrene and α-ethylhydroxystyrene.
Examples of the styrene structural unit include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, and the like.

(C-ii-3) Acrylic resin:
The acrylic resin as the component (c-ii-3) is not particularly limited as long as it is an alkali-soluble acrylic resin, but in particular, a structural unit derived from a polymerizable compound having an ether bond and a polymerizable group having a carboxyl group. Those containing a structural unit derived from a compound are preferred.

  Examples of the polymerizable compound having an ether bond include 2-methoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meta ), (Meth) acrylic acid derivatives having an ether bond and an ester bond such as methoxypolypropylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc., preferably 2-methoxyethyl acrylate, Methoxytriethylene glycol acrylate. These compounds can be used alone or in combination of two or more.

  Examples of the polymerizable compound having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid, 2-methacryloyloxyethyl succinic acid, and 2-methacryloyloxyethyl. Examples include maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethylhexahydrophthalic acid, and other compounds having a carboxyl group and an ester bond, and acrylic acid and methacrylic acid are preferred. These compounds can be used alone or in combination of two or more.

[1-10] (D-II) Acid Diffusion Control Agent Another example of the photosensitive composition of the embodiment of the present invention further includes ( D-II) An acid diffusion controller (hereinafter referred to as (D-II) component) is preferably contained.

  As the component (D-II), an arbitrary one can be appropriately selected from known ones as acid diffusion control agents in conventional chemically amplified resists. In particular, it is preferable to contain a nitrogen-containing compound, and if necessary, an organic carboxylic acid or an oxo acid of phosphorus or a derivative thereof can be contained.

  Next, a method for forming a member such as a spacer used in the microlens array of the present embodiment on the substrate using the photosensitive composition of the present embodiment will be described.

[2] Method for Forming Member such as Spacer The method for forming the member such as the spacer of the microlens array of the present embodiment uses the photosensitive composition of the present embodiment and performs the following steps (1) to (3). It is configured.

Step (1): A step of forming a coating film (hereinafter also referred to as “coating film”) obtained from the photosensitive composition of the present embodiment (hereinafter also referred to as “composition”) on the substrate.
Step (2): A step of exposing the coating film obtained in step (1) so as to correspond to the shape of a member such as a spacer.
Process (3): The process of developing the coating film after exposure obtained at the process (2).
Details of each step will be described below.

[2-1] Step (1)
In the step (1), a photosensitive composition is applied on the substrate. Then, if necessary, heat treatment (hereinafter also referred to as “pre-bake”) is performed to remove the solvent and form a coating film of the photosensitive composition.
As the substrate, a coating film of the photosensitive composition can be formed on a glass substrate, a plastic substrate, and a semiconductor substrate such as silicon. When the microlens array of this embodiment is formed, a glass substrate or a plastic substrate on which a transparent electrode such as ITO (Indium Tin Oxide) is formed is selected.

As a coating method of the photosensitive composition, any method can be used as long as it can uniformly coat the photosensitive composition. For example, a spray method, a roll coating method, a spin coating method (spin coating method). An appropriate method such as a slit die coating method, a bar coating method, or an ink jet method can be employed. In particular, a spin coating method or a slit die coating method is preferable because a coating film having a uniform film thickness can be obtained.
Moreover, when performing prebaking, the conditions can be suitably selected according to the type of each component, particularly the solvent, and the amount used, but preferably at 60 ° C to 160 ° C for about 30 seconds to 15 minutes.

  The film thickness of the coating film thus obtained is appropriately selected so as to correspond to the height of the target member such as a spacer. Preferably, the thickness of the coating film is the same as or thicker than the height of a member such as a target spacer. For example, it is preferable to set it as 10 micrometers-140 micrometers.

[2-2] Step (2)
In step (2), the coating film obtained in step (1) is exposed through a patterned mask as necessary so as to correspond to the shape of the target member such as a spacer, and a coating having a latent image is obtained. A film (coating after exposure) is formed.
Examples of the exposure light include semiconductor lasers, metal halide lamps, high-pressure mercury lamps (g-line, h-line, i-line, etc.), excimer lasers, extreme ultraviolet rays, and electron beams. A high-pressure mercury lamp is preferable because it has high transparency with respect to the above-described coating film and can form a pattern with high resolution.

Exposure amount, type of the exposure light is appropriately selected according to the shape of the members of the spacer or the like for the film thickness and the type and purpose of the coating, when the high-pressure mercury ^lamp, be 100mJ / cm ² ~1500mJ / cm 2 Is preferred.

  The coating film obtained by the step (1) using the photosensitive composition containing the component (A), the component (B) and the component (C) of the present embodiment described above is a negative type. Moreover, the coating film obtained by process (1) using (A-II) component and (B-II) component which is another example of the photosensitive composition of this embodiment mentioned above is a positive type.

  Here, when it demonstrates about the coating film obtained by a process (1) using the photosensitive composition of this embodiment which is negative type, the above-mentioned coating film can pattern the location which exposed. For this reason, it exposes to the above-mentioned coating film through the patterned mask designed so that the location corresponding to the target member such as a spacer has higher transmittance for exposure light than other locations. Further, an exposure method can be selected as appropriate depending on the size of a target member such as a spacer. When forming a member such as a fine spacer, exposure can be performed by a reduction projection method.

  Moreover, if the coating film obtained by process (1) is demonstrated using another example of the photosensitive composition of this embodiment which is a positive type, the above-mentioned coating film can pattern other than the exposed part. It is. For this reason, it exposes to the above-mentioned coating film through the patterned mask designed so that the location corresponding to the target member such as a spacer may have a lower transmittance to exposure light than the other locations.

  After the exposure, heat treatment (hereinafter, also referred to as “post-bake”) can be performed as necessary.

In the case of the coating film obtained by the step (1) using the negative photosensitive composition of this embodiment, the post-baking conditions are photosensitive polymerization initiators contained in each component, particularly the photosensitive composition. Although it can select suitably by the kind of (C), the usage-amount, etc., Preferably, it is 30 seconds-15 minutes at 60 to 160 degreeC.
In the case of a coating film obtained by step (1) using another example of the positive photosensitive composition of the present embodiment, the post-bake conditions are included in each component, particularly the photosensitive composition. (B-2) can be appropriately selected depending on the type and amount of component used.

[2-3] Step (3)
In step (3), the exposed coating film obtained in step (2) is contacted with a developer to remove a relatively highly soluble portion in the developer and form a patterned coating film. . That is, step (3) is a step of developing a coating film having a latent image, patterning the latent image, and forming a patterned coating film.

  Examples of the developer that can be used in the step (3) include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, diethylaminoethanol, di- n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, An aqueous solution of a basic compound such as 1,5-diazabicyclo [4.3.0] -5-nonane can be given. In addition, an aqueous solution obtained by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to an aqueous solution of such a basic compound can also be used as a developer. As a method for contacting the developer, for example, an appropriate method such as a liquid piling method, a dipping method, a rocking dipping method, or a shower method can be used.

The patterned coating film obtained by contact with the developer is preferably washed with water.
Moreover, in the case of the coating film obtained by process (1) using the negative photosensitive composition of this embodiment, the photosensitive polymerization initiator which remained in the patterned coating film and was not decomposed | disassembled by exposure light For the purpose of decomposing (C) or for the purpose of sufficiently curing the patterned coating film by proceeding the polymerization of the polyfunctional monomer (B) with the active species generated by the decomposition. Can also be irradiated (post-exposure) on the entire surface. Exposure amount in the exposure after the case is ^{preferably, 1mJ / cm 2 ~1500mJ / cm} 2. Furthermore, it is possible to post-bake for the purpose of sufficiently curing the patterned coating film. The post-baking conditions can be appropriately selected depending on the type and amount of each component, but are usually about 150 to 250 ° C. for about 10 to 120 minutes.

  As described above, a member such as a spacer used in the microlens array of this embodiment can be formed on the substrate as a pattern formed by patterning using the photosensitive composition of this embodiment. The formed members such as spacers can have a desired shape and height, have the necessary strength to maintain the distance between the substrates, and can be deformed or change in height when heated. Is insignificant. For example, the formed member such as a spacer may have a height of 10 μm to 100 μm. By appropriately selecting the formation conditions, it is possible to realize a height of 100 μm or more as necessary.

  In addition, as the shape of the spacer, in addition to the columnar shape, a lattice shape or the like is also preferable.

When the microlens array of this embodiment is manufactured, a member such as a spacer is formed on a substrate having electrodes, and then an alignment film for liquid crystal alignment is formed as described later. In order to form the alignment film, a heating step at a temperature of 200 ° C. or higher is usually required. Members such as spacers formed using the photosensitive composition of the present embodiment can suppress expansion and contraction due to heating at 200 ° C. to 5% or less. As a result, the distance between the substrates in the microlens array to be manufactured can be uniformly maintained in the plane even if there is a heat treatment step for forming an alignment film or bonding the substrates after forming a member such as a spacer.
Next, the microlens array of this embodiment will be described.

[3] Microlens Array The microlens array of this embodiment is a microlens array suitable for a lenticular stereoscopic image display device, and is configured to be able to cope with switching between planar image display and stereoscopic image display. The microlens array of this embodiment includes a pair of substrates having electrodes formed on opposite surfaces, a liquid crystal layer having refractive index anisotropy sandwiched between them, and the above-described photosensitivity of this embodiment. It is comprised from members, such as a spacer formed from the composition. When displaying a planar image on a stereoscopic image display device, it functions as a substantially transparent body. In displaying a stereoscopic image, the liquid crystal layer is driven by applying a voltage to control the alignment state of the liquid crystal, thereby acting as a lens. That is, the microlens array of this embodiment functions as a lenticular lens by applying a voltage.
Hereinafter, the microlens array of the present embodiment will be described in more detail with reference to the drawings.

  FIG. 1 is a cross-sectional view schematically illustrating the structure of the microlens array of the present embodiment.

The microlens array 1 according to the present embodiment includes a columnar spacer 7 which is an example of a member disposed between a pair of substrates 2 and 3.
That is, the microlens array 1 of the present embodiment includes a substrate 2 disposed on the light emitting side, a substrate 3 disposed on the light incident side, the liquid crystal layer 4 sandwiched between the substrate 2 and the substrate 3, Between the substrate 2 and the substrate 3, the common electrode 5 provided on the liquid crystal layer 4 side surface of the substrate 2, the comb-shaped comb electrode 6 provided on the liquid crystal layer 4 side of the substrate 3, and the substrate 2. And a spacer 7 erected.

  An alignment film 8 for liquid crystal alignment is formed on the surface of the substrate 2 where the common electrode 5 is formed and the surface of the substrate 3 where the comb electrode 6 is formed. The liquid crystal layer 4 is composed of a liquid crystal 9 which is a nematic liquid crystal. The side surface portion of the microlens array 1 is preferably sealed with an appropriate sealant (not shown).

  FIG. 2 is a plan view schematically illustrating the structure of the microlens array of the present embodiment.

  In FIG. 2, only the substrate 3, the comb-tooth electrode 6, and the spacer 7 are shown to explain the arrangement of the spacer 7, and other components of the microlens array 1 are omitted. As shown in FIG. 2, a plurality of spacers 7 are erected between the comb electrodes 6 at intervals.

  Each of the substrate 2 and the substrate 3 is preferably made of a material having a high visible light transmittance. For the substrates 2 and 3, for example, a transparent substrate made of glass such as float glass or soda glass, or a transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate is used. Is possible. As thickness of the board | substrate 2 and the board | substrate 3, respectively, it can be set as 20 micrometers-2000 micrometers, for example, and it is preferable to set it as 50 micrometers-1000 micrometers.

As a material constituting the common electrode 5 and the comb electrode 6, it is preferable to use a transparent conductor. For example, ITO composed of In ₂ O ₃ —SnO _2, NESA (registered trademark) composed of SnO _2, and the like are preferable. It is. Comb electrode 6 has a plurality of electrode elements arranged in parallel to each other, and a back portion where these electrode elements are electrically connected to each other at one end thereof. The shape when the electrode element is observed from a direction perpendicular to the substrate surface is preferably a rectangle having a short side and a long side. The comb electrode 6 can be formed by using a known photolithography method and forming a transparent conductor film made of ITO or NESA (registered trademark) on the substrate, followed by patterning. is there.

The width of the electrode element (the length of the short side) is the pixel width of the image display unit used in combination with the microlens array 1 of this embodiment (the width of the pixel unit for displaying the right-eye image or the left-eye image). 1% or more and less than 200%, preferably 2% or more and less than 100%, more preferably 2% or more and less than 50%. The length of the electrode element (long side length) can be approximately equal to the length of one side of the substrate 3. The pitch between adjacent electrode elements is preferably set to twice (200%) the pixel width of the image display unit used in combination with the microlens array 1 of the present embodiment.
In the microlens array 1 of the present embodiment, a flattening film may be provided between the layer made of the comb electrode 6 and the layer made of the alignment film 8.

  The liquid crystal layer 4 is preferably composed of a nematic liquid crystal 9 having positive dielectric anisotropy. The liquid crystal 9 preferably has positive refractive index anisotropy.

  Examples of the liquid crystal 9 having positive dielectric anisotropy constituting the liquid crystal layer 4 include biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, and dioxane. Examples thereof include liquid crystals, bicyclooctane liquid crystals, and cubane liquid crystals. It is preferable to use a liquid crystal having a positive dielectric anisotropy by mixing two or more of these liquid crystals, exhibiting a nematic phase in a desired temperature range including room temperature.

  The spacer 7 is a columnar spacer, and is disposed between the substrate 2 and the substrate 3 as shown in FIGS. 1 and 2. The spacer 7 functions as a support member for realizing the control of the thickness of the liquid crystal layer 4 with high accuracy. Formation of the spacer 7 is performed by the method mentioned above using the photosensitive composition of this embodiment. In the microlens array 1 of the present embodiment having the structure shown in FIG. 1, the microlens array 1 is erected between the electrode elements of the comb electrodes 6 on the substrate 3 on which the comb electrodes 6 are formed by the above-described forming method. Thereafter, an alignment film 8 is provided, and is placed between the substrate 2 and the substrate 3 by being superimposed on the substrate 2 on which the common electrode 5 and the alignment film 8 are formed.

The height of the spacer 7 is determined according to the thickness of the liquid crystal layer 4. The thickness of the liquid crystal layer 4 is preferably 20 μm to 100 μm, and the height of the spacer 7 is also set to 20 μm to 100 μm correspondingly. Then, in order to realize a desired alignment state of the liquid crystal with high accuracy, when the thickness of the liquid crystal layer is set to 30 μm to 70 μm, the height of the spacer 7 is set to 30 μm to 70 μm correspondingly. Is preferred.
In addition, although the spacer 7 of the microlens array 1 of the present embodiment shown in FIG. 2 has a circular cross-sectional shape, the spacer 7 may have other shapes. For example, the cross section may be a columnar shape having an elliptical shape, a rectangular shape, or a square shape.

  In the microlens array 1 of the present embodiment, as another configuration example, a spacer is erected on the substrate 2 on which the common electrode 5 is formed using the photosensitive composition of the present embodiment, and the alignment film 8 is formed. After that, the substrate 3 and the substrate 3 on which the comb electrode 6 and the alignment film 8 are formed are overlapped, so that a spacer is disposed between the substrate 2 and the substrate 3. Is possible.

  The alignment film 8 is disposed on the surface in contact with the liquid crystal layer 4 of the substrate 2 and the substrate 3. As the alignment film 8, any alignment film for parallel alignment that aligns the liquid crystal 9 of the liquid crystal layer 4 in a direction parallel to the substrate surface can be used. Such an alignment film 8 for parallel alignment includes, for example, polyamic acid, polyimide, polyorganosiloxane, polyamic acid ester, polyester, polyamide, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly ( It is possible to configure using an organic film made of meth) acrylate or the like. Then, these organic films are subjected to an alignment process such as a photo-alignment process using light, or a rubbing process in which the surface of the organic film is rubbed in one direction using a cloth such as nylon or polyester, and liquid crystal parallel to the substrate surface It can be used by realizing the orientation of the layer 4.

  Note that the direction of the alignment treatment in the alignment film 8 can be set so that the opposing substrate 2 and the substrate 3 are antiparallel to each other (antiparallel alignment).

  In the microlens array 1 according to the present embodiment, when no voltage is applied between the comb electrode 6 and the common electrode 5, the liquid crystal 9 of the liquid crystal layer 4 is the substrate 2 and the substrate 3 as shown in FIG. It is uniformly oriented parallel to the surface and functions as a simple transparent body. In this state, the microlens array 1 does not exhibit the lenticular lens function. On the other hand, in the microlens array 1 of the present embodiment, when a predetermined voltage for driving the liquid crystal is applied between the comb electrode 6 and the common electrode 5, the liquid crystal 9 of the liquid crystal layer 4 is And the substrate 3 change the alignment state, and a desired spatial alignment state is formed.

  FIG. 3 is a diagram schematically illustrating the alignment state of the liquid crystal in the microlens array of the present embodiment formed by voltage application.

  As shown in FIG. 3, in the microlens array 1, when a predetermined voltage is applied between the comb electrode 6 and the common electrode 5, the liquid crystal 9 of the liquid crystal layer 4 is between the substrate 2 and the substrate 3. The orientation state changes. An alignment state is realized between the substrate 2 and the substrate 3 that is oriented in parallel with the substrate 3 in the vicinity of the adjacent electrode elements of the comb-tooth electrode 6 but increases in inclination with respect to the substrate 3 as it approaches the common electrode 5. To do. As a result, a refractive index distribution that realizes a convex lens function is generated in the plane of the microlens array 1. Therefore, when a voltage is applied between the comb electrode 6 and the common electrode 5, the microlens array 1 has an elongated, so-called kamaboko-shaped convex lens portion corresponding to the formation pitch of the electrode elements of the comb electrode 6. It functions as a lenticular lens.

  The microlens array 1 of the present embodiment has a spacer 7 and can control the thickness of the liquid crystal layer 4 sandwiched between the substrate 2 and the substrate 3 in a plane with high accuracy. . The microlens array 1 can control the spatial alignment state of the liquid crystal 9 of the liquid crystal layer 4 with high accuracy by applying a voltage, and is suitable for switching between a planar image and a stereoscopic image. It becomes.

  In the microlens array 1 shown in FIG. 1, the spacer 7 can be erected at a desired position between the electrode elements of the comb electrode 6 on the substrate 3 between the substrate 2 and the substrate 3. . And the arrangement position with respect to the comb-tooth electrode 6 is not necessarily restricted between the electrode elements of the comb-tooth electrode 6. For example, it can be provided on the electrode element of the comb-tooth electrode 6 on the substrate 3.

  FIG. 4 is a cross-sectional view schematically illustrating the structure of a microlens array which is another example of the present embodiment.

  A microlens array 21, which is another example of the present embodiment shown in FIG. 4, is provided with a spacer 27 on the electrode element of the comb electrode 6 on the substrate 3, and other structures are described above. The same as the microlens array 1 described above. Therefore, the same reference numerals are used for components common to the microlens array 1 of FIG.

  The microlens array 21, which is another example of the present embodiment, includes a substrate 2 disposed on the light emitting side, a substrate 3 disposed on the light incident side, and a liquid crystal layer sandwiched between the substrate 2 and the substrate 3. 4, a common electrode 5 provided on the surface of the substrate 2 on the liquid crystal layer 4 side, a comb-shaped comb electrode 6 provided on the liquid crystal layer 4 side of the substrate 3, and the substrate 2 and the substrate 3. And a spacer 27 erected. An alignment film 8 for liquid crystal alignment is formed on the surface of the substrate 2 on which the common electrode 5 is formed and on the surface of the substrate 3 on which the comb-tooth electrode 6 is formed. The liquid crystal layer 4 is composed of a liquid crystal 9 which is a nematic liquid crystal. The side surface portion of the microlens array 21 is preferably sealed with an appropriate sealant (not shown).

  The spacer 27 of the microlens array 21 is a columnar spacer having the same shape as the spacer 7 of the microlens array 1 shown in FIG. 1 and is disposed between the substrate 2 and the substrate 3. Formation of the spacer 27 is performed according to the method described above using the photosensitive composition of the present embodiment. As shown in FIG. 4, in the microlens array 21 which is another example of the present embodiment, the spacer 27 stands on the electrode element of the comb electrode 6 on the substrate 3 on which the comb electrode 6 is formed. Established. Thereafter, an alignment film 8 is provided, and is placed between the substrate 2 and the substrate 3 by being superimposed on the substrate 2 on which the common electrode 5 and the alignment film 8 are formed.

  The microlens array 21, which is another example of the present embodiment, has a spacer 27, and controls the thickness of the liquid crystal layer 4 sandwiched between the substrate 2 and the substrate 3 in a plane with high accuracy. It is possible. The microlens array 21 can control the spatial alignment state of the liquid crystal 9 of the liquid crystal layer 4 with high accuracy by applying a voltage, like the microlens array 1 shown in FIG. A microlens array suitable for switching between an image and a stereoscopic image is obtained. In the microlens array 21, the spacer 27 is provided on the electrode element of the comb electrode 6 on the substrate 3, and the spacer 27 hinders spatial alignment control of the liquid crystal 9 by voltage application. Few.

  In the microlens array 21 of the present embodiment, as another configuration example, a spacer is erected on the substrate 2 on which the common electrode 5 is formed using the photosensitive composition of the present embodiment, and the alignment film 8 is formed. Is provided. Thereafter, the substrate 2 and the substrate 3 on which the comb electrode 6 and the alignment film 8 are formed are overlapped, so that a spacer is formed between the substrate 2 and the substrate 3 and on the electrode element of the comb electrode 6. It is also possible to adopt a configuration in which are arranged.

  Next, the stereoscopic image display device of this embodiment using the microlens array of this embodiment will be described.

[4] Stereoscopic image display apparatus The stereoscopic image display apparatus of the present embodiment includes a stereoscopic image having an image display unit that can switch between a planar image and a stereoscopic image and the above-described microlens array of the present embodiment. It is a display device.

  FIG. 5 is a cross-sectional view schematically illustrating the structure of the stereoscopic image display apparatus according to the present embodiment.

  The stereoscopic image display apparatus 100 according to the present embodiment includes the above-described microlens array 1 according to the present embodiment, and an image display unit 102 that can switch and display a planar image and a stereoscopic image in the order from the observer 101. Is arranged.

  The image display unit 102 of the stereoscopic image display apparatus according to the present embodiment includes a liquid crystal display method, an EL (Electro Luminescence) display method, a plasma display method, a CRT (Cathode Ray Tube) method, and an LED (Light Emitting Diode). : A light-emitting diode) type image display unit, and the like, but a liquid crystal display type, EL display type or plasma display type image display unit is preferable. The EL display method is preferably an organic EL display method.

  It is preferable to arrange at least one polarizing plate (not shown) between the image display unit 102 and the microlens array 1. This polarizing plate may be integrated with the image display unit 102 to constitute a part thereof.

  When displaying a stereoscopic image, the image display unit 102 of the stereoscopic image display apparatus 100 according to the present embodiment alternately forms a right-eye image and a left-eye image with parallax in a stripe pattern on the image display unit 102. Can be displayed. On the other hand, when displaying a planar image, a right-eye image forming portion and a left-eye image forming portion at the time of displaying a stereoscopic image can be used as unit pixels of a two-dimensional image, respectively. It is preferable that an image is displayed.

  The width of the unit pixel included in the image display unit 102 is preferably ½ of the formation pitch of the electrode elements of the comb electrodes 6 of the microlens array 1. In the stereoscopic image display device 100 of the present embodiment, when the image display unit 102 and the microlens array 1 of the present embodiment are combined, the lengths of the electrode elements of the comb electrodes 6 of the substrate 3 of the microlens array 1 are combined. The center line extending in the direction is preferably combined so as to coincide with the boundary line between the right-eye image forming portion and the left-eye image forming portion when the stereoscopic image is displayed on the image display unit 102.

  In the stereoscopic image display apparatus 100 according to the present embodiment, the image display unit 102, as described above, the right-eye image portion (R) for alternately forming the right-eye image and the left-eye image having a parallax in a stripe shape. And a left-eye image portion (L). When displaying a planar image, as shown in FIG. 5, the image display unit 102 uses the right-eye image portion (R) and the left-eye image portion (L) as unit pixels for forming a two-dimensional image. A high-definition two-dimensional image is output. At this time, the microlens array 1 is brought into a state in which no voltage is applied or a state in which a very small voltage is applied so that the liquid crystal 9 does not change its orientation. As a result, the liquid crystal 9 of the liquid crystal layer 4 sandwiched between the substrate 2 and the substrate 3 of the microlens array 1 is parallel to the substrate surface formed by the substrate 2 and the substrate 3 by the action of the alignment film 8. Orient. Therefore, the microlens array 1 does not function as a lenticular lens but functions as a simple transparent body. As a result, the observer 101 can observe a high-definition and high-luminance planar image on the stereoscopic image display device 100.

  FIG. 6 is a cross-sectional view schematically illustrating the structure of the stereoscopic image display apparatus according to the present embodiment having a microlens array to which a voltage is applied.

  On the other hand, as shown in FIG. 6, in the stereoscopic image display apparatus 100 according to the present embodiment, when displaying a stereoscopic image, the image display unit 102 displays the right-eye image portion (R) and the left-eye image portion (L). The right-eye image and the left-eye image having parallax are alternately formed in stripes and displayed. At this time, a voltage is applied to the microlens array 1, and the alignment state of the liquid crystal 9 of the liquid crystal layer 4 changes between the substrate 2 and the substrate 3, and the alignment state described with reference to FIG. Uniformly formed. As a result, the microlens array 1 functions as a lenticular lens, and exhibits a lenticular effect uniformly in the plane. Accordingly, the stereoscopic image display apparatus 100 can guide the right-eye image on the image display unit 102 to the right eye of the observer 101 and the left-eye image to the left eye of the observer 101, and the observer 101 is uniform. A stereoscopic image can be observed.

  In this way, the stereoscopic image display apparatus 100 according to the present embodiment can selectively switch between a high-definition and bright planar image and a stereoscopic image with high uniformity and display them.

  Hereinafter, embodiments of the present invention will be described more specifically based on examples. However, the present invention is not limited to these examples. In the examples, “parts” and “%” are based on mass unless otherwise specified.

<Synthesis of polymer (A-1)>
[Example 1]
In a reaction vessel, 5 parts of 2,2-azoisobutyronitrile as a polymerization catalyst, 150 parts of propylene glycol monomethyl ether acetate as a polymerization solvent, 11 parts of methacrylic acid (a3-1) as a monomer, 39 parts isobornyl acrylate (a2-1), 30 parts α-methyl-p-hydroxystyrene (a1-1), tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate ( 15 parts of a2-2), 5 parts of phenoxydiethylene glycol methacrylate (a3-2) and 0.2 part of tert-dodecyl mercaptan as a chain transfer agent were added to form a mixed solution. The resulting mixed solution was heated at 80 ° C. for 3 hours. After adding 2 parts of 2,2-azoisobutyronitrile to the mixed solution after heating, this was heated at 80 ° C. for 3 hours, and then heated at 100 ° C. for 1 hour. The mixed solution after heating was cooled to 23 ° C. to obtain a solution containing the polymer (A-1) which is an alkali-soluble resin.

<Synthesis of Resin (A-II-1) whose solubility in alkali is increased by the action of acid>
[Example 2]
A reaction vessel (flask) equipped with a stirrer, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then propylene glycol methyl ether acetate was charged as a solvent and stirring was started. Thereafter, the temperature of the solvent was raised to 80 ° C. 2,2′-Azobisisobutyronitrile as a polymerization catalyst in the dropping tank, 50% by mass of 1-ethylcyclohexyl methacrylate structural unit as (a-ii-1-1), and (a-ii-2-1) After charging 50% by mass of 2-ethoxyethyl acrylate structural unit and stirring until the polymerization catalyst was dissolved, this solution was uniformly dropped into the flask for 3 hours, followed by polymerization at 80 ° C. for 5 hours. Then, it cooled to room temperature and obtained resin (A-II-1) with a mass mean molecular weight 350,000.

<Synthesis of Novolak Resin (c-ii-1-1)>
[Example 3]
m-cresol and p-cresol were mixed at a mass ratio of 60:40, formalin was added thereto, and condensed by an ordinary method using an oxalic acid catalyst to obtain a cresol novolak resin. The resin was subjected to a fractionation treatment to cut a low molecular region to obtain a novolak resin having a mass average molecular weight of 15000. This resin was designated as novolak resin (c-ii-1-1)).

<Preparation of photosensitive composition>
[Example 4]
100 parts by mass of the polymer (A-1) obtained in Example 1, 60 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate as a polymerizable compound [B], and a phenol novolac epoxy resin ( Trade name “Epicoat 152”, Japan Epoxy Resin Co., Ltd.) 20 parts by mass, [C] 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name “Irgacure (registered trademark) 651) as a polymerization initiator "Ciba Specialty Chemicals Co., Ltd.) 19 parts by mass, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name" Lucirin (registered trademark) LR8953X ", manufactured by BASF) 4 parts by mass, Ethanon-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazo Ru-3-yl] -1- (O-acetyloxime) (Irgacure (registered trademark) OXE02, Ciba Specialty Chemicals Co., Ltd.), 2 parts by weight, tris- (3-trimethoxysilylpropyl) as an adhesion aid 3 parts by mass of isocyanurate (trade name “Y-11597”, manufactured by Momentive) and 0.1 part by mass of a fluorosurfactant (trade name “FTX-218F”, manufactured by Neos) as a surfactant are used as propylene as a solvent. A photosensitive composition was prepared by dissolving in glycol monomethyl ether acetate.

[Example 5]
<Preparation of photosensitive composition (positive type)>
50 parts by mass of the resin (A-II-1) obtained in Example 2 as the component (A-II), 1 part by mass of the compound (B-II-1) having the following chemical formula as the component (B-II), And 50 parts by mass of the novolak resin (c-ii-1-1) obtained in Example 3 as the component (C-II), mixed with propylene glycol monomethyl ether acetate to obtain a uniform solution, The mixture was filtered through a membrane filter to prepare a positive photosensitive composition.

<Formation of pattern by photosensitive composition>
[Example 6]
The photosensitive composition of Example 4 was applied on a glass substrate and heat-treated at 120 ° C. for 5 minutes on a hot plate to form a coating film having a thickness of 58 μm. The formed coating film was exposed to ultraviolet rays irradiated from a high-pressure mercury lamp through a patterned mask using an aligner (manufactured by Karl Suss, model “MA-150”). The coated film after the exposure was developed with an aqueous solution containing 2% by mass of potassium hydroxide for 90 seconds and then washed with water to form a pattern having a pattern width of 40 μm and a pattern height of 50 μm.

[Example 7]
The photosensitive composition of Example 4 was applied on a glass substrate and heat-treated at 120 ° C. for 5 minutes on a hot plate to form a coating film having a thickness of 58 μm. The formed coating film was exposed to ultraviolet rays irradiated from a high-pressure mercury lamp through a patterned mask using an aligner (manufactured by Karl Suss, model “MA-150”). The exposed coating film was developed at 25 ° C. with an aqueous tetramethylammonium hydroxide solution having a concentration of 0.40% by mass. Here, the development time was 80 seconds. Subsequently, running water was washed with ultrapure water for 1 minute, and then dried to form a pattern having a pattern width of 40 μm and a pattern height of 50 μm.

<Evaluation of pattern by photosensitive composition>
[Example 8]
The substrate having the pattern obtained in Example 6 was further heat-treated in an oven at 220 ° C. for 1 hour, and then the pattern height after the heat treatment was measured using a laser microscope (VK-8500, Keyence Corporation). It was measured. The pattern height after the heat treatment was measured. The pattern height after the heat treatment was 48 μm. As a result, the amount of change in the height of the pattern by the heat treatment at 220 ° C. is 4%, and the pattern formed using the photosensitive composition of Example 4 can be heated at 200 ° C. or higher after formation. It was found that expansion and contraction can be suppressed to 5% or less.

  When the substrate having the pattern obtained in Example 7 was subjected to the same evaluation method, the pattern formed using the photosensitive composition of Example 5 did not stretch even when heated at 200 ° C. or higher after formation. It turned out that it can suppress to 5% or less.

<Manufacture of microlens array>
[Example 9]
The microlens array of the present embodiment is a microlens array having spacers erected between the substrates as members disposed between the substrates.
First, the photosensitive composition of Example 4 was apply | coated on the glass substrate in which the comb-tooth electrode which consists of ITO was formed by the well-known photolithography method. Subsequently, it heat-processed at 120 degreeC with the hotplate for 5 minutes, and formed the coating film with a film thickness of 58 micrometers. The formed coating film was exposed to ultraviolet rays irradiated from a high-pressure mercury lamp through a patterned mask having a pattern corresponding to the spacer pattern, using an aligner (manufactured by Karl Suss, model “MA-150”). The exposed coating film is developed for 90 seconds in an aqueous solution containing 2% by weight of potassium hydroxide, and then washed with water, whereby a spacer pattern having a height of 50 μm is formed on the glass substrate on which the comb electrodes are formed. Formed.

Next, another glass substrate on which a common electrode made of ITO was formed was prepared. And the optical alignment film for aligning a liquid crystal in parallel was formed on each of the glass substrate in which the spacer pattern was formed, and the glass substrate in which the common electrode was formed. That is, a liquid crystal aligning agent for forming a photo-alignment film is applied on each substrate, pre-baked on a hot plate at 80 ° C. for 1 minute, and then heated at 180 ° C. for 1 hour to form a coating film having a thickness of 80 nm. Formed. Next, the surface of the coating film was irradiated with polarized ultraviolet rays 200 J / m ² containing a 313 nm emission line from the normal direction of the substrate using a Hg—Xe lamp and a Grand Taylor prism, and subjected to a photo-alignment treatment, whereby a liquid crystal was produced. A photo-alignment film for parallel alignment was formed.

  A microlens array was manufactured by using a pair of substrates on which alignment films were formed, sandwiching nematic liquid crystal having positive dielectric anisotropy between the substrates, and sealing the side surfaces with a sealant. The manufactured microlens array has a structure similar to that shown in FIG. The thickness of the liquid crystal layer was uniformly controlled in the plane and was 50 μm. The liquid crystal alignment state shown in FIG. 3 was realized by applying a voltage to the electrodes of the substrates sandwiching the liquid crystal layer.

[Example 10]
Using the photosensitive composition of Example 5, a microlens array was produced according to the same method as described above, except that a spacer pattern was formed in the same manner as described in Example 7. The manufactured microlens array has a structure similar to that shown in FIG. The thickness of the liquid crystal layer was uniformly controlled in the plane and was 50 μm. The liquid crystal alignment state shown in FIG. 3 was realized by applying a voltage to the electrodes of the substrates sandwiching the liquid crystal layer.

<Manufacture of stereoscopic image display device>
[Example 11]
A liquid crystal display type image display unit (liquid crystal display) was prepared as an image display unit. The liquid crystal display is a TN (twisted nematic) mode liquid crystal display, and has a structure in which a liquid crystal panel configured by sandwiching a twisted nematic liquid crystal between transparent substrates is further sandwiched between a pair of polarizing plates. The liquid crystal display is configured so that a stereoscopic image and a planar image can be switched and displayed. When displaying a stereoscopic image, a right-eye image and a left-eye image with parallax are alternately formed in a stripe shape. Can be displayed. On the other hand, when displaying a planar image, a high-definition planar image may be displayed using a right-eye image forming portion and a left-eye image forming portion when displaying a stereoscopic image as a unit pixel of a two-dimensional image. it can.
Using this liquid crystal display, the microlens array of Example 9 was overlaid to produce a stereoscopic image display device having the same structure as shown in FIG.

  In the manufactured stereoscopic image display device, it was possible to observe a high-definition and high-luminance planar image by forming a planar image on a liquid crystal display and applying a voltage to the microlens array. Further, in the manufactured stereoscopic image display device, when displaying a stereoscopic image, a right-eye image and a left-eye image having parallax are displayed on the right-eye image portion (R) and the left-eye image portion (L) of the liquid crystal display. The stripes were alternately formed, and a voltage was applied to the microlens array to function as a lenticular lens. Then, by guiding the right eye image on the liquid crystal display to the right eye of the observer and the left eye image to the left eye of the observer, it was possible to provide a stereoscopic image to the observer.

[Example 12]
A stereoscopic image display device having the same structure as that shown in FIG. 5 was manufactured in the same manner as in the manufacturing method described in Example 11 except that the microlens array of Example 10 was used as the microlens array.

  In the manufactured stereoscopic image display device, it was possible to observe a high-definition and high-luminance planar image by forming a planar image on a liquid crystal display and applying a voltage to the microlens array. Further, in the manufactured stereoscopic image display device, when displaying a stereoscopic image, a right-eye image and a left-eye image having parallax are displayed on the right-eye image portion (R) and the left-eye image portion (L) of the liquid crystal display. The stripes were alternately formed, and a voltage was applied to the microlens array to function as a lenticular lens. Then, by guiding the right eye image on the liquid crystal display to the right eye of the observer and the left eye image to the left eye of the observer, it was possible to provide a stereoscopic image to the observer.

As mentioned above, although embodiment of this invention was described, this invention is not limited to the said embodiment, A various deformation | transformation can be implemented in the range which does not deviate from the summary.
For example, the spacer 7 of the microlens array 1 of the present embodiment shown in FIGS. 1 and 2 has a columnar spacer structure with a circular cross section, but the present invention is not limited to such a structure.
In the present invention, the microlens array includes a spacer structure in which the cross section is formed in a stripe shape, a partition structure that is erected between the substrates so as to partition the liquid crystal layer sandwiched between the substrates, such as a lattice-shaped member. It is possible to arrange the members.

  In the present invention, in the microlens array, it is possible to divide the comb-teeth electrode into a plurality of pieces and apply a voltage to each of the divided comb-teeth electrodes. By doing so, it is possible to simultaneously form a voltage application region and a voltage non-application region in each one microlens. In that case, together with image formation in the image display unit, one stereoscopic image display device can be divided into a planar image display area and a stereoscopic image display area, and the planar image and the stereoscopic image can be displayed simultaneously.

DESCRIPTION OF SYMBOLS 1, 21 Microlens array 2, 3 Substrate 4 Liquid crystal layer 5 Common electrode 6 Comb electrode 7, 27 Spacer 8 Alignment film 9 Liquid crystal 100 Stereoscopic image display apparatus 101 Observer 102 Image display part 200 Lenticular lens

Claims (19)

A photosensitive composition containing an alkali-soluble resin,
A photosensitive composition, which is used for forming a member disposed between substrates of a microlens array configured by sandwiching a liquid crystal layer having a thickness of 20 μm to 100 μm between a pair of substrates. (A) an alkali-soluble resin,
The photosensitive composition according to claim 1, comprising (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator.   The photosensitive composition according to claim 2, wherein the alkali-soluble resin (A) is a polymer having a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group.   The photosensitive composition according to claim 2 or 3, wherein (B) the polyfunctional monomer contains a compound having an epoxy group. 2. The photosensitive material according to claim 1, comprising (A-II) a resin whose solubility in alkali is increased by the action of an acid, and (B-II) a compound which generates an acid upon irradiation with actinic rays or radiation. Sex composition. (A-II) The resin whose solubility in alkali is increased by the action of an acid contains a resin comprising a copolymer containing a structural unit having a specific structure represented by the following formula (11). Item 6. The photosensitive composition according to Item 5.

(In formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.)   The photosensitive composition according to claim 1, wherein the member disposed between the substrates has an expansion / contraction ratio of 5% or less when heated at 200 ° C. 7. A first substrate and a second substrate disposed opposite to each other; a liquid crystal layer sandwiched between the first substrate and the second substrate; and a liquid crystal side surface of the first substrate, A comb electrode having a plurality of electrode elements arranged in parallel to each other, and a common electrode provided on the liquid crystal side surface of the second substrate, and the gap between the comb electrode and the common electrode A microlens array that acts as a lens by driving the liquid crystal layer by applying a voltage,
A member between the first substrate and the second substrate;
The member is formed of a photosensitive composition containing an alkali-soluble resin.   The microlens array according to claim 8, wherein an alignment film for parallel alignment is provided on a surface of each of the first substrate and the second substrate that is in contact with the liquid crystal layer. The photosensitive composition is
(A) an alkali-soluble resin,
The microlens array according to claim 8 or 9, comprising (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator.   The microlens array according to claim 10, wherein the alkali-soluble resin (A) is a polymer having a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group.   The microlens array according to claim 10 or 11, wherein the (B) polyfunctional monomer contains a compound having an epoxy group. The photosensitive composition is
10. (A-II) a resin whose solubility in alkali is increased by the action of an acid, and (B-II) a compound capable of generating an acid upon irradiation with actinic rays or radiation. Micro lens array. (A-II) The resin whose solubility in alkali is increased by the action of an acid contains a resin comprising a copolymer containing a structural unit having a specific structure represented by the following formula (11). Item 14. The microlens array according to Item 13.

(In formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X forms a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which it is bonded.)   The microlens array according to any one of claims 8 to 14, wherein the liquid crystal layer includes a liquid crystal having a positive dielectric anisotropy.   The microlens array according to claim 8, wherein a thickness of the liquid crystal layer sandwiched between the substrates is 20 μm to 100 μm.   The microlens array according to any one of claims 8 to 16, wherein a member between the first substrate and the second substrate has an expansion / contraction ratio of 5% or less when heated at 200 ° C. . The microlens array according to any one of claims 8 to 17,
A stereoscopic image display device comprising: an image display unit that switches between a planar image and a stereoscopic image for display.   The stereoscopic image display device according to claim 18, wherein the image display unit is an image display unit of a liquid crystal display method, an EL display method, or a plasma display method.

Images