TWI550346B - Photosensitive composition, microlens array and 3d image display apparatus - Google Patents

Description

Photosensitive composition, microlens array, and stereoscopic image display device

The present invention relates to a photosensitive composition, a microlens array, and a stereoscopic image display device. More particularly, it relates to a photosensitive composition used in the formation of a microlens array suitable for switching planar images and stereoscopic images, a microlens array suitable for switching planar images and stereoscopic images, including the microlens array Moreover, a stereoscopic image display device that displays a planar image and a stereoscopic image can be switched.

In the field of image display devices using flat display panels, development of a stereoscopic image display device capable of displaying stereoscopic images has been carried out as a study for high functionality.

Regarding a technique of constructing a stereoscopic image on a stereoscopic image display device, various methods have been proposed. These methods can be classified into a method in which an observer requires special glasses when observing a stereoscopic image, and a method in which special glasses are not required.

A lenticular method or a parallax method is known in which a stereoscopic image (a three-dimensional image) is displayed without using dedicated glasses.

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

In the convex mirror mode, the lenticular lens 200 illustrated in Fig. 7 is used.

In the display of the stereoscopic image by the convex mirror method, the image for the right eye having the parallax and the image for the left eye are alternately arranged in a stripe shape on the image display portion of the stereoscopic image display device. The lenticular lens 200 is in a configuration with the strip The striated right-eye image is configured such that a long and thin convex lens is disposed on the surface so as to correspond to the image for the left eye. Further, the lenticular lens 200 is disposed in front of the image display unit, and the viewer's right eye is only observed for the right eye image, and the left eye is only observed for the left eye image, and the observer is provided with a stereoscopic image. image.

In the stereoscopic image display device, there is a case where it is required to display a planar image (two-dimensional image) depending on the use situation or the like. In this case, in the stereoscopic image display device using the convex mirror method, the image for the right eye and the image for the left eye can be made to be the same image without parallax, but the right eye is used. When the image and the image for the left eye are set to the same image, the resolution of the image display unit is halved. Moreover, the brightness of the planar image on the image display portion is lowered due to the lenticular lens disposed between the stereoscopic image display device and the observer.

In order to avoid such a problem of using the convex mirror method of the conventional lenticular lens, a microlens array configured to function as a lenticular lens when displaying a stereoscopic image and to lose a double when displaying a planar image has been proposed. The function of the convex lens functions as a simple transparent body (non-lens transparent body) (for example, refer to Patent Document 1 and Patent Document 2). Patent Document 1 discloses a technique in which a liquid crystal panel is constituted by a pair of substrates on which electrodes are formed on opposite surfaces and a liquid crystal layer having refractive index anisotropy sandwiched therebetween, and the liquid crystal panel is used as a micro Lens array. In the microlens array described in Patent Document 1, the liquid crystal can be aligned to a desired state by applying ON/OFF of a voltage, thereby adjusting the refractive index of the liquid crystal layer. Moreover, it functions as a lenticular lens when a voltage is applied, It functions as a non-lens transparent body when no voltage is applied. In the stereoscopic image display using the convex mirror method using such a microlens array, the above-described problem of reduction in resolution and reduction in luminance can be avoided.

In such a technique of using a liquid crystal microlens array, in order to display a high-quality stereoscopic image, it is necessary to uniformly function as a lenticular lens in the plane. Therefore, it is required to realize the alignment control of the liquid crystal with high precision by applying ON/OFF of the voltage. In order to realize high-precision alignment control of the liquid crystal, it is necessary to accurately control the thickness of the liquid crystal layer sandwiched between the pair of substrates in-plane. Therefore, in a microlens array having a convex mirror type suitable for switching a planar image and a stereoscopic image, which is formed by sandwiching a liquid crystal layer between a pair of substrates, a technique of uniformly controlling the thickness of the liquid crystal layer in the ground with high precision is required.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2000-102038

[Patent Document 2] Japanese Patent No. 4602369

The present invention has been made based on the above findings. That is, an object of the present invention is to provide a photosensitive composition suitable for forming a microlens array which is formed by sandwiching a liquid crystal layer between a pair of substrates, and is suitable for uniformly maintaining in a plane. The planar image and the stereoscopic image are switched in accordance with the thickness of the liquid crystal layer.

Another object of the present invention is to provide a microlens array which is formed by sandwiching a liquid crystal layer between a pair of substrates, and is suitable for uniformly maintaining the thickness of the liquid crystal layer in the plane to switch the planar image and the stereoscopic image. image.

Still another object of the present invention is to provide a stereoscopic image display device constructed by using a microlens array in which a liquid crystal layer is sandwiched between a pair of substrates, and is suitable for uniform in-plane The planar image and the stereoscopic image are switched while maintaining the thickness of the liquid crystal layer.

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

A first aspect of the invention relates to a photosensitive composition which is a photosensitive composition containing an alkali-soluble resin, and is characterized in that a liquid crystal layer having a thickness of 20 μm to 100 μm is sandwiched between a pair of substrates. A member of the microlens array that is disposed between the substrates.

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

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

In the first aspect of the invention, it is preferred that the (B) polyfunctional monomer contains a compound having an epoxy group.

In the first aspect of the present invention, it is preferred that the (A-II) resin having an increased solubility in alkali due to the action of an acid and (B-II) generate an acid by irradiation with active rays or radiation. compound of.

In the first aspect of the invention, it is preferred that the resin having an increased solubility in alkali due to the action of an acid (A-II) contains a resin containing a copolymer containing the following formula (11). ) the structural unit of a particular structure,

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

In the first aspect of the invention, it is preferred that the member disposed between the substrates has a expansion ratio of 5% or less when heated at 200 °C.

A second aspect of the present invention relates to a microlens array including 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 first substrate a comb electrode having a plurality of electrode elements arranged in parallel on the liquid crystal layer side, a common electrode provided on a surface of the second substrate on the liquid crystal layer side, and a liquid crystal driven by applying a voltage between the comb electrode and the common electrode Layer, thus acting as a lens, characterized by: A member is provided between the first substrate and the second substrate, and the member is formed of a photosensitive composition containing an alkali-soluble resin.

In the second aspect of the invention, it is preferable that 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.

In the second aspect of the invention, the photosensitive composition preferably contains (A) an alkali-soluble resin, (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator.

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

In the second aspect of the invention, it is preferred that the (B) polyfunctional monomer contains a compound having an epoxy group.

In the second aspect of the present invention, the photosensitive composition preferably contains (A-II) a resin having an increased solubility in alkali due to an action of an acid, and (B-II) by irradiation with active rays or A compound that emits radiation to produce an acid.

In the second aspect of the present invention, it is preferred that the resin having an increased solubility in alkali due to the action of an acid (A-II) contains a resin containing a copolymer having the following formula ( 11) The structural unit of the specific structure represented, [Chemical 2]

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

In the second aspect of the invention, it is preferred that the liquid crystal layer is composed of a liquid crystal having positive dielectric anisotropy.

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

In the second aspect of the invention, it is preferable that the member between the first substrate and the second substrate has a stretch ratio of 5% or less when heated at 200 °C.

A third aspect of the present invention relates to a stereoscopic image display device comprising: a microlens array according to a first aspect of the present invention; and an image display unit that switches between displaying a planar image and a stereoscopic image.

In the third aspect of the invention, it is preferable that the image display unit is an image display unit of a liquid crystal display method, an EL display method, or a plasma display method.

According to a first aspect of the present invention, there is provided a photosensitive composition suitable for forming a microlens array suitable for switching planes The image and the stereoscopic image function as a lenticular lens uniformly in the plane when the stereoscopic image is displayed.

Moreover, according to the second aspect of the present invention, a microlens array suitable for switching a planar image and a stereoscopic image and uniformly exhibiting in a plane as a lenticular lens when displaying a stereoscopic image can be provided. The function.

Further, according to a third aspect of the present invention, a stereoscopic image display device constructed using a microlens array suitable for switching a planar image and a stereoscopic image and displaying a stereoscopic image can be provided. The image functions as a lenticular lens uniformly in the plane.

The microlens array of the present invention is a microlens array suitable for a stereoscopic image stereoscopic image display device. Further, it is configured to correspond to a case where a display plane image and a stereoscopic image are switched in the stereoscopic image display device.

The microlens array of the present invention comprises: a pair of substrates on which electrodes are formed on opposite surfaces, and a liquid crystal layer having refractive index anisotropy sandwiched between the substrates. 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 spatial alignment state of the liquid crystal is controlled, thereby functioning as a lens. 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 stereoscopic image, it is necessary to uniformly function as a lenticular lens in the plane. The liquid crystal between the substrates is driven by the microlens array of the present invention to function as a lenticular lens In the case of energy, it is required to control the spatial alignment state of the liquid crystal layer with high precision by applying a voltage. Therefore, it is necessary to accurately control the thickness of the liquid crystal layer sandwiched between the pair of substrates in-plane.

The liquid crystal layer is sandwiched between a pair of substrates, and an element requiring high precision control of the thickness of the liquid crystal layer may be a different technical field, and a liquid crystal display element is known. In the field of such a liquid crystal display element, for example, a technique of using a lens spacer as described in Japanese Laid-Open Patent Publication No. 2008-281594 is known. In other words, a technique is known in which a spacer for a lens is provided between the substrates in order to accurately control the thickness of the liquid crystal layer sandwiched between the pair of substrates (hereinafter, simply referred to as a spacer unless otherwise specified) Keep the distance between the substrates at a fixed distance. The formation of the spacers typically utilizes photolithography. In this technique, a photosensitive composition is applied onto a substrate at a predetermined film thickness so as to have a thickness corresponding to the thickness of the target liquid crystal layer. Next, after ultraviolet exposure is performed by a predetermined mask, development is performed and patterned, and a spacer having a dot shape or a stripe shape having a height corresponding to the thickness of the liquid crystal layer is formed.

Therefore, the inventors of the present invention have conducted intensive studies to 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 accurately controlling the thickness of the liquid crystal layer sandwiched between the substrates. That is, in a microlens array including a pair of substrates on which electrodes are formed on opposite surfaces and a liquid crystal layer having refractive index anisotropy sandwiched therebetween, the substrate is patterned by photolithography Configuring the above structure A member that functions as a support member to constitute a microlens array of a novel structure.

When such a novel structure of the microlens array is provided, it is a problem that the technique of the spacer which is effective in the liquid crystal display element cannot be directly applied to the microlens array. For example, there is a problem related to the thickness of the liquid crystal layer sandwiched between the substrates shown below, and in order to be applicable to the microlens array, a new technique for solving the problem is required.

Although liquid crystal display elements have some differences due to the liquid crystal display mode, in recent liquid crystal television (TV) applications, the thickness of the liquid crystal layer is approximately 1 μm to 10 μm. Therefore, in the liquid crystal display device, a spacer having a height of 10 μm or less corresponding to the thickness of the liquid crystal layer is used.

On the other hand, in the microlens array of the present invention in which a liquid crystal layer is sandwiched between a pair of substrates, it is necessary to control the thickness distribution of the liquid crystal layer in order to control the refractive index distribution in the plane in order to achieve a desired alignment state of the liquid crystal. It is thicker than the original liquid crystal display element. For example, a thickness of 10 μm or more is required, and a thickness of 20 μm to 100 μm is preferably required. Further, in order to realize a desired alignment state of the liquid crystal with high precision, it is more preferable to set the thickness of the liquid crystal layer to 30 μm to 70 μm. Therefore, in the microlens array of the present invention, when it is desired to control the thickness of the liquid crystal layer sandwiched between a pair of substrates, it is necessary to correspond to such a thick liquid crystal layer. That is, in the microlens array of the present invention, when it is desired to control the thickness of the liquid crystal layer between the substrates by using the same spacer as the liquid crystal display element, it becomes necessary to form a spacer having the following height: A thickness of 10 μm or more corresponding to a thick liquid crystal layer which is not used in the liquid crystal display element.

In the formation of the spacer of the liquid crystal display element, the photosensitive composition becomes a main constituent element as described above. In the microlens array of the present invention, in order to form a member disposed between a pair of substrates sandwiching the liquid crystal layer, it is also effective to use a photolithography technique, and the photosensitive composition is an important constituent element. Therefore, in the case of the microlens array of the present invention, there is a strict requirement regarding the thickness of the above liquid crystal layer. 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 the liquid crystal layer, the previous photosensitive composition for the liquid crystal display element cannot be directly used.

Therefore, in the formation of the microlens array of the present invention, the coating film can be formed with a thick film as compared with the prior art, and patterning with excellent resolution can be realized, and as a result, it becomes necessary to be able to form a member having a desired height and shape. Photosensitive composition. Further, in order to maintain the thickness of the liquid crystal layer in order to maintain the distance between the substrates, the member to be formed must have strength as a supporting member. Further, such a member disposed between the substrates of the microlens array is required to have such a characteristic that the expansion and contraction due to heating after formation is slight, and it is difficult to generate the height due to the heating step when forming other constituent elements of the microlens array. Or a change in shape.

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 as described above, it is necessary to have a suitable photosensitive composition in the formation of members disposed between the substrates. Things. Further, as the member disposed between the substrates, it is preferable that the liquid crystal layer sandwiched between the substrates can be realized in addition to the lens spacer structure in which the cross-sectional structure in the direction parallel to the substrate surface is a dot shape or a stripe shape. Plan The desired structure such as the spacer structure between the substrates is erected in a minute manner, and the thickness of the liquid crystal layer sandwiched between the substrates is controlled with high precision. Therefore, it is preferable that the photosensitive composition is patterned by photolithography, and the structure of the member formed between the substrates is a photosensitive composition of the spacer structure or the separator structure.

The inventors of the present invention conducted intensive studies and found that the photosensitive composition can meet the above requirements. That is, it has been found that the photosensitive composition of the present embodiment which is suitable for forming a desired member having the following properties is disposed between a pair of substrates of the microlens array, and controls the liquid crystal layer sandwiched between the substrates with high precision. thickness. Further, by using the photosensitive composition of the present embodiment to form a member disposed between the substrates of the microlens array in which the liquid crystal layer is sandwiched between the pair of substrates, the microlens array of the present embodiment can be formed and used. This constitutes a stereoscopic image display device of the present embodiment.

Hereinafter, a photosensitive composition which is disposed between the pair of substrates sandwiching the liquid crystal layer of the microlens array of the present embodiment and which is disposed between the substrates is provided. A structure such as a lens spacer structure or a separator structure (hereinafter, simply referred to as a member such as a spacer unless otherwise specified).

[1] Photosensitive composition

The photosensitive composition of the present embodiment which is suitable for forming the microlens array of the present embodiment can form a coating film with a thick film of more than 10 μm, for example, and can realize patterning with excellent resolution. Moreover, as a pattern, a member having a desired height and shape can be formed. Moreover, the formed member may have a cross-sectional structure in a direction parallel to the substrate surface as described above. In addition to the dot-like or stripe-shaped lens spacer structure, a desired structure such as a spacer structure that is erected between the substrates so as to divide the liquid crystal layer sandwiched between the substrates is also selected. Further, the member such as the spacer has a strength necessary to maintain the thickness of the liquid crystal layer in order to function as a supporting member and maintain the distance between the substrates. Further, the member such as the spacer including the photosensitive composition of the present embodiment has a characteristic that the expansion and contraction due to heating is slight, and it is difficult to cause variations in height or shape due to heating.

The photosensitive composition of the present embodiment is composed of the following components (A) to (C). Further, it is preferred to contain the component (D): an organic solvent.

(A) component: alkali soluble resin

(B) Component: Polyfunctional monomer

(C) component: photosensitive polymerization initiator

(D) Ingredients: Organic solvent

[1-1] (A) component: alkali soluble resin

The alkali-soluble resin of the component (A) is not particularly limited as long as it is an alkali-developable resin, and various resins can be selected.

Further, the photosensitive composition of the present embodiment preferably has a polymer (polymer (A)) containing a structural unit (a1) having a phenolic hydroxyl group and a structural unit (a2) having an alicyclic hydrocarbon group as (A). An alkali-soluble resin of the component.

In the case of selecting the polymer (A) as the alkali-soluble resin of the component (A), the photosensitive composition of the present embodiment is characterized in that the function of inactivating the active species due to the phenolic hydroxyl group is due to the alicyclic ring. a hydrocarbon group to improve the transparency of the coating film to light, and due to phenolic hydroxyl groups and lipids The multiplier effect of the cycloalkyl group increases the heat resistance.

In other words, when the polymer (A) contains the structural unit (a2) having an alicyclic hydrocarbon group, the transmittance of the coating film to light can be increased, and the amount of exposure in the vicinity of the substrate and in the vicinity of the surface of the coating film can be increased. However, the coating film containing the polymer (A) (the polymer (A) contains the structural unit (a1) having a phenolic hydroxyl group) has a function of inactivating the active species, and thus the amount of the active species produced is The active species are inactivated in proportion. Therefore, the active species which are more generated in the vicinity of the surface of the coating film and in the vicinity of the substrate of the coating film are inactivated by the exposure. As a result, the amount of the active species uniform in the thickness direction of the coating film is obtained, and as a result, a member having a desired structure, that is, a member such as a spacer is formed.

Further, it is known that a polymer containing a structural unit having a phenolic hydroxyl group and a polymer having an alicyclic hydrocarbon group are excellent in heat resistance, and in the present embodiment, a polymer having the two structural units is used ( A), and it becomes more excellent in heat resistance. For the above reasons, the member of the present embodiment comprising the polymer (A) (the polymer (A) comprising the structural unit (a1) having a phenolic hydroxyl group and the structural unit (a2) having an alicyclic hydrocarbon group) is formed. A member such as a spacer obtained by using the photosensitive 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 is preferably from 25 parts by mass to 8,000 parts by mass, more preferably from 60 parts by mass to 6500 parts by mass, further preferably 90 parts by mass to 5500 parts by mass. When the content is in the range of 25 parts by mass to 8000 parts by mass, a member such as a spacer which can maintain a desired shape during heating can be preferably used.

The polystyrene-equivalent weight average molecular weight (Mw) of the polymer (A) by gel permeation column chromatography can be based on the kind of the monomer used in obtaining the polymer (A), the polymerization formula, and the polymer ( A) is suitably selected from the glass transition temperature, and is usually Mw = 5,000 to 20,000, preferably Mw = 8,000 to 12,000.

The content ratio of the polymer (A) used in the photosensitive composition of the present embodiment can be appropriately selected depending on the height of the member such as the spacer to be formed or the coating method, and all the components contained in the photosensitive composition are included. When it is 100% by mass, it is preferably 30% by mass to 90% by mass.

When all the components of the photosensitive composition of the present embodiment, which is the solvent (D), are 100% by mass, the content of the polymer (A) is preferably 30% by mass to 90% by mass. This is because the polymer (A) is used as a main component of a member such as a spacer, and a member such as a spacer that can maintain a desired shape during heating can be formed.

<Structural unit (a1) having a phenolic hydroxyl group>

The "phenolic hydroxyl group" means a hydroxyl group directly bonded to an aromatic ring such as a benzene ring or a naphthalene ring. Further, the "structural unit" is a structure indicating a polymer of one unit per monomer used in forming a polymer. The "structural unit having a phenolic hydroxyl group" can be polymerized by using a monomer having a phenolic hydroxyl group (a1'), or can be converted by using a monomer having a group convertible to a phenolic hydroxyl group. a phenolic hydroxyl group, which will The structural unit (a1) having a phenolic hydroxyl group is introduced into the structure of the polymer (A).

The content ratio of the structural unit (a1) having a phenolic hydroxyl group is preferably from 1% by mass to 40% by mass, more preferably from 5% by mass, based on 100% by mass of all the structural units in the polymer (A). %~30% by mass, further preferably 10% by mass to 20% by mass. When the content ratio of the structural unit (a1) having a phenolic hydroxyl group is from 1% by mass to 40% by mass, the photosensitive composition of the present embodiment having excellent resolution can be obtained.

The method of introducing the "structural unit (a1) having a phenolic hydroxyl group" by polymerization using a monomer (a1') having a phenolic hydroxyl group into the polymer (A) includes phenol or naphthalene. a method in which a phenol such as a phenol is introduced by condensation polymerization with a condensing agent such as an aldehyde, or a monomer having a polymerizable group such as a (meth)acryl fluorenyl group or a vinyl group and a phenolic hydroxyl group introduced by radical polymerization or cationic polymerization. Method etc. Among these methods, from the viewpoint of easily copolymerizing with a monomer having an alicyclic hydrocarbon group to be described later, or a member which is easily formed into a spacer which can maintain a desired shape upon heating, it is preferred to A method of introducing a monomer having a vinyl group and a phenolic hydroxyl group by radical polymerization.

The above monomer having a vinyl group and a phenolic hydroxyl group may, for example, be p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, α-methyl-p-hydroxystyrene, α-methyl-m-hydroxystyrene, α- A monomer represented by the following formula (1) such as methyl-o-hydroxystyrene.

[Chemical 3]

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

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

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

The monomer represented by the above formula (1) may be used alone or in combination of two or more. Further, the radical polymerization method can be obtained, for example, by a general method such as the method described in JP-A-2009-192613 or JP-A-2009-163080.

<Structural unit (a2) having an alicyclic hydrocarbon group>

The "alicyclic hydrocarbon group" means a group containing only carbon and hydrogen, and the carbon atom excluding the aromatic group is a cyclic structure (including a polycyclic structure). Base. Further, the "structural unit" is a structure indicating a polymer of one unit per monomer used in forming a polymer. The "structural unit having a phenolic hydroxyl group" can be polymerized by using a monomer (a2') having an alicyclic hydrocarbon group, thereby introducing a structural unit (a2) having an alicyclic hydrocarbon group into the polymer (A). .

When the content ratio of the structural unit (a2) having an alicyclic hydrocarbon group is 100% by mass in terms of all the structural units in the polymer (A), it is preferably 10% by mass in terms of transmittance. ~80% by mass, more preferably 30% by mass to 50% by mass.

The method of introducing a "structural unit (a2) having an alicyclic hydrocarbon group" obtained by polymerizing a monomer (a2') having an alicyclic hydrocarbon group into the polymer (A) is exemplified by radical polymerization. A method of introducing a monomer having a polymerizable group such as a (meth)acryl fluorenyl group or a vinyl group and an alicyclic hydrocarbon group, or the like by cationic polymerization or the like. In these methods, from the viewpoint of easily obtaining a copolymer with the monomer having a phenolic hydroxyl group or easily forming a member such as a spacer capable of maintaining a desired shape upon heating, it is preferred that A method of introducing a monomer having a (meth) acrylonitrile group and an alicyclic hydrocarbon group by radical polymerization.

The monomer having a (meth) acrylonitrile group and an alicyclic hydrocarbon group is exemplified by, for example, JP-A-2008-233346, JP-A-2009-192613, and JP-A-2009-163080. The monomer described below and the monomer represented by the following formula (3).

[Chemical 5]

(In the formula (3), R ³ represents a hydrogen atom or a methyl group. R ⁴ is an alicyclic hydrocarbon group having only 7 to 30 carbon atoms and a hydrogen atom)

The monomer having the structure represented by the above formula (3) may, for example, be a tricyclo[5.2.1.0 ^2,6 ]decane-8-yl methacrylate or a tricyclomethacrylate [5.2.1.0 ^2,6 ]癸Alken-8-yloxyethyl ester, tricyclo[5.1.02.5 ^2,6 ]decane-8-yl acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxyethyl acrylate Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, isobornyl acrylate, tetrahydrofuran methyl methacrylate, and the like. Among these compounds, from the viewpoint of easily forming a member such as a spacer which can maintain a desired shape upon heating, it is preferred to select tricyclo [5.2.1.0 ^2,6 ]nonane-8-yl methacrylate. , isobornyl acrylate.

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

[Chemical 6]

(In the formula (4), R ⁵ represents a hydrogen atom or a methyl group. R ⁶ is an alicyclic hydrocarbon group having only 7 to 30 carbon atoms and a hydrogen atom)

The monomer represented by the above formula (3) may be used alone or in combination of two or more kinds, and a monomer which is difficult to polymerize by radical polymerization may be introduced into the polymer. Further, the radical polymerization method can be obtained, for example, by a general method such as the method described in JP-A-2009-192613 or JP-A-2009-163080.

<Other structural units (a3)>

The polymer (A) which is a component of the photosensitive composition of the present embodiment can contain other structural units (a3) within a range that does not impair the effect of a member such as a spacer which can maintain a desired shape when heated. . The other structural unit (a3) includes a structural unit having a polyalkylene glycol group for the purpose of improving the adhesion to the substrate, and a carboxyl group for the purpose of adjusting the solubility of the polymer (A) with respect to the developer. Structural unit, etc.

The structural unit having a polyalkylene glycol group is not particularly limited as long as it has a polyalkylene glycol group, and a monomer having a phenolic hydroxyl group represented by the above formula (1) or a lipid represented by the above formula (3) is used. In the case of a monomer having a cycloalkyl group, it is preferably carried out from a monomer having a polymerizable group and a polyalkylene glycol group. It is introduced into the polymer (A) by base polymerization.

The monomer having a polymerizable group and a polyalkylene glycol group is exemplified by the monomer described in JP-A-2008-273820 and JP-A-2009-192613, and in the following formula (5). The monomer shown.

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

Examples of the monomer having a structure represented by the above formula (5) include phenoxy diethylene glycol (meth) acrylate, phenoxy triethylene glycol (meth) acrylate, and phenoxytetraethylene glycol. (Meth)acrylate, phenoxydipropylene glycol (meth) acrylate, phenoxytripropylene glycol (meth) acrylate, phenoxytetrapropylene glycol (meth) acrylate, dodecyloxydiethyl Glycol (meth)acrylic acid Ester, dodecyloxy triethylene glycol (meth) acrylate, dodecyloxytetraethylene glycol (meth) acrylate, dodecyloxy dipropylene glycol (meth) acrylate, twelve Alkoxytripropylene glycol (meth) acrylate, dodecyloxytetrapropylene glycol (meth) acrylate, and the like.

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

(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 a carbon number of 2 to 4. R ¹² represents a linear or cyclic group having a carbon number of 6 to 12. Or an aromatic hydrocarbon group or a substituted hydrocarbon group in which at least one hydrogen atom of the 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, and a monomer having a phenolic hydroxyl group represented by the above formula (1) or a monomer having an alicyclic hydrocarbon group represented by the above formula (3) is used. In the case, a monomer having a polymerizable group and a carboxyl group is usually subjected to radical polymerization to be introduced into the polymer.

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

The other structural unit (a3) may have a structural unit having a polyalkylene glycol group and a structural unit having a carboxyl group, and may be derived from Japanese Patent Laid-Open Publication No. 2009-192613 or Japanese Patent Laid-Open No. 2009-163080. The structural unit of the monomer described in the above.

[1-2] Component (B): Polyfunctional monomer

The polyfunctional monomer (polyfunctional monomer (B)) of the component (B) is a monomer having at least two or more polymerizable unsaturated bond groups. The polyfunctional monomer (B) is a component which can react with an active species generated by a photosensitive polymerization initiator of the component (C) due to the action of light to initiate polymerization to form a three-dimensional crosslinked structure, or A component such as an epoxy group which can form a crosslinked structure due to heat. As a result, in the coating film obtained from the photosensitive composition of the present embodiment, the position where the light is irradiated becomes difficult to dissolve with respect to the developer.

The content of the polyfunctional monomer (B) used in the photosensitive composition of the present embodiment can be appropriately selected according to the sensitivity and resolution in the method of forming a member such as a spacer of the microlens array of the present embodiment. When the content of the polymer (A) is 100 parts by mass, the content of the polyfunctional monomer (B) is preferably from 1 part by mass to 100 parts by mass.

The polyfunctional monomer (B) is exemplified by a polyfunctional monomer described in JP-A-2006-285035 and JP-A-2009-192613. Specific examples thereof include alkanediols such as ethylene glycol and propylene glycol. Di(meth)acrylates; di(meth)acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Poly(meth)acrylates of polyhydric alcohols or dicarboxylic acid modifications of such compounds; oligomerization of polyesters, epoxies, urethane resins, alkyd resins, fluorenone resins, spiro resins, etc. Methyl acrylates; di(meth)acrylic acid at both terminal hydroxylated poly-1,3-butadiene, two-terminal hydroxypolyisoprene, and two-terminal hydroxypolycaprolactone Esters; tris[2-(methyl)propenyloxyethyl]phosphates and the like.

Among these polyfunctional monomers, poly(meth)acrylates of polyhydric alcohols having a ternary value of 3 or more are preferred, and the dicarboxylic acid modified products are specifically trimethylolpropane tris(methyl). ) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc., especially trimethylolpropane Tris(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be preferably used by forming a member such as a spacer which can maintain a desired shape upon heating.

Examples of the polyfunctional monomer (B) include a compound having two or more 3,4-epoxycyclohexyl groups in one molecule: 3,4-epoxycyclohexylmethyl-3', 4'-ring Oxycyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-m-dioxane, bis(3,4-epoxy) Cyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexyl-3', 4'-epoxy-6'-methylcyclohexane formate, methylene bis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol 3,4-epoxy Cyclohexylmethyl)ether, ethyl bis(3,4-epoxycyclohexanecarboxylic acid) ester, lactone modified 3,4-epoxycyclohexylmethyl-3', 4'-epoxy ring Alkyl esters, etc.

Examples of the compound having two or more glycidyl groups in one molecule include bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and the like. Bisphenol such as hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether Diglycidyl ether of the compound; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene a polyglycidyl ether of a polyhydric alcohol such as an alcohol diglycidyl ether or a polypropylene glycol diglycidyl ether; or a method of adding one or more alkylene oxides to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerin; Polyglycidyl ether of the obtained polyether polyol; phenol novolak type epoxy resin; cresol novolac type epoxy resin; polyphenol type epoxy resin; cyclic aliphatic epoxy resin; aliphatic long chain dibasic acid Glycidyl ester; glycidyl ester of higher fatty acid; epoxidized soybean oil , epoxidized linseed oil, etc.

As such commercial products, for example: Examples of the bisphenol A type epoxy resin include Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, and Epikote 828 (above manufactured by Japan Epoxy Resins Co., Ltd.). (Epikote 807 (Japan Epoxy Resin Co., Ltd.), etc.; phenol novolac type epoxy resin, such as Epikote 152, Epikote 154, Epikote 157S65 (above, manufactured by Nippon Epoxy Co., Ltd.), EPPN (registered trademark) 201, EPPN 202 (manufactured by Nippon Kayaku Co., Ltd.), etc.; cresol novolac type epoxy resin can be listed as EOCN (registered trademark) 102, EOCN 103S, EOCN 104S, EOCN 1020, EOCN 1025, EOCN 1027 (The above is manufactured by Nippon Kayaku Co., Ltd.), Epikote 180S75 (Nippon Epoxy Co., Ltd.), etc.; and the polyphenol type epoxy resin is Epikote 1032H60, Epikote XY-4000 (manufactured by Nippon Epoxy Co., Ltd.), etc.; Examples of aliphatic epoxy resins include CY-175, CY-177, CY-179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above manufactured by Ciba Specialty Chemicals Co., Ltd.), ERL-4234, ERL -4299, ERL-4221, ERL-420 6 (above manufactured by UCC), Shodyne 509 (Showa Denko), Epiclon 200, Epiclon 400 (above manufactured by Dainippon Ink Co., Ltd.), Epikote 871, Epikote 872 (above manufactured by Nippon Epoxy Co., Ltd.), ED- 5661, ED-5662 (above manufactured by Celanese Coating Co., Ltd.), etc.; Examples of the aliphatic polyglycidyl ether include Epolight 100MF (Kyoeisha Chemical Co., Ltd.), EPIOL (registered trademark) TMP (Nippon Oil & Fats Co., Ltd.), and the like.

Among these, a phenol novolak type epoxy resin and a polyphenol type epoxy resin are preferably selected.

[1-3] (C) component: photosensitive polymerization initiator

The photosensitive polymerization initiator of the component (C) is an exposure light such as a semiconductor laser, a metal halide lamp, a high pressure mercury lamp (g line, h line, i line, etc.), an excimer laser, an extreme ultraviolet ray, and an electron beam. Further, a compound which can cause the above-mentioned polyfunctional monomer (B) to start polymerization can be produced.

The content of the photosensitive polymerization initiator (C) used in the photosensitive composition of the present embodiment can be based on the sensitivity and resolution of the exposure light in the method of forming a member such as a spacer of the microlens array of the present embodiment. When the content of the polymer (A) is 100 parts by mass, the content of the photosensitive polymerization initiator (C) is preferably from 1 part by mass to 50 parts by mass.

The photosensitive polymerization initiator (C) is exemplified by a photosensitive polymerization initiator described in JP-A-2006-285035 and JP-A-2009-192613. Specific examples thereof include an oxime ester compound, a fluorenyl phosphine oxide compound, a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, and a polynuclear ruthenium compound. A compound, a xanthone compound, a triazine compound, an O-indenyl compound or the like. These compounds may be used alone or in combination of two or more. Especially as a photosensitive polymerization primer in the present invention In the case of using a high-pressure mercury lamp including g-line, h-line, and i-line as exposure light, the hair agent (C) is preferably a sulfhydryl phosphine oxide system in order to form a member having a good shape and a good shape with good sensitivity. A combination of a compound and an acetophenone-based compound.

Examples of the oxime ester compound include 1,2-octanedione-1-[4-(phenylthio)-2-(O-benzamide)], and ethyl ketone-1-[9-ethyl-6- (2-Methylbenzylidene)-9H-carbazol-3-yl]-1-(O-acetamidine), 1-[9-ethyl-6-benzylidene-9H-carbazole -3-yl]-octane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzhydryl)-9H-carbazol-3-yl] -ethane-1-ketooxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzylidenyl)-9H-indazol-3-yl]-ethane -1-ketooxime-O-benzoate, ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylbenzylidene)-9H-indazol-3-yl ]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydropyranylbenzylidene)-9H-carbazole-3 -yl]-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-(2-methyl-5-tetrahydrofuranylbenzylidene)-9H-indazole-3- 1,-1-(O-acetamidine), ethyl ketone-1-[9-ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxan Cyclopentyl)methoxybenzylmethanyl}-9H-indazol-3-yl]-1-(O-acetyl) and the like.

Examples of the fluorenylphosphine oxide-based compound include bis(2,6-dichlorobenzylidene)-phenylphosphine oxide and bis(2,6-dichlorobenzylidene)-2,5-dimethylphenyl. Phosphine oxide, bis(2,6-dichlorobenzylidene)-4-ethoxyphenylphosphine oxide, bis(2,6-dichlorobenzylidene)-4-propylphenylphosphine oxide, Bis(2,6-dichlorobenzhydryl)-2-naphthylphosphine oxide, bis(2,6-dichlorobenzylidene)-1-naphthylphosphine oxide, bis(2,6-dichloro Benzamethylene)-4-chlorophenylphosphine oxide, bis(2,6-dichlorobenzylidene)-2,4-dimethoxyphenylphosphine oxide, bis(2,6-dichlorobenzene Mercapto)-mercaptophosphine oxide, Bis(2,6-dichlorobenzylidene)-4-octylphenylphosphine oxide, bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, bis(2,4, 6-trimethylbenzylidene)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzylidene)-2,5 - dimethylphenylphosphine oxide, bis(2,6-dichloro-3,4,5-trimethoxybenzylidene)-4-ethoxyphenylphosphine oxide, bis(2-methyl- 1-naphthylmethyl)-2,5-dimethylphenylphosphine oxide, bis(2-methyl-1-naphthylmethyl)-4-ethoxyphenylphosphine oxide, bis (2-A) Benz-1-naphthylmethyl)-2-naphthylphosphine oxide, bis(2-methyl-1-naphthylmethyl)-4-propylphenylphosphine oxide, bis(2-methyl-1- Naphthylmethyl)-2,5-dimethylphenylphosphine oxide, bis(2-methoxy-1-naphthylmethyl)-4-ethoxyphenylphosphine oxide, bis(2-chloro- 1-naphthylmethyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, etc. .

Examples of the acetophenone-based compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 2 -hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-methyl-1 -(4-methylthienyl)-2-morpholinopropan-1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)one, 2-benzyl -2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyl Ethane-1-one and the like.

[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 the component (D) is a compound which can dissolve the components other than the organic solvent (D) contained in the photosensitive composition of the present embodiment and does not react with the other components. No limit.

The content of the organic solvent (D) contained in the photosensitive composition of the present embodiment can be appropriately determined depending on the height of the member such as the coating method or the 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; and alkyl ethers of polyhydric alcohols such as propylene glycol monomethyl ether acetate. Acetate; aromatic hydrocarbons such as toluene; ketones such as methyl ethyl ketone; esters such as ethyl acetate. These organic solvents may be used alone or in combination of two or more.

Further, N-methylformamide, N,N-dimethylformamide, N-methylformamide, N-methylacetamide, N,N-dimethylacetamide can also be used. , N-methylpyrrolidone, dimethyl hydrazine, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, A high boiling organic solvent such as benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or phenyl cellosolve.

[1-5] Other ingredients

In the photosensitive composition of the present embodiment, a thermal polymerization inhibitor, a surfactant, a secondary builder, a solubility adjuster, a viscosity adjuster, or the like may be used as needed.

In the storage of the photosensitive composition of the present embodiment, the thermal polymerization inhibitor prevents the photosensitive polymerization initiator (C) from generating an active species due to heat, and acts on the polyfunctional monomer (B). . Examples of the thermal polymerization inhibitor include pyrogallol, benzoquinone, hydroquinone, monobenzyl ether, methyl hydroquinone, amyl hydrazine, pentyloxy hydroquinone, and the like.

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

Next, the auxiliary agent is a component for improving the adhesion between the member such as the spacer and the substrate. The adjuvant is then preferably a functional decane coupling agent. Further, the functional decane coupling agent is a decane coupling agent having a reactive substituent such as a carboxyl group, a methacryl group, an isocyanate group or an epoxy group. The above functional decane coupling agent is present in the presence of trimethoxydecyl benzoic acid, γ-methyl propylene methoxy propyl trimethoxy decane, vinyl triethoxy decane, vinyl trimethoxy decane, γ- Isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, β-(3,4-epoxycyclohexyl)ethyltrimethoxy decane, and the like.

The solubility adjusting agent is a component for preparing the coating film obtained by the photosensitive composition of the present embodiment with respect to the solubility of the developing solution. The solubility adjusting agent is preferably a low molecular carboxylic acid or a low molecular phenol compound when it is developed with an inorganic developing solution such as sodium hydroxide or potassium hydroxide. Low molecular carboxylic acids are monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-pentanoic acid, isovaleric acid, benzoic acid, cinnamic acid; lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid , hydroxycarboxylic acid such as salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, syringic acid, etc.; 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, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid Polycarboxylic acid; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, triacetic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, sodium Dicic anhydride, 1,2,3,4-butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, benzophenone tetramethyl Anhydride, B Bis trimellitic anhydride alcohol esters, glycerin triglycidyl ester of trimellitic anhydride anhydride.

The low-molecular-weight phenol compound is a compound having a phenolic hydroxyl group and having a molecular weight of 1,000 or less, and is disclosed in Japanese Laid-Open Patent Publication No. Hei-3-200251, Japanese Patent Application Laid-Open No. Hei-3-200252, Japanese Patent Laid-Open No. Hei 3-200254, Japanese Patent Laid-Open No. 4-1650, and Japanese Patent Laid-Open No. Hei 4-11260 The compound described in Japanese Laid-Open Patent Publication No. Hei 4-12356, 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-double [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- Tetrakis(4-hydroxyphenyl)ethane and the like.

The solubility adjusting agent may be used singly or in combination of two or more. In order to obtain a good member such as a separator, it is preferred to use both a low molecular carboxylic acid and a low molecular phenol compound.

The viscosity modifier is used for the purpose of improving the coatability by adjusting the viscosity of the photosensitive composition of the present embodiment. There are bentonite and silicone in the viscosity modifier.

[1-6] Modulation of photosensitive composition

The photosensitive composition of the present embodiment can be prepared by uniformly mixing the above components (A) to (D) and any other components added arbitrarily. The photosensitive composition of the present embodiment is used, for example, in a solution state in which other components are dissolved in the above-mentioned appropriate organic solvent (D). For example, a photosensitive composition in a solution state can be prepared by mixing (A) component to (C) component and any other component added in a predetermined ratio together with the organic solvent (D).

When the photosensitive composition of the present embodiment is prepared into a solution state, components other than the organic solvent (D) (that is, component (A) to (C) The ratio (solid content) of the component and the arbitrarily added other component to the solution can be arbitrarily set depending on the purpose of use, the desired film thickness value, and the like.

Next, a so-called positive photosensitive composition can be used as the photosensitive composition of the embodiment. That is, the photosensitive composition of another example of the present embodiment may have a positive photosensitive property.

In the same manner as the photosensitive resin of the above-described embodiment, the photosensitive composition of the embodiment of the present invention contains an alkali-soluble resin. Further, other examples of the photosensitive composition according to the embodiment of the present invention include the following components: (A-II) component: a resin having an increased solubility in alkali due to the action of an acid, and (B- II) Component: A compound which produces an acid by irradiation with active light or radiation. Hereinafter, the main components of the photosensitive composition of the embodiment of the present invention will be described.

[1-7] (A-II) Resin having increased solubility in alkali due to action of an acid

The resin (hereinafter also referred to as (A-II) component) in which the solubility of the base (A-II) used in the photosensitive composition of the embodiment of the present invention is increased by the action of an acid contains the following copolymer. The resin comprising (a-ii-1) a structural unit having a specific structure represented by the following formula (11) (hereinafter referred to as a unit (a-ii-1)): [Chemical 9]

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

(a-ii-1) unit: The unit (a-ii-1) 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 any of a linear form and a branched form, and examples thereof include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a sec-butyl group. , tert-butyl, various pentyl groups, etc., in these bases, from the viewpoint of achieving high contrast ratio sensitivity, resolution, depth of focus, etc., it is suitable that the carbon number is 2 to 4 Lower alkyl.

Further, X together with the carbon atom to which it is bonded forms a monocyclic or polycyclic hydrocarbon ring having a carbon number of 5-20.

The monocyclic hydrocarbon ring may, for example, be cyclopentane, cyclohexane, cycloheptane or cyclooctane.

The polycyclic hydrocarbon ring may, for example, be a 2-ring hydrocarbon ring, a 3-ring hydrocarbon ring or a 4-ring hydrocarbon ring. Specific examples thereof include a polycyclic hydrocarbon ring such as adamantane, norbornane, isobornane, tricyclodecane or tetracyclododecane.

The hydrocarbon ring having 5 to 20 carbon atoms formed by X together with the carbon atom to which it is bonded is particularly preferably a cyclohexane ring or an adamantane ring.

Preferred specific examples of the structural unit represented by the above formula (11) include 1-ethylcyclopentyl (meth)acrylate and 1-propylcyclopentyl (meth)acrylate. , 1-butylcyclopentyl (meth)acrylate, 1-ethylcyclohexyl (meth)acrylate, 1-propylcyclohexyl (meth)acrylate, (meth)acrylic acid- 1-butylcyclohexyl ester and the like.

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

Further, the component (A-II) is preferably a resin comprising a copolymer comprising the above-mentioned (a-ii-1) unit and (a-ii-2) a polymerizable compound having an ether bond. Derived structural unit. By including the (a-ii-2) structural unit (hereinafter referred to as a unit (a-ii-2)), the adhesion to the substrate during development is improved.

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

The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate. , 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (methyl a radically polymerizable compound such as an (meth)acrylic acid derivative having an ether bond or an ester bond such as an acrylate or a tetrahydrofuran methyl (meth)acrylate, preferably 2-methoxyB (meth)acrylate Ester, (meth)acrylic acid-2- Ethoxyethyl ester, methoxytriethylene glycol (meth) acrylate. These compounds may be used singly or in combination of two or more.

Further, in the (A-II) component, other polymerizable compounds may be contained as a monomer for the purpose of appropriately controlling physical and chemical properties. The "other polymerizable compound" herein means a polymerizable compound which constitutes a unit other than the unit (a-ii-1) and the unit (a-ii-2). Examples of such a polymerizable compound include a known radical polymerizable compound or an anionic polymerizable compound. For example, a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid, 2-methylpropenyloxyethyl succinic acid or 2-methyl group can be mentioned. a methyl group having a carboxyl group and an ester bond, such as acryloxyethyl maleic acid, 2-methylpropenyloxyethyl phthalic acid, 2-methylpropenyloxyethylhexahydrophthalic acid a radically polymerizable compound such as an acrylic acid derivative; an alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate or butyl (meth)acrylate; (meth)acrylic acid- Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl ester and 2-hydroxypropyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, etc. (methyl) Aryl acrylates; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyl toluene a vinyl-containing aromatic compound such as hydroxystyrene, α-methylhydroxystyrene or α-ethylhydroxystyrene; a vinyl group-containing aliphatic compound such as vinyl acetate a conjugated diene such as butadiene or isoprene; a polymerizable compound containing a nitrile group such as acrylonitrile or methacrylonitrile; a polymerizable compound containing chlorine such as vinyl chloride or vinylidene chloride; A polymerizable compound containing a guanamine bond such as an amine or methacrylamide.

The content of the unit (a-ii-1) in the component (A-2) is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. When 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 unit (a-ii-2) in the component (A-2) is preferably 10% by mass to 90% by mass, and more preferably 30% by mass to 70% by mass. When it exceeds 90% by mass, the residual film ratio tends to decrease, and when it is less than 10% by mass, the adhesion to the substrate during development tends to be deteriorated.

Further, the polystyrene-converted 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, still more preferably 230,000 to 550,000.

A resin having a degree of dispersion of the component (A-II) of 1.05 or more is preferred.

When the amount of the component (A-II) is contained in the case of containing another alkali-soluble resin which is a component (C-II) to be described later, the total mass of the component (A-II) and the component (C-II) It is 5 parts by mass to 95 parts by mass, preferably 10 parts by mass to 90 parts by mass, per 100 parts by mass. When the amount is 5 parts by mass or more and 95 parts by mass or less, the sensitivity tends to be improved. Therefore, the blending amount is preferred.

[1-8] (B-II) a compound which generates an acid by irradiation with active light or radiation

(B-II) used in another example of the photosensitive composition of the present embodiment, a compound which generates an acid by irradiation with active rays or radiation (hereinafter referred to as a component (B-II)) is an acid generator, and is The compound which generates an acid directly or indirectly by light is not particularly limited.

Specifically, 2,4-bis(trichloromethyl)-6-piperidin-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-( 2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)vinyl]-s-triazine, 2 ,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-propyl-2-furyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl) Vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]-s-triazine, 2,4-double (Trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-( 3-methoxy-5-ethoxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxy) Phenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo- 4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4methoxy)phenyl-s-triazine, 2,4 - bis-trichloromethyl-6-(2-bromo-4methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4) Oxy)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)vinyl]-4,6-bis ( Trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)vinyl]-4,6-bis(trichloromethyl)-1,3 ,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2- [2-(3,4-Dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylene-2 Oxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tri a halogen-containing triazine compound such as 2,3-dibromopropyl)-1,3,5-triazine or a tris(2,3-dibromopropyl)isocyanate such as the following formula (12) a halogen-containing triazine compound;

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

--(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(phenylsulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(phenylsulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α-(2-chlorophenylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethionioxyimino)-1-cyclo Pentenyl acetonitrile, 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, an unsaturated hydrocarbon group or an aromatic compound group, and n represents a natural number of 1 to 3 Here, the aromatic compound group is a group of a compound which exhibits a specific physical or chemical property in an aromatic compound, and examples thereof include an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heterocyclic ring such as a furyl group or a thienyl group. The group may have one or more suitable substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group, etc. Further, R ^{107 is} particularly preferably an alkyl group having 1 to 4 carbon atoms. Examples thereof include a methyl group, an ethyl group, a propyl group, and a butyl group. Particularly preferred is a compound wherein R ¹⁰⁶ is an aromatic compound group and R ¹⁰⁷ is a lower alkyl group. The acid generator represented by the above formula (13) is used. When n=1, a compound in which R ¹⁰⁶ is a phenyl group, a methylphenyl group or a methoxyphenyl group, and R ¹⁰⁷ is a methyl group, specifically α-(methylsulfonyloxyimino)- 1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl) ) Carbonitrile. N = 2 in the above formula (13) represented by the acid and specific examples include acid represented by the following chemical formula)

[化12]

Bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethionsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethyl Diphenylsulfonyl diazomethane such as diphenylmethanesulfonyl diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrate Base benzyl tosylate, dinitrobenzyl tosylate, nitro benzene sulfonate, Nitrobenzyl derivative such as nitrobenzyl carbonate or dinitrobenzyl carbonate; pyrogallol trimethylsulfonate, pyrogallol trimethylsulfonate, benzyl tosylate, benzyl Sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, N-methyl a sulfonate such as sulfomethoxy phthalimide; a triflate such as N-hydroxyphthalimide or N-hydroxynaphthyl imine; diphenyl iodonium Hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate a salt, (4-methoxyphenyl)diphenylphosphonium trifluoromethanesulfonate, a phosphonium salt such as (p-tert-butylphenyl)diphenylphosphonium trifluoromethanesulfonate; benzoin tosylate, A benzoin tosylate such as α-methylbenzoin tosylate; another diphenyliodonium salt, a triphenylsulfonium salt, a phenyldiazonium salt, a benzyl carbonate or the like.

Among the above compounds, the (B-II) component preferably has at least two of the following formula (14): [Chemical 13] R-SO ₂ ON=C(CN)- (14)

(In the formula (14), R is substituted or unsubstituted, for example, an alkyl group or an aryl group having 1 to 8 carbon atoms)

The oxime sulfonate-based compound represented, in particular, the following formula (15): [Chem. 14] R-SO ₂ ON=C(CN)-AC(CN)=N-OSO ₂ -R (15)

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

The compound represented. Here, the aromatic compound group is a group of a compound which exhibits a specific physical or chemical property in an aromatic compound, and examples thereof include an aromatic hydrocarbon group such as a phenyl group or a naphthyl group, or a heterocyclic group such as a furyl group or a thienyl group. . These groups may have one or more appropriate substituents on the ring, such as a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like. Further, more preferably, in the above formula (15), A is a phenylene group, and R is a compound having a lower alkyl group having 1 to 4 carbon atoms, for example.

The (B-II) component may be used singly or in combination of two or more.

The amount of the compound is 0.1 parts by mass to 20 parts by mass, preferably 0.2 parts by mass to 10 parts by mass, per 100 parts by mass of the total mass of the component (A-II) (the component (C-II)). When the amount is 0.1 part by mass or more, sufficient sensitivity is obtained, and when the amount is 20 parts by mass or less, there is a tendency that the solubility in a solvent is good, or a uniform solution, storage stability improve.

[1-9](C-II) other alkali soluble resin

In another example of the photosensitive composition of the embodiment of the present invention, it is preferred to contain (C-II) another alkali-soluble resin. (C-II) other alkali-soluble resin used in another example of the photosensitive composition of the embodiment of the present invention is A resin other than the resin containing the copolymer of the structural unit represented by the above formula (11) (hereinafter referred to as a component (C-II)). The component (C-II) can be appropriately selected from any of the compounds known as the alkali-soluble resin in the conventional chemically amplified resist. Particularly preferred among the compounds are a copolymer comprising (c-ii-1) phenolic resin, (c-ii-2) comprising a hydroxystyrene structural unit and a styrene structural unit, and (c-ii-3) Further, one or more resins of the acrylic resin further preferably contain a copolymer of (c-ii-1) phenol resin and/or (c-ii-2) comprising a hydroxystyrene structural unit and a styrene structural unit. Thereby, it becomes easy to control the coating property and development speed of a photosensitive composition.

(c-ii-1) Phenolic resin: The phenol resin as the component (c-ii-1) can be, for example, an aromatic compound having a phenolic hydroxyl group (hereinafter abbreviated as "phenol") and an aldehyde under an acid catalyst Obtained by addition condensation.

In this case, examples of the phenol to be used include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, and the like. p-Butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-di Cresol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, o-benzene Trisphenol, phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like.

Further, examples of the aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, and the like.

The catalyst in the addition condensation reaction is not particularly limited. For example, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid or the like can be used as the acid catalyst.

In particular, the development profile of a phenolic resin using only m-cresol as a phenol is particularly good and is preferably used.

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

Examples of the hydroxystyrene structural unit include hydroxystyrene structural units such as hydroxystyrene such as p-hydroxystyrene, α-methyl hydroxystyrene, and α-alkyl hydroxystyrene such as α-ethyl hydroxystyrene.

Examples of the styrene structural unit include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

(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, and particularly preferably an acrylic resin containing the following structural unit: having an ether bond A structural unit derived from a polymerizable compound, and a structural unit derived from a polymerizable compound having a carboxyl group.

The polymerizable compound having an ether bond can be exemplified by 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, and 3-methoxybutyl (meth)acrylate. Ester, ethyl carbitol (meth) acrylate, phenoxy polyethyl A (meth)acrylic acid derivative having an ether bond or an ester bond, such as a diol (meth) acrylate, a methoxypolypropylene glycol (meth) acrylate or a (meth) acrylic acid tetrahydrofuran methyl ester, is preferably used. 2-methoxyethyl acrylate, methoxy triethylene glycol acrylate. These compounds may be used singly or in combination of two or more.

The polymerizable compound having a carboxyl group may, for example, be a monocarboxylic acid such as acrylic acid, methacrylic acid or crotonic acid, a dicarboxylic acid such as maleic acid, fumaric acid or itaconic acid or 2-methylpropenyloxyethyl succinic acid. 2-methylpropenyloxyethyl maleic acid, 2-methylpropenyloxyethylphthalic acid, 2-methylpropenyloxyethylhexahydrophthalic acid, etc. having a carboxyl group and an ester The compound of the bond or the like is preferably acrylic acid or methacrylic acid. These compounds may be used singly or in combination of two or more.

[1-10](D-II) Acid Diffusion Control Agent

In another example of the photosensitive composition of the embodiment of the present invention, in order to improve the shape of the pattern obtained by patterning, the stability after exposure, and the like, it is preferable to further contain a (D-II) acid diffusion controlling agent (hereinafter referred to as (D-II) component).

The component (D-II) can be appropriately selected from any of the compounds known as acid diffusion controlling agents in the conventional chemically amplified resist. Particularly preferred is an oxoacid or a derivative thereof containing a nitrogen-containing compound and further containing an organic carboxylic acid or phosphorus as needed.

Next, a method of 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 of forming members such as spacers

In the method of forming a member such as a spacer of the microlens array of the present embodiment, the photosensitive composition of the present embodiment is used, and the following steps (1) to (3) are included.

Step (1): a step of forming a coating film (hereinafter also referred to as "coating film") obtained by the photosensitive composition (hereinafter also referred to as "composition") of the present embodiment on a substrate.

Step (2): a step of exposing the coating film obtained in the step (1) in a manner corresponding to the shape of the member such as the spacer.

Step (3): a step of subjecting the exposed coating film obtained in the step (2) to a development treatment.

The details of each step will be described below.

[2-1] Step (1)

In the step (1), a photosensitive composition is coated on the substrate. Further, if necessary, heat treatment (hereinafter also referred to as "prebake") is carried out to remove the solvent to form a coating film of the photosensitive composition.

As the substrate, a coating film of a photosensitive composition can be formed on a glass substrate, a plastic substrate, or a semiconductor substrate such as tantalum. Further, in the case of forming the microlens array of the present embodiment, a glass substrate or a plastic substrate on which a transparent electrode such as indium tin oxide (ITO) is formed is selected.

The method of applying the photosensitive composition may be any method as long as the photosensitive composition can be uniformly applied, and for example, a spray method, a roll coating method, a spin coating method (spin coating method), or a slit die coating method may be employed. A suitable method such as a bar coating method or an inkjet method. Especially spin coating or slit die coating A uniform film thickness coating film can be obtained by the method and is preferably used.

Further, in the case of prebaking, the conditions may be appropriately selected depending on the type of each component, particularly the solvent, the amount of use, and the like, and it is preferably carried out at 60 ° C to 160 ° C for about 30 seconds to 15 minutes.

The film thickness of the coating film thus obtained can be appropriately selected so as to correspond to the height of a member such as a target spacer. It is preferable that the thickness of the coating film is formed to be the same or thicker than the height of the member such as the target spacer. For example, it is preferably 10 μm to 140 μm.

[2-2] Step (2)

In the step (2), the coating film obtained in the step (1) is exposed to form a coating film having a latent image, in a manner corresponding to the shape of the member such as the target spacer, as needed, by interposing the patterned mask. (coating film after exposure).

Examples of the exposure light include a semiconductor laser, a metal halide lamp, a high pressure mercury lamp (g line, h line, i line, etc.), an excimer laser, an extreme ultraviolet ray, and an electron beam. A high-pressure mercury lamp is preferred from the viewpoint that the transparency of the coating film is high and the pattern can be formed with high resolution.

The amount of exposure can be appropriately selected depending on the type of the exposure light, the film thickness and type of the coating film, and the shape of the member such as the intended spacer. In the case of a high pressure mercury lamp, it is preferably 100 mJ/cm ² to 1500 mJ/cm ² .

The coating film obtained by the step (1) is a negative type using the photosensitive composition containing the component (A), the component (B), and the component (C) in the above embodiment. In addition, the coating film obtained by the step (1) is a positive type using the (A-II) component and the (B-II) component of the other examples of the photosensitive composition of the present embodiment.

Here, when the photosensitive film of the present embodiment is used for the negative type, the coating film obtained in the step (1) is described, and the position at which the coating film is exposed can be patterned. Therefore, the coating film is exposed by interposing a patterned mask which is designed such that the transmittance of the exposure light is higher than the position of the member corresponding to the target spacer or the like. Further, the exposure method can be appropriately selected according to the size of the member such as the target spacer, and when a member such as a fine spacer is formed, exposure can be performed by the reduced projection method.

In addition, when the coating film obtained in the step (1) is used as a positive example using another example of the photosensitive composition of the present embodiment, a portion other than the position at which the coating film is exposed can be patterned. Therefore, the coating film is exposed by interposing a patterning mask designed in such a manner that the transmittance of the exposure light is lower than the position of the member corresponding to the target spacer or the like.

After the exposure, heat treatment (hereinafter also referred to as "postbake") may be performed as needed.

When the coating film obtained in the step (1) is used as the photosensitive composition of the negative-type photosensitive material in the case of the post-baking condition, the photosensitivity contained in each component, particularly the photosensitive composition, can be used. The type and amount of the polymerization initiator (C) are appropriately selected, and it is preferably carried out at 60 ° C to 160 ° C for 30 seconds to 15 minutes.

Further, in the case of using the coating film obtained in the step (1) in another example of the positive photosensitive composition of the present embodiment, the post-baking conditions may be included in each component, particularly the photosensitive composition. (B-2) It is suitable for selection according to the type and amount of use.

[2-3] Step (3)

In the step (3), the exposed coating film obtained in the step (2) is brought into contact with the developer to remove a position having a high solubility relative to the developer to form a patterned coating film. That is, the step (3) is a step of developing a coating film having a latent image and patterning the latent image to form a patterned coating film.

Examples of the developer to be used in the step (3) include aqueous solutions of the following basic compounds: sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, ammonia, ethylamine, n-propylamine, and Ethylamine, diethylaminoethanol, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, acridine 1,8-diazabicyclo[5.4.0]-7-undecene, 1,5-diazabicyclo[4.3.0]-5-decane, and the like. Further, 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 may be used as the developer. The method of contacting the developing solution can be, for example, a suitable method such as a liquid coating method, a dipping method, a shaking dipping method, or a shower method.

The patterned coating film obtained by contact with the developer is preferably subjected to a cleaning treatment with water.

Further, when the coating film obtained in the step (1) is used as the photosensitive composition of the negative embodiment, the photosensitive film remaining in the patterned coating film which is not decomposed by the exposure light can be obtained. The polymerization initiator (C) is decomposed for the purpose, or the polyfunctional monomer (B) is polymerized by the active species generated by the decomposition, so that the patterned coating film is sufficiently hardened, and the entire surface is irradiated with light (after exposure). The exposure amount of the post exposure at this time is preferably from 1 mJ/cm ² to 1500 mJ/cm ² . Further, post-baking may be performed 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, and are usually carried out at 150 ° C to 250 ° C for about 10 minutes to 120 minutes.

As described above, the pattern formed by patterning can be formed by using the photosensitive composition of the present embodiment, and members such as spacers used in the microlens array of the present embodiment can be formed on the substrate. The member such as the spacer formed may have a desired shape and height, and has the strength necessary to maintain the distance between the substrates, even if heated, deformed or highly varied. For example, the member such as the spacer formed may have a height of 10 μm to 100 μm. The conditions can be formed by appropriate selection, and a height of 100 μm or more can be achieved as needed.

Further, the shape of the spacer is preferably a lattice shape or the like in addition to the lens.

In the case of manufacturing the microlens array of the present embodiment, after a member such as a spacer is formed on the substrate having the electrode, an alignment film for liquid crystal alignment is formed as will be described later. In order to form the alignment film, a heating step at a temperature of 200 ° C or higher is usually necessary. The member such as the spacer formed by using the photosensitive composition of the present embodiment can suppress the expansion and contraction due to heating at 200 ° C to 5% or less. As a result, even if the member such as the spacer has a heat treatment step for forming the alignment film or the bonded substrate, the distance between the substrates in the manufactured microlens array can be uniformly maintained in the plane.

Next, the microlens array of the present embodiment will be described.

[3] Microlens array

The microlens array of the present embodiment is a microlens array suitable for a stereoscopic image display device, and is configured to be compatible with switching between planar image display and stereoscopic image display. The microlens array of the present embodiment includes a pair of substrates on which electrodes are formed on opposite surfaces, and a liquid crystal layer having refractive index anisotropy sandwiched between the substrates, and the photosensitive composition of the above-described embodiment. And the components such as spacers are formed. When a flat image is displayed on the stereoscopic image display device, it functions as a substantially transparent body. When a stereoscopic image is displayed, the liquid crystal layer is driven by applying a voltage, and the alignment state of the liquid crystal is controlled, thereby exerting a lens action. That is, the microlens array of the present 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 showing the configuration of a microlens array of the embodiment.

The microlens array 1 of the present embodiment has a lens-shaped spacer 7 which is an example of a member disposed between the pair of the substrate 2 and the substrate 3.

In other words, the microlens array 1 of the present embodiment includes the substrate 2 disposed on the light exit side, the substrate 3 disposed on the light incident side, the liquid crystal layer 4 sandwiched between the substrates 2 and the substrate 3, and the substrate 2 disposed on the substrate 2. The common electrode 5 on the surface on the liquid crystal layer 4 side, the comb-shaped electrode 6 provided on the liquid crystal layer 4 side of the substrate 3, and the interval between the substrate 2 and the substrate 3 are erected Item 7.

The liquid crystal alignment alignment film 8 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 electrode 6 is formed. The liquid crystal layer 4 contains a liquid crystal 9 as a nematic liquid crystal. The side surface portion of the microlens array 1 is preferably sealed by a suitable sealant (not shown).

Fig. 2 is a plan view schematically showing the configuration of a microlens array of the embodiment.

In FIG. 2, in order to explain the arrangement of the spacers 7, only the substrate 3 and the comb electrodes 6 and the spacers 7 are shown, and other constituent elements 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.

The substrate 2 and the substrate 3 preferably each contain a material having a high transmittance of visible light. The substrate 2 and the substrate 3 may be, for example, a transparent substrate including glass such as float glass or soda glass, and may contain, for example, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, and polycarbonate. A transparent substrate of plastic such as ester. The thickness of the substrate 2 and the substrate 3 can be, for example, 20 μm to 2000 μm, and preferably 50 μm to 1000 μm.

The material constituting the comb-shaped common electrode 5 and the electrode 6 is preferably a transparent conductive material, for example, is desirable to include In ITO ₂ O ₃ -SnO _2, comprising SnO NESA ₂ (registered trademark). The comb electrode 6 includes a plurality of electrode elements arranged in parallel with each other, and the back side portions of the electrode elements which are electrically connected to each other at one end thereof. The shape when the electrode member is viewed from the direction perpendicular to the substrate surface is preferably a rectangle having a short side and a long side. The formation of the comb-shaped electrode 6 can be carried out by forming a transparent conductor film containing ITO or NESA on a substrate by a known photolithography method.

The pixel width of the width (the length of the short side) of the electrode element with respect to the image display unit used in combination with the microlens array 1 of the present embodiment (refers to the pixel for displaying the image for the right eye or the image for the left eye) The width of the unit is preferably 1% or more and less than 200%, more preferably 2% or more and less than 100%, still more preferably 2% or more and less than 50%. The length (length of the long side) of the electrode element can be set to be substantially equal to the length of one side of the substrate 3. The pitch between the adjacent electrode elements is preferably twice (200%) the pixel width of the image display unit used in combination with the microlens array 1 of the present embodiment.

Further, in the microlens array 1 of the present embodiment, a planarizing film may be provided between the layer including the comb electrode 6 and the layer including the alignment film 8.

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

Examples of the liquid crystal 9 having positive dielectric anisotropy constituting the liquid crystal layer 4 include a biphenyl liquid crystal, a phenylcyclohexane liquid crystal, an ester liquid crystal, a terphenyl liquid crystal, and a biphenyl cyclohexane liquid crystal. , pyrimidine liquid crystal, dioxane liquid crystal, dicyclooctane liquid crystal, cubic liquid crystal, and the like. Preferably, two or more of the liquid crystals are mixed, and a liquid crystal having a positive dielectric anisotropy is present in a nematic phase in a desired temperature range including room temperature.

The spacer 7 is a lens-shaped 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 thickness control of the liquid crystal layer 4 with high precision. The photosensitive composition of the present embodiment can be used, and the interval can be separated by the above method. Formation of piece 7. The microlens array 1 of the present embodiment having the structure shown in FIG. 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, the alignment film 8 is placed so as to overlap the substrate 2 on which the common electrode 5 and the alignment film 8 are formed, and is disposed between the substrate 2 and the substrate 3.

The height of the spacer 7 is determined in accordance with the thickness of the liquid crystal layer 4. The thickness of the liquid crystal layer 4 is preferably 20 μm to 100 μm, and is set to 20 μm to 100 μm in accordance with the height of the spacer 7. Further, when the thickness of the liquid crystal layer is set to 30 μm to 70 μm in order to realize the desired alignment state of the liquid crystal with high precision, it is preferable to set the height of the spacer 7 to 30 μm to 70 μm correspondingly. .

Further, the spacer 7 of the microlens array 1 of the present embodiment shown in FIG. 2 has a circular cross-sectional shape, and the shape of the spacer 7 may be other shapes. For example, it is also possible to adopt a lens shape in which the cross section is elliptical or rectangular or square.

Further, in the microlens array 1 of the present embodiment, as another configuration example, a spacer may be provided on the substrate 2 on which the common electrode 5 is formed by using the photosensitive composition of the present embodiment, and the alignment film 8 may be provided. Then, the substrate 3 and the substrate 3 on which the comb electrode 6 and the alignment film 8 are formed are superposed on each other, whereby a spacer is disposed between the substrate 2 and the substrate 3.

The alignment film 8 is disposed on the surface of the substrate 2 and the substrate 3 that is in contact with the liquid crystal layer 4. The alignment film 8 can be used as an alignment film for aligning the liquid crystals 9 of the liquid crystal layer 4 in a direction parallel to the substrate surface. Such flat The alignment film 8 for alignment may be formed, for example, by using an organic film containing a compound: polylysine, polyimine, polyorganosiloxane, polyphthalate, polyester, polyamide, cellulose. Derivatives, polyacetals, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates, and the like. Further, parallelization can be achieved by subjecting the organic films to an alignment treatment (for example, a photo-alignment treatment using light or a rubbing treatment in which the surface of the organic film is rubbed in one direction using a cloth such as nylon or polyester) It is used for the alignment of the liquid crystal layer 4 on the substrate surface.

Further, the alignment treatment direction in the alignment film 8 may be set to be antiparallel (antiparallel alignment) with respect to the substrate 3 on the opposite substrate 2.

In the microlens array 1 of the present embodiment, when no voltage is applied between the comb electrode 6 and the common electrode 5, as shown in FIG. 1, the liquid crystal 9 of the liquid crystal layer 4 is uniformly aligned in parallel with the substrate 2 and the substrate 3. It functions as a simple transparent body. In this state, the lenticular lens function is not exhibited in the microlens array 1. 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 between the substrate 2 and the substrate 3. A change in the alignment state is generated to form a desired spatial alignment state.

3 is a view schematically illustrating a liquid crystal alignment state of a microlens array according to an embodiment of the present invention formed by applying a voltage.

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 changes in the alignment state between the substrate 2 and the substrate 3. Moreover, on the substrate 2 An alignment state between the substrate 3 and the substrate 3 is achieved in the vicinity of the adjacent electrode elements of the comb electrode 6 in parallel with the substrate 3, but the slope with respect to the substrate 3 increases as approaching the common electrode 5. As a result, a refractive index distribution that realizes the function of the convex lens 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 functions as a lenticular lens having an elongated shape corresponding to the pitch of the electrode elements of the comb electrode 6. A convex lens portion in the form of a kammaboko.

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

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

Fig. 4 is a cross-sectional view schematically showing the configuration of a microlens array of another example of the embodiment.

The microlens array 21 of the other 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 the other configuration is the same as that of the above-described microlens array 1. Therefore, regarding the constituent elements common to the microlens array 1 of FIG. 1, the same symbol is used and the province is omitted. A slightly repeated explanation.

The microlens array 21 as 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, a liquid crystal layer 4 sandwiched between the substrates 2 and 3, and a substrate The common electrode 5 on the surface on the liquid crystal layer 4 side of 2, the comb-shaped electrode 6 provided on the liquid crystal layer 4 side of the substrate 3, and the spacer 27 which is provided upright between the substrate 2 and the substrate 3. The liquid crystal alignment alignment film 8 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 electrode 6 is formed. The liquid crystal layer 4 contains a liquid crystal 9 as a nematic liquid crystal. The side surface portion of the microlens array 1 is preferably sealed by a suitable sealant (not shown).

The spacer 27 of the microlens array 21 is a lens 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. The formation of the spacer 27 can be carried out in accordance with the above method by 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 is erected on the electrode element of the comb electrode 6 on the substrate 3 on which the comb electrode 6 is formed. Thereafter, the alignment film 8 is placed so as to overlap the substrate 2 on which the common electrode 5 and the alignment film 8 are formed, and is disposed between the substrate 2 and the substrate 3.

The microlens array 21 as another example of the present embodiment has the spacer 27, and the thickness of the liquid crystal layer 4 sandwiched between the substrate 2 and the substrate 3 can be controlled with high precision in the plane. Further, the microlens array 21 can control the spatial alignment state of the liquid crystal 9 of the liquid crystal layer 4 with high precision by applying a voltage as in the microlens array 1 shown in FIG. 3, and is suitable for switching plane images and standing. A microlens array of bulk images. Further, in the microlens array 21, the spacers 27 are provided on the electrode elements of the comb electrodes 6 on the substrate 3, and the spacers 27 have less obstruction by controlling the spatial alignment of the liquid crystals 9 by applying a voltage.

Further, in the microlens array 21 of the present embodiment, as the other configuration example, the spacers are provided upright on the substrate 2 on which the common electrode 5 is formed by using the photosensitive composition of the present embodiment, and the alignment film 8 is provided. Thereafter, the substrate 2 and the substrate 3 on which the comb electrode 6 and the alignment film 8 are formed are superposed on each other, whereby spacers may be disposed between the substrate 2 and the substrate 3 and on the electrode elements of the comb electrodes 6. Composition.

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

[4] stereoscopic image display device

The stereoscopic image display device of the present embodiment is a stereoscopic image display device including an image display unit that can switch between displaying a planar image and a stereoscopic image, and the microlens array of the above-described embodiment.

Fig. 5 is a cross-sectional view schematically showing the configuration of a three-dimensional image display device of the embodiment.

The three-dimensional image display device 100 of the present embodiment is configured such that the microlens array 1 of the present embodiment and the image display unit 102 that can switch between the display plane image and the stereoscopic image are arranged in order from the observer 101. .

The image display unit 102 of the stereoscopic image display device of the present embodiment includes a liquid crystal display method, an EL (Electro Luminescence) display method, a plasma display method, and a CRT (Cathode Ray Tube: The image display unit such as the Braun tube method or the LED (Light Emitting Diode) method is preferably an image display unit of a liquid crystal display method, an EL display method, or a plasma display method. The EL display mode is preferably an organic EL display mode.

Preferably, at least one polarizing plate (not shown) is disposed between the image display unit 102 and the microlens array 1. The polarizing plate may be integrated with the image display unit 102 to form a part thereof.

When the image display unit 102 of the stereoscopic image display device 100 of the present embodiment displays a stereoscopic image, the right-eye image having parallax and the left-eye image can be interactively formed on the image display unit 102. Displayed in stripes. On the other hand, in the case of displaying a planar image, it is preferable to use a configuration for the right-eye image forming portion and the left-eye image forming portion when the stereoscopic image is displayed as a two-dimensional image. The unit pixel, thus displaying a high-definition planar image.

The width of the unit pixel included in the image display unit 102 is preferably 1/2 of the pitch of the electrode elements of the comb electrodes 6 of the microlens array 1. Further, in the stereoscopic image display device 100 of the present embodiment, when the image display unit 102 is combined with the microlens array 1 of the present embodiment, it is preferable to use a comb electrode along the substrate 3 of the microlens array 1. The center line extending in the longitudinal direction of the electrode element of 6 is combined with the boundary line between the right-eye image forming portion and the left-eye image forming portion when the stereoscopic image of the image display unit 102 is displayed.

In the stereoscopic image display device 100 of the present embodiment, the image display unit 102 has an image for the right eye having parallax as described above. The left eye image is alternately formed into a stripe-shaped right-eye image portion (R) and a left-eye image portion (L). Further, when displaying a planar image, the image display unit 102 uses the right-eye image portion (R) and the left-eye image portion (L) as units for forming a two-dimensional image, as shown in FIG. Pixels that output high-resolution 2D images. At this time, the microlens array 1 is in a state in which no voltage is applied, or an extremely small applied voltage state in which the liquid crystal 9 does not undergo a change operation. Thereby, the liquid crystal 9 of the liquid crystal layer 4 sandwiched between the substrate 2 of the microlens array 1 and the substrate 3 is parallel to the substrate surface formed by the substrate 2 and the substrate 3 by the action of the alignment film 8. Orientation. 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-brightness planar image on the stereoscopic image display device 100.

Fig. 6 is a cross-sectional view schematically showing a configuration of a stereoscopic image display device of the embodiment having a microlens array to which a voltage is applied.

On the other hand, as shown in FIG. 6, when the stereoscopic image is displayed in the stereoscopic image display device 100 of the present embodiment, the image display unit 102 is in the image portion (R) for the right eye and the image for the left eye. The part (L) displays the right-eye image having the parallax and the left-eye image in a stripe shape. At this time, a voltage is applied to the microlens array 1, and the liquid crystal 9 of the liquid crystal layer 4 undergoes an alignment state change between the substrate 2 and the substrate 3, and an alignment state described using FIG. 3 is uniformly formed in the plane. As a result, in the microlens array 1, it functions as a lenticular lens, and the lens effect is uniformly displayed in the plane. Thereby, the stereoscopic image display device 100 becomes an image The image for the right eye on the display unit 102 leads to the right eye of the observer 101, and the image for the left eye is guided to the left eye of the observer 101, and the observer 101 can observe a uniform stereoscopic image.

As described above, the stereoscopic image display device 100 of the present embodiment can selectively switch between displaying a high-definition and bright planar image and a stereoscopic image having high uniformity.

[Example]

Hereinafter, embodiments of the present invention will be described in more detail based on examples. However, the invention is not limited by these examples. In addition, the "parts" and "%" in the examples are the quality standards unless otherwise specified.

<Synthesis of Polymer (A-1)> [Example 1]

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

<Resin (A-II-1) which has increased solubility in alkali due to the action of an acid Synthesis> [Example 2]

The reaction vessel (flask) with a stirring device, a reflux device, a thermometer, and a dropping tank was purged with nitrogen, and then propylene glycol methyl ether acetate as a solvent was charged, and stirring was started. Thereafter, the temperature of the solvent was raised to 80 °C. 2,2'-azobisisobutyronitrile as a polymerization catalyst and 50% by mass of a structural unit of 1-ethylcyclohexyl methacrylate as (a-ii-1-1) were placed in a dropping tank. And 50% by mass of the 2-ethoxyethyl acrylate structural unit of (a-ii-2-1), stirring was performed until the polymerization catalyst was dissolved, and the solution was uniformly added dropwise to the flask over 3 hours, followed by The polymerization was carried out at 80 ° C for 5 hours. Thereafter, the mixture was cooled to room temperature to obtain a resin (A-II-1) having a mass average molecular weight of 350,000.

<Synthesis of phenolic resin (c-ii-1-1)> [Example 3]

The m-cresol and p-cresol were mixed at a mass ratio of 60:40, and formalin was added thereto, and condensation was carried out by a usual method using an oxalic acid catalyst to obtain a cresol novolac resin. The resin was subjected to a separation treatment to cut off a low molecular region to obtain a phenol resin having a mass average molecular weight of 15,000. This resin was used as a phenol resin (c-ii-1-1).

<Modulation 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 the [B] polymerizable compound, and a phenol novolac type epoxy resin (product) name 20 parts by mass of "Epikote 152", Japan Epoxy Co., Ltd., 2,2-dimethoxy-1,2-diphenylethane-1-one as a [C] polymerization initiator (trade name "Irgacure" (registered trademark) 651", manufactured by Ciba Specialty Chemicals Co., Ltd.) 19 parts by mass of 2,4,6-trimethylbenzimidyldiphenylphosphine oxide (trade name "Lucirin (registered trademark) LR8953X", BASF (manufactured by BASF) 4 parts by mass of ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-B醯肟) (Irgacure (registered trademark) OXE02, Ciba Specialty Chemicals Co., Ltd.) 2 parts by mass of tris(3-trimethoxyformamidopropyl)isocyanate as a further auxiliary agent (trade name " 3 parts by mass of a fluorine-based surfactant (trade name "FTX-218F", manufactured by Nios), which is a surfactant, is dissolved in a solvent as a solvent. In the propylene glycol monomethyl ether acetate, a photosensitive composition was prepared.

[Example 5] <Modulation of photosensitive composition (positive type)>

50 parts by mass of the resin (A-II-1) obtained in Example 2 as the component (A-II), and 1 part by mass of the compound (B-II-1) of the following chemical formula as the component (B-II), And 50 parts by mass of the phenol resin (c-ii-1-1) obtained in Example 3 as the component (C-II), mixed in propylene glycol monomethyl ether acetate to prepare a uniform solution, and passed through the pore diameter The membrane filter of 1 μm was filtered to prepare a positive photosensitive composition.

<Forming a pattern using a photosensitive composition> [Example 6]

The photosensitive composition of Example 4 was applied onto a glass substrate, and heat-treated at 120 ° C for 5 minutes on a hot plate to form a coating film having a film thickness of 58 μm. Using an aligner (manufactured by Karl Suss, Model "MA-150"), the formed coating film was exposed to ultraviolet rays irradiated from the high pressure mercury lamp through a patterned mask. The exposed coating film was subjected to development treatment in an aqueous solution containing 2% by mass of potassium hydroxide for 90 seconds, and then subjected to a water washing treatment 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 onto a glass substrate, and heat-treated at 120 ° C for 5 minutes on a hot plate to form a coating film having a film thickness of 58 μm. Using an aligner (manufactured by Carl Hughes Co., model "MA-150"), the formed coating film was exposed to ultraviolet rays irradiated from the high pressure mercury lamp through a patterned photomask. The exposed coating film was developed at 25 ° C in an aqueous solution of tetramethylammonium hydroxide having a concentration of 0.40% by mass. Here, the development time was set to 80 seconds. Next, the 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 of Photosensitive Composition> [Example 8]

The substrate having the pattern obtained in Example 6 was further placed in an oven, The heat treatment was performed at 220 ° C for 1 hour, and thereafter, the height of the pattern after the heat treatment was measured using a laser microscope (VK-8500, Keyence). The height of the pattern after the heat treatment was measured. The pattern height after heat treatment was 48 μm. As a result, the amount of change in the pattern height due to the heat treatment at 220 ° C was 4%, and the pattern formed using the photosensitive composition of Example 4 was controlled to be expanded and contracted at 200 ° C or higher after the formation. 5% or less.

When the substrate having the pattern obtained in Example 7 was evaluated by the same evaluation method, the pattern formed using the photosensitive composition of Example 5 was controlled to be stretched at 200 ° C or higher after formation. 5% or less.

<Manufacture of Microlens Array> [Example 9]

The microlens array of the present example is a microlens array having spacers disposed between the substrates as members disposed between the substrates.

First, the photosensitive composition of Example 4 was applied onto a glass substrate on which a comb electrode containing ITO was formed by a known photolithography method. Next, heat treatment was performed on a hot plate at 120 ° C for 5 minutes to form a coating film having a film thickness of 58 μm. An aligner (manufactured by Karl Suss Co., model "MA-150") was used to intervene the formed coating film from the high pressure mercury lamp through a patterned reticle (the patterned reticle having a pattern corresponding to the spacer pattern). The ultraviolet rays that are irradiated. The exposed coating film was subjected to a development treatment for 90 seconds in an aqueous solution containing 2% by mass of potassium hydroxide, and then subjected to a water washing treatment, thereby forming a height of 50 on the glass substrate on which the comb electrode was formed. 间隔m spacer pattern.

Next, another glass substrate in which a common electrode including ITO is formed is prepared. Next, a photo-alignment film for parallel alignment of liquid crystals is formed on each of the glass substrate on which the spacer pattern is formed and the glass substrate on which the common electrode is formed. That is, a liquid crystal alignment agent for forming a photoalignment film was applied to each of the substrates, and prebaked on a hot plate at 80 ° C for 1 minute, and then heated at 180 ° C for 1 hour to form a coating having a film thickness of 80 nm. membrane. Next, using a Hg-Xe lamp and a Glan-Taylor prism, the surface of the coating film was irradiated with a polarized ultraviolet ray of 200 J/m ² including a bright line of 313 nm from the normal direction of the substrate, and photoalignment treatment was performed to form a parallel alignment of the liquid crystal. Light alignment film.

A pair of substrates on which an alignment film is formed is used, and a nematic liquid crystal having positive dielectric anisotropy is sandwiched between the substrates, and the side surface portion is sealed with a sealant to produce a microlens array. The manufactured microlens array has the same structure as that shown in FIG. The thickness of the liquid crystal layer was uniformly controlled in the plane to be 50 μm. Further, by applying a voltage to the electrodes of the respective substrates sandwiching the liquid crystal layer, the alignment state of the liquid crystal shown in Fig. 3 can be realized.

[Example 10]

A microlens array was produced in the same manner as described above except that the spacer pattern was formed in the same manner as the method described in Example 7 except that the photosensitive composition of Example 5 was used. The manufactured microlens array has the same structure as that shown in FIG. The thickness of the liquid crystal layer was uniformly controlled in-plane to 50 μm. Further, by applying a voltage to the electrodes of the respective substrates sandwiching the liquid crystal layer, the alignment state of the liquid crystal shown in Fig. 3 can be realized.

<Manufacture of stereoscopic image display device> [Example 11]

An image display unit (liquid crystal display) of a liquid crystal display system is prepared as an image display unit. The liquid crystal display is a liquid crystal display of a TN (Twisted Nematic) mode, and has a structure in which a liquid crystal panel is further sandwiched by a pair of polarizing plates (the liquid crystal panel is formed by sandwiching a twisted nematic liquid crystal between transparent substrates). . Further, the liquid crystal display is configured to switch between displaying a stereoscopic image and a planar image, and when displaying a stereoscopic image, the right-eye image having parallax and the left-eye image can be alternately formed into stripes. And display it. On the other hand, in the case of displaying a planar image, the right-eye image forming portion and the left-eye image forming portion when the stereoscopic image is displayed can be used as a unit pixel of the two-dimensional image to display a high-definition plane. image.

Using this liquid crystal display, a microlens array of Example 9 was combined to manufacture a stereoscopic image display device having the same structure as that shown in FIG.

In the manufactured stereoscopic image display device, a planar image is formed on the liquid crystal display, and the microlens array is in a state where no voltage is applied, whereby a high-definition and high-luminance planar image can be observed. Further, when a stereoscopic image is displayed in the manufactured stereoscopic image display device, the right-eye image having parallax is applied to the right-eye image portion (R) and the left-eye image portion (L) of the liquid crystal display. The image for the left eye is formed in a stripe shape by interaction, and a voltage is applied to the microlens array to function as a lenticular lens. Further, the image for the right eye on the liquid crystal display is guided to the right eye of the observer, and the image for the left eye is guided to the left eye of the observer, thereby providing a stereoscopic image to the observer.

[Example 12]

The microlens array was the same as the manufacturing method described in Example 11 except that the microlens array of Example 10 was used, and a stereoscopic image display device having the same configuration as that shown in Fig. 5 was produced.

In the manufactured stereoscopic image display device, a planar image is formed on the liquid crystal display, and the microlens array is in a state where no voltage is applied, whereby a high-definition and high-luminance planar image is observed. Further, when a stereoscopic image is displayed in the manufactured stereoscopic image display device, the right eye image having parallax is used in the right-eye image portion (R) and the left-eye image portion (L) of the liquid crystal display. The image is formed in stripes like the image for the left eye, and a voltage is applied to the microlens array to function as a lenticular lens. Further, the image for the right eye on the liquid crystal display is guided to the right eye of the observer, and the image for the left eye is guided to the left eye of the observer, thereby providing a stereoscopic image to the observer.

The embodiments of the present invention have been described above, but the present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit and scope of the invention.

For example, the spacer 7 of the microlens array 1 of the present embodiment shown in Figs. 1 and 2 has a lens spacer structure having a circular cross-sectional shape, but the present invention is not limited to this configuration.

In the present invention, a member having a spacer structure such as a spacer structure or a lattice-like member having a stripe shape may be disposed in the microlens array, and the spacer structure divides the liquid crystal layer sandwiched between the substrates. The way it is erected between the substrates.

Moreover, in the present invention, the comb-shaped electricity can also be used in the microlens array. The poles are divided into a plurality of poles, and are configured to apply a voltage to each of the divided comb electrodes. Thereby, it becomes possible to simultaneously form a region where a voltage is applied and a region where no voltage is applied in every one microlens. In this case, while forming an image of the image display unit, the inside of one stereoscopic image display device is divided into a planar image display region and a stereoscopic image display region, so that the planar image can be simultaneously displayed. With stereo images.

1, 21‧‧‧ microlens array

2, 3‧‧‧ substrate

4‧‧‧Liquid layer

5‧‧‧Common electrode

6‧‧‧ comb electrode

7, 27‧‧‧ spacers

8‧‧‧Alignment film

9‧‧‧LCD

100‧‧‧Three-dimensional image display device

101‧‧‧ Observers

102‧‧‧Image Display Department

200‧‧‧ lenticular lens

Fig. 1 is a cross-sectional view schematically showing the configuration of a microlens array according to an embodiment of the present invention.

Fig. 2 is a plan view schematically showing the configuration of a microlens array according to an embodiment of the present invention.

3 is a view schematically illustrating a liquid crystal alignment state of a microlens array according to an embodiment of the present invention formed by applying a voltage.

Fig. 4 is a cross-sectional view schematically showing the configuration of a microlens array of another example of the embodiment of the present invention.

Fig. 5 is a cross-sectional view schematically showing the configuration of a three-dimensional image display device according to an embodiment of the present invention.

Fig. 6 is a cross-sectional view schematically showing the configuration of a stereoscopic image display device according to an embodiment of the present invention having a microlens array to which a voltage is applied.

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

1‧‧‧Microlens array

2, 3‧‧‧ substrate

4‧‧‧Liquid layer

5‧‧‧Common electrode

6‧‧‧ comb electrode

7‧‧‧ spacers

8‧‧‧Alignment film

9‧‧‧LCD

Claims (19)

A photosensitive composition comprising a photosensitive resin composition containing an alkali-soluble resin, wherein a microlens array formed by sandwiching a liquid crystal layer having a thickness of 20 μm to 100 μm between a pair of substrates is disposed between the substrates Components. The photosensitive composition according to claim 1, which comprises (A) an alkali-soluble resin, (B) a polyfunctional monomer, and (C) a photosensitive polymerization initiator. The photosensitive composition according to claim 2, wherein the (A) alkali-soluble resin is a polymer comprising a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group. The photosensitive composition according to Item 2 or 3, wherein the (B) polyfunctional monomer comprises a compound having an epoxy group. The photosensitive composition according to claim 1, wherein the (A-II) resin having an increased solubility in alkali due to the action of an acid and (B-II) are irradiated with active light. Or a compound that emits radiation to produce an acid. The photosensitive composition according to claim 5, wherein the (A-II) resin having an increased solubility in alkali due to the action of an acid contains a resin containing a copolymer, and the copolymerization The structure includes a structural unit having a specific structure represented by the following formula (11), In the formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X together with the carbon atom to which it is bonded forms a hydrocarbon ring having 5 to 20 carbon atoms. The photosensitive composition according to claim 1, wherein the member disposed between the substrates has a stretch ratio of 5% or less when heated at 200 °C. A microlens array including a first substrate and a second substrate disposed opposite to each other, a liquid crystal layer interposed between the first substrate and the second substrate, and the liquid crystal provided on the first substrate a comb electrode having a plurality of electrode elements arranged in parallel with each other on the layer side, and a common electrode provided on a surface of the second substrate on the liquid crystal layer side, and passing through the comb electrode and A voltage is applied between the common electrodes to drive the liquid crystal layer to function as a lens, and a member is provided between the first substrate and the second substrate, and the member is photosensitive by an alkali-soluble resin. Formed by sexual composition. 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 microlens array according to claim 8 or 9, wherein the photosensitive composition comprises: (A) an alkali-soluble resin, (B) a polyfunctional monomer, and (C) Photosensitive polymerization initiator. The microlens array according to claim 10, wherein the (A) alkali-soluble resin is a polymer comprising a structural unit having a phenolic hydroxyl group and a structural unit having an alicyclic hydrocarbon group. The microlens array according to claim 10, wherein the (B) polyfunctional monomer comprises a compound having an epoxy group. The microlens array of claim 8 or 9, wherein the photosensitive composition comprises: (A-II) A resin having an increased solubility in alkali due to the action of an acid, and (B-II) a compound which generates an acid by irradiation with active rays or radiation. The microlens array according to claim 13, wherein the (A-II) resin having an increased solubility to alkali due to the action of an acid contains a resin containing a copolymer, the copolymer a structural unit having a specific structure represented by the following formula (11), (In the formula (11), R ¹⁰¹ represents a hydrogen atom or a methyl group, R ¹⁰² represents a lower alkyl group, and X together with a carbon atom to which it is bonded forms a hydrocarbon ring having 5 to 20 carbon atoms). The microlens array according to claim 8 or 9, wherein the liquid crystal layer is composed of a liquid crystal having positive dielectric anisotropy. The microlens array as described in claim 8 or 9 The column is characterized in that the thickness of the liquid crystal layer sandwiched between the substrates is 20 μm to 100 μm. The microlens array according to claim 8 or 9, wherein the member between the first substrate and the second substrate has a expansion ratio of 5% or less when heated at 200 °C. . A stereoscopic image display device comprising: the microlens array according to any one of claims 8 to 17, and an image display unit that switches between displaying a planar image and a stereoscopic image. 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.