JP2017116657A - Manufacturing method of line pattern, light control member and optical imaging member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a line pattern consisting of a plurality of linear members arranged in parallel with each other and having a cross section shape of almost rectangular, which can reduce development residual and is excellent in resolution of the line pattern.SOLUTION: There is provided a manufacturing method of the line pattern in a light control member having the line pattern consisting of a plurality of linear members arranged in parallel with each other, wherein a cross section shape of the linear members is almost rectangular, and a light reflection surface formed in a side surface of the linear member, having (a) a process for forming a film by using a radiation-sensitive composition, (b) a process for irradiating the film with radiation in a line pattern, (c) a process for forming a pattern by developing the film after radiation irradiation and (d) a process for applying air flow to the pattern.SELECTED DRAWING: None

Description

  The present invention relates to a method for manufacturing a line pattern included in a light control member, and more specifically, a method for manufacturing a line pattern included in a light control member having a plurality of planar light reflecting portions (light reflecting surfaces) arranged in parallel to each other. About.

  A stereoscopic image display device that forms an image of the object in the air using light emitted from the object surface is known (see Patent Document 1). An example of the stereoscopic image display device includes two light control members each having a plurality of planar light reflecting portions arranged in parallel with each other at regular intervals. These light control members (first and second light control members) are arranged to face each other in a state where the respective planar light reflection portions are orthogonal to each other.

  Light from the object is incident on the planar light reflecting portion of the first light control member, and the reflected light reflected by the light reflecting portion is reflected again by the planar light reflecting portion of the second light control member. The image of the object is displayed on the opposite side of the stereoscopic image display device by the reflected light obtained here.

  In the stereoscopic image display device, it is necessary to prepare a light control member having a plurality of planar light reflecting portions at regular intervals. The said light control member can be obtained by laminating | stacking the transparent substrate which has a light reflection part on both surfaces or one side using an adhesive agent, and cut | disconnecting the obtained laminated body by fixed width. However, the method is expensive and unsuitable for mass production.

  In order to solve the above problem, a method has been proposed in which a concavo-convex member is formed by a photolithography method, and a light reflecting portion is formed on a side surface of the convex portion (see Patent Document 2). However, in the use of the light control member, the conventional method is not sufficient in reducing the development residue and the resolution of the concavo-convex member. In particular, the development residue may cause the formation of a smooth light reflecting surface, which is an optical problem. Further improvement is desired from the viewpoint of characteristics.

Japanese Patent No. 4865088 Japanese Patent No. 5696264

  The present invention provides a method for producing a line pattern comprising a plurality of linear members having a substantially rectangular cross-sectional shape arranged in parallel to each other, and can reduce development residue and provide a method with excellent line pattern resolution. Is an issue.

  The present inventors have intensively studied to solve the above problems. As a result, the inventors have found that the above problems can be solved by the method described below, and have completed the present invention. That is, the present invention relates to the following [1] to [8], for example.

  [1] Light control comprising a plurality of linear members arranged in parallel to each other, and having a line pattern in which the cross-sectional shape of the linear member is substantially rectangular, and a light reflecting surface formed on a side surface of the linear member. A method for producing the line pattern in a member, comprising: (a) a step of forming a film using a radiation sensitive composition; (b) a step of irradiating the film with radiation in a line pattern; and (c) radiation. A method for producing a line pattern, comprising: a step of developing the film after irradiation to form a pattern; and (d) a step of applying an air flow to the pattern.

  [2] The method for producing a line pattern according to [1], further including a step of performing at least one treatment selected from heating and radiation irradiation on the pattern after step (e) (e).

  [3] The method for producing a line pattern according to [1] or [2], wherein the flow velocity of the airflow in the step (d) is 1 to 200 m / sec.

  [4] The line pattern according to any one of [1] to [3], wherein the radiation-sensitive composition contains an alkali-soluble polymer (A) and a radiation-sensitive compound (B). Production method.

  [5] (1) A step of forming a line pattern by the method described in any one of [1] to [4], and (2) a light reflecting surface on a side surface of the linear member constituting the line pattern. And a step of forming the light control member.

  [6] (3) The method for manufacturing a light control member according to [5], further including a step of forming a transparent member between the linear members.

  [7] Light control comprising a plurality of linear members arranged in parallel to each other, and having a line pattern in which the cross-sectional shape of the linear member is substantially rectangular, and a light reflecting surface formed on a side surface of the linear member An optical imaging member manufacturing method comprising: a member, wherein the light control member is manufactured by the method according to [5] or [6].

  [8] A plurality of linear members arranged in parallel to each other, and having a line pattern in which a cross-sectional shape of the linear member is substantially rectangular, and a light reflecting surface formed on a side surface of the linear member, An optical imaging member manufacturing method comprising one light control member and a second light control member, wherein at least one of the first light control member and the second light control member is the above-mentioned [5] or [6]. And then arranging the first light control member and the second light control member in a state where the line patterns of each of the first light control member and the second light control member intersect when viewed from above the light control member. A method for manufacturing an optical imaging member.

  According to the present invention, it is possible to reduce development residue and improve line pattern resolution in a method of manufacturing a line pattern including a plurality of linear members having a substantially rectangular cross-sectional shape arranged in parallel to each other. . By forming a light reflecting surface on the side surface of the linear member, it is possible to provide a light control member having a plurality of planar light reflecting portions (light reflecting surfaces) arranged in parallel to each other.

FIG. 1A is a perspective view of a member having a transparent substrate and a line pattern formed on the transparent substrate, FIG. 1B is a top view of the member, and FIG. 1C is the top view. It is AA sectional view. FIG. 2 is a cross-sectional view of an embodiment of a light control member. 3A is a perspective view of the optical imaging member, FIG. 3B is a cross-sectional view of the optical imaging member in the YZ plane for cutting the transparent member of the first light control member, and FIG. It is sectional drawing of the said optical imaging member in the XZ plane which cut | disconnects the transparent member of the light control member.

Hereinafter, modes for carrying out the present invention will be described.
[Line pattern manufacturing method]
The line pattern manufacturing method of the present invention includes a plurality of linear members arranged in parallel to each other, and a line pattern in which the cross-sectional shape of the linear member is substantially rectangular, and light formed on a side surface of the linear member. A method of manufacturing the line pattern in a light control member having a reflective surface, preferably a method of manufacturing the line pattern in an optical imaging member comprising the light control member,
(A) forming a film using the radiation-sensitive composition;
(B) irradiating the film with radiation in a line pattern;
(C) developing the film after irradiation to form a pattern;
(D) applying an air flow to the pattern.

  In the present invention, since the line pattern is formed by the photolithography method, a conventional display or a facility for manufacturing a semiconductor device can be used, and mass production of the light control member is easy.

  Hereinafter, the structure of the linear member, its cross section and side surfaces, and the structure of the line pattern will be described with reference to FIG. FIG. 1A is a perspective view of a member 1 having a transparent substrate 10 and a line pattern 20 made of a plurality of linear members 21 formed on the transparent substrate 10, and FIG. FIG. 1C is a cross-sectional view taken along line AA in the top view.

  The cross section of the linear member 21 is a cross section (YZ plane in FIG. 1A) perpendicular to the extending direction of the linear member 21 (X-axis direction in FIG. 1A). The cross-sectional shape of the linear member 21 is substantially rectangular. The side surface of the linear member 21 is a surface where the linear members 21 face each other, the side surface in the longitudinal direction in FIG. 1A, and the surface indicated by reference numeral 22 in FIGS. The plurality of linear members 21 are arranged so that their longitudinal directions are parallel to each other. The line pattern 20 has a plurality of linear members 21. The number of the linear members 21 is not particularly limited.

[Step (a)]
In the step (a), a film of the radiation sensitive composition is formed on a substrate, for example. For example, the radiation-sensitive composition is applied onto the substrate so that the dry film thickness is, for example, 50 μm or more, preferably 50 to 500 μm. Subsequently, in order to remove the solvent and the like, it is preferable to perform bre-baking. Pre-baking conditions are, for example, using a heating device such as an oven and a hot plate, the heating temperature is usually 80 to 150 ° C., preferably 90 to 140 ° C., and the heating time is usually 60 to 2000 seconds, preferably 600 to 1500 seconds. In this way, a film is formed on the substrate.

Details of the radiation-sensitive composition will be described later.
Although it does not specifically limit as a board | substrate, When using as a part of light control member, without removing a board | substrate, a transparent substrate is used. Examples of the transparent substrate include a glass substrate, a quartz substrate, and a transparent resin substrate. In the case of removing the substrate, for example, a ceramic substrate, a metal substrate such as aluminum or SUS can be used in addition to the transparent substrate. The thickness of a board | substrate is not specifically limited, For example, it is 200-1500 micrometers.

  Examples of the application method of the composition include a slit coating method, a dipping method, a spray method, a bar coating method, a roll coating method, a spin coating method, a curtain coating method, a gravure printing method, a silk screen method, and an inkjet method. .

[Step (b)]
In the step (b), the film is irradiated with radiation through a desired patterned mask. For example, the film is irradiated with radiation through a mask having parallel slits, and exposed portions and non-exposed portions are alternately formed. A mask having a slit width and a slit interval corresponding to the above-described line pattern shape is used.

For example, a contact aligner, a stepper, or a scanner is used as the exposure apparatus.
For radiation irradiation (hereinafter also referred to as “exposure”), for example, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams are used, preferably ultraviolet light and / or visible light is used, and more preferably, a wavelength of 300 to 300 is used. 450 nm light (eg, g-line (436 nm), h-line (405 nm), i-line (365 nm)) is used. The exposure amount varies depending on the type and content of each component in the composition and the film thickness, but when irradiating light containing i-line, the exposure amount is usually 500 to 4000 mJ / cm ^{2 in} terms of i-line. It is preferably 800 to 2000 mJ / cm ² . By setting it as such an aspect, the linear member which is excellent in patterning characteristics, such as high resolution, can be formed easily.

[Step (c)]
In step (c), a plurality of lines arranged in parallel to each other are developed by developing the film after irradiation and dissolving and removing the exposed portion in the positive type and the non-exposed portion in the negative type. And forming a desired line pattern in which the cross-sectional shape of the linear member is substantially rectangular.

  Examples of the development method include shower development, spray development, immersion development, paddle development, brush development, and ultrasonic development. The development conditions are, for example, a developer temperature of, for example, 20 to 50 ° C., preferably 20 to 30 ° C., and a development time of, for example, 30 to 600 seconds, preferably about 60 to 240 seconds.

  For development, an alkaline developer is preferably used. Examples of the alkaline developer include an alkaline aqueous solution containing an alkaline compound. The concentration of the alkaline compound in the alkaline aqueous solution is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass, from the viewpoint of adhesion of the developed pattern to the substrate. More preferably, it is 0.5-4.0 mass%.

Examples of the alkaline compound include at least one compound selected from a compound having a nitrogen atom, a compound having a sodium atom, and a compound having a potassium atom. Specifically, ammonia, tetramethylammonium hydroxide, Tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrahexylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide, choline, sodium hydroxide, sodium carbonate, sodium bicarbonate, hydroxide Examples include potassium, potassium carbonate, and potassium hydrogen carbonate. For example, a proper amount of a water-soluble organic solvent and a surfactant can be added to the alkaline aqueous solution.
In addition, after developing a film | membrane with an alkaline developing solution, you may wash | clean with water.

[Step (d)]
In step (d), an air stream is applied to the pattern obtained by development.
In the present invention, the airflow means a gas flow.
In the conventional method for producing a line pattern, when a pattern after development is heated, moisture present in the film after development can be removed by this heating. Therefore, there is no need to provide a step of applying an air current to the pattern. Not. However, the linear member included in the light control member may require a film thickness of 50 μm or more. In this case, when patterning is performed by development, unnecessary portions cannot be sufficiently removed and a residue (development residue) is likely to be generated. In addition, when an alkaline aqueous solution is used as the developer or when a washing process is performed, water traces (water unevenness) such as scales may remain on the surface of the linear member where water was present. Since these development residues and water unevenness can be a factor that hinders the formation of a smooth light reflecting surface when forming a light reflecting surface, which will be described later, the light control member may cause poor optical characteristics.

  In the present invention, since a step of applying an air flow to the pattern after development is provided, development residue and water unevenness are reduced, and therefore a line pattern having excellent patterning characteristics such as high resolution can be formed. Therefore, it is possible to obtain a light control member having a high reflection intensity, a high image binding property, and excellent brightness and image sharpness.

  Specific examples of the method of applying an airflow to the pattern include a method of blowing gas onto the pattern, such as a method of blowing air such as an air blow, an air knife, or ultrasonic air onto the pattern. Further, the method of applying an air current to the pattern includes a spin method in which an air current is relatively applied to the pattern by rotating the substrate having the developed pattern. In the present invention, the gas blowing method and the spinning method may be performed simultaneously.

  The step (d) is preferably a step capable of removing the development residue and moisture from the developed pattern by an air flow. A method of spraying a gas is preferable because a linear member in which development residue and water unevenness are further reduced uniformly over the entire surface can be obtained.

  For example, as a means for performing air blowing, any method can be used as long as it can provide an airflow to the surface of the pattern after development, such as a method of ejecting compressed gas from a nozzle or a method of blowing air with a propeller fan. it can.

Examples of the gas constituting the air stream include an inert gas such as nitrogen gas and a mixed gas such as air. From the viewpoint of simplicity of the manufacturing process and safety, it is preferable to use air.
The flow rate of the airflow is preferably 1 to 200 m / second, more preferably 1 to 100 m / second, and further preferably 5 to 100 m / second from the viewpoint of preventing pattern peeling from the substrate. The time for applying the airflow is preferably 3 to 600 seconds, more preferably 5 to 300 seconds, although it depends on the flow velocity. The temperature of the gas constituting the airflow is usually 10 to 70 ° C, preferably 15 to 50 ° C, more preferably 20 to 30 ° C.

  In the spinning method, the rotation speed of the substrate having a developed pattern is, for example, 100 to 5000 rpm, preferably 300 to 4000 rpm, more preferably 500 to 3000 rpm, although it depends on the size of the substrate.

[Step (e)]
If necessary, the pattern after step (d) is subjected to at least one treatment selected from heating (post-baking) and radiation irradiation, and the pattern is further cured, for example. Although heating conditions are not specifically limited, For example, it is 0.1 to 3 hours at 150-250 degreeC. In order to sufficiently advance the curing of the line pattern or to prevent deformation, it can be heated in multiple stages. For radiation irradiation, for example, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams are used, preferably ultraviolet light and / or visible light is used, and more preferably light having a wavelength of 300 to 450 nm is used. When irradiating light containing i-line, the exposure amount is usually 1000 to 5000 mJ / cm ² in terms of i-line. By performing such a process, cracks and peeling during film shrinkage can be suppressed.

As described above, a line pattern composed of a plurality of linear members can be obtained.
The height of the linear member is the thickness of the linear member in the Z-axis direction in FIG. 1A, and is usually 50 μm or more, preferably 50 to 500 μm. When the height of the linear member is 50 μm or more, a sufficiently high light reflecting surface can be secured, and therefore it is preferable in terms of optical characteristics.

  The width of the linear member at the position of 10% from the bottom surface with respect to the height of the linear member is the Bottom width, and the width of the linear member at the position of 90% from the bottom surface with respect to the height of the linear member is Top. When the width is defined, the absolute value of the difference between the Top width and the Bottom width (Top-Bottom) is defined as the Δ width of the linear member. The Δ width of the linear member is preferably 15% or less, more preferably 10% or less, and particularly preferably 5% or less of the larger value of the Top width and Bottom width. Since the Δ width is small, the linear member has a substantially rectangular cross-sectional shape, that is, a side surface substantially perpendicular to the flat plate surface of the light control member. For this reason, the light control member has a plurality of light reflecting surfaces parallel to each other.

  The width of the linear member is the thickness of the linear member in the Y-axis direction in FIG. 1A, and the Top width is usually 10 to 300 μm, preferably 15 to 250 μm; the spacing between the linear members (linear members The space width at the bottom is usually 50 to 400 μm, preferably 50 to 300 μm.

  The height, width, and space width of the linear member are measured by observation with a scanning electron microscope (SEM). Such a line pattern can be formed by performing exposure using a mask having a slit width and a slit interval corresponding to the width and the space width.

[Method for Manufacturing Light Control Member]
The manufacturing method of the light control member of the present invention includes:
(1) A step of forming a line pattern by the above-mentioned [Method for producing line pattern],
(2) forming a light reflecting surface on a side surface of the linear member constituting the line pattern;
If necessary,
(3) A step of forming a transparent member between the linear members.

[Step (1)]
In step (1), a line pattern is formed by the method described above.
[Step (2)]
In the step (2), a light reflecting surface is selectively formed on the side surface of the linear member by evaporating or sputtering metal, for example, on the side surface of the linear member. The light reflecting surfaces may be formed on one side surface or both side surfaces of each linear member, but are preferably formed on both side surfaces from the viewpoint of increasing the luminance.

Examples of the metal include at least one selected from aluminum, chromium, nickel, titanium, and silver.
For example, a metal film is formed by vapor-depositing metal on the surface of the linear member, a resist layer is formed on the side surface of the linear member, for example, by photolithography, the metal film is etched, and the resist layer is removed. . Thereby, a light reflection surface can be formed on the side surface of the linear member.

  Alternatively, the top surface of the linear member and the bottom surface of the space portion are covered with a resin that can be peeled off by light irradiation (in this case, the side surface of the linear member is exposed), and the top surface, side surface, and bottom surface of the space portion of the linear member A metal film is formed by vapor-depositing metal on the transparent substrate, and the resin formed on the top surface of the linear member and the bottom surface of the space portion is removed together with the metal film formed on the surface by irradiating ultraviolet rays from the transparent substrate side. To do. Thereby, a light reflection part can be formed in the side surface of a linear member.

[Step (3)]
In step (3), a linear member is obtained by filling a space portion of a line pattern with a photocurable and / or thermosetting transparent resin composition and curing the composition by light irradiation and / or heating. A transparent member is formed in the space (space part).

  Thereby, the difference in refractive index between the linear member and the space portion in the line pattern can be reduced, and the linear member can be prevented from falling, and thus the optical performance and strength of the light control member can be increased. When the surface of the linear member and the transparent member is uneven, the surface may be ground or polished. Thereby, the optical performance of the light control member can be enhanced.

  After forming the transparent member in the space portion, the substrate may be removed to obtain a light control member composed of a linear member, a light reflecting surface, and a transparent member. Subsequently, the surface of the light control member that has been in contact with the substrate may be ground or polished. Thereby, the optical performance of the light control member can be enhanced.

  As described above, a light control member can be obtained. The light control member includes a plurality of linear members arranged in parallel to each other, and includes a line pattern in which a cross-sectional shape of the linear member is substantially rectangular, and a light reflection surface formed on a side surface of the linear member. . For this reason, the light control member has a plurality of planar light reflecting portions (light reflecting surfaces) arranged in parallel with each other at regular intervals. One embodiment of the light control member has, for example, a flat plate shape, and has a plurality of the light reflection surfaces substantially perpendicular to the flat plate surface at regular intervals, and the light reflection surfaces are arranged in parallel to each other.

  FIG. 2 shows a cross-sectional view of one embodiment of the light control member. The light control member 100 includes a transparent substrate 10, a line pattern 20 made of a plurality of linear members 21 formed on the transparent substrate 10, and a transparent member 25 formed between the linear members 21. Light reflecting surfaces 30 and 30 are formed on both side surfaces 22 and 22 of the linear member 21.

[Method of manufacturing optical imaging member]
The optical imaging member of the present invention includes the light control member manufactured by the above-mentioned [Method for manufacturing light control member], and preferably includes a first light control member and a second light control member. The light control members are arranged so that the flat plate surfaces overlap. At least one of the first and second light control members is a light control member manufactured by the above-described [Method for manufacturing light control member].

  The method of manufacturing an optical imaging member of the present invention includes a step of manufacturing the light control member by the above-described [Method of manufacturing light control member], preferably at least one of the first and second light control members. One side is manufactured by the above [Method for manufacturing light control member], and the first and second light control members are crossed when the line pattern of each of them is viewed from above the light control member. Arranging.

  One of the first and second light control members may be manufactured or prepared by a conventionally known method, but both are preferably manufactured from the above [Method for manufacturing light control member] from the viewpoint of optical characteristics. .

  Here, the first light control member and the second light control member intersect when the line pattern of each light control member is viewed from above the light control member (when viewed in the XY plane in FIG. 3A). In this state, that is, in a state where the light reflecting surfaces formed on the side surfaces of the linear members of each light control member intersect.

  The first light control member and the second light control member are preferably stacked and arranged such that the line patterns that each has are opposed to each other. The first light control member and the second light control member are laminated using, for example, a transparent adhesive.

  The intersection angle between the line pattern of the first light control member and the line pattern of the second light control member is appropriately set depending on the position where the image is formed in the stereoscopic image display device, but these line patterns are orthogonal to each other. Preferably it is.

FIG. 3 shows an embodiment of the optical imaging member. FIG. 3A shows an optical imaging member in which a first light control member 101 and a second light control member 102 are stacked in a state where the line patterns of each are orthogonal to each other when viewed from above the light control member. 3B is a cross-sectional view of the first light control member 101 taken along the YZ plane, and FIG. 3C is a cross-sectional view of the second light control member 102 taken along the XZ plane. It is sectional drawing in a plane.
Although FIG. 3 shows the optical imaging member having the transparent substrate 10, the optical imaging member not having the transparent substrate 10 may be used.

[3D image display device]
The stereoscopic image display device includes the above-described optical imaging member, and includes, for example, a light emitting unit and an optical imaging member. The stereoscopic image display device can combine light radiated from a light emitting unit such as a liquid crystal display in the air, and can clearly display images such as still images and moving images, that is, functions as an aerial display.

  In the three-dimensional image display device, light from the light emitting unit is obliquely incident on a plurality of parallel light reflecting surfaces of the first light control member, and reflected light reflected by the light reflecting unit is second. An image can be displayed in the air by being incident on a plurality of light reflecting surfaces arranged in parallel in the light control member.

  In one embodiment of the stereoscopic image display device, the light reflecting surface of the first light control member and the light reflecting surface of the second light control member are arranged in a state of being orthogonal to each other. Therefore, the light incident obliquely on the optical imaging member is reflected on the light reflecting surface of the first light control member for the first time, and the reflected light is reflected on the light reflecting surface of the second light control member for the second time. Reflect. The second reflected light is emitted at the same angle as the incident angle of the incident light on the optical imaging member. For this reason, among the light incident on the optical imaging member from the light emitting portion, the reflected light continuously reflected by the light reflecting surface converges at a symmetrical position with respect to the light emitting portion with respect to the optical imaging member, An image is formed in the air.

[Radiation sensitive composition]
In the present invention, as the radiation-sensitive composition, either a positive composition or a negative composition can be used. However, from the viewpoint that the linear member can be easily prepared, the negative composition is used. It is preferable to use a product.

  The composition preferably contains an alkali-soluble polymer (A) and a radiation-sensitive compound (B) from the viewpoint of obtaining a linear member having a small change in properties over a long period of time. In addition to the above components, Furthermore, it is more preferable to contain a crosslinking agent (C).

[Alkali-soluble polymer (A)]
The alkali-soluble polymer (A) is used with respect to a developer used for developing a film formed from the above composition, particularly preferably an alkaline developer such as a 2.4% by mass tetramethylammonium hydroxide aqueous solution. A soluble or swellable polymer.

  The polymer (A) preferably has at least one functional group (hereinafter also referred to as “soluble group”) selected from a carboxyl group, a phenolic hydroxyl group and a silanol group from the viewpoint of alkali developability.

  Examples of the polymer (A) include (meth) acrylic resins, styrene resins, polyimides, polybenzoxazoles, polysiloxanes, polyolefins, resins having a cardo skeleton, and novolak resins. From the viewpoint of alkali solubility, (meth) acrylic resins, styrene resins, polyimides, polybenzoxazoles, polysiloxanes, polyolefins, resins having a cardo skeleton and novolak resins each having the above-mentioned soluble group are preferred.

Hereinafter, the following polymer (Aa) will be described as an example of the polymer (A).
The polymer (Aa) has a structural unit derived from an ethylenically unsaturated monomer (a1) having at least one functional group selected from a carboxyl group, a phenolic hydroxyl group, and a silanol group, and the (a1) And a structural unit derived from another ethylenically unsaturated monomer (a2) copolymerizable with the above (a1). That is, the polymer (Aa) is preferably a copolymer of the monomer (a1) and the monomer (a2). The polymer (Aa) may be, for example, a random copolymer or a block copolymer, but is a random copolymer in one embodiment.

  Examples of the compound having a carboxyl group in the monomer (a1) include unsaturated monocarboxylic acids such as (meth) acrylic acid; unsaturated dicarboxylic acids such as maleic acid or anhydrides thereof; monosuccinic acid [2- (Meth) acryloyloxyethyl], mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono [2- (meth) acryloyloxyethyl] phthalate; ω-carboxy Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as polycaprolactone mono (meth) acrylate. The ethylenically unsaturated monomer (a1) having a carboxyl group also includes an ethylenically unsaturated monomer having a carboxylic anhydride group. Among these, (meth) acrylic acid is preferable.

  Examples of the compound having a phenolic hydroxyl group in the monomer (a1) include vinyl monomers having a phenolic hydroxyl group such as o, m or p-hydroxystyrene, o, m or p-hydroxy-α-methylstyrene. It is done.

  Examples of the compound having a silanol group in the monomer (a1) include hydrolysates of alkoxysilyl group-containing vinyl monomers such as vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane, and vinylmethyldiethoxysilane. Can be mentioned.

A monomer (a1) may be used individually by 1 type, and may use 2 or more types together.
Examples of the monomer (a2) include aromatic ring-containing (meth) acrylates, aromatic vinyl compounds, N-substituted maleimide compounds, alkyl (meth) acrylates, alicyclic group-containing (meth) acrylates, and hydroxyalkyl (meth) ) Acrylate and halogen atom-containing (meth) acrylate, and at least one selected from these is preferable.

  Examples of the aromatic ring-containing (meth) acrylate include benzyl (meth) acrylate, phenyl (meth) acrylate, and 2-phenoxyethyl (meth) acrylate.

  Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o, m or p-vinyltoluene, o, m or p-methoxystyrene, o, m or p-vinylbenzylmethyl ether.

Examples of the N-substituted maleimide compound include N-phenylmaleimide, N-benzylmaleimide, and N-cyclohexylmaleimide.
Examples of the alkyl (meth) acrylate include alkyl (meth) acrylates having 1 to 12 carbon atoms in the alkyl group such as n-butyl (meth) acrylate.

Examples of the alicyclic group-containing (meth) acrylate include cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate; isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8. -Polycyclic group containing (meth) acrylates, such as yl (meth) acrylate, are mentioned.

  Examples of the hydroxyalkyl (meth) acrylate include hydroxyalkyl (meth) acrylates having 1 to 6 carbon atoms in the hydroxyalkyl group such as 2-hydroxyethyl (meth) acrylate.

Examples of the halogen atom-containing (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate.
A monomer (a2) may be used individually by 1 type, and may use 2 or more types together.

  Specific examples of the copolymer of the monomer (a1) and the monomer (a2) include, for example, JP-A-7-140654, JP-A-8-259876, JP-A-10-31308, It is disclosed in JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and International Publication No. 2015/133162. The copolymer which is mentioned.

  The polymer (Aa) is a structural unit derived from the monomer (a1), preferably more than 0% by mass and 50% by mass or less, more preferably 5 to 50% by mass, and still more preferably 10 to 35% by mass. The structural unit derived from the monomer (a2) is preferably 50% by mass or more and less than 100% by mass, more preferably 50 to 95% by mass, and still more preferably 65 to 90% by mass. By setting it as such an aspect, the composition excellent in alkali developability and storage stability can be obtained. Each structural unit amount can be measured by NMR.

  The polymer (A) can be produced by a known method. For example, JP 2003-222717 A, JP 2006-259680 A, International Publication No. 2007/029871, International Publication No. 2015/133162. Can be mentioned. In one embodiment, the polymer (Aa) is produced by radical polymerization using a polymerization initiator such as a thermal polymerization initiator or a photopolymerization initiator.

  The weight average molecular weight (Mw) in terms of polystyrene measured by the gel permeation chromatography (GPC) method of the polymer (A) is preferably 1,000 to 100,000, more preferably 3,000 to 50, 000. By setting it as such an aspect, a residual film rate, a pattern shape, resolution, and heat resistance can be improved further, and generation | occurrence | production of the dry foreign material at the time of application | coating can be suppressed at a high level.

A polymer (A) may be used individually by 1 type, and may use 2 or more types together.
In the radiation-sensitive composition, the content of the polymer (A) is usually 30% by mass or more, preferably 35% by mass or more, more preferably 40 to 80% by mass in 100% by mass of the solid content of the composition. More preferably, it is 40-65 mass%. A composition having a content of the polymer (A) in the above range is excellent in alkali developability and storage stability. In this specification, solid content is the sum total of each component remove | excluding the solvent from the said composition.

[Radiation sensitive compound (B)]
Examples of the radiation sensitive compound (B) include a photoacid generator and a photopolymerization initiator. A radiation sensitive composition can exhibit a radiation sensitive characteristic by having a compound (B), and can have favorable radiation sensitivity.

A compound (B) may be used individually by 1 type, and may use 2 or more types together.
The content of the compound (B) in the radiation-sensitive composition is usually 15% by mass or less, preferably 0.1 to 10% by mass, and more preferably 0.1% by mass in the solid content of 100% by mass of the composition. 1 to 5% by mass. By making content of a compound (B) into the said range, the difference of the solubility of the irradiated part with respect to a developing solution and the unirradiated part can be enlarged, and patterning performance can be improved.

《Photoacid generator》
The photoacid generator is a compound that generates an acid by a treatment including irradiation of radiation.
Examples of the photoacid generator include quinonediazide compounds, oxime sulfonate compounds, onium salts, N-sulfonyloxyimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonate ester compounds, and carboxylic acid ester compounds. For example, by using these compounds, a positive composition can be obtained. Among these, a quinonediazide compound is preferable.

  The quinonediazide compound generates carboxylic acid by processing including irradiation with radiation and development using an alkaline aqueous solution. Examples of the quinonediazide compound include a condensate of a phenolic compound or an alcoholic compound and 1,2-naphthoquinonediazidesulfonic acid halide.

<< Photopolymerization initiator >>
As the photopolymerization initiator, for example, acyl phosphine oxide initiator, oxime ester initiator, alkylphenone initiator, acetophenone initiator, benzophenone initiator, benzoin initiator, biimidazole initiator, Examples include triazine-based initiators and thioxanthone-based initiators. For example, a negative composition can be obtained by using these photopolymerization initiators and using an ethylenically unsaturated group-containing compound described later as the crosslinking agent (C). Of these, acylphosphine oxide initiators are preferred.

  Examples of the acylphosphine oxide initiator include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine. Examples thereof include oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

[Crosslinking agent (C)]
The crosslinking agent (C) is a compound having a crosslinkable functional group. As a crosslinking agent (C), the compound which has a 2 or more crosslinkable functional group in 1 molecule is mentioned, for example. When a crosslinking agent (C) is used, the heat resistance of a linear member can be improved.

  Examples of crosslinkable functional groups include ethylenically unsaturated groups, epoxy groups, oxetanyl groups, alkoxyalkyl groups, benzyloxymethyl groups, acetoxymethyl groups, benzoyloxymethyl groups, formyl groups, acetyl groups, dialkylaminomethyl groups. , Dimethylolaminomethyl group, diethylolaminomethyl group, morpholinomethyl group.

As the crosslinking agent (C), for example, an ethylenically unsaturated group-containing compound, an epoxy compound, an oxetane compound, and an alkoxyalkyl group-containing compound are preferable.
Examples of the ethylenically unsaturated group-containing compound include compounds having at least two ethylenically unsaturated groups in the molecule, and preferably a compound having at least two (meth) acryloyl groups (polyfunctional (meth) acrylate). Can be mentioned.

  Examples of the polyfunctional (meth) acrylate include trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth). ) Acrylate, tricyclodecane dimethanol di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide-added dipentaerythritol hexa (meth) acrylate, propylene oxide De adduct of dipentaerythritol hexa (meth) acrylate.

  Examples of the epoxy compound include polyglycidyl ether of bisphenol, polyglycidyl ether of polyhydric alcohol, aliphatic polyglycidyl ether of polyether polyol, and 3,4-epoxycyclohexyl group-containing compound.

  Examples of the oxetane compound include 4,4-bis [(3-ethyl-3-oxetanyl) methyl] biphenyl, 3,7-bis (3-oxetanyl) -5-oxanonane, 3,3 ′-[1,3 -(2-Methylenyl) propanediylbis (oxymethylene)] bis (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene.

  The alkoxyalkyl group-containing compound is not particularly limited as long as it contains an alkoxyalkyl group in the molecule. For example, an alkoxyalkyl group-containing melamine compound, an alkoxyalkyl group-containing benzoguanamine compound, an alkoxyalkyl group-containing urea compound, Examples include alkoxyalkyl group-containing phenol compounds.

A crosslinking agent (C) may be used individually by 1 type, and may use 2 or more types together.
In a radiation sensitive composition, content of a crosslinking agent (C) is 50-240 mass parts normally with respect to 100 mass parts of polymers (A), Preferably it is 55-200 mass parts, More preferably, it is 60-. 150 parts by mass. By setting it as such an aspect, the developability and sclerosis | hardenability of the said composition can be made favorable.

[Additive]
The radiation-sensitive composition can contain various additives such as adhesion assistants and surfactants as necessary. Examples of the adhesion assistant include a silane coupling agent, and specific examples thereof include the adhesion assistant described in JP-A No. 2012-256023. Examples of the surfactant include a fluorine-based surfactant and a silicone-based surfactant, and specific examples include the surfactants described in JP-A-2014-048428. Examples of other additives include the additives described in JP 2006-154434 A and JP 2007-293306 A.

  In the radiation-sensitive composition, the content of the adhesion assistant is preferably 1 to 10 parts by mass, more preferably 1 to 7 parts by mass with respect to 100 parts by mass of the alkali-soluble polymer (A); The content of the agent is preferably 0.1 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the alkali-soluble polymer (A). By setting it as such an aspect, the alkali developability of the said composition can be made favorable and the variation in the height of a linear member can be suppressed.

[solvent]
The radiation-sensitive composition may be prepared as a liquid composition by blending a solvent such as an organic solvent as necessary. The organic solvent can be appropriately selected and used as long as it dissolves or disperses the above components constituting the composition and does not react with these components and has appropriate volatility.

  Examples of the organic solvent include (poly) alkylene glycol monoalkyl ether, (poly) alkylene glycol monoalkyl ether acetate, (poly) alkylene glycol dialkyl ether, (poly) alkylene glycol diacetate, (cyclo) alkyl alcohol solvent, and lactic acid. Examples include alkyl ester solvents, formic acid alkyl ester solvents, fatty acid alkyl ester solvents, alkoxycarboxylic acid ester solvents, ketone solvents, amide solvents, lactam solvents, cyclic ether solvents, and keto alcohol solvents.

  Examples of the organic solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol from the viewpoint of solubility or dispersibility of each component and applicability of the composition. Monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, and ethyl lactate are preferred.

An organic solvent may be used individually by 1 type, and may use 2 or more types together.
In the radiation-sensitive composition, the content of the organic solvent is an amount such that the solid content concentration of the composition is usually 40 to 90% by mass, preferably 50 to 75% by mass. By setting it as such an aspect, the composition with favorable solubility or dispersibility of each component, applicability | paintability, and storage stability can be obtained.

[Production of radiation-sensitive composition]
A radiation sensitive composition can be manufactured by mixing each component using the well-known apparatus used for the process of a resin composition as needed. In addition, for the purpose of removing impurities, the obtained mixture can be appropriately filtered.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In the following description, “part” is used to mean “part by mass” unless otherwise specified.

[GPC analysis]
The weight average molecular weight (Mw) of the alkali-soluble polymer (A) was measured in terms of polystyrene using a gel permeation chromatography (GPC) method.
-Standard material: Polystyrene-Equipment: Tosoh Corporation, trade name: HLC-8020
Column: Tosoh Co., Ltd. guard column H _XL- H, TSK gel G7000H _XL , TSK gel GMH _XL , TSK gel G2000H _XL sequentially connected Solvent: Tetrahydrofuran Sample concentration: 0.7% by mass
・ Injection volume: 70 μL
・ Flow rate: 1mL / min

[Synthesis Example 1] Synthesis of Polymer (A1) According to [Synthesis Example 1] of International Publication No. 2015/133162, propylene glycol monomethyl ether acetate (PGMEA) was used as a solvent, 13 parts of methacrylic acid, benzyl methacrylate From 46 parts, 13 parts of styrene, 16 parts of N-phenylmaleimide, 2 parts of n-butyl methacrylate and 10 parts of 2-hydroxyethyl methacrylate, a PGMEA solution containing a polymer (A1) having a solid content concentration of 45% by mass was obtained. Mw of the obtained polymer (A1) was 12,000.

[Use ingredients]
Each component used for preparation of a radiation sensitive composition is shown below.
B1: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name “Irgacure 819”, manufactured by BASF)
C1: Dipentaerythritol hexaacrylate D1: Methacryloxypropyltrimethoxysilane (trade name “XIAMETER OFS-6030 SILANE”,
(Toray Dow Corning Co., Ltd.)
E1: Fluorosurfactant (trade name “FTX-218”, manufactured by Neos Co., Ltd.)

[Preparation Example 1] Preparation of radiation-sensitive composition 100 parts of PGMEA solution of polymer (A1) obtained in Synthesis Example 1 in terms of polymer (A1), 5 parts of (B1), and (C1) 100 Part, (D1) 5 parts, (E1) 1 part, and PGMEA were mixed, and the radiation sensitive composition 1 with a solid content concentration of 60 mass% was obtained.

[Examples and Comparative Examples]
Using the radiation-sensitive composition obtained in the above preparation example, a line pattern composed of a plurality of linear members was produced by the method described below. The radiation sensitive composition is applied to a glass wafer with a slit coater for high viscosity, heat treated (prebaked) at 120 ° C. for 20 minutes on a hot plate, and the height (the length in the direction corresponding to the Z-axis direction in FIG. 1A). A) A 240 μm film was formed. Table 1 in terms of i-line, using an exposure machine (“MPA-600FA” (ghi line mixture) manufactured by Canon Inc.) through a patterned mask of line / space width = 100 μm / 100 μm on the film. Irradiation was performed at the exposure amount described in 1. The exposed film was developed with an aqueous solution containing tetramethylammonium hydroxide (TMAH) at the concentration shown in Table 1 at 23 ° C. and with the development time shown in Table 1, and then washed with water. It was. Thereafter, air blowing was performed at a flow rate shown in Table 1 for 20 seconds to remove development residues and moisture. However, in Comparative Example 1, no air blow was performed. Then, after using an exposure machine (“MPA-600FA” manufactured by Canon Inc. (mixed with ghi line)), it was irradiated at an exposure amount of ² J / cm ^{2 in} terms of i-line, and then at 180 ° C. on a hot plate at 30 ° C. A heat treatment (post-bake) was performed for a minute to obtain a cured film having a line pattern of height: about 200 μm, width: about 100 μm, and space width: about 100 μm.

[Evaluation]
The linear members obtained in Examples and Comparative Examples were evaluated by the following methods.

[Resolution]
The width of the linear member at the position of 10% from the glass wafer surface with respect to the height of the linear member is the bottom width, and the width of the linear member at the position of 90% from the glass wafer surface with respect to the height of the linear member. Is defined as the Top width. The cross-sectional shape of the obtained linear member was observed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model “S-4200”), and the Top width and Bottom width were measured. The absolute value of the difference between the Top width and the Bottom width / the value of the larger of the Top width and the Bottom width × 100% is 15% or less as “AA”, and when it exceeds 15%, it is “BB”.

[Pattern adhesion]
Using a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model “SU4200”), the obtained line pattern was observed, and the case where the line pattern was peeled in the range of 5 to 10% of the entire surface was “ It was judged as “slightly peeled”, and the case of peeling in the range of less than 5% or the case of not peeling was judged as “no”.

[Development residue and water unevenness]
Using the scanning electron microscope (Hitachi High Technology Co., Ltd .: SU3500), the surface of the obtained linear member was visually confirmed at any 10 points. “No” when there was no development residue or water unevenness, “Slightly present” when 1 to 3 (1 to 3 locations), and “Yes” when 3 (3 locations) were exceeded. .

DESCRIPTION OF SYMBOLS 1 ... Member 10 ... Transparent substrate 20 ... Line pattern 21 ... Linear member 22 ... Side surface 25 of a linear member ... Transparent member 30 ... Light reflection surface 100 ... Light control member 101 ... Light control member 102 ... Light control member 200 ... Optical Imaging member

Claims (8)

The light control member comprising a plurality of linear members arranged in parallel to each other, and having a line pattern in which a cross-sectional shape of the linear member is substantially rectangular, and a light reflecting surface formed on a side surface of the linear member. A method of manufacturing a line pattern,
(A) forming a film using the radiation-sensitive composition;
(B) irradiating the film with radiation in a line pattern;
(C) developing the film after irradiation to form a pattern;
(D) A method of producing a line pattern, comprising: applying an air flow to the pattern. (E) The method for producing a line pattern according to claim 1, further comprising a step of performing at least one treatment selected from heating and radiation irradiation on the pattern after step (d).   The manufacturing method of the line pattern of Claim 1 or 2 whose flow velocity of the airflow in a process (d) is 1-200 m / sec. The radiation sensitive composition is
An alkali-soluble polymer (A);
The manufacturing method of the line pattern of any one of Claims 1-3 containing a radiation sensitive compound (B). (1) A step of forming a line pattern by the method according to any one of claims 1 to 4,
(2) A method of manufacturing a light control member, comprising: forming a light reflection surface on a side surface of a linear member constituting the line pattern. (3) The method for producing a light control member according to claim 5, further comprising a step of forming a transparent member between the linear members. A light control member comprising a plurality of linear members arranged in parallel to each other and having a line pattern in which the cross-sectional shape of the linear member is substantially rectangular and a light reflecting surface formed on a side surface of the linear member is provided. A method for producing an optical imaging member,
A method for manufacturing an optical imaging member, wherein the light control member is manufactured by the method according to claim 5. First light comprising a plurality of linear members arranged in parallel to each other, and having a line pattern in which a cross-sectional shape of the linear member is substantially rectangular, and a light reflecting surface formed on a side surface of the linear member. A method for producing an optical imaging member comprising a control member and a second light control member,
At least one of the first light control member and the second light control member is manufactured by the method according to claim 5 or 6,
A method of manufacturing an optical imaging member, wherein the first light control member and the second light control member are arranged in a state where the line patterns of the first light control member and the second light control member intersect each other when viewed from above the light control member.

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