JP2011128590A - Method for manufacturing transparent pixel, transparent pixel, color filter, and photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition with which a coating film is formed in such a manner that a signal of an alignment mark is not disturbed and a transparent pixel having high transparency as transparent pixel is formed, in a radiation sensitive composition for forming a transparent pixel used in a method of manufacturing a color filter in which a transparent pixel is previously formed, to provide a method of manufacturing the transparent pixel using the photosensitive composition, and to provide the transparent pixel obtained by the method of manufacturing the transparent pixel, and a color filter having the transparent pixel. <P>SOLUTION: The method of manufacturing the transparent pixel includes a step of applying a photosensitive composition containing an alkali-soluble resin (A), a polyfunctional monomer (B) and a photoinitiator (C), wherein the component (B) is contained in an amount of 60-150 pts.wt based on 100 pts.mass of the component (A), onto a substrate, and then an exposure/development process. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a transparent pixel manufacturing method, a transparent pixel, a color filter, and a photosensitive composition. More specifically, it is suitable for manufacturing a color filter used for a transmissive liquid crystal display element, a transflective liquid crystal display element, a reflective liquid crystal display element (LCOS or the like), or a solid-state imaging element (CCD or CMOS). The present invention relates to a transparent pixel manufacturing method, a transparent pixel, a color filter having the transparent pixel, and a photosensitive composition used for a transparent pixel manufacturing method.

In displays such as projectors and rear professional televisions, a reflective liquid crystal display element (Liquid Crystal on Silicon, also referred to as “LCOS” for short) in which a liquid crystal layer is sandwiched between a mirror-like silicon chip and the glass on the surface is used. Yes. LCOS is used as a high-luminance display because a circuit for driving pixels can be arranged on the back side of a silicon chip.
By the way, in the color filter used for LCOS, since light passes through the color filter twice, the luminance tends to decrease. Therefore, in the LCOS, a transparent pixel (also referred to as a white subpixel or a white pixel) is usually used.
As a method for creating a transparent pixel, usually, other pixels (for example, a red pixel, a green pixel, and a blue pixel in the case of an RGB color filter) are first formed with a photosensitive composition for forming a colored layer. After that, it has been made in the form of embedding a photosensitive composition for forming a transparent layer for forming a transparent pixel together with a planarizing film (for example, Patent Documents 1 to 5).
However, in particular, in the LCOS color filter, since the size of each pixel is fine, in the photosensitive composition for forming a colored layer containing a large amount of pigment, incident light that has passed through the mask is reflected on the silicon substrate. There is a photosensitive composition for forming a colored layer in which rectangular pixels cannot be formed by reflected light. Further, since the pixel to be formed first is exposed to the developer more often than the pixel to be formed thereafter, resistance to the developer is required. In particular, when the size of each pixel becomes fine, resistance to a developing solution is required more than ever, but since the coloring layer forming photosensitive composition usually contains a coloring agent, the coloring agent Some types have low resistance to the developer. For this reason, after forming the rectangular pixel containing a transparent pixel previously, it is thought that the photosensitive composition for colored layer formation which cannot form a rectangular pixel is embedded later and formed.

JP 2007-264378 A JP 2006-309125 A JP 2006-077098 A JP 2003-002924 A JP 2001-166128 A

  By the way, when forming a pixel with a photosensitive composition in a form that inhibits the signal of the alignment mark, the pixel cannot be formed at an accurate position. The coating film in such a way as to inhibit the signal is formed so as to eliminate the step related to the alignment mark formed on the silicon substrate. Since these are compositions having flatness, when these compositions are used, a coating film is formed in such a way as to inhibit the alignment mark signal.

  The present invention has been made in view of the above-described problems of the prior art, and the object of the present invention is to form transparent pixels used in a method of manufacturing a color filter that forms transparent pixels first. A photosensitive composition that can form a coating film in a form that does not inhibit the signal of the alignment mark, and can form a transparent pixel with high transparency as a transparent pixel such as LCOS, It is providing the transparent pixel obtained by the manufacturing method of the transparent pixel using a property composition, the manufacturing method of the said transparent pixel, and the color filter which has the said transparent pixel.

The present invention is as follows.
[1] An alkali-soluble resin (A), a polyfunctional monomer (B), and a photopolymerization initiator (C), and (B) with respect to 100 parts by mass of the component (A) The manufacturing method of the transparent pixel used for the color filter which has the process of apply | coating the photosensitive composition containing 60-150 weight part of components on a board | substrate, exposing and developing sequentially.
[2] The method for producing a transparent pixel according to [1], wherein the polyfunctional monomer (B) is a compound having four or more (meth) acrylate groups.
[3] A transparent pixel obtained by the method for producing a transparent pixel according to [1] or [2].
[4] A color filter including the four pixels of the transparent pixel, the red pixel, the green pixel, and the blue pixel according to [3].
[5] An alkali-soluble resin (A), a polyfunctional monomer (B) and (C) a photoradical generator, and the component (B) with respect to 100 parts by mass of the component (A) The photosensitive composition used for the manufacturing method of the transparent pixel as described in said [1] which contains 60-150 weight part.
[6] The photosensitive composition according to [5], wherein the polyfunctional monomer (B) is a compound having four or more (meth) acrylate groups.

According to the method for producing a transparent pixel of the present invention, a coating film can be formed in a form that does not inhibit the signal of the alignment mark, and a transparent pixel with high transparency can be formed as a transparent pixel such as LCOS.
In addition, when the polyfunctional monomer (B) contained in the photosensitive composition is a compound having four or more (meth) acrylate groups, a coating film is formed in a form that does not inhibit the signal of the alignment mark. it can.
And the transparent pixel obtained by the manufacturing method of the said transparent pixel does not inhibit the signal of an alignment mark, Therefore A pixel can be formed more correctly.
In addition, a color filter composed of the transparent pixel and the four pixels of the red pixel, the green pixel, and the blue pixel can be suitably used particularly as a color filter for LCOS.
Moreover, according to the photosensitive composition used for the manufacturing method of the transparent pixel of this invention, since a coating film can be formed in the form which does not inhibit the signal of an alignment mark, it is possible to form a pixel correctly.
Furthermore, when the polyfunctional monomer (B) contained in the photosensitive composition is a compound having four or more (meth) acrylate groups, a coating film is formed in a form that does not inhibit the signal of the alignment mark. Therefore, it is possible to form pixels more accurately.

It is the figure which showed the evaluation criteria of the level | step difference coverage of an alignment mark. It is the figure which showed the evaluation criteria of the shape of a pattern.

  Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, and based on ordinary knowledge of those skilled in the art without departing from the spirit of the present invention. It should be understood that modifications, improvements, and the like appropriately added to the embodiments described above fall within the scope of the present invention.

I. Method for Producing Transparent Pixel The method for producing a transparent pixel of the present invention comprises an alkali-soluble resin (A), a polyfunctional monomer (B), and (C) a photo radical generator, and the component (A) A photosensitive composition containing 60 to 150 parts by weight of the component (B) with respect to 100 parts by mass (hereinafter, also simply referred to as “photosensitive composition”) is sequentially applied on a substrate, exposed and developed. Process.

First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition the pixel forming portion, and after applying a photosensitive composition on this substrate, pre-baking is performed to evaporate the solvent. To form a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby the transparent pixel pattern has a predetermined arrangement. The transparent pixels arranged at are formed.
The photosensitive composition used in the method for producing a transparent pixel of the present invention will be described in detail in the following “IV. Photosensitive composition”.

Substrates used for forming pixels include soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, and image sensors. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, a complementary metal oxide semiconductor (CMOS), and a planarization film made of an organic compound. In particular, when a transparent pixel to be used for LCOS is created, a mirror-reflective substrate such as a silicon substrate is naturally used.
In addition, these substrates may be appropriately treated by chemical treatment with a silane coupling agent or silazanes (for example, hexamethyldisilazane), plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. An undercoat layer can also be applied for pretreatment or planarization of the substrate surface.

In addition, as described in “III. Color filter” described later, on these substrates, before and after forming transparent pixels, other pixels (for example, red pixels and green pixels in the case of RGB color filters). Or a blue pixel), and therefore an alignment mark is provided on the substrate in order to determine the position with other pixels.
An alignment mark is a mark used for positioning, and has a shape including a step. In this method, the step of the alignment mark is detected with an optical element or the like, and the location is specified by superimposing the detected signal with the strength of the S / N ratio.
When applying the photosensitive composition to the substrate, an appropriate application method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method or the like should be adopted. However, in particular, spin coating is preferred when coating on a silicon substrate.

The coating film thickness is usually 0.3 to 2 μm as the film thickness after drying.
As exposure light used when forming a pixel, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, and the like can be used, but exposure light having a wavelength in the range of 190 to 450 nm is used. preferable. Examples of the exposure method include a contact exposure method, a reflective projection exposure method, a reduced projection exposure method, and the like. When forming fine pixels, a reduced projection exposure method is used.
The exposure amount of exposure light is generally 10 to 1,000 mJ / cm ² .

Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

II. Transparent Pixel The transparent pixel of the present invention is obtained by the above-mentioned “I. Method for manufacturing transparent pixel”. The light transmittance of the transparent pixel is particularly preferably higher for light with a wavelength of 400 to 800 nm (approximately 100% T). The size of the transparent pixel of the present invention is usually 0.3 to 2 μm in thickness, 0.1 to 10 μm in length, and 0.1 to 10 μm in width.

III. Color Filter The color filter of the present invention includes the transparent pixel of the present invention and other pixels (also referred to as “colored pixels”. For example, in the case of an RGB color filter, a red pixel, a green pixel, or a blue pixel). It is to be prepared.
In the color filter of the present invention, the transparent pixel is not formed last, for example, in the formation of a color filter including the above-described transparent pixel, red pixel, green pixel, and blue pixel, There are the following forming methods (1) to (3).
(1) First, a transparent pixel is formed, and then a red pixel, a green pixel, and a blue pixel are formed in random order.
(2) First, after forming any one of a red pixel, a green pixel, and a blue pixel, a transparent pixel is formed, and then pixels other than the previously formed colored pixels are formed in any order.
(3) First, after forming any two of red pixels, green pixels, and blue pixels in random order, forming transparent pixels, and then forming pixels other than the previously formed colored pixels.

Hereinafter, a method for forming a color filter by the above-described method (1) will be described.
First, transparent pixels are formed on a substrate. With respect to the method for forming the transparent pixel, the transparent pixel is formed according to the method described in “I. Method for manufacturing transparent pixel” described above.
Next, one of a red pixel, a green pixel, and a blue pixel is formed. Usually, among these pixels, the resistance to the developing solution is the weakest. In particular, among these pixels, a rectangular pixel is formed. The difficult pixel is formed last.

  For example, when the red pixel is formed last, a liquid composition of each photosensitive composition for forming a colored layer in which a green or blue pigment is dispersed on a substrate on which a transparent pixel is formed is used. Instead of using the photosensitive composition for forming each colored layer, the coating, pre-baking, exposure, development and post-treatment of each liquid composition were performed in the same manner as in “I. Method for producing transparent pixel” described above. Baking is performed to sequentially form green and blue pixels on the same substrate.

Thereafter, a liquid composition of a photosensitive composition in which a red pigment is dispersed is applied, pre-baked, exposed, developed, and post-baked on the substrate having transparent pixels, green pixels, and blue pixels, and red. Pixels are formed.
Alternatively, a liquid composition of a photosensitive composition in which a red pigment is dispersed is applied to the substrate having transparent pixels, green pixels, and blue pixels in a form of embedding, and post baking is performed to form red pixels. To do.
In this way, a color filter including transparent pixels, red pixels, green pixels, and blue pixels can be obtained.

IV. Photosensitive Composition The photosensitive composition of the present invention contains an alkali-soluble resin (A), a polyfunctional monomer (B), and (C) a photoradical generator, and 100 parts by mass of the component (A). 60-150 weight part of said (B) component is contained with respect to a part. In particular, since the photosensitive composition of the present invention has the above components, it is excellent in transparency and can form a rectangular pixel. Since it is excellent, even if it is a coating method that applies a large load to the coating film, such as a spin coating method, it is excellent in step following ability.

(A) Alkali-soluble resin (A) Alkali-soluble resin used by this invention is a component which is soluble with respect to the alkali developing solution used in the image development process at the time of forming a transparent layer. Among them, an ethylenically unsaturated monomer having a structure represented by the following formula (1) or (2) (hereinafter referred to as “unsaturated compounds (a1) and (a2)”) and other copolymers, respectively. A copolymer with a possible ethylenically unsaturated monomer (hereinafter referred to as “copolymer (A1)”) is preferred.

（式（１）中、Ｒ^１は炭素数１〜１２のアルキル基または炭素数６〜１２のアリール基である。）

(In formula (1), R ¹ is an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms.)

（式（２）中、Ｒ^２〜Ｒ^７はそれぞれ独立に、水素原子、ハロゲン原子、水酸基、ヒドロキシメチル基またはカルボキシル基である。）

(In formula (2), R ^{2 to} R ⁷ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a hydroxymethyl group, or a carboxyl group.)

  Examples of the unsaturated compound (a1) include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N -N-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like can be mentioned. Of these unsaturated compounds (a1), N-cyclohexylmaleimide and N-phenylmaleimide are preferable, and N-phenylmaleimide is particularly preferable. In the copolymer (A1), the unsaturated compound (a1) can be used alone or in admixture of two or more.

  Examples of the unsaturated compound (a2) include acenaphthylene, 5-chloroacenaphthylene, 5-hydroxymethylacenaphthylene, 5-hydroxyacenaphthylene and the like. Of these unsaturated compounds (a2), acenaphthylene and 5-chloroacenaphthylene are preferable, and acenaphthylene is particularly preferable. In the copolymer (A1), the unsaturated compound (a2) can be used alone or in admixture of two or more.

  The copolymer component of the copolymer (A1) includes a polymerizable unsaturated compound having at least one acidic functional group such as a carboxyl group and a phenolic hydroxyl group in the molecule (hereinafter referred to as “unsaturated compound”). (A3) ") and other polymerizable unsaturated compounds (hereinafter referred to as" unsaturated compounds (a4) ").

As the unsaturated compound (a3), for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are trade names of light ester HOA-MS and light ester HOA-MPE (above, manufactured by Kyoeisha Chemical Co., Ltd.), respectively. Is commercially available.

Moreover, as unsaturated compound (a3) other than the above, for example, o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o -Unsaturated phenols such as isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol;
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols.

Of these unsaturated compounds (a3), (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol and the like are preferable. In particular, (meth) acrylic acid is preferred.
In the copolymer (A1), the unsaturated compound (a3) can be used alone or in admixture of two or more.

Examples of the unsaturated compound (a4) include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, Aromatics such as p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether Vinyl compounds;
Indenes such as indene and 1-methylindene;

  Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) Acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (Meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturated carboxylic esters such as (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
In the copolymer (A1), the unsaturated compound (a4) can be used alone or in admixture of two or more.

In the present invention, as a preferable copolymer (A1), more specifically, for example,
(I) unsaturated compounds (b1) and (b2), (ii) (meth) acrylic acid comprising at least one selected from the group consisting of N-phenylmaleimide, N-cyclohexylmaleimide, acenaphthylene, and 5-chloroacenaphthylene , Succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate at least one unsaturated compound (b3), and (iii) styrene, methyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer of Unsaturated compounds comprising at least one selected from (b4) can be mentioned copolymers,

As a particularly preferred copolymer (A1), for example,
(I) At least one of N-phenylmaleimide and acenaphthylene, (ii) (meth) acrylic acid, and (iii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) Other unsaturated compounds (a4) comprising at least one selected from the group consisting of acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer Can be mentioned.

In the copolymer (A1), the copolymerization ratio of the unsaturated compound (a1) or (a2) is preferably 1 to 70% by weight, particularly preferably 1 to 40% by weight, and the unsaturated compound (a3) The copolymerization ratio is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and the copolymerization ratio of the unsaturated compound (a4) is preferably 1 to 90% by weight, particularly preferably 5 to 70%. % By weight.
In this invention, the photosensitive composition which shows the outstanding developability can be obtained by making the copolymerization ratio of each unsaturated compound in a copolymer (A1) into the said range.

  Copolymer (A1) and other carboxyl group-containing alkali-soluble resins are, for example, unsaturated compound (a1) or (a2), unsaturated compound (a3) and unsaturated compound (a4) in a suitable solvent. Radicals such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) It can manufacture by superposing | polymerizing in presence of a polymerization initiator.

  The copolymer (A1) can be purified through a reprecipitation method using two or more organic solvents having different polarities after radical polymerization of the polymerizable unsaturated compound as described above.

  Further, the copolymer (A1) contains the above radical polymerization initiator, pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, tetraethylthiuram disulfide, bis (pyrazole-1 -Ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (5-methyl-pyrazol-1-y Molecular weights that act as iniferters such as ruthiocarbonyl) disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide The presence of a control agent, in an inert solvent, the reaction temperature, usually, 0 to 150 ° C., preferably as a 50 to 120 ° C., can also be produced by living radical polymerization.

  In the present invention, for example, an unsaturated isocyanate such as 2- (meth) acryloyloxyethyl isocyanate is added to a copolymer (A1) obtained by copolymerizing an unsaturated compound having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate. A polymerizable unsaturated bond can be introduced into the side chain of the copolymer (A1) by reacting the narate compound.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (A1) in the present invention is usually 1,000 to 45,000. 000, preferably 3,000 to 20,000.
In addition, the number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (A1) in the present invention is usually 1,000 to. 45,000, preferably 3,000 to 20,000.
In this case, if the Mw is less than 1,000, the remaining film ratio of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. If it exceeds 000, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

  In this invention, a copolymer (A1) can be used individually or in mixture of 2 or more types.

(B) Polyfunctional monomer The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
Examples of the polyfunctional monomer include di (meth) acrylates of alkylene glycol such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like, and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
Examples thereof include tris [2- (meth) acryloyloxyethyl] phosphate and isocyanuric acid ethylene oxide-modified triacrylate.

Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having a valence of 4 or more and their dicarboxylic acid-modified products, specifically pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are preferred. It is preferable in that a coating film with improved resistance can be formed and a pixel excellent in resistance to a developer can be obtained.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 60-150 weight part with respect to 100 weight part of (A) alkali-soluble resin, Preferably it is 80-130 weight part. When the amount used is 60 to 150 parts by weight, the step following property of the coating film to the alignment mark is improved, and in particular, the step following property to the convex alignment mark is improved, so that the alignment signal is not hindered. A coating film can be formed.

In the present invention, a polyfunctional monomer and a monofunctional monomer having one polymerizable unsaturated bond can be used in combination.
Examples of the monofunctional monomer include (A) compounds similar to the carboxyl group-containing unsaturated monomers and copolymerizable unsaturated monomers exemplified for the alkali-soluble resin, and N- (meth). In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, examples of commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer.

(C) Photopolymerization initiator The photopolymerization initiator in the present invention can be obtained by exposing the (B) polyfunctional monomer by exposure to exposure light such as visible light, ultraviolet light (i-line, etc.), far ultraviolet light, electron beam, X-ray or the like. A compound that generates an active species capable of initiating polymerization of a monomer and optionally a monofunctional monomer.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferred.

  In this invention, the general usage-amount of a photoinitiator is 0.01-120 weight normally with respect to a total of 100 weight part of (B) polyfunctional monomer and a monofunctional monomer. Parts, preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to arrange the transparent layer pattern according to a predetermined arrangement, while 120 parts by weight. If it exceeds 1, the formed transparent layer tends to be detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one, 1,2-octanedione, 2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione, 2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of (B) the polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 part by weight, curing by exposure may be insufficient, and the transparent layer pattern may be difficult to arrange according to a predetermined arrangement, while 80 parts by weight If it exceeds, the formed transparent layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned. .

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, the transparent layer pattern without an undercut can be arranged according to a predetermined arrangement.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (B) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of the biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and the transparent layer pattern may be difficult to arrange according to a predetermined arrangement, while 40 parts by weight. If it exceeds 1, the developed transparent layer tends to fall off from the substrate and the surface of the transparent layer tends to come off.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed transparent layer does not easily fall off from the substrate during development and has high sensitivity.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

  In the present invention, the amount used when the hydrogen donor is used in combination with the biimidazole compound is preferably 0 with respect to 100 parts by weight of the total of (B) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to be reduced. On the other hand, if it exceeds 40 parts by weight, the formed transparent layer is detached from the substrate during development. It tends to be easy to do.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, when the triazine compound is used as the photopolymerization initiator, the amount used is preferably 0 with respect to 100 parts by weight of the total of (B) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to arrange the transparent layer pattern according to a predetermined arrangement, while 40 weights. If it exceeds the area, the formed transparent layer tends to fall off the substrate during development.

  Specific examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio). Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole -3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetate) Ruokishimu) ethanone 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl Ruben benzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl) Oxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

Of these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9 . H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyl) Oxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In this invention, the usage-amount in the case of using an O-acyl oxime type compound as a photoinitiator is (B) with respect to a total of 100 weight part of a polyfunctional monomer and a monofunctional monomer, Preferably it is 0.01-40 weight part, More preferably, it is 1-30 weight part, Most preferably, it is 1-20 weight part. In this case, if the amount of the O-acyloxime compound used is less than 0.01 part by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the transparent layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed transparent layer tends to be detached from the substrate during development.

(E) Additives The photosensitive composition of the present invention may contain various additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (provided that the solubility of the photosensitive composition in an alkaline developer is further improved and the action of further suppressing the remaining undissolved product after development, etc.) The hydrogen donor is excluded).

The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Of these organic acids, aliphatic dicarboxylic acids are preferred as the aliphatic carboxylic acids from the viewpoints of alkali solubility, solubility in a solvent described later, and prevention of background contamination and film residue on the unexposed substrate. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the entire photosensitive composition. In this case, when the usage-amount of organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed transparent layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino- Mono (cyclo) alkanolamines such as 1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclo Di (cyclo) alkanolamines such as hexanol) amine;
Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 -Tri (cyclo) alkanolamines such as cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1, 2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, from the viewpoints of solubility in a solvent described later, prevention of background contamination and film residue on the unexposed portion of the substrate, aliphatic amines include mono (cyclo) alkanolamines, amino ( Cyclo) alkanediols are preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3. -Propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The usage-amount of an organic amino compound is 15 weight% or less normally with respect to the whole photosensitive composition, Preferably it is 10 weight% or less. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed transparent layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, for example,
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

(D) Solvent The photosensitive composition of the present invention contains the components (A) to (C) and an optionally added (E) additive, but usually contains (D) a solvent. To prepare a liquid composition.
As said solvent, (A)-(C) component and (E) additive component which comprise a photosensitive composition are disperse | distributed or melt | dissolved, and it does not react with these components, but has moderate volatility. As long as it is, it can be selected and used as appropriate.

As such a solvent, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether Acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, ethylene glycol monobutyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3 -Methoxybu (Poly) alkylene glycol monoalkyl ether acetates such as Rupuropioneto;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono-n -Butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, diethylene glycol Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2 Heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate Ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferably from the viewpoints of applicability and storage stability of the resulting photosensitive composition, 5 to 50% by weight, more preferably 10 to 40% by weight.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Here, “part” and “%” are based on mass unless otherwise specified.

1. Preparation of photosensitive composition
1-1. Synthesis of alkali-soluble resin (A1) In a flask equipped with a condenser and a stirrer, 20 g of methacrylic acid, 15 g of N-phenylmaleimide, 12 g of styrene, 10 g of benzyl methacrylate, 15 g of 2-hydroxyethyl methacrylate, 28 g of 2-ethylhexyl methacrylate and α -5 g of methylstyrene dimer was dissolved in 140 g of propylene glycol monomethyl ether acetate. After purging the flask with nitrogen for 20 minutes, the reaction solution was heated to 70 ° C. with stirring. Subsequently, a solution prepared by dissolving 3 g of 2,2-azobisisobutyronitrile in 60 g of propylene glycol monomethyl ether was added. The reaction solution was heated to 80 ° C. with stirring, and this temperature was maintained for 3 hours. Then, a solution of 0.5 g of 2,2-azobisisobutyronitrile in 10 g of propylene glycol monomethyl ether was added. And after hold | maintaining at 80 degreeC for 1 hour, it heated to 100 degreeC and hold | maintained this temperature for 1 hour. In this way, a polymerization solution containing 32% by mass of the alkali-soluble resin (A1) was obtained. The weight average molecular weight (Mw) in terms of polystyrene by GPC of this alkali-capable resin (A1) was 11900.

1-2. Preparation of photosensitive composition [Examples 1 to 8 and Comparative Examples 1 and 2]
The components shown in Table 1 below were mixed to prepare the photosensitive compositions of Examples 1 to 8 and Comparative Examples 1 and 2. The details of each component in Table 1 are as follows.

B1: Polybasic acid-modified acrylic oligomer (trade name “Aronix M-520”, manufactured by Toagosei Co., Ltd.)
B2: Dipentaerythritol hexaacrylate C1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)
C2: 2-benzyl-2-dimethylamino-4′-morpholinobutyrophenone D1: propylene glycol monomethyl ether acetate D2: ethylene glycol monobutyl ether acetate E1: 3-methacryloxypropyltrimethoxysilane E2: fluorosurfactant (product) Name "Megafuck F475" (manufactured by DIC)
E3: Fluorosurfactant (trade name “FTX-218”, manufactured by Neos)

2. Evaluation
2-1. Preparation of alignment mark stepped substrate On a 6-inch silicon wafer, using an automatic coating and developing apparatus (Tokyo Electron Co., Ltd. clean track MARK-Vz), the negative photosensitive composition shown below was spin coated. After coating, baking was performed at 100 ° C. for 120 seconds to form a coating film having a thickness of 1 μm. Next, the substrate is cooled to room temperature, and a reduction projection exposure machine (trade name “NSR-2005i10D”, manufactured by Nikon Corporation) is passed through a photomask (a mask having a line-shaped translucent portion) on the coating film on the substrate. the lens numerical aperture = 0.63) was used to expose the exposure amount of 30~500mJ / cm ² at 10 mJ / cm ² intervals at a wavelength of 365 nm (i line). Then, heat treatment was performed at 110 ° C. for 2 minutes on a hot plate, and then paddle (liquid accumulation) development was performed for 60 seconds with an aqueous 2.38 wt% tetramethylammonium hydroxide solution in an automatic coating phenomenon apparatus, and ultrapure water was used. After rinsing and spin drying, post baking was performed at 150 ° C. for 120 seconds on a hot plate to form a pattern substrate having a line pattern with a width of 10 μm.

Negative photosensitive composition: A composition containing the following (Z1) to (Z6).
(Z1): 100 parts by weight of polymer (p-hydroxystyrene-derived structural unit / styrene-derived structural unit = 85/15 (molar ratio), polystyrene-equivalent weight average molecular weight = 18000).
(Z2): 3 parts by weight of methoxyphenyl-bis (trichloromethyl) -s-triazine (Z3): 35 parts by weight of melamine resin (trade name “CYMEL305”, manufactured by Mitsui Cyanamid) (Z4): 200 parts by weight of ethyl lactate Part (Z5): 80 parts by weight of propylene glycol monoethyl ether (Z6): 120 parts by weight of propylene glycol monomethyl ether acetate

2-2. Step coverage of alignment mark Using the above-mentioned pattern substrate, the step coverage of the alignment mark was evaluated. First, the photosensitive composition described in the above “1. Photosensitive composition” is applied onto the pattern substrate by a spin coating method (maximum rotation speed: 2000 rpm), and then baked at 90 ° C. for 150 seconds. A coating film having a thickness of 0.6 μm at a portion having no step was formed. The obtained coating film was evaluated with respect to the step coverage (step coverage of the alignment mark) at a stepped portion with a stylus type film thickness meter. The results are shown in Table 2. The evaluation criteria for the step coverage are shown in FIG.

2-3. Measurement of Light Transmittance The photosensitive composition was applied on a glass substrate using a spin coater, and then heat-treated on a hot plate at 90 ° C. for 2 minutes and 30 seconds. Next, the substrate was cooled to room temperature, and the entire surface of the coating film was exposed to ultraviolet rays using an exposure apparatus (trade name “TME-400PRS”, manufactured by TOPCON). The exposure amount at this time was 100 mJ / m ² . Thereafter, heat treatment was performed for 5 minutes on a hot plate at 230 ° C., and further, heat treatment was performed for 12 minutes on a hot plate at 250 ° C. to form a film thickness (film thickness 0.6 μm). The film obtained was measured for light transmittance (% T) at wavelengths of 400 nm and 800 nm using a visible light transmittance meter. The results are shown in Table 2.

2-4. Pattern shape A photosensitive composition was applied on a 6-inch silicon wafer by a spin coating method using an automatic coating and developing apparatus (Clean Track MARK-Vz, manufactured by Tokyo Electron Ltd.), and then at 90 ° C. for 150 seconds. Pre-baking was performed to form a coating film having a thickness of 0.9 μm. Thereafter, the obtained substrate was cooled to room temperature, and a reduction projection exposure machine (NSR-2005i10D manufactured by Nikon Corporation) was passed through a photomask (dot pattern of 1.0 to 10.0 μm) on the coating film on the substrate. the lens numerical aperture = 0.63) was used to expose the exposure amount of 30~500mJ / cm ² at 10 mJ / cm ² intervals at a wavelength of 365 nm (i line). Subsequently, in an automatic coating phenomenon apparatus, a paddle (liquid accumulation) development with 0.05 wt% tetramethylammonium hydroxide aqueous solution is performed for 90 seconds, rinsed with ultrapure water, spin-dried, and then 230 on a hot plate. A dot pattern was formed by post-baking at 300 ° C. for 300 seconds. Evaluation of the pattern shape of the obtained dot pattern was performed according to the criteria shown in FIG.

Claims (6)

  The alkali-soluble resin (A), the polyfunctional monomer (B), and the photopolymerization initiator (C) are contained, and the component (B) is added to 60 parts by mass of the component (A). The manufacturing method of the transparent pixel used for the color filter which has the process of apply | coating, exposing, and image-developing the photosensitive composition containing -150 weight part on a board | substrate sequentially.   The method for producing a transparent pixel according to claim 1, wherein the polyfunctional monomer (B) is a compound having four or more (meth) acrylate groups.   The transparent pixel obtained by the manufacturing method of the transparent pixel of Claim 1 or 2.   The color filter comprised by four pixels of the transparent pixel of Claim 3, a red pixel, a green pixel, and a blue pixel.   The alkali-soluble resin (A), the polyfunctional monomer (B), and (C) a photo radical generator are contained, and the component (B) is added to 60 to 100 parts by mass of the component (A). The photosensitive composition used for the manufacturing method of the transparent pixel of Claim 1 containing 150 weight part.   The photosensitive composition according to claim 5, wherein the polyfunctional monomer (B) is a compound having four or more (meth) acrylate groups.

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