JP2006309157A - Radiation-sensitive resin composition, protrusion and spacer formed of the same, and liquid crystal display element equipped with them - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition which is suitably used for simultaneously forming protrusions and spacers of a vertical alignment liquid crystal display element. <P>SOLUTION: The radiation-sensitive resin composition for simultaneously forming the protrusions and the spacers for the vertical alignment liquid crystal display element is characterized to contain: a copolymer [A], obtained by copolymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (a1), and an unsaturated compound (a2) other than the component (a1), a polymerizable unsaturated compound [B], and a radiation-sensitive polymerization initiator [C] having a specified structure, represented by ethanone, 1-[9-ethyl-6-(2-methyl-4-tetrahydrofuranylmethoxy benzoyl)-9.H.-carbazole-3-yl]-, 1-(O-acetyloxime). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a radiation-sensitive resin composition suitable for simultaneously forming protrusions and spacers of a vertical liquid crystal display element, protrusions and spacers formed therefrom, and a liquid crystal display element having the same.

Liquid crystal display panels are most widely used today among flat panel displays. Especially, TFT (thin film transistor) type liquid crystal display panels (TFT-LCD) are used in office automation equipment such as personal computers and word processors, liquid crystal televisions, etc. With the widespread use, the required performance for display quality has become increasingly severe.
The most widely used method among TFT-LCDs is a TN (Twisted Neematic) type LCD. This method includes two polarizing films arranged on the outside of two transparent electrodes, each having a polarization direction different by 90 degrees. An alignment film is arranged inside one transparent electrode, and a nematic liquid crystal is arranged between the two alignment films so that the alignment direction of the liquid crystal is twisted 90 degrees from one electrode side to the other electrode side. Is. When non-polarized light is incident in this state, the linearly polarized light transmitted through one polarizing plate is transmitted through the liquid crystal while the polarization direction is shifted, so that it can be transmitted through the other polarizing plate, resulting in a bright state. Next, when a voltage is applied to both the electrodes to make the liquid crystal molecules stand upright, the linearly polarized light reaching the liquid crystal is transmitted as it is, so that it cannot be transmitted through the other polarizing plate and becomes dark. Thereafter, when the voltage is not applied again, the light state is restored.
Such a TN-type LCD has the same or better CRT as the contrast and color reproducibility in the front due to recent technological improvements. However, the TN type LCD has a big problem that the viewing angle is narrow.

In order to solve these problems, STN (Super Twisted Nematic) type LCDs and MVA (Multi-domain Vertically Aligned) type LCDs (vertical alignment type liquid crystal display panels) have been developed. Among these, the STN type LCD is a nematic type liquid crystal of a TN type LCD that is blended with a chiral agent that is a photoactive substance so that the alignment axis of liquid crystal molecules is twisted by 180 degrees or more between two electrodes. It is. The MVA type LCD uses a negative type liquid crystal having negative dielectric anisotropy and a vertical alignment film, and utilizes the birefringence mode instead of the optical rotation mode of the TN type LCD. The alignment direction of the liquid crystal at a position close to the alignment film is maintained almost vertical even in a non-exposed state, so that the contrast, viewing angle, etc. are excellent, and there is no need for rubbing treatment to align the liquid crystal. The process is also excellent (see Non-Patent Document 1 and Patent Document 1).
In the MVA type LCD, in order to allow the liquid crystal to take a plurality of orientation directions in one pixel region, the display-side electrode has a slit in one pixel region as a domain regulating means, In the same pixel region on the light incident side electrode, the position of the electrode is shifted from the position of the electrode to form a protrusion having a slope (for example, a triangular pyramid shape, a semi-convex lens shape, etc.).
Such protrusions are usually formed by photolithography, which has the advantage that microfabrication is possible and shape control is easy.

On the other hand, it is necessary to install a predetermined spacer in the liquid crystal panel in order to keep the distance between the two substrates constant. Conventionally, spacer particles such as glass beads and plastic beads having a predetermined particle diameter have been used as such spacers. However, since these spacer particles are randomly distributed on the glass substrate, if the spacer is present in the effective pixel portion, the spacer is reflected or the incident light is scattered and the contrast of the liquid crystal panel is lowered. There was a problem. In order to solve these problems, a method has been adopted in which a spacer other than the effective pixel portion is formed by photolithography using a radiation sensitive resin composition.

The same process can be used for the protrusion formation and the spacer formation in that photolithography using a radiation sensitive resin is used, but the required performance differs as described below.
(1) The required film thickness differs between the protrusion and the spacer.
(2) The required shape is that the protrusion is a semi-convex lens shape, whereas the spacer is different from a columnar shape or a forward tapered shape.

In addition, since it is necessary to form an alignment film on the protrusions, sufficient wettability to the alignment film material is required so that no repelling occurs when the alignment film is formed in a later step.
On the other hand, the spacer is required to have a high compressive strength so as not to be deformed even by an external pressure applied to the liquid crystal panel.
Furthermore, both the protrusion and the spacer need to be resistant to heat applied in the subsequent panel assembly process.

When the alignment film is formed on the protrusion, if the taper angle of the protrusion with respect to the substrate is too large, for example, if it is 30 degrees or more, the alignment film is printed on the upper portion of the protrusion, and a display defect occurs after the panel is formed. The possibility increases. Therefore, the taper angle of the protrusion with respect to the substrate is preferably 30 degrees or less.

As described above, since the protrusion and the spacer are required to have different shapes and chemical properties, conventionally, it has been necessary to use different radiation-sensitive materials and form them in different steps. Patent Document 2 discloses that a negative photosensitive material can be used to form a protrusion and a spacer at the same time. However, in this publication, there is a feeling that should be used for such an application. No specific embodiment of the radiation composition is disclosed, and a radiation sensitive composition for forming the protrusion and the spacer at the same time is not yet known, and there is a strong demand for providing such a material. It has been.

Arihiro Takeda, Liquid Crystal, Japanese Liquid Crystal Society, April 25, 1999, Vol. 3, No. 2, 117 Japanese Patent Laid-Open No. 11-258605 JP 2001-83517 A

In recent years, the mother glass substrate has been increased in size (for example, about 1,500 × 1,800 mm) from the viewpoint of increasing the area of the liquid crystal display element and improving productivity. However, since the conventional substrate size (about 680 × 880 mm) is smaller than the mask size, it was possible to cope with the batch exposure method. However, in the case of a large substrate, the size is about the same as the substrate size. It is almost impossible to produce a mask, and it is difficult to cope with the batch exposure method.
Therefore, a step exposure method has been proposed as an exposure method that can be applied to a large substrate. However, in the step exposure method, since a single substrate is exposed several times, and each exposure requires time for alignment and step movement, reduction of throughput is regarded as a problem compared to the batch exposure method. .
In addition, in the batch exposure method, an exposure amount of about 3,000 J / m ² is possible, but in the case of the step exposure method, it is necessary to lower the exposure amount at each time, which is conventionally used for forming a spacer. In the radiation sensitive resin composition, it was difficult to achieve a sufficient spacer shape and film thickness with an exposure dose of 1,200 J / m ² or less.

The present invention has been made in view of the above circumstances, and the object thereof is high sensitivity, a sufficient shape can be obtained even with an exposure amount of about 1,200 J / m ² or less, and the protrusion of the vertical alignment type liquid crystal display element. An object of the present invention is to provide a projection and a spacer formed from a radiation-sensitive resin composition suitably used for forming a spacer at the same time, and a liquid crystal display device including them.

According to the present invention, the above problem is firstly
[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) a copolymer [B] a polymerizable unsaturated compound obtained by copolymerizing an unsaturated compound other than the component (a1), and [C] represented by the following formula (1) or (2) Radiation sensitive polymerization initiator comprising a compound

Here, R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ₂ and R ₃ are each a hydrogen atom or an alkyl having 1 to 20 carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), The substituent of the phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, and R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, the number of carbon atoms A nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms; n is an integer of 1-5, m is 0-5. A number, a n + m ≦ 5,

Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are as defined above, l is an integer from 0 to 6, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m, n and l are mutually independent;
It achieves by the radiation sensitive resin composition for forming simultaneously the protrusion and spacer of a vertical alignment type liquid crystal display element characterized by including.

According to the present invention, the above problem is secondly,
This is achieved by a forming method for simultaneously forming a protrusion and a spacer, characterized by including at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.

According to the present invention, thirdly, the above object is achieved by the protrusions and spacers formed from the radiation sensitive resin composition described above.

According to the present invention, fourthly, the above object is achieved by a liquid crystal display device comprising the above-described protrusion and spacer.

Hereinafter, the present invention will be described in detail.
Radiation sensitive resin composition [A] copolymer:
The copolymer (A) used in the radiation-sensitive resin composition of the present invention comprises (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride, (a2) other unsaturated components other than (a1) component. Obtained by copolymerizing compounds.

[A] Among the components constituting the copolymer, (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride (hereinafter collectively referred to as “(a1) unsaturated carboxylic acid compound”) ), For example,
Monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The anhydride of the said dicarboxylic acid etc. can be mentioned.

Among these (a1) unsaturated carboxylic acid compounds, acrylic acid, methacrylic acid, 2 are preferable because of copolymerization reactivity, solubility of the resulting [A] copolymer in an alkaline developer, and easy availability. -Acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, etc. are preferable.
[A] In the copolymer, (a1) unsaturated carboxylic acid compounds may be used alone or in admixture of two or more.

[A] In the copolymer, the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is 5 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 40% by weight [ However, (a1) + (a2) = 100% by weight, and so on. In this case, if the content of the repeating unit derived from the (a1) unsaturated carboxylic acid compound is less than 5% by weight, the solubility in an alkali developer tends to be reduced, whereas if it exceeds 60% by weight, There is a possibility that the solubility of the polymer in an alkaline developer becomes too large.

(A2) Examples of other unsaturated compounds include epoxy group-containing unsaturated compounds.
As an epoxy group-containing unsaturated compound, for example,
Acrylates such as glycidyl acrylate, 2-methylglycidyl acrylate, 4-hydroxybutyl acrylate glycidyl ether, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate (Cyclo) alkyl esters;
Methacrylic acid epoxy (cyclo) alkyl esters such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate;
α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl, α-ethyl acrylate 6,7-epoxyheptyl, α-ethyl acrylate 3,4-epoxycyclohexyl, etc. Other α-alkyl acrylic acid epoxy (cyclo) alkyl esters;
Examples thereof include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

Among these epoxy group-containing unsaturated compounds, glycidyl methacrylate, 2-methylglycidyl methacrylate, 6,7-epoxyheptyl methacrylate, 4-hydroxybutyl from the viewpoint of copolymerization reactivity and the strength of spacers and protrusions Acrylate glycidyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like are preferable.
[A] In the copolymer, the (a2) epoxy group-containing unsaturated compound can be used alone or in admixture of two or more.

In addition, as the other unsaturated compound (a2), in addition to the epoxy group-containing unsaturated compound, for example,
Alkyl acrylates such as methyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;

Cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] acrylate Acrylic alicyclic esters such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 2- (tricyclo [5.2.1.0 ^2,6 ] methacrylate) Decane-8-yloxy) ethyl, methacrylic acid alicyclic esters such as isobornyl methacrylate;

Unsaturated dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;

Acrylic esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl acrylate, tetrahydropyran-2-yl acrylate, 2-methyltetrahydropyran-2-yl acrylate;
Methacrylate esters having an oxygen-containing hetero 5-membered ring or an oxygen-containing hetero 6-membered ring such as tetrahydrofuran-2-yl methacrylate, tetrahydropyran-2-yl methacrylate, 2-methyltetrahydropyran-2-yl methacrylate;

Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene;
In addition to conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene,
Examples include acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, and vinyl acetate.
Among the unsaturated compounds (a2) other than the epoxy group-containing unsaturated compound, from the viewpoint of copolymerization reactivity and solubility of the obtained [A] copolymer in an alkaline aqueous solution, 2-methylcyclohexyl acrylate, Preferred are t-butyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, 1,3-butadiene and the like. .
[A] In the copolymer, (a2) other unsaturated compounds other than the epoxy group-containing unsaturated compound can be used alone or in admixture of two or more.

[A] In the copolymer, two or more types of (a2) may be used, and the total content of repeating units derived therefrom is 40 to 95% by weight, preferably 50 to 90% by weight, more preferably 60 ~ 85% by weight. In this case, if the total content of the repeating units derived from (a2) is less than 40% by weight, there is a tendency to cause swelling during development and increase in the viscosity of the solution. Tend to decrease. There is a tendency to cause swelling during development and increase in viscosity of the solution.

[A] The copolymer is obtained, for example, by polymerizing an unsaturated compound other than (a1) an unsaturated carboxylic acid compound and (a2) (a2) in an appropriate solvent in the presence of a radical polymerization initiator. Can be manufactured.

As the solvent used for the polymerization, for example,
Alcohols such as methanol, ethanol, n-propanol, i-propanol;
Ethers such as tetrahydrofuran and dioxane;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether;
Ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate;

Ethylene glycol monoalkyl ether propionates such as ethylene glycol monomethyl ether propionate, ethylene glycol monoethyl ether propionate, ethylene glycol mono-n-propyl ether propionate, ethylene glycol mono-n-butyl ether propionate ;
Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether;
Dipropylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;

Propylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, propylene glycol mono-n-butyl ether acetate;
Propylene glycol monoalkyl ether propionates such as propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol mono-n-propyl ether propionate, propylene glycol mono-n-butyl ether propionate ;

Aromatic hydrocarbons such as toluene and xylene;
Ketones such as methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone;

Methyl 2-methoxypropionate, ethyl 2-methoxypropionate, n-propyl 2-methoxypropionate, n-butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-ethoxypropion N-propyl acid, n-butyl 2-ethoxypropionate, methyl 2-n-propoxypropionate, ethyl 2-n-propoxypropionate, n-propyl 2-n-propoxypropionate, 2-n-propoxypropionic acid n-butyl, methyl 2-n-butoxypropionate, ethyl 2-n-butoxypropionate, n-propyl 2-n-butoxypropionate, n-butyl 2-n-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, 3-methoxy N-propyl propionate, n-butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, n-propyl 3-ethoxypropionate, n-butyl 3-ethoxypropionate, 3-n -Methyl propoxypropionate, ethyl 3-n-propoxypropionate, n-propyl 3-n-propoxypropionate, n-butyl 3-n-propoxypropionate, methyl 3-n-butoxypropionate, 3-n- Alkyl alkoxypropionates such as ethyl butoxypropionate, n-propyl 3-n-butoxypropionate, n-butyl 3-n-butoxypropionate,

Methyl acetate, ethyl acetate, n-propyl acetate, n-butyl acetate, methyl hydroxyacetate, ethyl hydroxyacetate, n-propyl hydroxyacetate, n-butyl hydroxyacetate, methyl lactate, ethyl lactate, n-propyl lactate, n-lactic acid Butyl, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl 3-hydroxypropionate, 3-hydroxy N-butyl propionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, n-propyl methoxyacetate, n-butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, n-propyl ethoxyacetate, Ethoxyacetic acid n- Chill, n-propoxyacetate methyl, n-propoxyacetate ethyl, n-propoxyacetate n-propyl, n-propoxyacetate n-butyl, n-butoxyacetate methyl, n-butoxyacetate, n-butoxyacetate n-propyl, Other esters such as n-butyl n-butoxyacetate can be mentioned.

Of these solvents, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.
The amount of the solvent used is 150 to 450 parts by weight, preferably 200 to 400 parts by weight, based on 100 parts by weight of the total amount of components (a1) and (a2).

The radical polymerization initiator is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2 , 2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4′-azobis (4-cyanovaleric acid), dimethyl-2,2′-azobis (2-methylpropionate), Azo compounds such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1-bis (t-butylperoxy) cyclohexane, etc. And organic peroxides such as hydrogen peroxide.
Moreover, when using a peroxide as a radical polymerization initiator, it is good also as a redox type initiator using it together with a reducing agent.
These radical polymerization initiators can be used alone or in admixture of two or more.

The usage-amount of a radical polymerization initiator is 1-20 weight part with respect to 100 weight part of total amounts of (a1) and (a2) component, Preferably it is 3-15 weight part.

In addition, in the radical polymerization, a surfactant, a continuous transfer agent, and the like can be used in combination.
The radical polymerization conditions are such that the temperature is 50 to 110 ° C., preferably 60 to 100 ° C., and the polymerization time is 180 to 480 minutes, preferably about 240 to 420 minutes.

[A] The polystyrene-reduced weight average molecular weight (hereinafter referred to as “Mw”) of the copolymer by gel permeation chromatography (GPC) is 2,000 to 100,000, preferably 5,000 to 50,000. In this case, if the Mw is less than 2,000, there is a possibility that the alkali developability, the remaining film ratio, etc. of the resulting film may be reduced, and the pattern shape, heat resistance, etc. may be impaired. If it exceeds 1, the resolution may be reduced, or the pattern shape may be impaired.
[A] The molecular weight of the copolymer depends on the amount of the solvent, the amount of the radical polymerization initiator, the polymerization time, the polymerization temperature, and the use of a chain transfer agent relative to the total amount of the copolymer (a1) and (a2) components. Can be adjusted.

[B] Polymerizable unsaturated compound:
[B] The polymerizable unsaturated compound comprises an unsaturated compound that is polymerized by exposure to radiation in the presence of a radiation-sensitive polymerization initiator.
Such a [B] polymerizable unsaturated compound is not particularly limited. For example, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic esters have good copolymerizability. From the viewpoint of improving the strength of the obtained protrusions and spacers.

Examples of the monofunctional (meth) acrylic acid esters include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3 -Methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, etc. As a trade name, for example, Aronix M-101, M-111, M-114 (above, manufactured by Toa Gosei Co., Ltd.); KAYAARDTC-110S, TC 120S (manufactured by Nippon Kayaku Co.); Viscoat 158, the 2311 (manufactured by Osaka Organic Chemical Industry Ltd.) and the like.

Examples of the bifunctional (meth) acrylic acid esters include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1,6 -Hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9-nonanediol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate, polyester both ends (meta ) Acrylic modification, Polypropylene glycol both ends (meth) acrylic modification, Polytetramethylene Glycol In addition, as a commercial product, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toa Gosei Co., Ltd.), KAYARADHDDA, HX-220, R-604 (above, Nippon Kayaku Co., Ltd.), Biscote 260, 312, 335HP (above, Osaka Organic Chemical Industries, Ltd.), U-108A, U- 200AX, UA-4100, UA-4400, UA-340P, UA-2235PE, UA-160TM, UA-6100, U-2PPA200A (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc., UN-9000PEP, UN-9200A , UN-7600, UN-5200, UN-1003, UN-1255, UN-6060PTM, UN-6060P, SH-500B Or more, and the like Negami Kogyo Co., Ltd.).

Further, the trifunctional or higher functional (meth) acrylic acid esters include, for example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate. , Dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, and 9 functional As the above (meth) acrylic acid esters, linear alkylene groups and alicyclic rings A compound having a structure and having two or more isocyanate groups, one or more hydroxyl groups in the molecule, and having three, four or five acryloyloxy groups and / or methacryloyloxy groups The polyfunctional urethane acrylate type compound obtained by making it react with a compound can be mentioned.

Commercially available products of tri- or higher functional (meth) acrylic acid esters are trade names, for example, Aronix M-309, M-400, M-405, M-450, M-7100, M -8030, M-8060, TO-1450 (above, manufactured by Toa Gosei Co., Ltd.), KAYARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.) and commercial products containing polyfunctional urethane acrylate compounds New Frontier R-1150 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), KAYARADDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), U-4HA, U- HA, U-6LPA, U-15HA, UA-32P, U-324A, U-4H, U-6H (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), UN-9000H, UN-3320HA, UN-3320HB, And UN-3320HC, UN-901T, UN-1200TPK (manufactured by Negami Industrial Co., Ltd.).

Of these monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters, bifunctional or higher functional (meth) acrylic acid esters are more preferable, and particularly, polyester both-end acrylic modification, trimethylolpropane triacrylate. Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and a commercial product containing a polyfunctional urethane acrylate compound are preferred.
The monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters can be used alone or in admixture of two or more.

In the radiation-sensitive resin composition of the present invention, the amount of the [B] polymerizable unsaturated compound used is preferably 1 to 120 parts by weight, more preferably 3 to 100 parts by weight of the [A] copolymer. 100 parts by weight. In this case, if the amount of the [B] polymerizable unsaturated compound used is less than 1 part by weight, there is a risk of developing residue during development. On the other hand, if it exceeds 120 parts by weight, the adhesion of the resulting protrusions and spacers decreases. Tend to.

[C] Radiation sensitive polymerization initiator:
[C] The radiation-sensitive polymerization initiator comprises an O-acyloxime type photopolymerization initiator, particularly a compound represented by the formula (1) or (2) (hereinafter referred to as “photopolymerization initiator [C]”). Is preferred).
The photopolymerization initiator as used in the present invention means a component that generates an active species capable of initiating polymerization of the polymerizable compound [B] by exposure with visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray or the like. To do.

In the “photopolymerization initiator [C]” represented by the formula (1) or (2), R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group. It is. R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms ( However, except a C7-C8 cycloalkyl group). Substituents of the substituted phenyl group are alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, phenyl groups, and halogen atoms. These substituents can be 1-5. R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, a nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms. R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms, or an alkoxyl group having 1 to 12 carbon atoms. n is an integer of 1 to 5, m is an integer of 0 to 5, n + m ≦ 5, and l is an integer of 0 to 6.
The alkyl group having 1 to 20 carbon atoms of R _{1 in} the formula (1) or (2) can be a linear or branched alkyl group, and specific examples thereof include, for example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, An n-decyl group, an n-undecyl group, and an n-dodecyl group can be exemplified. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.

The alkyl group having 1 to 20 carbon atoms R ₂ and R ₃ may be linear or branched, and specific examples thereof include a methyl group, an ethyl group, n- propyl group, i- Propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n- An undecyl group and n-dodecyl group can be mentioned. Examples of the cycloalkyl group having 3 to 8 carbon atoms include a cyclopentyl group and a cyclohexyl group.
The alkyl group having 1 to 6 carbon atoms which is a substituent of the substituted phenyl group of R ₂ and R ₃ can be linear, branched or cyclic, and specific examples thereof include a methyl group, an ethyl group, Examples thereof include an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a cyclopentyl group, and a cyclohexyl group.
The alkoxy group having 1 to 6 carbon atoms can be linear, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n- Examples thereof include a butoxy group and a t-butoxy group. Examples of the halogen atom include a fluorine atom and a chlorine atom.
Examples of alicyclic groups having 7 to 20 carbon atoms (excluding cycloalkyl groups having 7 to 8 carbon atoms) include bicycloalkyl groups, tricycloalkyl groups, spiroalkyl groups, ter-cycloalkyl groups, and terpene skeletons Group, adamantyl skeleton-containing group and the like.

Examples of the nitrogen-containing heterocyclic group having 4 to 20 carbon atoms, the oxygen-containing heterocyclic group having 4 to 20 carbon atoms, and the sulfur-containing heterocyclic group having 4 to 20 carbon atoms of R ₄ include, for example, thiolanyl group, azepinyl group, dihydro Azepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, dioxaindanyl group, dihianaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, Isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, pyrazinyl group, pyrrolinyl group, morpholyl group, piperazinyl group, quinuclidinyl group, indolyl group, isoindolyl group, benzofuranyl group, benzothiophenyl Group, indolizinyl group, Romenyl group, quinolinyl group, isoquinolinyl group, purinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, thioxanthenyl group, phenazinyl group, phenothiazinyl group, phenoxathinyl group Group, phenoxazinyl group, thiantenyl group, tetrahydrofuranyl group, tetrahydropyranyl group and the like. Of these, a tetrahydrofuranyl group, a tetrahydropyranyl group, and the like are particularly preferable.
The alkyl group having 1 to 12 carbon atoms of R ₅ can be linear, branched or cyclic, and specific examples thereof include, for example, methyl group, ethyl group, n-propyl group, i-propyl group. N-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group , N-dodecyl group, cyclopentyl group, cyclohexyl group and the like.
In addition, the alkoxy group having 1 to 12 carbon atoms may be linear, branched or cyclic, and specific examples thereof include methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group. Group, t-butoxy, n-pentyloxy group and the like.
Among these, R ₅ is particularly preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, or an ethoxy group.
n is preferably 1. m is preferably any one of 0, 1, 2 and particularly preferably 1, and l is preferably any one of 0, 1, 2 and particularly preferably 1.

Specific examples of the compound [C] include
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -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-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -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-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-acetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O-benzoylacetyloxime);
Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime)
Etc.

Of these, 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-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) and ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime) is preferred.
These photopolymerization initiators [C] may be used alone or in combination of two or more.

As the photopolymerization initiator [C], an O-acyloxime photopolymerization initiator other than the formula (1) (hereinafter referred to as “photopolymerization initiator [C-2]”) can be used in combination.
Specific examples of these photopolymerization initiators [C-2] include 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [ 4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octadione-1 -[4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime)), etc. Can be mentioned. Of these, 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable. The photopolymerization initiator [C-2] is preferably used at 30% by weight or less of the photopolymerization initiator [C].

In the present invention, by using the [C] radiation-sensitive polymerization initiator, a sufficient sensitivity can be achieved even with an exposure amount of 1,200 J / m ² or less, and a protrusion or spacer having good adhesion can be obtained. Is possible.

In the radiation sensitive resin composition of the present invention, the amount of the [C] radiation sensitive polymerization initiator used is preferably 5 to 30 parts by weight, more preferably 100 parts by weight of the [B] polymerizable unsaturated compound. Is 5 to 20 parts by weight. In this case, if the amount of [C] radiation sensitive polymerization initiator used is less than 5 parts by weight, the residual film ratio during development tends to decrease. There is a tendency for the solubility in a developing solution to fall.

Furthermore, in the radiation sensitive resin composition of this invention, 1 or more types of other radiation sensitive polymerization initiators can also be used together with [C] radiation sensitive polymerization initiator.
Examples of the other photopolymerization initiator include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds. A compound etc. can be mentioned. Of these, acetophenone compounds (hereinafter sometimes referred to as “component (D)”) and biimidazole compounds (hereinafter sometimes referred to as “component (E)”) are preferred. Examples of the other radiation sensitive polymerization initiator include, for example, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, thioxanthone compounds, phosphine compounds, Examples include triazine compounds, among which acetophenone compounds and biimidazole compounds are preferable.

Component (D): Acetophenone compound As the acetophenone compound, for example, an α-hydroxyketone compound, an α-aminoketone compound, and other compounds can be mentioned.
Specific examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1 -On, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone and the like can be mentioned. Specific examples of the α-aminoketone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino And phenyl) -butanone-1,2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. Specific examples of compounds other than these include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

These acetophenone compounds can be used alone or in admixture of two or more.
By using these acetophenone compounds, it is possible to further improve the sensitivity, the shape of spacers and protrusions, and the compressive strength.

(E) component: biimidazole compound As a specific example of a biimidazole compound,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
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′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

Among the 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 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1, is particularly preferable. 2'-biimidazole.
The biimidazole compounds can be used alone or in admixture of two or more.

By using these biimidazole compounds, sensitivity, resolution, and adhesion can be further improved.
Moreover, in order to sensitize a biimidazole type compound, the aliphatic or aromatic type compound (henceforth "sensitizer [E-2]") which has a dialkylamino group can be used.

Specific examples of the sensitizer [E-2] include, for example, N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, p-dimethylaminobenzoic acid. Examples include ethyl acrylate, i-amyl p-dimethylaminobenzoate, and the like. Of these sensitizers, 4,4′-bis (diethylamino) benzophenone is preferred.
These sensitizers [E-2] may be used alone or in combination of two or more.
The amount of the sensitizer [E-2] used is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of [A].
When the amount of the sensitizer [E-2] is less than 0.1 parts by weight, there is a tendency for the resulting spacer and protrusions to slip and pattern shape defects tend to occur. A pattern shape defect tends to occur.

When a biimidazole compound is used, a thiol compound (hereinafter sometimes referred to as “thiol compound [E-3]”) can be used as the hydrogen donor compound. The biimidazole compound is sensitized by a benzophenone compound having a dialkylamino group, and the biimidazole compound is cleaved to generate an imidazole radical. In this case, a high radical polymerization initiating ability is not expressed, and an unfavorable shape such as a reverse tapered shape is often obtained. This problem is alleviated by adding the thiol compound [E-3] to a system in which a biimidazole compound and a benzophenone compound having a dialkylamino group coexist. A hydrogen radical is donated from the thiol compound to the imidazole radical, thereby generating a compound having a neutral imidazole and a sulfur radical having a high polymerization initiating ability. Thereby, it becomes a more preferable forward taper shape from a reverse taper shape.

The use ratio of the thiol-based compound [E-3] is preferably 0.1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the compound [C]. . When the amount of the thiol-based compound [E-3] is less than 0.1 parts by weight, the resulting spacer and protrusions tend to suffer from film slippage and pattern shape defects, and when the amount exceeds 50 parts by weight, A pattern shape defect tends to occur.

Specific examples thereof include aromatic thiols such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole, 3 -Aliphatic monothiols such as mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate and octyl 3-mercaptopropionate. Examples of the bifunctional or higher aliphatic thiol include 3,6-dioxa-1,8-octanedithiol, pentaerythritol tetra (mercaptoacetate), pentaerythritol tetra (3-mercaptopropionate), and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone.

Examples of the phosphine compounds include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethylphosphine oxide, and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. Can do.

The use ratio of the other photopolymerization initiator is preferably 100 parts by weight or less, more preferably 80 parts by weight or less, and particularly preferably 60 parts by weight or less with respect to 100 parts by weight of the total photopolymerization initiator. In this case, if the use ratio of the other photopolymerization initiator exceeds 100 parts by weight, the intended effect of the present invention may be impaired.

Additive:
In the radiation-sensitive resin composition of the present invention, a surfactant, an adhesion assistant, a storage stabilizer, a heat resistance, in addition to the above components, if necessary, within a range that does not impair the intended effect of the present invention. Additives such as property improvers can also be blended.

The surfactant is a component having an effect of improving applicability, and a fluorine surfactant and a silicone surfactant are preferable.
The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group in at least one of the terminal, main chain and side chain. Specific examples thereof include 1,1,2,2- Tetrafluorooctyl (1,1,2,2-tetrafluoro-n-propyl) ether, 1,1,2,2-tetrafluoro-n-octyl (n-hexyl) ether, octaethylene glycol di (1,1 , 2,2-tetrafluoro-n-butyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2, 2-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro-n- Nethyl) ether, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10-decafluoro-n-dodecane, Sodium perfluoro-n-dodecylsulfonate, sodium fluoroalkylbenzenesulfonates, sodium fluoroalkylphosphonates, sodium fluoroalkylcarboxylates, fluoroalkylpolyoxyethylene ethers, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether) ), Fluoroalkyl ammonium iodides, fluoroalkyl betaines, fluoroalkyl polyoxyethylene ethers, perfluoroalkyl polyoxyethanols, perfluoroalkyl alkoxylates, fluorine alkyl esters It can be mentioned.

Moreover, as a commercial item of a fluorine-type surfactant, it is a brand name, for example, BM-1000, the same -1100 (above, the product made from BMCHEMIE), MegaFuck F142D, the same F172, the same F173, the same F183, the same F178, F191, F471, F476 (above, manufactured by Dainippon Ink & Chemicals, Inc.), Florard FC170C, FC-171, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (above, manufactured by Asahi Glass Co., Ltd.), Ftop EF301, EF303, EF352 (above, manufactured by Shin-Akita Kasei Co., Ltd.), footer FT-100, FT-110, FT-140A, FT-150, FT-250, FT-251, FTX-251, FTX-218, FT-300, FT-310, FT-400S (above, manufactured by Neos Co., Ltd.).

As said silicone type surfactant, it is a commercial item and is a brand name, for example, Toray silicone DC3PA, same DC7PA, same SH11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, same SH-190, same SH-193 SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, -4300, -4445, -4446 -4460, -4442 (above, manufactured by GE Toshiba Silicone Co., Ltd.).

Furthermore, as surfactants other than the above, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxy Polyoxyethylene aryl ethers such as ethylene n-nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; For example, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow No. 57, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).
The said surfactant can be used individually or in mixture of 2 or more types.
The compounding amount of the surfactant is preferably 5 parts by weight or less, and more preferably 2 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. In this case, when the compounding amount of the surfactant exceeds 5 parts by weight, there is a tendency that film roughening is likely to occur during coating.

The adhesion aid is a component having an action of further improving the adhesion between the protrusions or spacers and the substrate, and a functional silane coupling agent is preferable.
Examples of the functional silane coupling agent include compounds having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, and an epoxy group, and more specifically, trimethoxysilyl. Benzoic acid, γ-methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimethoxysilane and the like.
These adhesion assistants can be used alone or in admixture of two or more.
The blending amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the [A] copolymer. In this case, when the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that a development residue is likely to occur.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenyl. Examples include hydroxylamine aluminum.
These storage stabilizers can be used alone or in admixture of two or more.
The amount of the storage stabilizer is preferably 3 parts by weight or less, more preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the [A] copolymer. In this case, if the amount of the storage stabilizer exceeds 3 parts by weight, the sensitivity may decrease and the pattern shape may be impaired.

Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, and compounds having two or more epoxy groups.
Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N, N-tetra (methoxymethyl) glycoluril, N, N, N, N-tetra (ethoxymethyl) glycoluril, N, N , N, N-tetra (n-propoxymethyl) glycoluril, N, N, N, N-tetra (i-propoxymethyl) glycoluril, N, N, N, N-tetra (n-butoxymethyl) glycoluril , N, N, N, N-tetra (t-butoxymethyl) glycoluril and the like.
Of these N- (alkoxymethyl) glycoluril compounds, N, N, N, N-tetra (methoxymethyl) glycoluril is particularly preferred.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N, N, N, N-hexa (methoxymethyl) melamine, N, N, N, N, N, N-hexa (ethoxy). Methyl) melamine, N, N, N, N, N, N-hexa (n-propoxymethyl) melamine, N, N, N, N, N, N-hexa (i-propoxymethyl) melamine, N, N, Examples thereof include N, N, N, N-hexa (n-butoxymethyl) melamine, N, N, N, N, N, N-hexa (t-butoxymethyl) melamine and the like.
Among these N- (alkoxymethyl) melamine compounds, N, N, N, N, N, N-hexa (methoxymethyl) melamine is particularly preferable, and a commercial product thereof is, for example, Nicalac N- 2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.) and the like.

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diester. Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol A diglycidyl ether , Ortho-cresol novolac type epoxy resin and commercial products For example, Epolite 40E, 100E, 200E, 70P, 200P, 400P, 1500NP, 1600, 80MF, 100MF, 3002, and 4000 (more from Kyoeisha Chemical Co., Ltd.), EOCN102 103S, 104S, 1020, 1025, 1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S (manufactured by Japan Epoxy Resin Co., Ltd.), and the like.
The above heat resistance improvers can be used alone or in admixture of two or more.
The blending amount of the heat resistance improver is preferably 30 parts by weight or less, more preferably 20 parts by weight or less with respect to 100 parts by weight of the [A] copolymer. In this case, when the compounding amount of the heat resistance improver exceeds 30 parts by weight, the storage stability of the radiation-sensitive resin composition tends to decrease.

The radiation-sensitive resin composition of the present invention is preferably used as a composition solution dissolved in an appropriate solvent.
As the solvent, those components that uniformly dissolve each component constituting the radiation-sensitive resin composition, do not react with each component, and have moderate volatility are used. Alcohols, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, diethylene glycol alkyl ethers, propylene glycol monoalkyl ether acetates, alkyl alkoxypropionates In particular, benzyl alcohol, 2-phenylethanol, 3-phenyl-1-propanol, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ester Ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate are preferred.
The said solvent can be used individually or in mixture of 2 or more types.

In the present invention, a high boiling point solvent may be used in combination with the above solvent.
Examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, Examples thereof include ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.
These high boiling point solvents can be used alone or in admixture of two or more.
The amount of the high-boiling solvent used is preferably 50% by weight or less, more preferably 30% by weight or less in the total solvent.
Moreover, the usage-amount of the above solvent is the quantity from which the solid content concentration of the radiation sensitive resin composition of this invention will be 15 to 45 weight% normally, Preferably it is about 20 to 40 weight%.
In addition, the composition solution prepared as described above can be used after being filtered using a Millipore filter having a pore diameter of about 0.5 μm.

Especially the radiation sensitive resin composition of this invention can be used very suitably for formation of the processus | protrusion and spacer of a vertical alignment type liquid crystal display element.

Method for forming protrusions and spacers Next, a method for forming the protrusions and spacers of the present invention using the radiation-sensitive resin composition of the present invention will be described.
The formation of the protrusion and spacer of the present invention includes at least the following steps in the order described below.
(A) forming a film of the radiation sensitive resin composition of the present invention on a substrate;
(B) exposing at least a part of the coating;
(C) a step of developing the coated film after exposure, and (d) a step of heating the coated film after development.

Hereinafter, each of these steps will be described sequentially.
(I) Process:
A transparent conductive film is formed on one surface of a transparent substrate, and a radiation-sensitive resin composition is applied onto the transparent conductive film, preferably as a composition solution, and then the coated surface is heated (prebaked) to form a coating film. Form.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, Examples thereof include a resin substrate made of a plastic such as polyethersulfone, polycarbonate, and polyimide.
As the transparent conductive film provided on one surface of the transparent substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), or the like can be used. .
As a coating method of the composition solution, for example, an appropriate 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, or an ink jet coating method can be employed. However, the spin coating method and the slit die coating method are particularly preferable.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., it is normally about 1 to 15 minutes at 70-120 degreeC.

(B) Process:
Next, at least a part of the formed film is exposed. In this case, when exposing a part of the film, the exposure is usually performed through a photomask having a predetermined pattern.
Here, it is preferable that the region to be the protrusion and the region to be the spacer are exposed with substantially the same exposure amount in consideration of productivity. In this case, under a constant exposure gap, the exposure illuminance decreases as the mask opening width decreases, so the degree of cross-linking decreases, and as a result, the flow tends to flow during post-baking, resulting in a difference in height. It becomes.
Moreover, it can also expose through the pattern mask which has a part with a large radiation transmittance and a part with a small radiation transmittance.

As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used. However, radiation having a wavelength in the range of 190 to 450 nm is preferable, and particularly radiation containing 365 nm ultraviolet light. Is preferred.
The exposure dose is usually 100 to 3,000 J / m ² , preferably 200 to 1,200 J / m, as a value obtained by measuring the intensity of the exposed radiation at a wavelength of 365 nm with an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.). ² .

(C) Process:
Subsequently, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
As the developer used for development, an alkali developer is preferable, and examples thereof include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; ethylamine, n Aliphatic primary amines such as propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole and piperidine , N-methylpiperidine, N-methylpyrrolidine, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene 3 Secondary amines: aromatics such as pyridine, collidine, lutidine, quinoline 3 Examples include quaternary amines; alkanolamines such as ethanoldimethylamine, methyldiethanolamine, and triethanolamine; and aqueous solutions of alkaline compounds such as quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide.
Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the aqueous solution of the alkaline compound.
As a developing method, any of a liquid piling method, a dipping method, a shower method and the like may be used, and the developing time is usually about 10 to 180 seconds.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

(2) Process:
Next, the obtained pattern is heated at a predetermined temperature, for example, 150 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, for 30 to 180 minutes in the oven, by a heating device such as a hot plate or an oven. Predetermined protrusions and spacers can be obtained by heating (post-baking).

The radiation sensitive resin composition of the present invention can form projections and spacers of a vertical alignment type liquid crystal display element with high sensitivity at the same time, and a sufficient pattern shape can be obtained. Spacer strength, rubbing resistance, adhesion to a transparent substrate, Protrusions and spacers for a vertical alignment type liquid crystal display element excellent in heat resistance and the like can be formed.
Further, the vertical alignment type liquid crystal display element of the present invention is provided with protrusions and spacers having excellent performance such as pattern shape, spacer strength, rubbing resistance, adhesion to a transparent substrate, heat resistance, etc. High reliability can be expressed.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. Here, parts and% are based on weight.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts of 2,2′-azobis (isobutyronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 35 parts of 2-methacryloyloxyethyl succinic acid, n methacrylate. -After charging 25 parts of butyl methacrylate and 35 parts of benzyl methacrylate and replacing with nitrogen, 5 parts by weight of 1,3-butadiene was further added, and the temperature of the solution was raised to 90 ° C while gently stirring. By keeping the polymerization for a time, an [A] copolymer solution having a solid content concentration of 28.0% was obtained. This is referred to as [A-1] polymer.
With respect to the obtained [A-1] polymer, Mw was measured using GPC (Gel Permeation Chromatography) HLC-8020 (trade name, manufactured by Tosoh Corporation) and found to be 12,000.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 18 parts by weight of methacrylic acid and methacrylic acid. After charging 40 parts by weight of glycidyl, 5 parts by weight of styrene, and 32 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, and substituting with nitrogen, 5 parts by weight of 1,3-butadiene is further added. The temperature of the solution was raised to 70 ° C. while gently stirring, and the temperature was maintained for 5 hours for polymerization to obtain a solution of copolymer [A-2].
The solid content concentration of this solution was 33.0% by weight, and Mw of the copolymer [A-2] was 11,000.

Example 1
Preparation of Composition Solution As component [A], 100 parts of polymer solution (A-1) obtained in Synthesis Example 1 as polymer (A-1) and dipentaerystol hexaacrylate (product) as component [B] Name KAYARDADDHA, manufactured by Nippon Kayaku Co., Ltd.) 60 parts, [C] component, ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazole After mixing 5 parts of -3-yl]-, 1- (O-acetyloxime) and dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration is 30%, it is filtered through a Millipore filter with a pore size of 0.5 μm. Thus, a composition solution was prepared.

Formation of protrusions and spacers The above composition solution was applied on an alkali-free glass substrate using a spinner, and then pre-baked on a hot plate at 80 ° C. for 3 minutes to form a film having a thickness of 4.0 μm. Formed.
Next, the obtained coating film was exposed to ultraviolet rays having an intensity of 250 W / m ² at 365 nm for 4 seconds through a photomask having a 5 μm and 15 μm round pattern, leaving an exposure gap of 200 μm. The effective exposure amount at this time corresponds to 1000 J / m ² . Then, after developing with a 0.05% by weight aqueous solution of potassium hydroxide at 25 ° C. for a predetermined time, washing with pure water for 1 minute, and further heating in an oven at 220 ° C. for 60 minutes, the protrusions and spacers are removed once. Formed simultaneously by exposure. Protrusions were formed through a 5 μm remaining pattern photomask, and spacers were formed through a 15 μm round remaining pattern photomask.
Next, various evaluations were performed in the following manner. The evaluation results are shown in Table 2.

(1) Sensitivity evaluation

In the pattern obtained in the above, it can be said that the sensitivity is good when the sensitivity at which the remaining film ratio after development is 90% or more is 1200 J / m ² or less.

(2) Evaluation of cross-sectional shape The cross-sectional shapes of the obtained protrusions and spacers were observed with a scanning electron microscope and evaluated according to which of A to E shown in FIG. In the case of protrusions, the cross-sectional shape is good when it is a semi-convex lens shape as shown in FIG. 1D, and when it is a regular triangle shape as shown in FIG. is not.
On the other hand, when the spacer is formed in a columnar shape as shown in FIG. 1A or a forward taper shape as shown in FIG. On the other hand, as shown in FIG. 1C, a pattern is also formed during the subsequent rubbing process even in the case of an inversely tapered shape (a cross-sectional shape and an inverted triangle shape in which the side of the film surface is longer than the side on the substrate side). Since the risk of peeling off becomes very large, it can be said that the cross-sectional shape is poor.

(3) Evaluation of spacer strength About the obtained spacer, using a micro compression tester (trade name MCTM-200, manufactured by Shimadzu Corporation), with a flat indenter with a diameter of 50 μm, a load speed of 2.6 mN / sec. The amount of deformation when a load of 10 mN was applied was measured (measurement temperature 23 ° C.). When this value is 0.5 μm or less, it can be said that the strength of the spacer is good.

(4) Evaluation of rubbing resistance AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal alignment agent was applied to a substrate on which a spacer was formed by a printing machine for applying a liquid crystal alignment film, and then dried at 180 ° C. for 1 hour. A film of a liquid crystal aligning agent having a thickness of 0.05 μm was formed.
Thereafter, the coating film was subjected to a rubbing treatment with a rubbing machine having a roll around which a polyamide cloth was wound, with a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern shaving or peeling was evaluated.

(5) Evaluation of adhesion After forming a cured film in the same manner as the spacer formation except that no photomask was used, 8 of the adhesion tests of JISK-5400 (1900) 8.5 Evaluation was performed by the cross-cut tape method of. At this time, the number of remaining grids out of 100 grids is shown in Table 2.

(6) Evaluation of heat resistance A cured film was formed in the same manner as in the above spacer formation except that no photomask was used, and then heated in an oven at 240 ° C. for 60 minutes to measure the film thickness before and after heating. Then, the remaining film ratio (film thickness after heating × 100 / initial film thickness) was evaluated.

Examples 2-8, Comparative Examples 1-4
In Example 1, each component shown in Table 1 was used as an adhesion assistant, 5 parts of γ-glycidoxypropyltrimethoxysilane, as a surfactant, 0.5 part of FTX-218, and as a storage stabilizer, 4 parts. -It mixed with 0.5 parts of methoxyphenol, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 30%, and then filtered through a Millipore filter having a pore size of 0.5 µm to prepare a composition solution. Thereafter, protrusions and spacers were formed in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The evaluation results are shown in Table 2.

In Table 1, each component other than the polymer is as follows.
[B] Component B-1: Dipentaerystol hexaacrylate (trade name: KAYARADDDPHA)
B-2: Commercial product containing a polyfunctional urethane acrylate compound (trade name: KAYARDADDHA-40H)

[C] Component C-1: Ethanone, 1- [9-Ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9.H.-carbazol-3-yl]-, 1- (O- Acetyl oxime)
C-2: Ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl]-, 1- (O-acetyloxime)
D-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
D-2: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name Irgacure 379, manufactured by Ciba Specialty Chemicals)
E-1: 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole E-2: 2,2′-bis (2 -Chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,
E-3: 4,4′-bis (diethylamino) benzophenone E-4: 2-mercaptobenzothiazole F-1: 2,4-diethylthioxanthone F-2: 2,4,6-trimethylbenzoyldiphenylphosphine oxide

It is a schematic diagram which illustrates the cross-sectional shape of a spacer.

Claims (4)

[A] (a1) unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride,
(A2) a copolymer [B] a polymerizable unsaturated compound obtained by copolymerizing an unsaturated compound other than the component (a1), and [C] represented by the following formula (1) or (2) Radiation sensitive polymerization initiator comprising a compound

Here, R ₁ is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and R ₂ and R ₃ are each a hydrogen atom or an alkyl having 1 to 20 carbon atoms. A cycloalkyl group having 3 to 8 carbon atoms, a substituted or unsubstituted phenyl group, or an alicyclic group having 7 to 20 carbon atoms (excluding a cycloalkyl group having 7 to 8 carbon atoms), The substituent of the phenyl group is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a phenyl group or a halogen atom, and R ₄ is an oxygen-containing heterocyclic group having 4 to 20 carbon atoms, the number of carbon atoms A nitrogen-containing heterocyclic group having 4 to 20 carbon atoms or a sulfur-containing heterocyclic group having 4 to 20 carbon atoms, R ₅ is hydrogen, an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms; n is an integer of 1-5, m is 0-5. A number, a n + m ≦ 5,

Where R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m and n are as defined above, l is an integer from 0 to 6, and R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , m, n and l are mutually independent;
A radiation-sensitive resin composition for simultaneously forming protrusions and spacers of a vertical alignment type liquid crystal display element, comprising: A forming method for simultaneously forming protrusions and spacers of a vertical alignment type liquid crystal display element, comprising the following steps in the following order.
(1) The process of forming the coating film of the radiation sensitive composition of Claim 1 on a board | substrate,
(2) A step of irradiating at least a part of the coating film with radiation,
(3) Development step, and (4) Heating step.   A protrusion and a spacer of a vertical alignment type liquid crystal display element formed by the method of claim 2. A liquid crystal display element comprising the protrusions and spacer formation of the vertical alignment type liquid crystal display element according to claim 3.

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