KR101948069B1 - Array substrate, liquid crystal display device, and process for producing the array substrate - Google Patents

Abstract

An array substrate having an insulating film formed of a low-temperature-curable negative-type radiation-sensitive resin composition and a method of manufacturing the same are provided, and a liquid crystal display element is provided using the array substrate.
(1) a copolymer comprising a constituent unit formed of at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a constituent unit formed from an epoxy group-containing unsaturated compound, 2) to form the insulating film 12, thereby fabricating the array substrate 1. Then, as shown in Fig. A liquid crystal display element is constituted from the array substrate 1.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to an array substrate, a liquid crystal display device, and a method of manufacturing an array substrate,

The present invention relates to an array substrate, a liquid crystal display element, and a method of manufacturing an array substrate.

The liquid crystal display element is constituted by sandwiching a liquid crystal on a pair of substrates such as a glass substrate. It is possible to form an alignment film for controlling the alignment of the liquid crystal on the surfaces of the pair of substrates. The liquid crystal display element functions as a fine shutter with respect to light emitted from a light source such as a backlight or an external light, and partially transmits or shields light to perform display. The liquid crystal display element has a feature of being thin, lightweight, and the like.

At first, the liquid crystal display element was used as a display element of an electronic calculator or a clock, centering on a character display. Thereafter, development of a simple matrix system facilitated dot matrix display, extending the application to display devices of notebook PCs and the like. In addition, by developing the active matrix type, it is possible to realize a good image quality with excellent contrast ratio and response performance, thereby overcoming the problems of fixed definition, colorization, and wide viewing angle. In recent years, a wider viewing angle, higher-speed response of the liquid crystal, improvement of display quality, and the like have been realized, and they have been used as a large-sized display device for a television. Further, the liquid crystal display element is required to have further improved image quality and brightness.

In an active matrix type liquid crystal display device, gate wirings and signal wirings are arranged in a lattice form on one of a pair of substrates sandwiching liquid crystal, thin film transistors (TFTs) are formed at intersections of gate wirings and signal wirings, Transistors) are provided to constitute an array substrate. On the array substrate, pixel electrodes are arranged in a region surrounded by gate wirings and signal wirings, and pixels serving as display units are constituted by the pixel electrodes.

In a liquid crystal display element, in order to realize improvement in brightness, it is effective to enlarge the pixel electrode. The brightness can be increased by increasing the area of the pixel electrode as much as possible and improving the aperture ratio. In this case, for example, as disclosed in Patent Document 1, there is known a technique of superimposing a pixel electrode on a gate wiring or a signal wiring to improve the aperture ratio. Patent Document 1 discloses an array substrate in which an insulating film made of an organic material of a thick film is formed between a wiring and a pixel electrode so that the coupling capacitance between the pixel electrode and the wiring is prevented from increasing, A liquid crystal display device has been proposed.

Japanese Patent Application Laid-Open No. 2001-264798

When an insulating film made of an organic material with a thick film is formed between the wiring and the pixel electrode in the array substrate as in the liquid crystal display element described in Patent Document 1, the electrical connection between the switching element such as the TFT and the pixel electrode , And a contact hole formed in the insulating film.

When a contact hole is formed in an insulating film made of an organic material, the use of a photolithography technique is effective. In this case, as the material for forming the insulating film, the use of a radiation-sensitive resin composition (hereinafter referred to as a radiation-sensitive resin composition) is preferable, and a radiation-sensitive resin composition is preferably selected from a so-called positive type. In an insulating film using a positive-type radiation-sensitive resin composition, when it is exposed to radiation, the solubility in a developing solution increases, and the sensitive portion is removed. Therefore, when a positive-type radiation sensitive resin composition is used, contact holes can be relatively easily formed by irradiating a portion of the insulating film where the contact holes are formed with radiation. In the present invention, the term " radiation " is a concept including visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle rays and the like.

However, in the case of a positive-type radiation-sensitive resin composition, a special material is required, for example, a compound that generates an acid by irradiation with radiation as a component. Such a special material is not easily available, and the range of material selection is narrow. Therefore, application of a negative-type radiation-sensitive resin composition which can be applied to a photolithography technique and which can realize a composition using various materials which are easily available is required. The negative radiation sensitive resin composition is a radiation sensitive resin composition in which the radiation sensitive resin composition is sensitive to radiation to lower the solubility in a developing solution and the sensitive portion remains after development.

However, when a contact hole is to be formed in an insulating film using a negative-type radiation-sensitive resin composition, as described above, a method of irradiating a residual portion of an insulating film other than the contact hole (hereinafter referred to as "exposure" And the reaction is caused. Thereafter, the insulating film is formed by heat curing or the like. Therefore, there is a case where the variation of the size of the insulating film is larger than that of the positive type in the manufacturing process of the insulating film which is followed by exposure, development, and heat curing. Particularly, in the case of using the conventional negative radiation-sensitive resin composition, it is necessary to perform the exposure and the curing after development at a very high temperature of about 230 캜 to 260 캜. Therefore, the size variation such as thermal expansion or contraction in the heat hardening step becomes large, and there arises a problem in formation of the contact hole strictly required to control the arrangement position and size.

From the above, it is desired to form an insulating film on an array substrate by using a negative-type radiation-sensitive resin composition, and to make it possible to form a contact hole by suppressing thermal expansion or contraction. In order to do so, a negative radiation-sensitive resin composition which can be cured at a low temperature of, for example, 200 캜 or less is required instead of the conventional curing step by heating at high temperature. The negative radiation-sensitive resin composition having such a curing property makes it possible to provide a desired insulating film.

In addition, from the viewpoint of energy saving, in recent years, a reduction in the temperature of the heating process in the production of a liquid crystal display element having an array substrate is required. In other words, in manufacturing an array substrate or a liquid crystal display device using the same, it is required to realize energy saving by lowering the temperature of a process requiring heating, such as a curing process of each component.

From the above, it is strongly desired to realize a negative radiation-sensitive resin composition capable of forming an insulating film having a contact hole by low-temperature curing. It is strongly desired to realize an array substrate having an insulating film that is cured at a low temperature using the negative radiation-sensitive resin composition. In addition, realization of a liquid crystal display device constructed using such an array substrate is strongly desired.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an array substrate having an insulating film formed of a negative-type radiation-sensitive resin composition capable of low-temperature curing and a method of manufacturing the same.

Another object of the present invention is to provide a liquid crystal display element using an array substrate having an insulating film formed of a negative radiation-sensitive resin composition capable of low-temperature curing.

According to a first aspect of the present invention, there is provided a semiconductor device comprising a switching active element,

An insulating film disposed on the switching active element,

A contact hole formed in the insulating film,

And a pixel electrode electrically connected to the switching active element via the contact hole,

The insulating film may be a negative type radiation sensitive resin containing a copolymer containing a constituent unit formed of at least one kind selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and a constituent unit formed from an epoxy group containing unsaturated compound The present invention relates to an array substrate formed of a composition.

In the first embodiment of the present invention, the radiation-sensitive resin composition comprises a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, An amide compound, a thiol compound, a block isocyanate compound, and an imidazole ring-containing compound.

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group, provided that at least one of R ¹ to R ⁶ is an electron-withdrawing group and R ¹ to R ⁶ At least one of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;

In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that at least one of R ⁷ to R ¹⁶ is an amino group; The amino group may be substituted with all or a part of the hydrogen atoms by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group).

In the first embodiment of the present invention, it is preferable that the insulating film is formed at a curing temperature of 200 캜 or less.

In a first embodiment of the present invention, there is provided a liquid crystal display device having a transparent electrode on an insulating film, a liquid crystal aligning agent containing a radiation sensitive polymer having a photo aligning group and a liquid crystal aligning layer containing a polyimide having no photo aligning group, It is preferable to have an alignment film obtained by using any of the alignment agents.

In the first embodiment of the present invention, it is preferable that the alignment film is an alignment film obtained by using a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo aligning group.

A second embodiment of the present invention relates to a liquid crystal display element having an array substrate according to the first embodiment of the present invention.

According to a third aspect of the present invention,

[1] A negative radiation-sensitive resin composition comprising a copolymer comprising a constituent unit formed of at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride and a constituent unit formed from an epoxy group- Forming a coating film of the composition on a substrate on which a switching active element is formed,

[2] a step of irradiating at least a part of the coated film of the radiation sensitive resin composition with radiation,

[3] a step of developing the coating film irradiated with the radiation in the step [2] to obtain a coating film on which the contact hole is formed, and

[4] A method for manufacturing an array substrate, characterized by having a step of forming an insulating film by curing the coating film obtained at the step [3] at 200 ° C or less.

In the third embodiment of the present invention, the radiation-sensitive resin composition contains a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, An amide compound, a thiol compound, a block isocyanate compound, and an imidazole ring-containing compound.

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group, provided that at least one of R ¹ to R ⁶ is an electron-withdrawing group and R ¹ to R ⁶ At least one of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;

In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that at least one of R ⁷ to R ¹⁶ is an amino group; The amino group may be substituted with all or a part of the hydrogen atoms by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group).

In the third embodiment of the present invention, it is preferable to further include a step of forming the alignment film at 200 DEG C or lower.

In the third embodiment of the present invention, the step of forming the alignment film at 200 ° C or lower includes a step of forming a liquid crystal alignment agent containing a radiation sensitive polymer having a photo aligning group and a liquid crystal aligning agent containing a polyimide having no photo aligning group It is preferable to form the alignment film by using any of them.

According to the present invention, there is provided an array substrate having an insulating film formed of a negative-type radiation-sensitive resin composition capable of low-temperature curing and a manufacturing method thereof.

According to the present invention, there is also provided a liquid crystal display element comprising an array substrate having an insulating film formed of a negative radiation sensitive resin composition capable of low temperature curing.

FIG. 1 is a schematic cross-sectional view showing the main part of the array substrate of the embodiment. FIG.
2 is a schematic electrode wiring diagram of the array substrate of this embodiment.
3 is a schematic cross-sectional view of the liquid crystal display element of the present embodiment.

(Mode for carrying out the invention)

An array substrate and a liquid crystal display element according to embodiments of the present invention will be described.

<Liquid crystal display element>

The liquid crystal display element of the present embodiment is a color liquid crystal display element constructed using the array substrate of the present embodiment. Hereinafter, the structure of the array substrate of this embodiment and the structure of the liquid crystal display element of this embodiment will be described with reference to the drawings.

The liquid crystal display element of the present embodiment can be, for example, an active matrix type color liquid crystal display element. The liquid crystal display element of the present embodiment can have a structure in which the array substrate of the present embodiment in which the switching active element, the electrode and the insulating film are formed, and the color filter substrate on which the transparent electrode is formed face each other with the liquid crystal layer interposed therebetween.

1 is a schematic cross-sectional view showing a recessed portion structure of an array substrate of the present embodiment.

2 is a schematic electrode wiring diagram of the array substrate of the present embodiment.

The array substrate 1 shown in Fig. 1 is an example of the array substrate of the present embodiment. On one surface of the transparent substrate 4, a switching active element 8 is arranged. A source electrode 5, a drain electrode 6 and a gate electrode 7, which are connected to the switching active element 8, are arranged. An insulating film 12 is formed on the switching active element 8 and a transparent electrode 9 which is a pixel electrode is disposed on the insulating film 12. The transparent electrode 9 is formed of a transparent conductive film made of ITO (Indium Tin Oxide: indium oxide doped with tin) or the like. On the transparent electrode 9, it is possible to form an alignment film 10 for controlling the alignment of the liquid crystal as shown in the figure. The concave structure formed to penetrate the insulating film 12 is a contact hole 17 through which the transparent electrode 9 and the drain electrode 6 are electrically connected. As a result, electrical connection between the transparent electrode 9, which is a pixel electrode, and the switching active element 8 becomes possible. 2, on the array substrate 1, the source wiring 18 and the gate wiring 19 are arranged in a matrix. A switching active element 8 is provided in the vicinity of the intersection of the source wiring 18 and the gate wiring 19. The source electrode 5 is connected to the source wiring 18, (19). In this way, each pixel partitioned on the array substrate 1 is constituted.

The insulating film 12 is formed on the substrate 4 on which the electrodes such as the source electrode 5 and the switching active element 8 are formed as will be described later on the array substrate 1 of the present embodiment, Sensitive patterned resin composition of the present invention is applied and patterned after the formation of the contact hole 17, etc., and then cured. The radiation-sensitive resin composition of the present embodiment used for forming the insulating film 12 is a negative radiation-sensitive resin composition unless otherwise specified, and hereinafter, it is simply referred to as a radiation-sensitive resin composition .

The radiation sensitive resin composition of the present embodiment is characterized in that the insulating film 12 can be formed by low temperature curing at 200 DEG C or less. Therefore, the insulating film 12 can suppress the variation in size in the heat hardening step, and can form the contact hole 17 of a desired arrangement position and size. In the array substrate 1 of the present embodiment, the insulating film 12 can be formed by low-temperature curing at a temperature of 200 占 폚 or less, and production by low-temperature heating becomes possible.

In the array substrate 1 of the present embodiment, after the transparent electrode 9 is formed, it is possible to form the alignment film 10 for liquid crystal alignment. The alignment film 10 can be obtained by using a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-aligning group or a liquid crystal aligning agent containing a polyimide having no photo-aligning group, as described later. In this case, it becomes possible to form an alignment film at a heating temperature of 200 DEG C or less. Therefore, in the array substrate 1 of the present embodiment, the insulating film 12 can be formed by low-temperature curing at 200 DEG C or less, and the alignment film 10 can be formed by low-temperature curing at 200 DEG C or less, Production by low-temperature heating becomes possible.

Next, the liquid crystal display element of this embodiment using the array substrate of the present embodiment will be described.

3 is a schematic cross-sectional view of the liquid crystal display element of the present embodiment.

The liquid crystal display element 21 shown in Fig. 3 is a color liquid crystal display element comprising the array substrate 1 and the color filter substrate 22, and is an example of the liquid crystal display element of this embodiment. The liquid crystal display element 21 is, for example, a TN (Twisted Nematic) mode liquid crystal display element of a thin film transistor type, in which the array substrate 1 and the color filter substrate 22 of this embodiment shown in Fig. And has a structure that faces the liquid crystal layer 23 made of liquid crystal.

3, the array substrate 1 is provided with a source electrode 5, a drain electrode 6, a gate electrode 7 and a source electrode 5 on the surface of the transparent substrate 4 on the liquid crystal layer 23 side. A switching active element 8, and an insulating film 12 are disposed. On the insulating film 12, a transparent electrode 9 which is a pixel electrode is provided. A contact hole 17 penetrating the insulating film 12 is formed in the insulating film 12 and the transparent electrode 9 and the drain electrode 6 are electrically connected to each other through this portion. As a result, electrical connection between the transparent electrode 9, which is a pixel electrode, and the switching active element 8 becomes possible. On the transparent electrode 9, an alignment film 10 for liquid crystal alignment control is formed.

The color filter substrate 22 is provided with a minute colored pattern 15 of red, green and blue and a black matrix 13 on the surface of the transparent substrate 11 on the liquid crystal layer 23 side. The red, green, and blue colored patterns 15 are arranged in a regular shape such as a lattice shape. The color of the coloring pattern 15 is not limited to the three colors of red, green and blue described above, but it is also possible to select another color or to add a yellow color to form a coloring pattern of four colors. The color filter substrate can be formed by arranging the coloring patterns of the respective colors.

On the colored pattern 15 and the black matrix 13, a transparent common electrode 14 is provided. On the surface of the color filter substrate 22 which is in contact with the liquid crystal layer 23, the same alignment film 10 as the array substrate 1 is formed. The alignment film 10 of the array substrate 1 and the color filter substrate 22 is subjected to an alignment treatment to form a liquid crystal layer 23 sandwiched between the array substrate 1 and the color filter substrate 22 ) Can be uniformly aligned.

The distance between the array substrate 1 and the counter substrate 22 opposed to each other via the liquid crystal layer 23 is held by a spacer (not shown), and is usually 2 m to 10 m. The array substrate 1 and the color filter substrate 22 are fixed to each other by a sealing material (not shown) provided at the peripheral portion.

In the array substrate 1 and the color filter substrate 22, a polarizing plate 28 is disposed on the side opposite to the side in contact with the liquid crystal layer 23, respectively.

3, reference numeral 27 denotes backlight irradiated from the backlight unit (not shown) which is a light source of the liquid crystal display element 21 toward the liquid crystal layer 23. [ As the backlight unit, for example, a structure having a combination of a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate can be used. Further, a backlight unit using a white LED as a light source may also be used. As the white LED, for example, a white LED which obtains white light by using a red LED having an independent spectrum, a green LED and a blue LED, a white LED which obtains white light by mixing a red LED, a green LED and a blue LED, A white LED that obtains white light by mixing a LED with a red LED and a green phosphor, a white LED that combines a blue LED, a red light emitting phosphor, and a green light emitting phosphor to obtain white light by mixing, a mixture of a blue LED and a YAG- A white LED that obtains white light by mixing blue light, a blue LED, an orange light emitting phosphor and a green light emitting phosphor, a combination of an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor And a white LED for obtaining white light by mixing color.

The liquid crystal mode of the liquid crystal display element 21 of the present embodiment can be changed to a super twisted nematic (STN), an in-plane switching (IPS), a vertical aligntone (VA), or an optically compensated birefringence ) Or the like. In this case, in particular, with respect to the alignment film 10, an alignment film which realizes the alignment of the liquid crystal layer optimum for each liquid crystal mode is selected. For example, when the liquid crystal display element of this embodiment mode is a VA mode liquid crystal display element, an orientation film of a vertical alignment type is used for the orientation film.

As described above, the liquid crystal display element 21 of the present embodiment has the array substrate 1 of the present embodiment. The array substrate 1 realizes the electrical connection between the transparent electrode 9 and the drain electrode 6 via the contact hole 17 formed in the insulating film 12. The insulating film 12 of the array substrate 1 is formed by low temperature curing at 200 占 폚 or less using the radiation sensitive resin composition of the present embodiment. Therefore, in the liquid crystal display element 21 of the present embodiment, the contact hole 17 having the desired arrangement position and size is used to connect the transparent electrode 9 and the drain electrode 6 It is possible to realize an electrical connection.

Next, the formation of an insulating film which is a main component of the array substrate of the liquid crystal display element of the present embodiment and which can be cured at low temperatures will be described in detail. The insulating film of the array substrate of this embodiment is formed using the radiation sensitive resin composition of the present embodiment. Therefore, the composition of the radiation sensitive resin composition of the present embodiment will be specifically described.

<Radiation-Resistant Resin Composition>

The radiation-sensitive resin composition used for producing the insulating film of the array substrate of the present embodiment contains the [A] alkali-soluble resin, the [B] polymerizable compound and the [C] polymerization initiator. And may also contain a [D] compound. In addition, other optional components may be contained as long as the effect of the present invention is not impaired. Hereinafter, each component contained in the radiation sensitive resin composition will be described.

<[A] Alkali-soluble resin>

The alkali-soluble resin [A] is not particularly limited as long as it has a carboxyl group and thus is a resin having alkali developability. Further, it is preferably a copolymer containing at least one structural unit selected from the group consisting of a structural unit having a (meth) acryloyloxy group and a structural unit having an epoxy group. When the alkali-soluble resin [A] contains the specific structural unit, a cured film having excellent surface curability and deep part curability can be formed.

 The alkali-soluble resin [A] includes at least one kind selected from the group consisting of (A1) unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter also referred to as "(A1) compound") and (A2) epoxy group- , "(A2) compound") can be copolymerized and synthesized. The [A] alkali-soluble resin is a copolymer comprising a constituent unit formed of at least one kind selected from the group consisting of an unsaturated carbonic acid and an unsaturated carbonic anhydride and a constituent unit formed from an epoxy group-containing unsaturated compound.

[A] The alkali-soluble resin is produced, for example, by copolymerizing a compound (A1) imparting a carboxyl group-containing structural unit and a compound (A2) imparting an epoxy group-containing structural unit in a solvent in the presence of a polymerization initiator . The copolymer (A3) may also be prepared by further adding a hydroxyl group-containing unsaturated compound giving a hydroxyl group-containing structural unit (hereinafter also referred to as "(A3) compound"). In the preparation of the alkali-soluble resin (A), the compound (A1), the compound (A2) and the compound (A3) An unsaturated compound imparting a structural unit other than the derived structural unit) may be further added to form a copolymer. Hereinafter, each compound will be described in detail.

[(A1) compound]

Examples of the compound (A1) include mono [(meth) acryloyloxyalkyl] esters of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, polyvalent carboxylic acids, mono ( (Meth) acrylate, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.

Examples of the unsaturated monocarbonic acid include acrylic acid, methacrylic acid, crotonic acid and the like;

Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;

As the anhydride of the unsaturated dicarboxylic acid, for example, an anhydride of the compound exemplified as the dicarboxylic acid;

Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ] Etc;

Examples of the mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at both terminals include? -Carboxypolycaprolactone mono (meth) acrylate and the like;

Examples of the unsaturated polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto- [2.2.1] hept-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] And the like.

Of these compounds, monocarboxylic acid, dicarboxylic acid anhydride, acrylic acid, methacrylic acid and maleic anhydride are preferable, and acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity, solubility in alkaline aqueous solution, desirable. These compounds (A1) may be used alone or in combination of two or more.

The proportion of the compound (A1) used is preferably 5% by mass to 30% by mass, based on the total amount of the compound (A1) and the compound (A2) (optionally, the compound (A3) , And more preferably 10% by mass to 25% by mass. When the proportion of the compound (A1) used is from 5% by mass to 30% by mass, the solubility of the [A] alkali-soluble resin in an alkali aqueous solution is optimized and an insulating film having excellent radiation sensitivity is obtained.

[(A2) compound]

(A2) is an epoxy group-containing unsaturated compound having a radical polymerizing property. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure).

Examples of the unsaturated compound having an oxiranyl group include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, glycidyl? -Ethyl acrylate, glycidyl? -N-propyl acrylate Epoxycyclohexyl acrylate, glycidyl acrylate, glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyhexyl acrylate, 6,7- Vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxycyclohexylmethyl methacrylate, and the like can be used. . Of these, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p Vinylbenzyl glycidyl ether and 3,4-epoxycyclohexyl methacrylate are preferable from the viewpoints of improvement of copolymerization reactivity and solvent resistance such as an insulating film and the like.

As the unsaturated compound having an oxetanyl group, for example,

3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- Oxyethyl) -3-ethyloxetane, and 3- (2-acryloyloxyethyl) -2-phenyloxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- , 2-difluorooxetane and the like, and the like.

Among these compounds (A2), glycidyl (meth) acrylate is preferable. These compounds (A2) may be used alone or in combination of two or more.

The proportion of the compound (A2) used is preferably 5% by mass to 60% by mass based on the total amount of the compound (A1) and the compound (A2) (optional compound (A3) and compound (A4) , And more preferably 10% by mass to 50% by mass. The insulating film can be formed as a cured film having excellent curability and the like by making the use ratio of the compound (A2) 5% by mass to 60% by mass.

[(A3) compound]

As the compound (A3), first, a (meth) acrylic acid ester having a hydroxyl group, a (meth) acrylic acid ester having a phenolic hydroxyl group, and hydroxystyrene can be given.

Examples of the acrylic acid ester having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, and 6-hydroxyhexyl acrylate.

Examples of the methacrylic ester having a hydroxyl group include 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, methacrylic acid 6-hydroxyhexyl, and the like.

Examples of the acrylic acid ester having a phenolic hydroxyl group include 2-hydroxyethyl acrylate, 4-hydroxyphenyl acrylate, and the like. Examples of the methacrylic acid ester having a phenolic hydroxyl group include 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate and the like.

As the hydroxystyrene, o-hydroxystyrene, p-hydroxystyrene, and? -Methyl-p-hydroxystyrene are preferable. These (A3) compounds may be used alone or in combination of two or more.

The proportion of the compound (A3) used is preferably 1% by mass to 30% by mass, based on the total amount of the compound (A1), the compound (A2) and the compound (A3) , And more preferably from 5% by mass to 25% by mass.

[(A4) compound]

(A4) compound is not particularly limited as long as it is an unsaturated compound other than the above-mentioned (A1) compound, (A2) compound and (A3) compound. (A4) compounds include, for example, methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, acrylic acid chain alkyl esters, acrylic acid cyclic alkyl esters, methacrylic acid aryl esters, acrylic acid aryl esters, unsaturated dicarboxylic acid diesters, Unsaturated compounds having a cyclic unsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, and other unsaturated compounds.

Examples of the methacrylic acid chain alkyl ester include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate , Isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Examples of the methacrylic acid cyclic alkyl esters include cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-methacrylate, methacrylic acid tri Cyclo [5.2.1.0 ^2,6 ] decan-8-yloxyethyl, isobornyl methacrylate, and the like.

Examples of the acrylic acid chain alkyl ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, , N-stearyl acrylate, and the like.

Examples of acrylic acid cyclic alkyl esters include cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, and isobornyl acrylate.

Examples of the methacrylic acid aryl esters include phenyl methacrylate and benzyl methacrylate.

Examples of the acrylic acid aryl esters include phenyl acrylate and benzyl acrylate.

Examples of the unsaturated dicarboxylic acid diester include diethyl maleate, diethyl fumarate, diethyl itaconate and the like.

Examples of the bicyclounsaturated compound include bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, and 5-ethoxybicyclo [2.2.1] hept-2-ene.

Examples of the maleimide compound include N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) Maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

Examples of the unsaturated aromatic compound include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene and the like.

Examples of the conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Examples of the unsaturated compound containing a tetrahydrofuran skeleton include tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxypropionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxytetrahydro Furan-2-one, and the like.

Examples of the unsaturated compound containing a furan skeleton include 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) 2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) 2-yl-1-methyl-ethyl ester, 6- (2-furyl) -6-methyl-1-heptene- - on.

Examples of the unsaturated compound containing a tetrahydropyran skeleton include (tetrahydropyran-2-yl) methyl methacrylate, 2,6-dimethyl-8- (tetrahydropyran- 1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester and 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one.

Examples of the unsaturated compound containing a pyran skeleton include 4- (1, 4-dioxa-5-oxo-6-heptenyl) -6- -6-oxo-7-octenyl) -6-methyl-2-pyran.

Examples of other unsaturated compounds include acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, and vinyl acetate.

Among these compounds (A4), a methacrylic acid chain alkyl ester, a methacrylic acid cyclic alkyl ester, a methacrylic acid aryl ester, a maleimide compound, a tetrahydrofuran skeleton, a furan skeleton, a tetrahydropyran skeleton, a pyran skeleton, an unsaturated aromatic compound , And acrylic acid cyclic alkyl esters are preferable. Of these, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane- (Meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, methacryloxypropylmethacrylate, methacryloxypropylmethacrylate, (Meth) acryloyloxytetrahydrofuran-2-one is more preferable in terms of copolymerization reactivity and solubility in an aqueous alkali solution. These (A4) compounds may be used alone or in combination of two or more.

The proportion of the compound (A4) to be used is preferably 10% by mass to 80% by mass based on the total amount of the compound (A1), the compound (A2) and the compound (A4) .

<Synthesis Method 1 of [A] Alkali-Soluble Resin>

The alkali-soluble resin [A] can be produced, for example, by copolymerizing the above-mentioned (A1) compound and (A2) compound (optionally, (A3) compound and (A4) compound in the presence of a polymerization initiator in a solvent) can do. According to this synthesis method, a copolymer containing at least an epoxy group-containing structural unit can be synthesized.

Examples of the solvent used in the polymerization reaction for producing the [A] alkali-soluble resin include alcohols, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, dipropylene glycol Dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, propylene glycol monoalkyl ether propionates, ketones, and esters.

As the polymerization initiator used in the polymerization reaction for producing [A] the alkali-soluble resin, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis - (4-methoxy-2,4-dimethylvaleronitrile), and the like.

In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight regulator may be used to adjust the molecular weight. Examples of the molecular weight regulator include halogenated hydrocarbon such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; residues such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Genus; Terpinolene, alpha -methylstyrene dimer, and the like.

The weight average molecular weight (Mw) of the alkali-soluble resin [A] is preferably 1,000 to 30,000, more preferably 5,000 to 20,000. By setting the Mw of the alkali-soluble resin [A] within the above range, the sensitivity and developability of the radiation-sensitive resin composition can be enhanced. The Mw and the number average molecular weight (Mn) of the polymer in the present specification were measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: GPC-101 (manufactured by Showa Denko K.K.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<Synthesis Method 2 of [A] Alkali-Soluble Resin>

The alkali-soluble resin (A) can be obtained, for example, by copolymerizing a copolymer (hereinafter also referred to as a "specific copolymer") that can be synthesized by using one or more of the above-mentioned compounds (A1) Can be synthesized. According to this synthesis method, a copolymer containing a structural unit having at least a (meth) acryloyloxy group can be synthesized.

The structural unit having a (meth) acryloyloxy group contained in the [A] alkali-soluble resin is represented by the following formula (3). This structural unit is obtained by reacting a carboxyl group in a specific copolymer derived from the (A1) compound with an epoxy group of the compound (A2) to form an ester bond.

In the above formula (3), R ²⁰ and R ²¹ are each independently a hydrogen atom or a methyl group. c is an integer of 1 to 6; R ²² is a divalent group represented by the following formula (4-1) or (4-2).

In the formula (4-1), R ²³ is a hydrogen atom or a methyl group. In the formulas (4-1) and (4-2), * represents a bonding site with an oxygen atom.

With respect to the structural unit represented by the formula (3), for example, a compound having a carboxyl group is reacted with a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate as the compound (A2) , R ²² in the formula (3) becomes the formula (4-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted as the compound (A2), R ²² in the formula (3) becomes the formula (4-2).

In the synthesis of the specific copolymer, a compound other than the compound (A1), for example, the compound (A3), the compound (A4) described above may be used as a copolymerization component. These compounds include methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] methacrylic acid, Octane, decane-8-yl, styrene, p-methoxystyrene, tetrahydrofuran-2-yl methacrylate, and 1,3-butadiene.

As a method for copolymerizing a specific copolymer, for example, there can be mentioned a method of polymerizing (A1) a compound and (A3) compound, if necessary, in the presence of a radical polymerization initiator in a solvent.

Examples of the radical polymerization initiator include those exemplified above in the section [A] of the alkali-soluble resin. The amount of the radical polymerization initiator to be used is usually 0.1% by mass to 50% by mass, preferably 0.1% by mass to 20% by mass, based on 100% by mass of the polymerizable unsaturated compound. The specific copolymer may be provided in the production of the alkali-soluble resin [A] as the polymerization reaction solution, or may be provided in the production of the alkali-soluble resin [A] after the copolymer is once separated from the solution.

The Mw of the specific copolymer is preferably 2,000 to 100,000, more preferably 5,000 to 50,000. By setting the Mw to 2,000 or more, it is possible to obtain a sufficient developing margin of the insulating film, to prevent a reduction in the residual film ratio (proportion of the pattern thin film remaining properly) of the formed coating film, It can be kept good. On the other hand, when the Mw is 100,000 or less, a high sensitivity can be maintained and a good pattern shape can be obtained. The molecular weight distribution (Mw / Mn) of the specific copolymer is preferably 5.0 or less, more preferably 3.0 or less. By setting the Mw / Mn to 5.0 or less, the shape of the obtained pattern can be kept good. The insulating film containing a specific copolymer having a specific range of Mw / Mn in the specific range has a high developing property and can easily form a predetermined pattern shape in a developing process without causing development remaining.

The content of the structural unit derived from the compound (A1) in the alkali-soluble resin is preferably 5% by mass to 60% by mass, more preferably 7% by mass to 50% by mass, even more preferably 8% Is particularly preferable.

The content of the structural unit derived from the compound (A3) or the compound (A4) other than the compound (A1) of the alkali-soluble resin is 10% by mass to 90% by mass and 20% by mass to 80% by mass .

In the reaction of the specific copolymer with the compound (A2), an unsaturated compound having an epoxy group is preferably added to a solution of a copolymer containing a polymerization inhibitor, optionally in the presence of a suitable catalyst, And stirred for a predetermined time. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 hours to 12 hours.

The proportion of the compound (A2) used is preferably 5% by mass to 99% by mass, and more preferably 10% by mass to 97% by mass, based on the carboxyl group derived from the compound (A1) in the copolymer. By setting the ratio of the compound (A2) within the above range, the reactivity with the copolymer and the curing property of the cured film are further improved. (A2) may be used alone or in admixture of two or more.

&Lt; [B] Polymerizable compound >

The [B] polymerizable compound contained in the radiation sensitive resin composition of the present embodiment used in the production of the insulating film of the array substrate of this embodiment will be described.

Examples of the polymerizable compound which can be used as the [B] polymerizable compound include ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) (Meth) acrylate such as 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (Meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, 2- (2-hydroxyethyl) -3- Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (meth) acrylate, trimethylolpropane tri Hexa (meta) (Meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate and the like, straight chain alkylene groups and (Meth) acrylate compound obtained by reacting a compound having an alicyclic structure and two or more isocyanate groups and a compound having at least one hydroxyl group and three to five (meth) acryloyloxy groups in the molecule And the like.

Commercially available products of the usable [B] polymerizable compound include, for example,

ARONIX (registered trademark) M-400, M-402, M-405, M-450, M-1310, M-1600, M-1960, M-7100 , M-8030, M-8060, M-8100, M-8530, M-8560, M-9050, Aronix (registered trademark) TO-756, TO-1450, TO-1382 KAARAD (registered trademark) DPHA, copper DPCA-20, copper DPCA-30, copper DPCA-60, copper DPCA-120 and copper MAX-3510 (all manufactured by TOAGOSE KOGYO Co., ), VISCOAT 295, 300, Copper 360, Copper GPT, Copper 3PA, Copper 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and urethane acrylate compound as NEW FRONTIER KAYARAD (registered trademark) DPHA-40H, UX-5000 (manufactured by Nippon Kayaku K.K.), ARTRESIN UN-9000H (manufactured by Nippon Kayaku Co., M-5300, M-5600, M-5700, M-210, M-220, M-240, M-2, KAYARAD (registered trademark) HDDA, KAYARAD (registered trademark) HX-70, M-6200, M-305, M-309, M- 2201, H-620, R-526, R-167, R-604, R-684, R-551, 3201, UX-3301, UX-4101, UX-6101, UX-7101, UX-8101, UX- 0937, MU-2100, MU-4001 (all of which are manufactured by Nippon Kayaku Co., ), ART resin UN-9000 PEP, UN-9200A, UN-7600, UN-333, UN-1003, UN-1255, UN-6060P, , Niseko Kogyo Co., Ltd.), Viscot 260, Copper 312, Copper 335 HP (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

[B] The polymerizable compounds may be used alone or in combination of two or more. The content of the [B] polymerizable compound in the radiation-sensitive resin composition is preferably 20 parts by mass to 200 parts by mass, more preferably 40 parts by mass to 160 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin . By setting the ratio of the [B] polymerizable compound within the above range, it is possible to form a cured film having excellent adhesiveness and sufficient hardness even at a low exposure dose, and an excellent insulating film can be provided.

<[C] Polymerization initiator>

The [C] polymerization initiator contained in the radiation sensitive resin composition of the present embodiment used in the production of the insulating film of the array substrate of this embodiment will be described.

[C] The polymerization initiator is a radiation-sensitive polymerization initiator and is a component that generates active species capable of initiating polymerization of the [B] polymerizable compound in response to radiation. Examples of these [C] polymerization initiators include O-acyloxime compounds, acetophenone compounds, and imidazole compounds. These compounds may be used singly or in combination of two or more kinds.

Examples of the O-acyloxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ -9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-l- Yl-oxo-O-benzoate, 1- [9-ethyl-6- benzoate, ethanone-1- [9-ethyl-6- (2-ethylbenzoyl) -9H-carbazol- Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime), ethanone- 1- [ (9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol- ) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone- 1- [ - dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) Can.

Among them, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone- 1- [ (9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-3 -1- (O-acetyloxime) or ethanone-1- [9-ethyl-6- {2-methyl- 4- (2,2- dimethyl- 1, 3- dioxoranyl) methoxybenzoyl } -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.

Examples of the acetophenone compound include an? -Amino ketone compound and? -Hydroxy ketone compound.

Examples of the? -amino ketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) have.

Examples of the? -hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2- 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone and 1-hydroxycyclohexyl phenyl ketone.

Of these,? -Amino ketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane- .

Examples of the imidazole compound include 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 or 2,2'-bis (2,4,6-trichlorophenyl) 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferable, and 2,2'-bis (2,4-dichlorophenyl) -4,4' 5'-tetraphenyl-1,2'-biimidazole is more preferable.

[C] The polymerization initiator may be used alone or in combination of two or more. The content of [C] polymerization initiator is preferably 1 part by mass to 40 parts by mass, more preferably 5 parts by mass to 30 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the ratio of the [C] polymerization initiator to be 1 part by mass to 40 parts by mass, the radiation-sensitive resin composition can form an insulating film having high solvent resistance, high hardness and high adhesion even at a low exposure dose.

&Lt; [D] Compound >

The radiation-sensitive resin composition of the present embodiment used in the production of the insulating film of the array substrate of this embodiment may contain the [D] compound. The [D] compound is a compound that fulfills its function as a curing agent. Therefore, for convenience, they may be referred to as [D] compound (curing agent) or [D] curing agent. The [D] compound is a compound represented by the following formula (1), a compound represented by the following formula (2), a tertiary amine compound, an amine salt, a phosphonium salt, an amidine salt, an amide compound, a thiol compound, a block isocyanate compound, At least one compound selected from the group consisting of a polycyclic aromatic ring-containing compound and a polycyclic aromatic ring-containing compound. The radiation-sensitive resin composition contains the [D] compound selected from the specific compound group to realize low-temperature curing of the insulating film. In addition, the storage stability of the radiation sensitive resin composition may be improved. Hereinafter, each compound will be described in detail.

[Compound represented by formula (1) and formula (2)

The [D] compound is preferably at least one compound selected from the group consisting of the compounds represented by the following formulas (1) and (2). By selecting the aforementioned specific compound having an amino group and an electron-deficient group as the [D] compound, low temperature curing of the insulating film can be realized. In addition, the storage stability of the radiation sensitive resin composition may be improved. Further, the voltage holding ratio of the liquid crystal display element including the obtained array substrate having the insulating film can be further improved.

In the above formula (1), R ¹ to R ⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group. Provided that at least one of R ¹ to R ⁶ is an electron-withdrawing group, and at least one of R ¹ to R ⁶ is an amino group, and all or part of the hydrogen atoms are substituted with an alkyl group having 1 to 6 carbon atoms .

In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group. Provided that at least one of R ⁷ to R ¹⁶ is an amino group. The amino group may be substituted with an alkylene group having 2 to 6 carbon atoms in all or a part of hydrogen atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. The methylene group and the alkylene group may be substituted with a cyano group, a halogen atom or a fluoroalkyl group in all or a part of hydrogen atoms.

Examples of the electron attractive group represented by R ¹ to R ^{16 in} the formulas (1) and (2) include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, An alkyloxysulfonyl group, a dicyanovinyl group, a tricyanovinyl group, a sulfonyl group and the like. Of these, a nitro group, an alkyloxysulfonyl group and a trifluoromethyl group are preferable. As the group represented by A, a methylene group which may be substituted with a sulfonyl group or a fluoroalkyl group is preferable.

As the compounds represented by the formulas (1) and (2)

Aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4'-diaminobenzophenone, 4,4'-diaminophenylbenzo 4,4'-diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino- , 1,4-diamino-2-nitrobenzene, 1,4-diamino-2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5- Diaminobenzoic acid, 2,2'-dichlorobenzidine, 2,2'-dibromobenzidine, 2,2'-diiodobenzidine, 2,2'-dinitrobenzidine, 2,2'-bis N, N-dimethyl-4-nitroaniline is preferable, and it is preferable to use N, N-dimethylaniline, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, More preferred are acid ethyl, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene and N, N-dimethyl-4-nitroaniline.

The compounds represented by the formulas (1) and (2) may be used alone or in combination of two or more. The content of the compound represented by the formula (1) and the formula (2) is preferably from 0.1 part by mass to 20 parts by mass, more preferably from 0.2 part by mass to 10 parts by mass, per 100 parts by mass of the [A] Do. By setting the content ratio of the compound represented by the formula (1) and the formula (2) within the above range, the curing of the insulating film formed of the radiation sensitive resin composition can be promoted. In addition, the storage stability of the radiation sensitive resin composition can be improved, and the voltage holding ratio of the liquid crystal display element provided with the array substrate having the obtained insulating film can be maintained at a high level.

[Tertiary amine compound]

When a general primary amine compound or secondary amine compound having high reactivity is allowed to coexist with an epoxy compound, the curing reaction proceeds due to the nucleophilic attack of the amine on the epoxy group during the preservation of the composition solution, thereby deteriorating the quality of the product. However, in the case of using a tertiary amine, storage stability is improved even when the tertiary amine is coexistent with the epoxy compound in the cognitive and composition parts due to the relatively low reactivity.

As the tertiary amine compound, at least one member selected from the group consisting of the compounds represented by the following formula (5) can be used.

In the formula (5), R ²⁴ to R ²⁶ each independently represent an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. Provided that R ²⁴ and R ²⁵ may be bonded to each other to form a ring structure together with the nitrogen atom to which they are bonded. The alkyl group, aryl group and aralkyl group may be substituted with a part or all of hydrogen atoms.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ²⁴ to R ²⁶ in the formula (5) include straight or branched chain methyl, ethyl, propyl, butyl, pentyl, hexyl, A decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group have.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ²⁴ to R ²⁶ in the formula (5) include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to 30 carbon atoms represented by R ²⁴ to R ²⁶ in the formula (5) include a benzyl group and a phenethyl group.

Examples of the tertiary amine compound include N, N-dimethylbenzylamine, triphenylamine, tributylamine, trioctylamine, tridodecylamine, dibutylbenzylamine, trinaphthylamine, N-ethyl-N N-dimethyl-4-bromoaniline, N, N-dimethyl-4-methylaniline, N, N-dimethylaniline, N, N-phenylpiperidine, N- (4-methoxyphenyl) piperidine, N-phenyl-1,2,3,4-tetrahydroisoquinoline, 6-benzyloxy- Methoxy-1,2,3,4-tetrahydroisoquinoline, N, N'-dimethylpiperazine, N, N-dimethylcyclohexylamine, 2-dimethylaminomethylphenol, 2,4,6- Tris (dimethylaminomethyl) phenol, and the like.

Of these tertiary amine compounds, trioctylamine, 2-dimethylaminomethylphenol, N, N-diethylaniline and the like are preferable. The tertiary amine compounds may be used alone or in combination of two or more. The content of the tertiary amine compound in the radiation-sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content ratio of the tertiary amine compound within the above-specified range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

[Amine salts and phosphonium salts]

As the amine salt and the phosphonium salt, at least one species selected from the group consisting of the compounds represented by the following formula (6) can be used.

In the formula (6), A ¹ is a nitrogen atom or a phosphorus atom. Each of R ²⁷ to R ³⁰ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 18 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. However, these groups may be substituted with some or all of the hydrogen atoms. Q ^- is a monovalent anion.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ²⁷ to R ³⁰ in the formula (6) include linear or branched alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, A decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group have.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ²⁷ to R ³⁰ in the above formula (6) include a phenyl group and a naphthyl group.

Examples of the aralkyl group having 7 to ³⁰ carbon atoms represented by R ²⁷ to R ³⁰ in the formula (6) include a benzyl group and a phenethyl group.

Examples of the monovalent anion represented by Q ^- in the formula (6) include a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a nitrate ion, a nitrite ion, a hypochlorite ion, a chlorite ion, , A perchlorate ion, a permanganate ion, a bicarbonate ion, a hydrogen dihydrogen ion, a hydrogen sulfide ion, a thiocyanate ion, a carbonic acid ion, a sulfonate ion, a phenoxide ion, a tetrafluoroborate ion, And antimonate ions.

When A ¹ in the formula (6) is a nitrogen atom, that is, the ammonium salt includes, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, Benzyltrimethylammonium chloride, benzyltrimethylammonium chloride, benzalkonium chloride, benzalkonium bromide, dibutylchloride, dibutyltin chloride, dibutyltin dichloride, dibutyltin dichloride, dibutyltin dichloride, dibutyltin dichloride, dibutyltin dichloride, Silyldimethylammonium chloride, distearyldimethylammonium chloride, and the like.

When A ¹ is a phosphorus atom, that is, as the phosphonium salt, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethyl Tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-methoxyphenyl) borate, tetraphenylphosphonium tetra Tetra (m-tolyl) borate, tetraphenylphosphonium tetra (m-methoxyphenyl) borate, tri (p- tolyl) phenylphosphonium tetra (P-tolyl) borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate (p-tolyl) borate, , Methyltriphenylphosphonium thiocyanate, p-tolyl tri Phenylphosphonium thiocyanate, and the like.

Of these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferable. The amine salt and the phosphonium salt may be used alone or in admixture of two or more. The content of the amine salt and the phosphonium salt in the radiation-sensitive resin composition is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin . By setting the content ratio of the amine salt and the phosphonium salt within the above-specified range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

[Amidine salt]

As the amidine salt, at least one species selected from the group consisting of salts of the compound represented by the following formula (7) can be used.

In the formula (7), m is an integer of 2 to 6. Provided that some or all of the hydrogen atoms of the alkylene group may be substituted with an organic group. The alkylene group refers to both an alkylene group in the tetrahydropyrimidine ring and an alkylene group represented by (CH ₂ ) _m in the formula (7).

Examples of organic groups that the alkylene group may have as a substituent include, for example,

An alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, isopropyl group, n-butyl group, t-butyl group and n-hexyl group;

Hydroxypropyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxy-t-butyl group, a 6-hydroxypropyl group, a 2-hydroxypropyl group, A hydroxyalkyl group having 1 to 6 carbon atoms such as a hydroxyhexyl group;

And dialkylamino groups having 2 to 12 carbon atoms such as dimethylamino group, methylethylamino group, diethylamino group, diisopropylamino group, dibutylamino group, t-butylmethylamino group and di-n-hexylamino group.

Examples of the compound represented by the above formula (7) include 1,5-diazabicyclo [4,3,0] -nonen-5 (DBN), 1,5-diazabicyclo [4.4.0] Diazabicyclo [5.4.0] undecene-7 (DBU), 5-hydroxypropyl-1,8-diazabicyclo [5.4.0] undecene-7, 5-dibutylamino-1,8-diazabicyclo [5,4,0] -undecene-7, and the like. Of these, DBN and DBU are preferred.

Examples of the acid for forming the salt of the compound represented by the formula (7) include an organic acid and an inorganic acid.

Examples of the organic acid include carbonic acid, monoalkyl carbonic acid, aromatic hydroxy compound, and sulfonic acid.

Among these acids, a carboxylic acid, an aromatic hydroxy compound and a sulfonic acid are preferable, and a saturated fatty acid, an aromatic hydroxy compound, and a sulfonic acid are more preferable, and a sulfonic acid which is a strong acid is particularly preferable, and toluenesulfonic acid, methanesulfonic acid and octylbenzenesulfonic acid Preferred examples of the amidine salt include a salt of DBU and toluenesulfonic acid, a salt of DBU and octylbenzenesulfonic acid, a salt of DBN and toluenesulfonic acid, and a salt of DBU and octylbenzenesulfonic acid.

The amidine salt may be used alone or in admixture of two or more. The content of the amidine salt in the radiation-sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content ratio of the amidine salt within the above-specified range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

[Amide compound]

As the amide compound, at least one kind selected from the group consisting of compounds having an amide group represented by the following formulas (8) to (10) can be used.

In the formula (8), R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group or a 2-pyridyl group. The alkyl, phenyl and naphthyl groups of 1 to 12 carbon atoms may be substituted with an alkyl group having 1 to 6 carbon atoms, a halogen atom, a hydroxyl group, a carboxyl group or an acetyl group.

In the formula (9), R ³³ and R ³⁴ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyclohexyl group. A ² is a methylene group, an alkylene group having ² to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a halogen atom.

In the formula (10), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cyclohexyl group. A ³ is a methylene group, an alkylene group having 2 to 12 carbon atoms, a phenylene group, a naphthylene group, or a vinylene group. The methylene group, the alkylene group having 2 to 12 carbon atoms, the phenylene group and the naphthylene group may be substituted with an alkyl group having 1 to 6 carbon atoms or a halogen atom.

The amide compound represented by the formula (8) is a compound having one amide bond in the molecule. Specific examples thereof include acetamide, N-methylacetamide, N-ethylacetamide, phthalamidic acid, acrylamide, benzamide, naphtoamide, nicotinamide, isonicotinamide and the like.

Of these, acetamide, N-methylacetamide and phthalamidic acid are preferable from the viewpoint of improving the storage stability at room temperature, the heat resistance of the obtained insulating film, the voltage holding ratio, and the like.

The compound represented by the formula (9) and the formula (10) is a compound having two amide bonds in the molecule. Specific examples thereof include, for example, phthalamide, isophthalamide, terephthalamide, malonamide, succinamide, N, N'-diacetyl-p-phenylenediamine, N, N'-diacetyl-hexamethylenediamine, N, N'-diacetyl-dodecyl methylenediamine, and the like.

Of these, from the viewpoint of compatibility between storage stability and low-temperature curing at a high level, it is preferable to use an isophthalamide, adipinamide, N, N'-diacetyl-p-phenylenediamine, N, N'-diacetyl- Methylenediamine is preferred.

The amide compounds may be used alone or in combination of two or more. The content of the amide compound in the radiation-sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content of the amide compound within the above-specified range, both the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be achieved at a higher level.

[Thiol compound]

The thiol compound is a compound having two or more mercapto groups in one molecule. The thiol compound is not particularly limited as far as it has two or more mercapto groups in one molecule, but at least one selected from the group consisting of the compounds represented by the following formula (11) can be used.

In the formula (11), R ³⁷ is a methylene group or an alkylene group having 2 to 10 carbon atoms. Provided that some or all of the hydrogen atoms may be substituted with an alkyl group. Y ¹ is a single bond, -CO- or O-CO- ^* . However, the combined hand affixed * is combined with R ^37. n is an integer of 2 to 10; A ⁴ is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or a plurality of ether bonds, or when n is 3, a group represented by the following formula (12).

In the formula (12), R ³⁸ to R ⁴⁰ each independently represent a methylene group or an alkylene group having 2 to 6 carbon atoms. The &quot; * &quot;

As the compound represented by the formula (11), typically an esterified product of mercaptocarboxylic acid and polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid and 3-mercaptopentanoic acid. Examples of the polyhydric alcohol constituting the esterified product include ethylene glycol, propylene glycol, trimethylol propane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, pentaerythritol, .

Examples of the compound represented by the formula (11) include trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptopentylate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine- 4,6 (1H, 3H, 5H) -tione is preferred.

As the compound having two or more mercapto groups in one molecule of the thiol compound, compounds represented by the following formulas (13) to (15) may be used.

In the above formula (13), R ⁴¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms. R ⁴² is a methylene group or a straight or branched alkylene group having 2 to 6 carbon atoms. k is an integer of 1 to 20;

In the formula (14), R ⁴³ to R ⁴⁶ each independently represent a hydrogen atom, a hydroxyl group or a group represented by the following formula (15). Provided that at least one of R ⁴³ to R ⁴⁶ is a group represented by the following formula (15).

In the formula (15), R ⁴⁷ is a methylene group or a straight-chain or branched alkylene group having 2 to 6 carbon atoms.

The thiol compounds may be used alone or in combination of two or more. The content of the thiol compound in the radiation-sensitive resin composition is preferably 1 part by mass to 20 parts by mass, more preferably 5 parts by mass to 15 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content of the thiol compound within the above-specified range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

[Block isocyanate compound]

The block polyisocyanate compound is obtained by reacting an isocyanate group with an active hydrogen group-containing compound (block agent) and making it inert at room temperature. When the block polyisocyanate compound is heated, the block is dissociated and the isocyanate group is regenerated. When the radiation-sensitive resin composition contains the block polyisocyanate, the isocyanate-hydroxyl group crosslinking reaction proceeds as an effective crosslinking agent, and the storage stability and the low-temperature curing of the radiation-sensitive resin composition can be made compatible at a high level.

The block polyisocyanate compound is obtained by a known reaction between a polyisocyanate derived from an aliphatic or alicyclic diisocyanate and a compound having an active hydrogen (block).

Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4- (Isocyanatomethyl) cyclohexane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis , Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, trinidine diisocyanate, xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethyl cyclohexyl diisocyanate, and the like.

As a commercially available product, for example,

B80E, TPA-B80X, E402-B80T, MF-B60XN, MF-B60X, MF-B80M (available from DERANATE TM) as an isocyanate group blocked with an oxime of methyl ethyl ketone , Asahi Kasei High School, Ltd.);

Duraanate (registered trademark) MF-K60X (manufactured by Asahi Kasei Kogyo K.K.) blocked with isocyanate group with active methylene;

KARENZ (registered trademark) MOI-BP, and CALENS (registered trademark) MOI-BM (manufactured by Showa Denko K.K.) as block bodies of an isocyanate compound having a (meth) acryloyl group, have. Of these, Duralate (registered trademark) E402-B80T and MF-K60X are preferably used because they exhibit high flexibility and can be freely controlled in their hardness by being used in a mixed system with others.

Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, buret type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, and the like. From the viewpoint of curability, isocyanurate type polyisocyanate is preferable.

As the blocking agent, for example, an alcohol compound, a phenol compound, an active methylene compound, a mercaptan compound, an acid amide compound, an acid imide compound, an imidazole compound, a pyrazole compound, Based compounds, amine-based compounds, imine-based compounds, and pyridine-based compounds.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol and the like;

Examples of the phenol compound include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, hydroxybenzoic acid ester and the like;

Examples of the active methylene compound include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone;

Examples of the mercapane-based compound include butyl mercaptan, dodecyl mercaptan, and the like;

As the acid amide compound, for example, acetanilide, acetic acid amide,? -Caprolactam,? -Valerolactam,? -Butyrolactam, etc.

Examples of the acid imide compound include succinic acid imide, maleic acid imide and the like;

Examples of imidazole-based compounds include imidazole, 2-methylimidazole and the like;

Examples of the pyrazole-based compound include 3-methylpyrazole, 3,5-dimethylpyrazole, and 3,5-ethylpyrazole;

Examples of the urea compound include urea, thiourea, ethylene urea and the like;

Examples of the oxime compounds include formaldeooxime, acetaldoxime, acetoxime, methylethylketooxime, cyclohexanone oxime and the like;

Examples of the amine-based compound include diphenylamine, aniline, carbazole and the like;

Examples of the imine compound include ethyleneimine, polyethyleneimine and the like;

Examples of the pyridine compound include 2-hydroxypyridine, 2-hydroxyquinoline, and the like.

The block polyisocyanate compound may be used alone or in admixture of two or more. The content of the block polyisocyanate compound in the radiation-sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content ratio of the block polyisocyanate compound within the above range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

 [Imidazole ring-containing compound]

As the imidazole ring-containing compound, at least one member selected from the group consisting of the compounds represented by the following formula (16) can be used.

In formula (16), A ⁵ , A ⁶ , A ⁷ and R ⁴⁸ are each independently a hydrogen atom or a straight, branched or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent. A ⁶ and A ⁷ may be connected to each other to form a ring.

As the linear, branched or cyclic hydrocarbon group of 1 to 20 carbon atoms represented by A ⁵ , A ⁶ , A ⁷ and R ⁴⁸ , for example,

Butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-hexyl group, N-pentyldecyl group, n-hexadecyl group, n-hexadecyl group, n-hexadecyl group, n-octadecyl group, An alkyl group having 1 to 20 carbon atoms such as a heptadecyl group, an n-octadecyl group, an n-nonadecyl group, and an n-eicosyl group;

A cycloalkyl group having 3 to 20 carbon atoms such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group;

An aryl group having 6 to 20 carbon atoms such as a phenyl group, a toluyl group, a benzyl group, a methylbenzyl group, a xylyl group, a mesityl group, a naphthyl group and an anthryl group;

Bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as a norbornyl group, a tricyclodecanyl group, a tetracyclododecyl group, an adamantyl group, a methyladamantyl group, an ethyladamantyl group and a butyladamantyl group, etc. .

The hydrocarbon group may be substituted, and specific examples of the substituent include,

A hydroxyl group;

A carboxyl group;

Hydroxyethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1 -hydroxybutyl group, , A 3-hydroxybutyl group, a 4-hydroxybutyl group, and other hydroxyalkyl groups having 1 to 4 carbon atoms;

An alkoxyl group having 1 to 4 carbon atoms such as a methoxyl group, an ethoxyl group, an n-propoxyl group, an i-propoxyl group, an n-butoxyl group, a 2-methylpropoxyl group, ;

Cyano;

A cyanoalkyl group having 2 to 5 carbon atoms such as a cyano group, a cyanomethyl group, a 2-cyanoethyl group, a 3-cyanopropyl group and a 4-cyanobutyl group;

An alkoxycarbonyl group having 2 to 5 carbon atoms such as a methoxycarbonyl group, ethoxycarbonyl group and t-butoxycarbonyl group;

An alkoxycarbonylalkoxyl group having 3 to 6 carbon atoms such as a methoxycarbonylmethoxyl group, an ethoxycarbonylmethoxyl group and a t-butoxycarbonylmethoxyl group;

Halogen atoms such as fluorine and chlorine;

And fluoroalkyl groups such as a fluoromethyl group, a trifluoromethyl group and a pentafluoroethyl group.

The ring formed by connecting A ⁶ and A ⁷ together is preferably an aromatic ring or a saturated or unsaturated nitrogen-containing heterocyclic ring having 2 to 20 carbon atoms. Examples of the imidazole ring-containing compound in which the ring formed by A ⁶ and A ⁷ are bonded to each other is a benzene ring, include the compounds represented by the following formula (17).

In the formula (17), R ⁴⁸ and A ⁵ have the same meanings as in the formula (16). R ⁴⁹ to R ⁵² each independently represents a linear, branched or cyclic hydrocarbon group of 1 to 20 carbon atoms which may have a substituent. The hydrocarbon group represented by R ⁴⁹ to R ⁵² may be the same as the hydrocarbon group represented by the formula (16).

As the imidazole ring-containing compound, 2-phenylbenzimidazole, 2-methylimidazole, and 2-methylbenzimidazole are preferable. The imidazole ring-containing compounds may be used alone or in admixture of two or more. The content of the imidazole ring-containing compound is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] alkali-soluble resin. By setting the content ratio of the imidazole ring-containing compound within the above-specified range, the storage stability of the radiation-sensitive resin composition and the low-temperature curing can be compatible at a higher level.

&Lt; Other optional components >

The radiation sensitive resin composition of the present embodiment, which is used for forming the insulating film of the array substrate of the present embodiment, contains, in addition to the above-mentioned [A] alkali-soluble resin, [B] polymerizable compound and [C] Other optional components such as a surfactant, a storage stabilizer, an adhesive aid, and a heat resistance improving agent may be added as needed within the range that does not impair the effects of the present invention, in addition to the [D] compounding agent (curing agent). These optional components may be used alone or in combination of two or more. Hereinafter, each component will be described in detail.

[Surfactants]

The surfactant can be used for further improving the film formability of the radiation-sensitive resin composition. Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, and other surfactants.

As the fluorine-containing surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least any of the terminal, main chain and side chain is preferable.

Examples of commercial products of the fluorinated surfactants include FTERGENT (registered trademark) FT-100, 110, -140A, -150, -250, -251, -300, 310, Dong-400S, Fotent (registered trademark) FTX-218, Dong-251 (above, Neos, Ltd.).

Examples of commercially available silicone surfactants include TORAY SILICON DC3PA, Copper DC7PA, Copper SH11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH-190, Copper SH-193, Copper SZ- 6032, SF-8428, DC-57 and DC-190 (trade names, Toray, Dow Corning, Silicones Inc.).

The amount of the surfactant to be used is preferably 1.0 part by mass or less, more preferably 0.8 part by mass or less, based on 100 parts by mass of the [A] alkali-soluble resin. If the amount of the surfactant used exceeds 1.0 part by mass, film unevenness of the coating film tends to occur.

[Storage stabilizer]

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitroso compounds and the like, and more specifically, 4-methoxyphenol, N-nitroso- Phenylhydroxylamine aluminum and the like.

The amount of the preservative stabilizer to be used is preferably 3.0 parts by mass or less, more preferably 1.0 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. If the blending amount of the preservative stabilizer exceeds 3.0 parts by mass, the sensitivity may be lowered and the pattern shape may be deteriorated.

[Adhesion preparation]

The adhesion aid can be used to further improve the adhesion between the obtained insulating film and the underlying layer or substrate. As the adhesion aid, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group and an oxiranyl group is preferable, and for example, trimethoxysilylbenzoic acid,? -Methacryloxypropyl Trimethylsilane, trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? - (3,4-epoxycyclohexyl) Ethyl trimethoxysilane and the like.

The amount of the adhesion aid to be used is preferably 20 parts by mass or less, more preferably 15 parts by mass or less based on 100 parts by mass of the [A] alkali-soluble resin. When the amount of the adhesive aid used exceeds 20 parts by mass, development residue tends to be easily generated.

[Heat resistance improving agent]

Examples of the heat resistance improving agent include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.

Examples of the N- (alkoxymethyl) glycol uril compound include N, N ', N ", N"' - tetra (methoxymethyl) glycoluril, N, N, N ' N, N ', N'-tetra (i-propoxymethyl) glycoluril, N, N', N'- , N ', N'-tetra (n-butoxymethyl) glycoluril and N, N, N', N'-tetra (t-butoxymethyl) glycoluril. Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ', N'-tetra (methoxymethyl) glycoluril are preferred.

Examples of the N- (alkoxymethyl) melamine compound include N, N, N ', N', N '', N '' - hexa (methoxymethyl) N, N ', N', N ', N' ', N' '- hexa (ethoxymethyl) melamine, , N '' - hexa (i-propoxymethyl) melamine, N, N ', N', N ' N ", N "-hexa (t-butoxymethyl) melamine, and the like. Of these N- (alkoxymethyl) melamine compounds, N, N, N ', N', N ", N" - hexa (methoxymethyl) melamine are preferred. Commercially available products include, for example, NICALAC N-2702 and MW-30M (available from Sanwa Chemical Co., Ltd.).

The amount of the heat resistance improving agent to be used is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the [A] alkali-soluble resin. When the blending amount of the heat resistance improver exceeds 50 parts by mass, the sensitivity of the radiation-sensitive resin composition is lowered and the pattern shape may be deteriorated.

&Lt; Preparation method of radiation-sensitive resin composition >

The radiation sensitive resin composition of the present embodiment, which is used for forming the insulating film of the array substrate of the present embodiment, contains, in addition to the [A] alkali-soluble resin, the [B] polymerizable compound and the [C] D] compound (curing agent) and other optional components added as necessary. The radiation-sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state. The solvents may be used alone or in combination of two or more.

As the solvent used in the preparation of the radiation-sensitive resin composition, an essential component and an optional component are dissolved uniformly and reacted with each component is used. Examples of such a solvent include the same solvents exemplified as the solvents that can be used for producing the above-described [A] alkali-soluble resin.

For example, from the viewpoints of solubility of each component, reactivity with each component, ease of forming a coating film, and the like, among these solvents, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene Diethylene 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, tri Ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, Dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol No methyl ether, tripropylene glycol monoethyl ether and (poly) alkylene glycol monoalkyl ether;

Acetic acid ethylene glycol monomethyl ether, acetic acid ethylene glycol monoethyl ether, acetic acid ethylene glycol mono-n-propyl ether, acetic acid ethylene glycol mono-n-butyl ether, acetic acid diethylene glycol monomethyl ether, acetic acid diethylene glycol monoethyl ether, 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, Acetic acid (poly) alkylene glycol monoalkyl ethers such as methoxybutyl;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Methylhexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy- Ketones;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;

Propyl acetate, n-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylacetate , N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butylate, i-propyl butylate, n- Ethyl acetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n- Other esters such as methyl acetoacetate, ethyl acetoacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutylate and ethyl 2-oxobutylate;

Aromatic hydrocarbons such as toluene and xylene;

And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol Diethyl acetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, Amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butylate, n-butyl butyl acetate and ethyl pyruvate are preferable. The solvent may be used alone or in combination of two or more.

Also, together with the above-mentioned solvent, there may be mentioned benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, A high boiling solvent such as ethyl, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, or ethylene glycol monophenyl ether acetate may be used in combination. The high boiling point solvent may be used alone or in combination of two or more.

The content of the solvent is not limited, but from the viewpoints of coating properties, stability, etc. of the resulting radiation-sensitive resin composition, the amount by which the total concentration of each component other than the solvent of the radiation-sensitive resin composition is 5% by mass to 50% , More preferably 10% by mass to 40% by mass. When the radiation sensitive resin composition is prepared in a solution state, the solid concentration (component other than the solvent in the composition solution) may be adjusted to any desired concentration (for example, 5% 50% by mass). More preferably, the solid concentration differs depending on the method of forming the coating film on the substrate, which will be described later. The thus prepared composition solution may be filtered after using a millipore filter having a pore diameter of about 0.5 mu m and then provided for use.

The radiation-sensitive resin composition according to the above components and the preparation method can form an insulating film having a contact hole by low-temperature curing. Specifically, an insulating film having good reliability such as solvent resistance can be obtained at a curing temperature of 200 DEG C or less, and even if the curing temperature is 180 DEG C or less, an insulating film having good reliability such as solvent resistance can be obtained. The array substrate of the present embodiment can be provided by low-temperature curing.

Next, the array substrate of this embodiment can have an alignment film for controlling alignment of liquid crystal. An alignment film formed on the array substrate of the present embodiment is formed using the liquid crystal aligning agent of the present embodiment. Therefore, the main components of the alignment treatment agent of the present embodiment will be described below.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present embodiment for forming an alignment film on the array substrate of the present embodiment contains the [L] radiation-sensitive polymer having a photo aligning group or the [M] polyimide having no photo aligning group as a main component Which is a liquid crystal aligning agent. All of these can form an alignment film at a low temperature such as 200 DEG C or less. In particular, it is preferable that a liquid crystal aligning agent containing an [L] radiation-sensitive polymer having a photo aligning group is capable of forming an alignment film at a lower temperature. As described above, since the liquid crystal aligning agent of the present embodiment can form an orientation film by a low-temperature heating process, the orientation film can be formed without being exposed to the state of high temperature heating of the insulating film due to low temperature curing in the lower layer .

The liquid crystal aligning agent of the present embodiment for forming an alignment film on the array substrate of the present embodiment may contain other components as long as the effect of the present invention is not impaired. Hereinafter, these components will be described.

[[L] Sensitizing Radiation Polymer]

The [L] radiation-sensitive polymer contained in the liquid crystal aligning agent of the present embodiment is a polymer having a photo-orientable group. The photo-orientable group of the [L] radiolabeled polymer is a functional group that imparts anisotropy to the film by light irradiation. In the present embodiment, in particular, by generating at least one of a photo-isomerization reaction and a photo- .

Specific examples of the photo-aligning group include azobenzene, stilbene,? -Imino-? -Ketoester, spiropyran, spirooxazine, cinnamic acid, chalcone, stilbazole, benzylidene phthalimidine, coumarin, Is a group having a structure derived from at least one compound selected from the group consisting of rhenium and anthracene. Among the above-mentioned photo-orientable groups, groups having a structure derived from cinnamic acid are particularly preferable.

As the [L] radiation-sensitive polymer having a photo-orientable group, it is preferable that the above-mentioned photo-orientable group is a polymer bonded directly or via a linking group. As such a polymer, for example, there may be mentioned one in which at least one polymer of polyamic acid and polyimide is bonded to the above-mentioned photo-orientable group, and the above-mentioned photo-orientable group is bonded to a polymer different from polyamic acid and polyimide. In the latter case, examples of the basic skeleton of the polymer having a photo-orientable group include poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, polyolefin, and polyorganosiloxane.

As the radiation-sensitive polymer, it is preferable that the basic skeleton is polyamic acid, polyimide or polyorganosiloxane. Among them, a polyorganosiloxane is particularly preferable and can be obtained, for example, by the method described in International Publication (WO) 2009/025386.

[[M] polyimide]

The [M] polyimide contained in the liquid crystal aligning agent of the present embodiment is a polyimide having no photo-aligning group.

The [M] polyimide having no photo-aligning group can be obtained by imidizing a polyamic acid having no photo-aligning group by dehydration ring closure. These polyamic acids can be obtained, for example, by reacting tetracarboxylic dianhydrides with diamines and can be obtained as described in JP-A-2010-97188.

The [M] polyimide may be a completely imidized product in which all of the arboric acid structure of the polyamic acid which is a precursor thereof is dehydrated and cyclized, and only a part of the arboric acid structure is subjected to dehydration ring closure, It may be de cargo. The [M] polyimide preferably has an imidization rate of 30% or more, more preferably 50% to 99%, and still more preferably 65% to 99%. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring or may be obtained, for example, as described in JP-A-2010-97188.

[[N] other ingredients]

The liquid crystal aligning agent of the present embodiment may contain other components than the radiation sensitive polymer having a photo aligning group and the polyimide having no photo aligning group. [N] Other components include, for example, a polymer other than the [L] radiation-sensitive polymer having a photo-aligning group and the [M] polyimide having no photo-aligning group, a curing agent, a curing catalyst, a curing accelerator, A silane compound, a silane compound, a surfactant, and a photosensitizer.

The main components of the array substrate of the present embodiment have been described above. Next, a method of manufacturing the array substrate of this embodiment will be described.

&Lt; Insulating Film, Orientation Film, and Manufacturing Method of Array Substrate &

In the production of the array substrate of the present embodiment, the main step includes a step of producing the insulating film from the radiation sensitive resin composition of the present embodiment described above. The insulating film on which the contact hole is formed is formed by this insulating film manufacturing process. In order to form an alignment film on the array substrate of the present embodiment, a step of forming an alignment film from the above-described liquid crystal aligning agent of the present embodiment is included as a manufacturing step. Hereinafter, a manufacturing method of the array substrate of the present embodiment having the insulating film and the alignment film will be described.

In the method of manufacturing an array substrate according to the present embodiment, it is preferable that an insulating film is formed on a substrate and at least the following steps [1] to [4] are included in the following order. Further, in order to form an alignment film on the array substrate, it is preferable to include the step [5] after the step [4].

[1] The coating film of the radiation-sensitive resin composition is referred to as a switching active element, an electrode or the like (sometimes referred to as an electrode or the like hereinafter as a source electrode, a drain electrode, a gate electrode, a source wiring, (Hereinafter sometimes referred to as &quot; [1] step &quot;),

[2] A process for irradiating at least a part of a coating film of a radiation-sensitive resin composition formed in the step [1] (hereinafter sometimes referred to as "step [2]")

[3] A process for developing a coating film irradiated with radiation in the process [2] (hereinafter sometimes referred to as "process [6]")

[4] The step of forming the insulating film by curing the coated film at a temperature of 200 ° C or less (hereinafter sometimes referred to as "step [4]") in the step [3]

[5] A step of forming a coating film of a liquid crystal aligning agent on a substrate having a cured insulating film in the step [4] and heating the coating film at a temperature of 200 ° C or lower to form an alignment film (hereinafter referred to as "step [5] )

Between the steps [4] and [5], it is preferable to have a step of forming a transparent electrode on the insulating film formed in the step [4].

By the method of manufacturing the array substrate according to the present embodiment including each of the above steps, the radiation sensitive resin composition of the present embodiment can be used to form on the substrate on which the switching active elements, electrodes, and the like are formed, Can be formed. An alignment film can be formed on the substrate using the liquid crystal aligning agent of the present embodiment. As a result, the array substrate of the present embodiment having the insulating film formed at a desired position of the contact hole of a desired size and having the insulating film formed at a low temperature can be formed by the manufacturing method of the array substrate of this embodiment.

The array substrate manufactured as described above is an array substrate which is also suitable for the case where it is desired to lower the temperature of the heating process from the viewpoint of energy saving.

Each step will be described in detail below.

[[1] Process]

In this step, a coating film of the radiation sensitive resin composition of the present embodiment is formed on a substrate. A switching active element, a source electrode, a drain electrode, a gate electrode, a source wiring, a gate wiring, and the like are formed on this substrate. These switching active elements and the like are formed by a known method such as repeating etching on a substrate by a normal semiconductor film forming film, a known insulating film forming film, and a photolithography method.

A radiation-sensitive resin composition is coated on the surface of the substrate such as a switching active element and the like, followed by pre-baking to evaporate the solvent to form a coating film.

Examples of the material of the substrate include glass such as soda lime glass and alkali-free glass, silicon, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, aromatic polyamide, polyamideimide, polyimide, . These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition or the like, if desired.

Examples of the application method of the radiation sensitive resin composition include a spray method, a roll coating method, a spin coating method (sometimes referred to as a spin coating method or a spinner method), a slit coating method (slit die coating method) Method, an inkjet coating method, or the like can be employed. Of these, a spin coating method or a slit coating method is preferable.

The above-described prebaking conditions are preferably 70 deg. C to 120 deg. C, and vary from 1 minute to 15 minutes, depending on the kind of each component and the blending ratio. The thickness of the coating film after pre-baking is preferably 0.5 to 10 mu m, more preferably 1.0 to 7.0 mu m.

[[2] Process]

Subsequently, at least a part of the coating film formed in the step [1] is irradiated with radiation. At this time, in the case of irradiating only a part of the coated film, for example, a method of irradiating through a photomask of a pattern corresponding to the formation of a desired contact hole can be adopted.

Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among them, radiation having a wavelength in the range of 200 nm to 550 nm is preferable, and radiation containing ultraviolet light of 365 nm is more preferable.

The radiation dose (exposure dose) is a value measured by a light meter (OAI model 356, manufactured by Optical Associates Inc.) of the irradiated radiation at a wavelength of 365 nm in a range of 10 J / m 2 to 10,000 J / M 2 to 5,000 J / m 2, and more preferably from 200 J / m 2 to 3,000 J / m 2.

The radiation-sensitive resin composition used for forming the insulating film of the array substrate of the present embodiment has a radiation sensitivity higher than 700 J / m 2, more preferably not more than 600 J / m 2 It has an advantage that an insulating film having a desired film thickness, good shape, excellent adhesion, and high hardness can be obtained.

[3] Process

Next, the coating film after irradiation with the radiation is developed to remove unnecessary portions, thereby obtaining a coated film having a desired shape and a desired contact hole.

Examples of the developer used in the development include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, -Diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] -5-nonene and the like can be used. A water-soluble organic solvent such as methanol, ethanol or the like may be added in an appropriate amount to the above-described aqueous solution of the alkaline compound. The surfactant may be used alone or in an appropriate amount by adding the above-described water-soluble organic solvent.

As the developing method, any of a puddle method, a dipping method, a shower method and a spray method may be used. The developing time is from 5 seconds to 300 seconds at room temperature, preferably from 10 seconds to 180 seconds at room temperature. Following the developing treatment, for example, water washing is carried out for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen to obtain a desired pattern.

[4] Process

Subsequently, the coating film obtained in the process [3] is cured (also referred to as post-baking) by a suitable heating apparatus such as a hot plate or an oven to obtain an insulating film as a cured film. A contact hole of a desired arrangement is formed in the insulating film. The curing temperature is preferably 200 DEG C or less. An insulating film having sufficient characteristics can be obtained even at 180 캜 or less. Concretely, 100 ° C to 200 ° C is preferable, and 150 ° C to 180 ° C is more preferable when low-temperature curing and reliable performance are intended to be compatible at a high level. As the curing time, for example, it is preferably 5 minutes to 30 minutes on a hot plate, and 30 minutes to 180 minutes in an oven. Since the radiation-sensitive resin composition contains the [D] compound as described above, such low-temperature curing can be realized. In addition, it realizes storage stability and has sufficient radiation sensitivity and resolution.

Accordingly, the radiation sensitive resin composition is suitably used as a material for forming an insulating film having a contact hole, and can form an insulating film of the array substrate of the present embodiment.

It is preferable to have a step of forming an insulating film in the step [4], and then forming a transparent electrode on the insulating film. For example, a transparent conductive layer made of ITO can be formed on the insulating film by sputtering or the like. Subsequently, the transparent conductive layer is etched by photolithography, and a transparent electrode can be formed on the insulating film. The transparent electrode constitutes a pixel electrode, and enables the electrical connection with the switching active element on the substrate by interposing the contact hole of the insulating film. Further, the transparent electrode can be formed using a transparent material having high transmittance and conductivity for visible light besides ITO. For example, IZO (Indium Zinc Oxide), ZnO (zinc oxide), tin oxide, or the like.

[5] Process

After the transparent electrode is formed on the insulating film as described above using the substrate having the insulating film obtained in the step [4], the liquid crystal aligning agent of the present embodiment is coated on the transparent electrode. As a coating method, for example, a suitable coating method such as a roll coater method, a spinner method, a printing method, and an inkjet method can be used. Subsequently, the substrate coated with the liquid crystal aligning agent is pre-baked, and thereafter, post-baked to form a coated film, thereby fabricating an array substrate. The prebaking condition is, for example, at 40 to 120 캜 for 0.1 to 5 minutes. The post-baking conditions are preferably 120 to 230 占 폚, more preferably 150 to 200 占 폚, and even more preferably 150 to 180 占 폚, preferably 5 to 200 minutes, more preferably 10 minutes ~ 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

The solid concentration of the liquid crystal aligning agent (ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent in the total mass of the liquid crystal aligning agent) used when applying the liquid crystal aligning agent is suitably selected in consideration of viscosity, , But preferably ranges from 1% by mass to 10% by mass.

When a liquid crystal aligning agent comprising a [L] radiation-sensitive polymer having a photo-aligning group is used as the liquid crystal aligning agent, the aforementioned coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation, . The irradiation of the polarized radiation corresponds to the alignment treatment of the alignment film. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In particular, ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable as the radiation. When the radiation to be used is linearly polarized light or partially polarized light, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an oblique direction to give a pretilt angle, or may be performed in combination. In the case of irradiating non-polarized radiation, the irradiation direction needs to be inclined.

The irradiation dose of the radiation is preferably 1 J / m 2 or more and less than 10,000 J / m 2, and more preferably 10 J / m 2 to 3,000 J / m 2.

When a liquid crystal aligning agent containing [M] polyimide having no photo-aligning group is used as the liquid crystal aligning agent, the post-baked coating film can be used as the alignment film as it is. If desired, the coating film after post-baking may be subjected to a rubbing treatment (rubbing treatment) in a predetermined direction with a roll formed of a fiber such as nylon, rayon or cotton to give a liquid crystal aligning ability Do.

As described above, when an alignment film is formed on an array substrate, it is possible to form an alignment film at a heating temperature of 200 DEG C or less and a heating temperature of 180 DEG C or less by using the above-mentioned liquid crystal aligning agent. Therefore, the insulating film formed in the above-described [1] to [4] steps can be prevented from being exposed to the high temperature state in the formation step of the alignment film. The array substrate of the present embodiment can have an insulating film and an orientation film, and can be manufactured by low-temperature curing at 200 占 폚 or less.

[Example]

Hereinafter, embodiments of the present invention will be described in detail on the basis of examples, but the present invention is not limited to these examples.

&Lt; Preparation of radiation-sensitive resin composition >

Example 1

[Synthesis of [A] alkali-soluble resin (A-I)] [

7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether were placed in a flask equipped with a condenser and a stirrer. Subsequently, 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 38 parts by mass of methyl methacrylate, 10 parts by mass of styrene, glycidyl methacrylate 20 (A1) was obtained by heating the solution to 70 DEG C while gently stirring the solution, and maintaining the temperature at that temperature for 4 hours to obtain a solution containing the copolymer (AI) (solid concentration = 34.4 mass%, Mw = 8,000, Mw / Mn = 2.3). Also, the solid concentration means the ratio of the copolymer mass in the total mass of the copolymer solution.

Example 2

[Preparation of radiation-sensitive resin composition]

(B) 100 parts by mass of dipentaerythritol hexaacrylate as the polymerizable compound [B] was added to 100 parts by mass of the copolymer (AI) obtained in Example 1, which was the alkali-soluble resin [A] -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (IRUGACURE OXE02, Chiba Specialty Chemicals Co., 5 parts by mass as a [D] compound and 4,4'-diaminodiphenylsulfone as a [D] compound were mixed, and further, 5 parts by mass of? -Glycidoxypropyltrimethoxysilane as a bonding assistant, FTX-218, NEOS Co., Ltd.), and 0.5 mass part of 4-methoxyphenol as a storage stabilizer were mixed and propylene glycol monomethyl ether acetate was added thereto so as to have a solid content concentration of 30 mass% Of a Millipore filter to prepare a radiation-sensitive resin composition.

&Lt; Formation and evaluation of insulating film &

Example 3

[Formation of insulating film]

The solution of the radiation sensitive resin composition prepared in Example 2 was coated on a non-alkali glass substrate by a spinner and then prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film having a film thickness of 4.0 탆. Subsequently, the obtained coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 700 J / m 2. Subsequently, post baking was performed in an oven at a curing temperature of 180 캜 and a curing time of 30 minutes to form an insulating film.

Example 4

Evaluation of storage stability

An insulating film was formed from the radiation sensitive resin composition of Example 2 immediately after the preparation by the forming method of Example 3 and the film thickness was measured (hereinafter referred to as &quot; film thickness immediately after preparation &quot; After preparing by the method of Example 2, the solution of the radiation-sensitive resin composition was stored at 25 占 폚 for 5 days, and the film thickness of the same insulating film formed after 5 days was measured (in the following formula, Film thickness &quot; hereinafter). The film thickness increase rate (%) was calculated from the following equation.

Film thickness increase rate (%) = {(Film thickness after 5 days-Film thickness immediately after preparation) / (Film thickness immediately after preparation)} x 100

It was judged that the film thickness increase rate was 3% or less and the storage stability was good.

Evaluation of Light Resistance

The insulating film formed by the forming method of Example 3 was further irradiated with 800,000 J / m 2 at an illuminance of 130 mW with a UV irradiator (UVX-02516 S1JS01, Ushio Denki Kabushiki Kaisha) to investigate the film reduction amount. The film reduction was 2% or less, and the light resistance was judged to be good.

Evaluation of heat resistance

The insulating film formed by the forming method of Example 3 was further heated in an oven at 230 DEG C for 20 minutes and the film thickness before and after this heating was measured with a stylus type film thickness meter (ALPHA-STEP) IQ, KLA Tencor Co.). Then, the residual film ratio ((film thickness after treatment / film thickness before treatment) x 100) was calculated, and the residual film ratio was regarded as heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Evaluation of Chemical Resistance

The insulating film formed by the forming method of Example 3 was immersed in an orientation film peeling liquid CHEMICLEAN TS-204 (Sanyo Chemical Industries, Ltd.) heated at 60 캜 for 15 minutes, washed with water, , And dried at 120 DEG C for 15 minutes. The film thickness before and after this treatment was measured with a contact type film thickness meter (Alpha Step IQ, KLA Tencor Co.) to calculate the residual film ratio ((film thickness after processing / film thickness before processing) x 100) I made it with chemical resistance. The residual film ratio was 99%, and the chemical resistance was judged to be good.

Evaluation of resolution

The solution of the radiation sensitive resin composition prepared in Example 2 was coated on a non-alkali glass substrate by a spinner and then prebaked on a hot plate at 100 캜 for 2 minutes to form a coating film having a film thickness of 4.0 탆. Subsequently, the obtained coating film was irradiated with a high-pressure mercury lamp through a photomask having a plurality of ring-shaped remnant patterns each having a diameter different from 6 탆 to 15 탆, with an exposure amount of 700 J / m 2 . Thereafter, a 0.40 mass% tetramethylammonium hydroxide aqueous solution was used for the development by the puddle method at 25 占 폚, followed by pure water rinsing for 1 minute. Further, post-baking was performed in an oven at a curing temperature of 180 ° C and a curing time of 30 minutes to form an insulating film as a patterned cured film. As a result of evaluating the formed insulating film, it was confirmed that a pattern was formed in a photomask of 8 μm or less, and it was determined that the resolution was good.

&Lt; Fabrication of array substrate &

Example 4

The solution of the radiation-sensitive resin composition obtained in Example 2 was applied to a substrate having a switching active element, electrodes and the like formed thereon by a slit die coater. A switching active element, a source electrode, a drain electrode, a gate electrode, a source wiring, a gate wiring, and the like are formed on this substrate. These switching active elements and the like are formed by a known method by repeating etching on a substrate by a conventional semiconductor film forming film, a known insulating film forming film, and a photolithography method.

Next, the coating film was pre-baked on a hot plate at 90 DEG C for 5 minutes to form a coating film. Subsequently, the resulting coating film was irradiated with a high-pressure mercury lamp through a photomask having a pattern at an exposure dose of 700 J / m 2. Thereafter, a 0.40 mass% tetramethylammonium hydroxide aqueous solution was used for the development by the puddle method at 25 占 폚, followed by pure water rinsing for 1 minute. By developing, unnecessary portions were removed to form a coating film having a predetermined shape in which a contact hole was formed. Further, the film was heated in an oven at 180 DEG C for 60 minutes to form an insulating film having a film thickness of 4.0 mu m.

Subsequently, on the substrate on which the insulating film was formed, a transparent conductive layer made of ITO was formed on the insulating film by sputtering. Subsequently, the transparent conductive layer was etched by photolithography, and a transparent electrode was formed on the insulating film.

Thus, the array substrate of this embodiment was manufactured. In the obtained array substrate of the present embodiment, a contact hole of a desired size was formed at a desired position of the insulating film, so that electrical connection between the transparent electrode and the drain electrode was realized.

Example 5

[Production of array substrate having photo alignment layer]

In this embodiment, a photo alignment film is formed using the liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-aligning group by using the array substrate obtained in Example 4. [

First, as a liquid crystal aligning agent containing a radiation-sensitive polymer having a photo-aligning group, on the transparent electrode of the array substrate of Example 4, the liquid crystal aligning agent A-1 described in Example 6 of WO 2009/025386, 1 is applied by a spinner. Subsequently, the substrate was pre-baked on a hot plate at 80 DEG C for 1 minute, and then heated in an oven where the inside was replaced with nitrogen at 180 DEG C for 1 hour to form a coating film having a thickness of 80 nm. Subsequently, polarizing ultraviolet rays 200 J / m &lt; 2 &gt; including a bright line of 313 nm were irradiated onto the surface of the coating film from a direction inclined 40 DEG with respect to the direction perpendicular to the surface of the substrate using an Hg-Xe lamp and a Glane Taylor prism, An array substrate having an orientation film was produced.

Example 6

[Production of array substrate having vertical alignment film]

In this embodiment, a vertical alignment film is formed using the liquid crystal aligning agent containing polyimide having no photo aligning group by using the array substrate obtained in Example 4. [

First, AL60101 (manufactured by JSR Corporation) for forming a vertical alignment film was applied as a liquid crystal aligning agent containing polyimide having no photo-aligning group on the transparent electrode of the array substrate of Example 4 by a spinner. Subsequently, the substrate was pre-baked on a hot plate at 80 DEG C for 1 minute, and then heated in an oven where the inside was replaced with nitrogen at 180 DEG C for 1 hour to form a coating film having a thickness of 80 nm to prepare an array substrate having a vertical alignment film .

&Lt; Production of liquid crystal display element &

Example 7

The array substrate obtained in Example 5 was used. Then, a color filter substrate manufactured by a known method was prepared. In this color filter substrate, a minute colored pattern of three colors of red, green, and blue and a black matrix are arranged in a lattice pattern on a transparent substrate, and a transparent common electrode is disposed on the colored pattern. Then, the same photo-alignment film as that formed on the array substrate in Example 5 was formed on the common electrode of the color filter substrate to obtain an opposing substrate having the alignment film formed thereon. Using the pair of substrates, the TN liquid crystal layer was sandwiched to manufacture a color liquid crystal display device. The liquid crystal display element of this embodiment has the same structure as the liquid crystal display element shown in Fig. 3 described above. The liquid crystal display element of this embodiment exhibited excellent operation characteristics, display characteristics, and reliability performance.

The present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the gist of the present invention. For example, a constitution comprising a constituent unit formed from at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carbonic anhydride constituting the negative type radiation sensitive resin composition of the present embodiment and an epoxy group-containing unsaturated compound Unit can be used to form a positive radiation-sensitive resin composition together with a radiation-sensitive acid-generating compound such as a quinone diazide compound, and an insulating film having a contact hole can be formed by low-temperature curing It is possible to provide an array substrate. The insulating film using the positive-type radiation sensitive resin composition can be cured at a low temperature, and an insulating film of a desired array substrate can be formed.

The array substrate of the present invention can be easily manufactured by low-temperature curing and has high reliability. Therefore, the array substrate of the present invention can be suitably used for a large-sized liquid crystal television in which excellent display quality and reliability are required.

1: array substrate
4, 11: substrate
5: source electrode
6: drain electrode
7: gate electrode
8: Switching active element
9: Transparent electrode
10: Orientation film
12: Insulating film
13: Black Matrix
14: common electrode
15: Coloring pattern
17: Contact hole
18: source wiring
19: gate wiring
21: Liquid crystal display element
22: Color filter substrate
23: liquid crystal layer
27: backlight light
28: polarizer

Claims (10)

A switching active element,
An insulating film disposed on the switching active element,
A contact hole formed in the insulating film,
And a pixel electrode electrically connected to the switching active element via the contact hole, the array substrate comprising:
Wherein,
[A] a copolymer comprising a constituent unit formed of at least one member selected from the group consisting of an unsaturated carbonic acid and an unsaturated carbonic anhydride, and a constituent unit formed from an epoxy group-containing unsaturated compound,
[B] the polymerizable compound,
[C] a polymerization initiator, and
[D] at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2)
Wherein the radiation-sensitive resin composition comprises:

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, an electron attractive group or an amino group, and the electron attractive group is a halogen atom, An alkyloxysulfonyl group, a dicyanovinyl group, a tricyanovinyl group or a sulfonyl group, provided that at least one of R ¹ to R ⁶ is the electron-withdrawing group and at least one of R ¹ to R ⁶ The amino group may be substituted with an alkyl group having 1 to 6 carbon atoms in whole or part of the hydrogen atom;
In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that at least one of R ⁷ to R ¹⁶ is an amino group; The amino group may be substituted with all or a part of the hydrogen atoms by an alkylene group having 2 to 6 carbon atoms; A represents a single bond, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group). The method according to claim 1,
A liquid crystal aligning agent having a transparent electrode on the insulating film and having a liquid crystal aligning agent containing a radiation sensitive polymer having a photo aligning group and a liquid crystal aligning agent containing a polyimide having no photo aligning group, And an insulating layer formed on the substrate. 3. The method of claim 2,
Wherein the alignment film is an alignment film obtained using a liquid crystal aligning agent comprising a radiation sensitive polymer having a photo aligning group. A liquid crystal display element comprising the array substrate according to any one of claims 1 to 3. [1] A resin composition comprising a copolymer comprising at least one structural unit selected from the group consisting of [A] an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, and a constituent unit formed from an epoxy group-
[B] the polymerizable compound,
[C] a polymerization initiator, and
[D] at least one compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2)
A step of forming a coating film of a radiation-sensitive resin composition containing a polymerizable compound on a substrate on which a switching active element is formed,
[2] a step of irradiating at least a part of the coated film of the radiation sensitive resin composition with radiation,
[3] A process for producing a coated film on which a contact hole is formed by developing the coated film irradiated with radiation in the process [2], and
[4] Step of forming an insulating film by curing the coating film obtained in the step [3] at 200 ° C or less
The method comprising the steps of:

(Wherein R ¹ to R ⁶ are each independently a hydrogen atom, an electron attractive group or an amino group, and the electron attractive group is a halogen atom, An alkyloxysulfonyl group, a dicyanovinyl group, a tricyanovinyl group or a sulfonyl group, provided that at least one of R ¹ to R ⁶ is the electron-withdrawing group and at least one of R ¹ to R ⁶ The amino group may be substituted with an alkyl group having 1 to 6 carbon atoms in whole or part of the hydrogen atom;
In the formula (2), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron-withdrawing group or an amino group; Provided that at least one of R ⁷ to R ¹⁶ is an amino group; The amino group may be substituted with all or a part of the hydrogen atoms by an alkylene group having 2 to 6 carbon atoms; A represents a single bond, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; Provided that all or part of the hydrogen atoms may be substituted with a cyano group, a halogen atom or a fluoroalkyl group). 6. The method of claim 5,
And forming an alignment film at 200 DEG C or less. The method according to claim 6,
The step of forming the alignment film at a temperature of 200 캜 or lower may be carried out by using any one of a liquid crystal aligning agent containing a radiation sensitive polymer having a photo aligning group and a liquid crystal aligning agent containing a polyimide having no photo aligning group to form the alignment film Wherein the substrate is a silicon substrate. delete delete delete

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