KR20130011924A - Array substrate, liquid crystal display device, and process for producing the array substrate - Google Patents

Abstract

PURPOSE: An array substrate, a liquid crystal display device, and a process for producing the array substrate are provided to form negative type radiation sensitive resin composition for low temperature. CONSTITUTION: An insulating layer(12) is arranged on a switching active circuit device(8). A contact hole(17) is formed in the insulating layer. A pixel electrode is interposed in the contact hole and electrically touches the switching active circuit device. The insulating layer is made of negative type radiation sensitive resin composition. The insulating layer is formed in the hardening temperature of less than 200°C.

Description

ARRAY SUBSTRATE, LIQUID CRYSTAL DISPLAY DEVICE, AND PROCESS FOR PRODUCING THE ARRAY SUBSTRATE}

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

A liquid crystal display element is comprised by clamping a liquid crystal on a pair of board | substrates, such as a glass substrate, for example. It is possible to form an alignment film for controlling the alignment of the liquid crystal on the surfaces of the pair of substrates. A liquid crystal display element functions as a fine shutter with respect to the light radiated | emitted from a light source, such as a backlight and external light, and displays it by partially transmitting light or shielding it. A liquid crystal display element has the characteristics excellent in thin shape, light weight, etc.

In the beginning of development, a liquid crystal display element was used as a display element of an electronic calculator or a clock centering on a character display. Since then, the development of a simple matrix method has facilitated dot matrix display, and its use has been extended to display elements of note PCs. In addition, the development of an active matrix type enables realization of good image quality with excellent contrast ratio and response performance, and overcomes the problems of high definition, colorization, and viewing angle expansion, and has been used for monitors of desktop computers. In recent years, wider viewing angles, high-speed response of liquid crystals, improvement in display quality, and the like have been realized, and have been used as display devices for large-sized thin televisions. In addition, the liquid crystal display device is required to further improve image quality and brightness.

In an active matrix liquid crystal display device, a gate wiring and a signal wiring are disposed in a lattice shape on one of a pair of substrates sandwiching the liquid crystal, and a thin film transistor (TFT: Thin Film) is formed at the intersection of the gate wiring and the signal wiring. Switching active elements, such as a transister, are provided and comprise an array substrate. A pixel electrode is arranged in an area surrounded by the gate wiring and the signal wiring on the array substrate, and the pixel which is a display unit is formed by this pixel electrode.

In the liquid crystal display device, when it is desired to improve the brightness, increasing the pixel electrode becomes effective. The brightness can be increased by making the area of the pixel electrode as large as possible and improving the aperture ratio. In that case, for example, as described in Patent Literature 1, a technique is known in which a pixel electrode is overlapped with a gate wiring or a signal wiring to improve the aperture ratio. In Patent Literature 1, in an array substrate, by forming an insulating film made of a thick film organic material between a wiring and a pixel electrode, the aperture ratio is suppressed while increasing the coupling capacitance between the pixel electrode and the wiring. The liquid crystal display element which improved this is disclosed.

Japanese Patent Laid-Open No. 2001-264798

In the case of forming an insulating film made of a thick film organic material between the wiring and the pixel electrode in the array substrate as in the liquid crystal display device described in Patent Document 1, the electrical connection between the switching element such as TFT and the pixel electrode is This is realized by using a contact hole formed in the insulating film.

When contact holes are formed in an insulating film made of an organic material, the use of photolithography technology is effective. In that case, use of a radiation sensitive resin composition (hereinafter referred to as a radiation sensitive resin composition) is preferable as a material for forming the insulating film, and in particular, the so-called positive type selection of the radiation sensitive resin composition is preferable. In the insulating film using a positive radiation sensitive resin composition, when sensitive to radiation, the solubility in a developer increases, and the sensitive portion is removed. Therefore, when using a positive radiation sensitive resin composition, a contact hole can be formed comparatively easily by irradiating a radiation radiation to the formation part of the contact hole of an insulating film. In addition, in this invention, a "radiation ray" is a concept containing visible ray, an ultraviolet-ray, far ultraviolet ray, X-ray, charged particle beam, etc.

However, in the case of the positive radiation-sensitive resin composition, a special material is required, for example, containing a compound that generates an acid upon irradiation with radiation as a component. Such special materials are not easy to obtain, and the range of material selection is narrowed. Therefore, the application of the negative radiation sensitive resin composition which can be applied to photolithography technique and can implement | achieve a composition using the various material which is easy to obtain is calculated | required. A negative radiation sensitive resin composition is a radiation sensitive resin composition in which the solubility to a developing solution falls when irradiated with radiation and it responds to radiation, and a sensitive part remains after image development.

However, when a contact hole is to be formed in an insulating film using a negative radiation sensitive resin composition, as described above, the remaining portions of the insulating film other than the contact hole are irradiated with radiation (hereinafter referred to as "exposure"). Reaction), and then, heat curing and the like are performed to form an insulating film. Therefore, in the manufacturing process of the insulating film which leads to exposure, image development, and heat hardening, the fluctuation | variation of the size of an insulating film may become large compared with a positive type. In particular, when a conventional negative radiation-sensitive resin composition is used, curing after exposure and development needs to be performed at a very high temperature of about 230 ° C to 260 ° C. Therefore, the fluctuations in size such as thermal expansion or contraction in the heat curing step become large, which may cause problems in the formation of contact holes that require strict control of the placement position and size.

As mentioned above, while forming the insulating film on an array substrate using a negative radiation sensitive resin composition, it is desired to enable formation of a contact hole by suppressing thermal expansion and contraction. For that purpose, the negative radiation sensitive resin composition which can harden | cure the hardening process after exposure and image development by the low temperature of 200 degrees C or less instead of the conventional hardening process by conventional high temperature heating is needed. The negative radiation-sensitive resin composition provided with such curing characteristics enables the provision of a desired insulating film.

Moreover, in recent years, also from the viewpoint of energy saving, the low temperature of the heating process in manufacture of the liquid crystal display element which has an array substrate is calculated | required. That is, in manufacture of an array substrate and the liquid crystal display element using the same, the realization of the energy saving by the low temperature of the process which requires heating, such as the hardening process of each component, is calculated | required.

As mentioned above, the realization of the negative radiation sensitive resin composition which can form the insulating film provided with a contact hole by low temperature hardening is strongly desired. And the realization of the array substrate which has the insulating film hardened | cured at low temperature using the negative radiation sensitive resin composition is strongly desired. Moreover, the realization of the liquid crystal display element comprised using such an array board | substrate is strongly desired.

This invention is made | formed in view of the above subjects. That is, an object of the present invention is to provide an array substrate having an insulating film formed of a negative radiation-sensitive resin composition which can be cured at a low temperature, and a method of manufacturing the same.

Moreover, another object of this invention is to provide the liquid crystal display element comprised using the array substrate which has the insulating film formed from the negative radiation sensitive resin composition which can be hardened at low temperature.

A first embodiment of the present invention, the switching active element,

An insulating film disposed on the switching active element,

A contact hole formed in the insulating film,

An array substrate for a liquid crystal display element having a pixel electrode electrically connected to a switching active element via the contact hole,

The insulating film is a negative radiation-sensitive resin containing a copolymer comprising a structural unit formed of at least one selected from the group consisting of unsaturated carbonic acid and unsaturated carbonic anhydride and a structural unit formed of an epoxy group-containing unsaturated compound. It relates to an array substrate, characterized in that formed from the composition.

In the first embodiment of the present invention, the radiation-sensitive resin composition 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, It is preferable to contain at least one compound selected from the group consisting of an amide compound, a thiol compound, a block isocyanate compound and an imidazole ring containing compound:

(Formula (1) of, R ¹ ~ R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group; However, R ¹ ~ R ⁶ at least one of which is an electron-withdrawing group, and R ¹ ~ R ⁶ At least one of which is an amino group, wherein all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;

In formula (2), R <^7> -R <^16> is respectively 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; Moreover, all or one part of hydrogen atoms may be substituted by the C2-C6 alkylene group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; However, all or part of the hydrogen atom may be substituted by the cyano group, the halogen atom, or the fluoroalkyl group in the said methylene group and the alkylene group).

In the first embodiment of the present invention, the insulating film is preferably formed at a curing temperature of 200 ° C or lower.

1st Embodiment of this invention WHEREIN: The liquid crystal which has a transparent electrode on an insulating film, and the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group on this transparent electrode, and the polyimide which does not have a photo-alignment group It is preferable to have the alignment film obtained using either of the alignment agents.

In 1st Embodiment of this invention, it is preferable that an oriented film is an oriented film obtained using the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group.

2nd Embodiment of this invention is related with the liquid crystal display element which has an array substrate of 1st Embodiment of this invention.

In a third embodiment of the present invention,

[1] Negative radiation-sensitive resin containing a copolymer comprising a structural unit formed of at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and structural units formed of epoxy group-containing unsaturated compounds Forming a coating film of the composition on a substrate on which a switching active element is formed,

[2] irradiating at least a portion of the coating film of the radiation-sensitive resin composition with radiation;

[3] a step of developing the coating film to which the radiation is irradiated in step [2] to obtain a coating film with contact holes; and

[4] A method for manufacturing an array substrate, comprising the step of curing the coating film obtained in the step [3] at 200 ° C. or lower to form an insulating film.

In the third embodiment of the present invention, the radiation-sensitive resin composition 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, It is preferable to contain at least one compound selected from the group consisting of an amide compound, a thiol compound, a block isocyanate compound and an imidazole ring containing compound:

(Formula (1) of, R ¹ ~ R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group; However, R ¹ ~ R ⁶ at least one of which is an electron-withdrawing group, and R ¹ ~ R ⁶ At least one of which is an amino group, wherein all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;

In formula (2), R <^7> -R <^16> is respectively 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; Moreover, all or one part of hydrogen atoms may be substituted by the C2-C6 alkylene group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; However, all or part of the hydrogen atom may be substituted by the cyano group, the halogen atom, or the fluoroalkyl group in the said methylene group and the alkylene group).

In 3rd Embodiment of this invention, it is preferable to further have the process of forming an oriented film at 200 degrees C or less.

In the 3rd Embodiment of this invention, the process of forming an oriented film at 200 degrees C or less is the liquid crystal aligning agent containing the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group, and the polyimide which does not have a photo-alignment group. It is preferable to form the said alignment film using either.

According to this invention, the array substrate which has an insulating film formed from the negative radiation sensitive resin composition which can be hardened at low temperature, and its manufacturing method are provided.

Moreover, according to this invention, the liquid crystal display element which consists of an array substrate which has the insulating film formed from the negative radiation sensitive resin composition which can be hardened at low temperature is provided.

1 is a schematic cross-sectional view showing the main part structure of the array substrate of this embodiment.
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)

The array substrate and liquid crystal display element of embodiment of this invention are demonstrated.

<Liquid crystal display element>

The liquid crystal display element of this embodiment is a color liquid crystal display element comprised using the array substrate of this embodiment. Hereinafter, the structure of the array substrate of this embodiment and the structure of the liquid crystal display element of this embodiment are demonstrated using drawing.

The liquid crystal display element of this embodiment can be made into the active liquid crystal type color liquid crystal display element, for example. The liquid crystal display element of this embodiment can have a structure where the array substrate of this embodiment in which the switching active element, the electrode, and the insulating film were formed, and the color filter substrate in which the transparent electrode were formed, oppose via a liquid crystal layer.

1 is a schematic cross-sectional view showing the main part structure of the array substrate of this embodiment.

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

The array substrate 1 shown in FIG. 1 is an example of the array substrate of this embodiment. On one surface of the transparent substrate 4, the switching active element 8 is disposed. The source electrode 5, the drain electrode 6, and the gate electrode 7 connected to the switching active element 8 are disposed. 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). On the transparent electrode 9, as shown in the figure, it is possible to form the alignment film 10 which controls the alignment of the liquid crystal. The recess structure formed so as to penetrate the insulating film 12 is the contact hole 17, and the transparent electrode 9 and the drain electrode 6 are electrically connected through this part. As a result, electrical connection between the transparent electrode 9 which is a pixel electrode and the switching active element 8 becomes possible. As shown in FIG. 2, the source wiring 18 and the gate wiring 19 are arranged in a matrix on the array substrate 1. In the vicinity of the intersection of the source wiring 18 and the gate wiring 19, a switching active element 8 is provided, the source electrode 5 is connected to the source wiring 18, and the gate electrode 7 is a gate wiring. (19). In this way, each pixel partitioned on the array substrate 1 is comprised.

As described later, in the array substrate 1 of the present embodiment, the insulating film 12 is the present embodiment on the substrate 4 on which electrodes such as the source electrode 5 and the switching active element 8 are formed. After the negative radiation sensitive resin composition of this application | coating and patterning which require formation of the contact hole 17 etc. are performed, it hardens | cures and is formed. In addition, the radiation sensitive resin composition of this embodiment used for formation of the insulating film 12 is a negative radiation sensitive resin composition, unless it mentions specially, In the following, it will only be called a radiation sensitive resin composition. .

The radiation sensitive resin composition of this embodiment is equipped with the characteristic that the insulating film 12 can be formed by low-temperature hardening of 200 degrees C or less. Therefore, the insulating film 12 suppresses the variation in the size in the heat curing step, and enables the formation of the contact hole 17 having the desired arrangement position and size. And in the array substrate 1 of this embodiment, the insulating film 12 can be formed by low-temperature hardening of 200 degrees C or less, and manufacture by low temperature heating is attained.

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 orientation film 10 can be obtained using the liquid crystal aligning agent containing the polyimide which does not have the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group, or a photo-alignment group as mentioned later. In that case, it becomes possible to form an alignment film at the heating temperature of 200 degrees C or less. Therefore, in the array substrate 1 of this embodiment, the insulating film 12 can be formed by the low temperature hardening of 200 degrees C or less, and the alignment film 10 can be formed by the low temperature hardening of 200 degrees C or less, Production by low temperature heating becomes possible.

Next, the liquid crystal display element of this embodiment using the array substrate of this embodiment is demonstrated.

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 which consists of 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 a thin film transistor type TN (Twisted Nematic) mode liquid crystal display element, for example, and the array substrate 1 and the color filter substrate 22 of this embodiment shown in FIG. It has a structure which opposes via the liquid crystal layer 23 which consists of liquid crystals.

As shown in FIG. 3, the array substrate 1 has a source electrode 5, a drain electrode 6, a gate electrode 7, and a surface on the side of the liquid crystal layer 23 of the transparent substrate 4. And a switching active element 8 and an insulating film 12. And on the insulating film 12, the transparent electrode 9 which is a pixel electrode is provided. The contact hole 17 which penetrates the insulating film 12 is formed in the insulating film 12, and the transparent electrode 9 and the drain electrode 6 are electrically connected through this part. 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, the alignment film 10 for liquid crystal alignment control is formed.

As for the color filter substrate 22, the red, green, and blue fine coloring pattern 15 and the black matrix 13 are arrange | positioned at the surface of the transparent substrate 11 at 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. In addition, about the color of the coloring pattern 15, it is not limited to said three colors of red, green, and blue, It is also possible to select another color, or to add yellow and to make a four color coloring pattern. And the coloring pattern of each color can be arranged and a color filter board | substrate can be comprised.

The transparent common electrode 14 is provided on the coloring pattern 15 and the black matrix 13. The same alignment film 10 as that of the array substrate 1 is formed on the surface of the color filter substrate 22 in contact with the liquid crystal layer 23. The alignment film 10 of the array substrate 1 and the color filter substrate 22 is subjected to an alignment process if necessary, and the liquid crystal layer 23 sandwiched between the array substrate 1 and the color filter substrate 22. To achieve a uniform orientation.

And the distance between the array substrate 1 which opposes through the liquid crystal layer 23, and the opposing board | substrate 22 is hold | maintained by the spacer which is not shown in figure, and is 2 micrometers-10 micrometers normally. The array substrate 1 and the color filter substrate 22 are fixed to each other by a sealing material (not shown) provided in the peripheral portion.

In the array substrate 1 and the color filter substrate 22, the polarizing plates 28 are arranged on the side opposite to the side in contact with the liquid crystal layer 23, respectively.

In FIG. 3, reference numeral 27 denotes backlight light irradiated toward the liquid crystal layer 23 from a backlight unit (not shown) serving as a light source of the liquid crystal display element 21. 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. It is also possible to use a backlight unit having a white LED as a light source. As the white LED, for example, a white LED which obtains white light by using a red LED, a green LED, and a blue LED having an independent spectrum, and a white LED that obtains white light by mixing color by combining a red LED, a green LED, and a blue LED, and blue White LED, which combines LED, red LED, and green phosphor to obtain white light by mixing, white LED, blue LED, which combines red-emitting phosphor and green light emitting phosphor, and obtains white light by mixing, mixing of blue LED and YAG-based phosphor White LED, blue LED, orange light emitting phosphor and green light emitting phosphor obtained by combining white light, ultraviolet LED, red light emitting phosphor, green light emitting phosphor, and blue light emitting phosphor obtained by mixing White LED etc. which obtain white light by mixing are mentioned.

About the liquid crystal mode of the liquid crystal display element 21 of this embodiment, in addition to TN mode mentioned above, STN (Super Twisted Nematic), IPS (In-Planes Switching), VA (Vertical Alignment), or OCB (Optically Compensated Birefringence) Or liquid crystal mode. In that case, in particular, for the alignment film 10, an alignment film for realizing the alignment of the liquid crystal layer that is optimal for each liquid crystal mode is selected. For example, when the liquid crystal display element of this embodiment is a liquid crystal display element of VA mode, the alignment film of a vertical alignment type is used for an orientation film.

As mentioned above, the liquid crystal display element 21 of this embodiment has the array substrate 1 of this embodiment. In the array substrate 1, the electrical connection between the transparent electrode 9 and the drain electrode 6 is realized through the contact hole 17 formed in the insulating film 12. The insulating film 12 of the array substrate 1 is formed by low-temperature hardening of 200 degrees C or less using the radiation sensitive resin composition of this embodiment. Therefore, in the liquid crystal display element 21 of this embodiment, in the array board | substrate 1, the contact hole 17 of a desired arrangement | positioning position and a size of the transparent electrode 9 and the drain electrode 6 is carried out. It is possible to realize the electrical connection.

Next, formation of the insulating film which is a main component of the array substrate of the liquid crystal display element of this embodiment and which can be hardened at low temperature is demonstrated in detail. The insulating film of the array substrate of this embodiment is formed using the radiation sensitive resin composition of this embodiment. Therefore, the composition component of the radiation sensitive resin composition of this embodiment is demonstrated especially.

<Radiation-Resistant Resin Composition>

The radiation sensitive resin composition used for manufacture of the insulating film of the array substrate of this embodiment contains [A] alkali-soluble resin, [B] polymeric compound, and [C] polymerization initiator. And it can also contain a [D] compound. Moreover, you may contain other arbitrary components, unless the effect of this invention is impaired. Hereinafter, each component contained in a radiation sensitive resin composition is demonstrated.

<[A] alkali-soluble resin>

As alkali-soluble resin (A), if it has resin which has alkali developability by having a carboxyl group, it will not specifically limit. And it is preferable that it is a copolymer containing at least 1 sort (s) of structural unit chosen from the group which consists of a structural unit which has a (meth) acryloyloxy group, and a structural unit which has an epoxy group. When the (A) alkali-soluble resin contains the said specific structural unit, the cured film which has the outstanding surface hardenability and deep part hardenability can be formed.

 (A) Alkali-soluble resin is (A1) at least 1 sort (s) (hereinafter also called "(A1) compound") chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and (A2) epoxy-group-containing unsaturated compound (henceforth). , (Also referred to as "(A2) compound") can be copolymerized to synthesize. And [A] alkali-soluble resin becomes a copolymer containing the structural unit formed from the structural unit formed from at least 1 sort (s) chosen from the group which consists of unsaturated carbonic acid and unsaturated carbonic anhydride, and an epoxy-group-containing unsaturated compound.

(A) Alkali-soluble resin can be manufactured by copolymerizing the compound (A1) which gives a carboxyl group containing structural unit and the compound (A2) which gives an epoxy group containing structural unit in presence of a polymerization initiator, for example. Can be. Moreover, the hydroxyl group containing unsaturated compound (henceforth a "(A3) compound" hereafter) giving a hydroxyl group containing structural unit (A3) is further added, and it can also be set as a copolymer. In addition, in manufacture of alkali-soluble resin [A], with the said (A1) compound, the (A2) compound, and the (A3) compound, to the (A4) compound (the said (A1), (A2), and (A3) compound) Unsaturated compound which gives structural units other than the derived structural unit) can be further added, and it can also be set as a copolymer. Hereinafter, each compound is explained in full detail.

[(A1) Compound]

Examples of the compound (A1) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydride of unsaturated dicarboxylic acid, mono [(meth) acryloyloxyalkyl] ester of polyhydric carbonic acid, and mono ((meth) acryloyloxyalkyl] ester of a polycarboxylic acid. And meta) acrylates, unsaturated polycyclic compounds having a carboxyl group, and anhydrides thereof.

As unsaturated monocarboxylic acid, For example, acrylic acid, methacrylic acid, crotonic acid, etc .;

As unsaturated dicarboxylic acid, For example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, etc .;

As anhydride of unsaturated dicarboxylic acid, For example, anhydride etc. of the compound illustrated as said dicarboxylic acid;

As mono [(meth) acryloyloxyalkyl] ester of polyhydric carboxylic acid, for example, succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl ] Etc;

As mono (meth) acrylate of the polymer which has a carboxyl group and a hydroxyl group in both terminal, For example, (omega)-carboxy polycaprolactone mono (meth) acrylate;

Examples of the unsaturated polycyclic compound having a carboxyl group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hepto-2-ene and 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride Etc. can be mentioned.

Among these (A1) compounds, monocarboxylic acid, dicarboxylic acid anhydride, acrylic acid, methacrylic acid and maleic anhydride are preferable, and acrylic acid, methacrylic acid and maleic anhydride are more preferable in terms of copolymerization reactivity, solubility in aqueous alkali solution and ease of obtaining. desirable. These (A1) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A1), 5 mass%-30 mass% are preferable based on the sum total of (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed), 10 mass%-25 mass% are more preferable. By setting the use ratio of the compound (A1) to 5% by mass to 30% by mass, the solubility in the aqueous alkali solution of the [A] alkali-soluble resin is optimized, and an insulating film excellent in the radiation sensitivity is obtained.

[(A2) Compound]

The compound (A2) is an epoxy group-containing unsaturated compound having radical polymerizability. As an epoxy group, an oxiranyl group (1, 2- epoxy structure) and an oxetanyl group (1, 3- epoxy structure) are mentioned.

As an unsaturated compound which has an oxiranyl group, For example, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycine (alpha)-n-propyl acrylate Dill, α-n-butylacrylate acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α- Ethyl acrylate-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexylmethyl, etc. Can be mentioned. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinyl benzyl glycidyl ether and methacrylic acid 3,4-epoxycyclohexyl are preferable from a viewpoint of improvement of copolymer reactivity and solvent resistance, such as an insulating film.

As an unsaturated compound which has an oxetanyl group, for example,

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyl Oxymethyl) -2-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -2-ethyloxetane, 3- (2-acryloyl Acrylic acid esters such as oxyethyl) -3-ethyloxetane and 3- (2-acryloyloxyethyl) -2-phenyloxetane;

3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- ( Methacryloyloxymethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -2-ethyloxetane, 3- (2-Methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -2-phenyloxetane, 3- (2-methacryloyloxyethyl) -2 Methacrylic acid ester, such as a 2-difluoro oxetane, etc. are mentioned.

Among these (A2) compounds, glycidyl (meth) acrylate is preferable. These (A2) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of (A2) compound, 5 mass%-60 mass% are preferable based on the sum total of (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed). 10 mass%-50 mass% are more preferable. By setting the use ratio of the compound (A2) to 5% by mass to 60% by mass, an insulating film can be formed as a cured film having excellent curability or the like.

[(A3) Compound]

As a (A3) compound, the (meth) acrylic acid ester which has a hydroxyl group, the (meth) acrylic acid ester which has a phenolic hydroxyl group, and hydroxy styrene are mentioned first.

As acrylic acid ester which has a hydroxyl group, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, 6-hydroxyhexyl acrylate, etc. are mentioned.

Moreover, as methacrylic acid ester which has a hydroxyl group, 2-hydroxyethyl methacrylic acid, 3-hydroxypropyl methacrylic acid, 4-hydroxybutyl methacrylic acid, 5-hydroxypentyl methacrylic acid, methacrylic acid 6-hydroxyhexyl etc. are mentioned.

As acrylic acid ester which has a phenolic hydroxyl group, 2-hydroxyethyl acrylate, 4-hydroxyphenyl acrylate, etc. are mentioned. As methacrylic acid ester which has a phenolic hydroxyl group, 2-hydroxyethyl methacrylate, 4-hydroxyphenyl methacrylate, etc. are mentioned.

As hydroxy styrene, o-hydroxy styrene, p-hydroxy styrene, (alpha) -methyl- p-hydroxy styrene is preferable. These (A3) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A3), 1 mass%-30 mass% are preferable based on the sum total of (A1) compound, (A2) compound, and (A3) compound (optional (A4) compound as needed). 5 mass%-25 mass% are more preferable.

[(A4) Compound]

The compound (A4) is not particularly limited as long as it is an unsaturated compound other than the compound (A1), the compound (A2) and the compound (A3). As the (A4) compound, for example, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, acrylic acid chain alkyl ester, acrylic acid cyclic alkyl ester, methacrylic acid aryl ester, acrylic acid aryl ester, unsaturated dicarboxylic acid diester, And unsaturated compounds having bicyclo unsaturated compounds, maleimide compounds, unsaturated aromatic compounds, conjugated dienes, tetrahydrofuran skeletons, furan skeletons, tetrahydropyran skeletons, pyran skeletons, and the like, and other unsaturated compounds.

As methacrylic acid linear alkylester, for example, 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.

As methacrylic acid cyclic alkylester, for example, methacrylic acid cyclohexyl, methacrylic acid 2-methylcyclohexyl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid tri Cyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, isobornyl methacrylate, and the like.

Examples of the acrylic acid chain alkyl esters include methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate and tridecyl acrylate. And n-stearyl acrylate.

As acrylic acid cyclic alkylester, For example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yloxyethyl acrylate, isobornyl acrylate, and the like.

As methacrylic acid aryl ester, methacrylic acid phenyl, benzyl methacrylate, etc. are mentioned, for example.

As acrylic acid aryl ester, phenyl acrylate, benzyl acrylate, etc. are mentioned, for example.

As unsaturated dicarboxylic acid diester, diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. are mentioned, for example.

Examples of the bicyclo unsaturated compound include bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene and 5-ethylbicyclo [2.2.1] hepto -2-ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, etc. are mentioned.

As a maleimide compound, N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N- (4-hydroxyphenyl) maleimide, N- (4-hydroxybenzyl) malee, for example Mead, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Propionate, N- (9-acridinyl) maleimide, and the like.

As an unsaturated aromatic compound, styrene, (alpha) -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxy styrene, etc. are mentioned, for example.

As a conjugated diene, 1, 3- butadiene, isoprene, 2, 3- dimethyl- 1, 3- butadiene, etc. are mentioned, for example.

As an unsaturated compound containing a tetrahydrofuran skeleton, tetrahydrofurfuryl (meth) acrylate, 2-methacryloyloxypropionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydro Furan-2-one etc. are mentioned.

As an unsaturated compound containing a furan skeleton, for example, 2-methyl-5- (3-furyl) -1-penten-3-one, furfuryl (meth) acrylate, 1-furan-2-butyl-3 -En-2-one, 1-furan-2-butyl-3-methoxy-3-en-2-one, 6- (2-furyl) -2-methyl-1-hexen-3-one, 6- Furan-2-yl-hex-1-ene- 3-one, acrylic acid-2-furan-2-yl-1-methyl-ethylester, 6- (2-furyl) -6-methyl-1-heptene-3 -On etc. can be mentioned.

As an unsaturated compound containing a tetrahydropyran skeleton, it is (tetrahydropyran-2-yl) methylmethacrylate, 2,6-dimethyl-8- (tetrahydropyran-2-yloxy) -octo- 1-en-3-one, 2-methacrylic acid tetrahydropyran-2-yl ester, 1- (tetrahydropyran-2-oxy) -butyl-3-en-2-one, etc. are mentioned.

As an unsaturated compound containing a pyran skeleton, it is 4- (1, 4- dioxa-5-oxo-6-heptenyl) -6-methyl- 2-pyran, 4- (1, 5- dioxa, for example. -6-oxo-7-octenyl) -6-methyl-2-pyran etc. are mentioned.

As another unsaturated compound, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate etc. are mentioned, for example.

Of these (A4) compounds, methacrylic acid chain alkyl ester, methacrylic acid cyclic alkyl ester, methacrylic acid aryl ester, maleimide compound, tetrahydrofuran skeleton, furan skeleton, tetrahydropyran skeleton, pyran skeleton, unsaturated aromatic compound And acrylic acid cyclic alkyl esters are preferable. Among them, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, p -Methoxy styrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexyl maleimide, tetrahydrofurfuryl (meth) acrylate, polyethylene glycol (n = 2-10) mono (meth) acryl The rate and 3- (meth) acryloyloxytetrahydrofuran-2-one are more preferable at the point of copolymerization reactivity and the solubility to aqueous alkali solution. These (A4) compounds may be used independently or may be used in mixture of 2 or more type.

As a usage ratio of a compound (A4), 10 mass%-80 mass% are preferable based on the sum total of (A1) compound, (A2) compound, and (A4) compound (optional (A3) compound as needed). .

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

[A] Alkali-soluble resin is manufactured by copolymerizing the said (A1) compound and (A2) compound (optional (A3) compound and (A4) compound as needed) in presence of a polymerization initiator, for example. can do. According to this synthesis method, the copolymer containing at least an epoxy group containing structural unit can be synthesize | combined.

[A] As a solvent used in the polymerization reaction for producing alkali-soluble resin, for example, alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, dipropylene glycol Dialkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, ketone, ester and the like.

As a polymerization initiator used for the polymerization reaction for manufacturing [A] alkali-soluble resin, what is generally known as a radical polymerization initiator can be used. As a radical polymerization initiator, 2,2'- azobisisobutyronitrile (AIBN), 2,2'- azobis- (2, 4- dimethylvaleronitrile), 2,2'- azobis, for example Azo compounds, such as-(4-methoxy-2,4-dimethylvaleronitrile), are mentioned.

In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight regulator may be used to adjust the molecular weight. As a molecular weight modifier, For example, halogenated hydrocarbons, such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; xantho such as dimethyl xanthogen sulfide and diisopropyl xanthogen disulfide Gens; Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

[A] As a weight average molecular weight (Mw) of alkali-soluble resin, 1,000-30,000 are preferable and 5,000-20,000 are more preferable. By making Mw of alkali-soluble resin into the said range, the sensitivity and developability of a radiation sensitive resin composition can be improved. In addition, Mw and the number average molecular weight (Mn) of the polymer in this specification were measured by the gel permeation chromatography (GPC) by the following conditions.

Device: GPC-101 (manufactured by Showa Denko KK)

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

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0mL / min

Sample concentration: 1.0 mass%

Sample injection volume: 100 μL

Detector: parallax refractometer

Standard material: monodisperse polystyrene

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

In addition, [A] alkali-soluble resin is a copolymer (Hereinafter, it is also called a "specific copolymer") and the said (A2) compound which can be synthesize | combined using one or more types of above-mentioned (A1) compounds, for example. It can be synthesized by reacting. According to this synthesis method, the copolymer containing the structural unit which has at least a (meth) acryloyloxy group can be synthesize | combined.

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

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

In said formula (4-1), R <^23> is a hydrogen atom or a methyl group. In said formula (4-1) and formula (4-2), * represents the site | part couple | bonded with an oxygen atom.

About the structural unit represented by said formula (3), for example, the copolymer which has a carboxyl group reacted with compounds, such as glycidyl methacrylate and 2-methylglycidyl methacrylate, as (A2) compound In this case, R ²² in formula (3) becomes formula (4-1). On the other hand, in the case of reacting a compound such as methacrylic acid 3,4-epoxycyclohexylmethyl as the compound (A2), R ²² in formula (3) becomes formula (4-2).

In the synthesis of the specific copolymer, compounds other than the compound (A1), for example, the compound (A3) and the compound (A4) described above may be used as the copolymerization component. As these compounds, in terms of copolymerization reactivity, methyl methacrylate, n-butyl methacrylate, benzyl methacrylate, 2-hydroxyethyl ester of methacrylic acid, tricyclomethacrylic acid [5.2.1.0 ^2,6 ] Preferred are decan-8-yl, styrene, p-methoxystyrene, methacrylic acid tetrahydrofuran-2-yl, 1,3-butadiene.

As a method of copolymerization of a specific copolymer, the method of superposing | polymerizing (A1) compound and (A3) compound etc. as needed using a radical polymerization initiator in a solvent is mentioned, for example.

As a radical polymerization initiator, the thing similar to what was illustrated by the term of the above-mentioned [A] alkali-soluble resin is mentioned. As a usage-amount of a radical polymerization initiator, it is 0.1 mass%-50 mass% normally with respect to 100 mass% of polymerizable unsaturated compounds, Preferably they are 0.1 mass%-20 mass%. A specific copolymer may be used for manufacture of [A] alkali-soluble resin as it is, or may be used for manufacture of [A] alkali-soluble resin after separating a copolymer from a solution once.

As Mw of a specific copolymer, 2,000-100,000 are preferable and 5,000-50,000 are more preferable. By setting Mw to 2,000 or more, a sufficient development margin of the insulating film is obtained, and a decrease in the remaining film ratio (ratio of the pattern-shaped thin film remaining appropriately) of the formed coating film is prevented, and thus the shape, heat resistance, and the like of the obtained pattern are further reduced. It can be kept well. On the other hand, by setting Mw to 100,000 or less, high sensitivity can be preserved and a good pattern shape can be obtained. Moreover, as molecular weight distribution (Mw / Mn) of a specific copolymer, 5.0 or less are preferable and 3.0 or less are more preferable. By making Mw / Mn 5.0 or less, the shape of the pattern obtained can be kept favorable. Moreover, the insulating film containing the specific copolymer which has Mw / Mn of the said specific range has high developability, and can develop a predetermined pattern shape easily, without developing development residual in a developing process.

As content rate of the structural unit derived from the compound (A1) of alkali-soluble resin, 5 mass%-60 mass% are preferable, 7 mass%-50 mass% are more preferable, 8 mass%-40 mass% Is particularly preferred.

[A] As content rate of structural units derived from compounds, such as (A3) compound and (A4) compound, other than (A1) compound of alkali-soluble resin, they are 10 mass%-90 mass%, 20 mass%-80 mass%. .

In the reaction between the specific copolymer and the compound (A2), an unsaturated compound having an epoxy group is added to a solution of a copolymer containing a polymerization inhibitor, preferably in the presence of a suitable catalyst, if necessary, under heating. Stir for a predetermined time. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxy phenol etc. are mentioned, for example. As reaction temperature, 70 degreeC-100 degreeC is preferable. As reaction time, 8 hours-12 hours are preferable.

As a usage ratio of (A2) compound, 5 mass%-99 mass% are preferable with respect to the carboxyl group derived from the (A1) compound in a copolymer, and 10 mass%-97 mass% are more preferable. By making the use ratio of a (A2) compound into the said range, the reactivity with a copolymer, the curability of a cured film, etc. improve more. (A2) A compound can be used individually or in mixture of 2 or more types.

<[B] polymerizable compound>

The [B] polymeric compound contained in the radiation sensitive resin composition of this embodiment used for manufacture of the insulating film of the array substrate of this embodiment is demonstrated.

[B] The polymerizable compound can be used, for example,? -Carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol fluorenedi (Meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy) ethyl ( Meta) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meta) Carboxylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, succinic acid modified pentaerythritol tri (meth) acrylate, etc. Urethane (meth) acrylate compound obtained by making the compound which has an alicyclic structure and has two or more isocyanate groups, and the compound which has one or more hydroxyl groups in a molecule, and has three to five (meth) acryloyloxy groups reacts. Etc. can be mentioned.

As a commercial item of the [B] polymerizable compound which can be used, 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 (Above, Toagose Co., Ltd.), KAYARAD (registered trademark) @ DPHA, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120, East MAX-3510 (above, Nippon Kayaku Co., Ltd. ), VISCOAT 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400 (above, Osaka Yugigaku Kogyo Co., Ltd.), urethane acrylate-based compounds (NEW FRONTIER) (registration) Trademark) R-1150 (Daiichi-Kyosei Seikaku Co., Ltd.), KAYARAD (registered trademark) @ DPHA-40H, East UX-5000 (Nippon Kayaku Co., Ltd.), Atresin (ARTRESIN) UN-9000H (Negami High School) Corporation), Aaronics (registered trademark) M-5300, M-5600, M-5700, M-210, M-220, M-240, M-2 70, M-6200, M-305, M-309, M-310, M-315 (above, Toagose Co., Ltd.), KAYARAD (registered trademark) HDDA, KAYARAD (registered trademark) HX- 220, East HX-620, East R-526, East R-167, East R-604, East R-684, East R-551, East R-712, East UX-2201, East UX-2301, East UX- 3204, East UX-3301, East UX-4101, East UX-6101, East UX-7101, East UX-8101, East UX-0937, East MU-2100, East MU-4001 (above, Nippon Kayaku Co., Ltd.) ), Atresin UN-9000 PEP, East UN-9200A, East UN-7600, East UN-333, East UN-1003, East UN-1255, East UN-6060PTM, East UN-6060P, East SH-500B , Negami Kogyo Kogashi Co., Ltd., Biscot 260, East 312, East 335HP (above, Osaka Yugigaku Kogyo Co., Ltd.), etc. are mentioned.

[B] The polymerizable compounds may be used alone or in combination of two or more. As a content rate of the [B] polymeric compound in a radiation sensitive resin composition, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 40 mass parts-160 mass parts are more preferable. . By setting the use ratio of the polymerizable compound (B) in the above range, a cured film having excellent adhesiveness and sufficient hardness even at a low exposure amount can be formed, and an excellent insulating film can be provided.

<[C] polymerization initiator>

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

The polymerization initiator (C) is a radiation sensitive polymerization initiator, and is a component that generates active species capable of initiating polymerization of the polymerizable compound [B] in response to radiation. As these [C] polymerization initiators, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned. These compounds may be used independently or may be used in mixture of 2 or more type.

Examples of the O-acyl oxime compound include 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)] and ethanone-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1- Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9- n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2- Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4- Tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl ) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3 -Dioxoranyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. Can.

Among them, 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H- Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazole-3 -Yl] -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.

As an acetophenone compound, the (alpha)-amino ketone compound and the (alpha)-hydroxy ketone compound are mentioned, for example.

As an α-amino ketone compound, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, etc. are mentioned. have.

As an alpha-hydroxy ketone compound, it is 1-phenyl-2-hydroxy-2-methyl propane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methyl propane, for example. -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

Of these, α-aminoketone compounds are preferable, and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one and 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are more preferable. .

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2,2'-, for example. 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, among which 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is more preferable.

[C] The polymerization initiator can be used alone or in combination of two or more thereof. As a content rate of the [C] polymerization initiator, 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 5 mass parts-30 mass parts are more preferable. By setting the use ratio of the polymerization initiator (C) to 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 adhesiveness even in the case of a low exposure amount.

&Lt; [D] Compound >

The radiation sensitive resin composition of this embodiment used for manufacture of the insulating film of the array substrate of this embodiment can contain a [D] compound. The compound [D] is a compound that fulfills a function as a curing agent. Therefore, for convenience, it may be called a [D] compound (hardening | curing agent), a [D] hardening | curing agent, etc. in some cases. The compound [D] 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, and already It is at least 1 compound chosen from the group which consists of a polyazole ring containing compound. Low temperature hardening of an insulating film can be implement | achieved by the radiation sensitive resin composition containing the [D] compound chosen from the specific compound group. Moreover, the storage stability of a radiation sensitive resin composition can also be improved. Hereinafter, each compound is explained in full detail.

[Compound represented by Formula (1) and Formula (2)]

It is preferable that it is at least 1 sort (s) of compound chosen from the group which consists of a compound represented by following formula (1) and following formula (2) as a compound [D]. By selecting the above-mentioned specific compound having an amino group and an electron deficient group as the compound [D], low-temperature curing of the insulating film can be realized. Moreover, the storage stability of a radiation sensitive resin composition can also be improved. Moreover, the voltage holding ratio of the liquid crystal display element provided with the array substrate which has the obtained insulating film can be improved more.

In said formula (1), R <^1> -R <^6> is a hydrogen atom, an electron withdrawing group, or an amino group each independently. 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, in which all or part of the hydrogen atoms are substituted with an alkyl group having 1 to 6 carbon atoms. You may be.

In said formula (2), R <^7> -R <^16> is a hydrogen atom, an electron withdrawing group, or an amino group each independently. Provided that at least one of R ⁷ to R ¹⁶ is an amino group. In addition, all or a part of hydrogen atoms may be substituted with the C2-C6 alkylene group of the amino group. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group, or a C2-C6 alkylene group. However, all or part of the hydrogen atom may be substituted by the cyano group, the halogen atom, or the fluoroalkyl group in the said methylene group and the alkylene group.

As an electron-withdrawing group which R <^1> -R <^16> of the said Formula (1) and said Formula (2) shows, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, an acyl group, an alkylsulfo, for example A silyl group, an alkyloxy sulfonyl group, a dicyano vinyl group, a tricyano vinyl group, a sulfonyl group, etc. are mentioned. Of these, nitro groups, alkyloxysulfonyl groups, and trifluoromethyl groups are preferable. As group which A represents, the methylene group which may be substituted by the sulfonyl group and the fluoroalkyl group is preferable.

As a compound represented by said Formula (1) and Formula (2),

2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) succinonitrile, 4,4'-diaminobenzophenone, 4,4'-diaminophenylbenzo 8,4,4'-diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene, 1,4-diamino-2-iodobenzene , 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 (trifluor Romethyl) benzidine, 3-aminobenzenesulfonic acid ethyl, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline are preferable, 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, 3-aminobenzenesulphone More preferred are acid ethyl, 3,5-bistrifluoromethyl-1,2-diaminobenzene, 4-aminonitrobenzene, N, N-dimethyl-4-nitroaniline.

The compound represented by said Formula (1) and said Formula (2) can be used individually or in mixture of 2 or more types. As a content rate of the compound represented by said Formula (1) and said Formula (2), 0.1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.2 mass part-10 mass parts are more preferable. Do. By making the content rate of the compound represented by said Formula (1) and said Formula (2) into the said range, hardening acceleration of the insulating film formed from a radiation sensitive resin composition can be implement | achieved. In addition, the storage stability of the radiation-sensitive resin composition can be improved, and the voltage holding ratio of the liquid crystal display device provided with the array substrate having the obtained insulating film can be maintained at a high level.

[Third Amine Compound]

When a highly reactive general primary amine compound and secondary amine compound coexist with an epoxy compound, hardening reaction advances by nucleophilic attack of an amine to an epoxy group during storage of a composition solution, and there exists a possibility that the quality as a product may be impaired. However, when tertiary amine is used, it is due to relatively low reactivity, and even if it coexists with an epoxy compound in a composition part, storage stability becomes favorable.

As a tertiary amine compound, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (5) can be used.

In said formula (5), R <^24> -R <^26> is a C1-C20 alkyl group, a C6-C18 aryl group, or a C7-C30 aralkyl group each independently. However, R ²⁴ and R ²⁵ may be bonded to each other and may form a ring structure with the nitrogen atom to which they are bonded. Some or all of the hydrogen atoms may be substituted for the alkyl group, the aryl group, and the aralkyl group.

As said C1-C20 alkyl group which R <^24> -R <^26> in said formula (5) shows, a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Octyl group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group have.

As a C6-C18 aryl group which R <^24> -R <^26> in said formula (5) shows, a phenyl group, a naphthyl group, etc. are mentioned, for example.

As a C7-C30 aralkyl group which R <^24> -R <^26> in said formula (5) shows, a benzyl group, a phenethyl group, etc. are mentioned, for example.

As the tertiary amine compound, for example, N, N-dimethylbenzylamine, triphenylamine, tributylamine, trioctylamine, tridodecylamine, dibutylbenzylamine, trinaphthylamine, N-ethyl-N -Methylaniline, N, N-diethylaniline, N-phenyl-N-methylaniline, N, N-dimethyl-p-toluidine, N, N-dimethyl-4-bromoaniline, N, N-dimethyl-4 -Methoxyaniline, N-phenylpiperidine, N- (4-methoxyphenyl) piperidine, N-phenyl-1,2,3,4-tetrahydroisoquinoline, 6-benzyloxy-N-phenyl -7-methoxy-1,2,3,4-tetrahydroisoquinoline, N, N'-dimethylpiperazine, N, N-dimethylcyclohexylamine, 2-dimethylaminomethylphenol, 2,4,6- Tris (dimethylaminomethyl) phenol etc. are mentioned.

Among these tertiary amine compounds, trioctylamine, 2-dimethylaminomethylphenol, N, N-diethylaniline, and the like are preferable. A tertiary amine compound can be used individually or in mixture of 2 or more types. As a content rate of the tertiary amine compound in a radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of a tertiary amine compound into the said specific range, the storage stability of a radiation sensitive resin composition and low temperature hardening can be compatible at a higher level.

[Amine salts and phosphonium salts]

As an amine salt and a phosphonium salt, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (6) can be used.

In said formula (6), A <^1> is a nitrogen atom or a phosphorus atom. R ²⁷ to R ³⁰ are each independently 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, some or all of the hydrogen atoms may be substituted for these groups. Q ⁻ is a monovalent anion.

As a C1-C20 alkyl group which R <^27> -R <^30> in the said Formula (6) shows, linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Octyl group, nonyl group, decyl group, lauryl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group have.

As a C6-C18 aryl group which R <^27> -R <^30> in said formula (6) shows, a phenyl group, a naphthyl group, etc. are mentioned, for example.

As a C7-C30 aralkyl group which R <^27> -R <^30> in said formula (6) shows, a benzyl group, a phenethyl group, etc. are mentioned, for example.

Examples of the monovalent anion represented by Q ⁻ in the formula (6) include chloride ions, bromide ions, iodide ions, cyanide ions, nitrate ions, nitrite ions, hypochlorite ions, chlorite ions, and chlorate ions. , Perchlorate ion, permanganate ion, hydrogen carbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carbonic acid ion, sulfonic acid ion, phenoxide ion, tetrafluoroborate ion, tetraarylborate ion, hexafluoro And antimonate ions.

In the formula (6), when A ¹ is a nitrogen atom, that is, as an ammonium salt, for example, tetramethylammonium chloride, tetrabutylammonium chloride, dodecyldimethylbenzylammonium chloride, octyltrimethylammonium chloride, decyltrimethylammonium chloride, Dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, hexadecyltrimethylammonium bromide, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzalkonium chloride, benzalkonium chloride, didecide chloride Sildimethylammonium and distearyldimethylammonium chloride.

In the case where A ¹ is a phosphorus atom, that is, as a phosphonium salt, for example, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium tetra (p-ethyl Phenyl) borate, tetraphenylphosphonium tetra (p-methoxyphenyl) borate, tetraphenylphosphonium tetra (p-ethoxyphenyl) borate, tetraphenylphosphonium tetra (p-tert-butoxyphenyl) borate , Tetraphenylphosphonium tetra (m-tolyl) borate, tetraphenylphosphonium tetra (m-methoxyphenyl) borate, tri (p-tolyl) phenylphosphonium tetra (p-tolyl) borate, tetra (p -Tolyl) phosphonium tetra (p-tolyl) borate, tri (p-methoxyphenyl) phenylphosphonium tetra (p-tolyl) borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate , Methyl triphenyl phosphonium thiocyanate, p-tolyl tri Phenyl phosphonium thiocyanate etc. are mentioned.

Of these amine salts and phosphonium salts, tetramethylammonium chloride and butyltriphenylphosphonium thiocyanate are preferred. An amine salt and a phosphonium salt can be used individually or in mixture of 2 or more types. As a content rate of the amine salt and phosphonium salt in a radiation sensitive resin composition, 0.05 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.1 mass part-5 mass parts are more preferable. . By making the content rate of an amine salt and a phosphonium salt into the said specific range, the storage stability of a radiation sensitive resin composition and low temperature hardening can be compatible at a higher level.

[Amidine Salt]

As an amidine salt, at least 1 sort (s) chosen from the group which consists of a salt of the compound represented by following formula (7) can be used.

In said formula (7), m is an integer of 2-6. However, one part or all part of the hydrogen atom which an alkylene group has may be substituted by the organic group. Further, the alkylene group refers to, tetrahydro-pyrimidine in the alkylene group and the formula (7) in dinhwan refers to both of the alkylene group represented by (CH _{2) m.}

As the organic group which the alkylene group may have as a substituent, for example,

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

Hydroxymethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxyisopropyl group, 3-hydroxy-t-butyl group, 6 C1-C6 hydroxyalkyl groups, such as a hydroxyhexyl group;

C2-C12 dialkylamino groups, such as a dimethylamino group, a methylethylamino group, a diethylamino group, a diisopropylamino group, a dibutylamino group, a t-butylmethylamino group, and a di-n-hexylamino group, etc. are mentioned.

Examples of the compound represented by the formula (7) include 1,5-diazabicyclo [4,3,0] -nonene-5 (DBN) and 1,5-diazabicyclo [4,4,0] -decene-5 , 1,8-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. Among these, DBN and DBU are preferable.

As an acid for the compound represented by said Formula (7) to form a salt, an organic acid and an inorganic acid are mentioned.

As an organic acid, a carbonic acid, a monoalkyl carboxylic acid, an aromatic hydroxy compound, sulfonic acid, etc. are mentioned, for example.

Of these acids, carbonic acid, aromatic hydroxy compound and sulfonic acid are preferable, saturated fatty acid, aromatic hydroxy compound and sulfonic acid are more preferable, and sulfonic acid which is a strong acid is particularly preferable, and toluenesulfonic acid, methanesulfonic acid and octylbenzenesulfonic acid are most preferred. As the amidine salt, salts of DBU and toluenesulfonic acid, salts of DBU and octylbenzenesulfonic acid, salts of DBN and toluenesulfonic acid, and salts of DBN and octylbenzenesulfonic acid are preferable.

Amidine salt can be used individually or in mixture of 2 or more types. As a content rate of the amidine salt in a radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an amidine salt into the said specific range, the storage stability and low temperature hardening of a radiation sensitive resin composition can be compatible at a higher level.

[Amide compound]

As an amide compound, at least 1 sort (s) chosen from the group which consists of a compound which has an amide group represented by following formula (8)-following formula (10) can be used.

In said formula (8), R <^31> and R <^32> is a hydrogen atom, a C1-C12 alkyl group, a cyclohexyl group, a phenyl group, a naphthyl group, a vinyl group, or 2-pyridyl group each independently. However, the said C1-C12 alkyl group, a phenyl group, and a naphthyl group may be substituted by the C1-C6 alkyl group, a halogen atom, a hydroxyl group, a carboxyl group, or an acetyl group.

In said formula (9), R <^33> and R <^34> is a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group each independently. A <^2> is a methylene group, a C2-C12 alkylene group, a phenylene group, a naphthylene group, or a vinylene group. However, the said methylene group, a C2-C12 alkylene group, a phenylene group, and a naphthylene group may be substituted by the C1-C6 alkyl group and a halogen atom.

In said formula (10), R <^35> and R <^36> is a hydrogen atom, a C1-C12 alkyl group, or a cyclohexyl group each independently. A <^3> is a methylene group, a C2-C12 alkylene group, a phenylene group, a naphthylene group, or a vinylene group. However, the said methylene group, a C2-C12 alkylene group, a phenylene group, and a naphthylene group may be substituted by the C1-C6 alkyl group and 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, phthalamic acid, acrylamide, benzamide, naphthoamide, nicotinamide, isnicotinamide, and the like.

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

The compounds represented by the formulas (9) and (10) are compounds having two amide bonds in the molecule. As specific examples thereof, for example, phthalamide, isophthalamide, terephthalamide, malonamide, succinamide, N, N'-diacetyl-p-phenylenediamine, N, N'-diacetyl-hexamethylenediamine, N, N'- diacetyl- dodecyl methylene diamine, etc. are mentioned.

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.

An amide compound can be used individually or in mixture of 2 or more types. As a content rate of the amide compound in a radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an amide compound into the said specific range, the storage stability and low temperature hardening of a radiation sensitive resin composition can be compatible at a higher level.

[Thiol Compound]

As a thiol compound, it is a compound which has two or more mercapto groups in 1 molecule. Although the thiol compound is not specifically limited as long as it has two or more mercapto groups in 1 molecule, At least 1 sort (s) chosen from the group which consists of a compound represented by following formula (11) can be used.

In said formula (11), R <^37> is a methylene group and a C2-C10 alkylene group. However, some or all of the hydrogen atoms in these groups may be substituted by the alkyl group. Y ¹ is a single bond, -CO- or O-CO- ^* . Provided that a bond attached with * binds to R ³⁷ . n is an integer of 2-10. A <^4> is a C2-C70 n-valent hydrocarbon group which may have one or more ether bonds, or when n is 3, it is group represented by following formula (12).

In said formula (12), R <^38> -R <^40> is a methylene group or a C2-C6 alkylene group each independently. "*" Represents a bond.

As the compound represented by the formula (11), typically, an esterified product of mercaptocarboxylic acid and a polyhydric alcohol can be used. Examples of the mercaptocarboxylic acid constituting the esterified product include thioglycolic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 3-mercaptopentanoic acid, and the like. Moreover, as a polyhydric alcohol which comprises esterification, ethylene glycol, propylene glycol, trimethylol propane, pentaerythritol, tetraethylene glycol, dipentaerythritol, 1, 4- butanediol, pentaerythritol, etc. are mentioned, for example. Can be.

As a compound represented by said Formula (11), trimethylol propane tris (3-mercapto propionate), pentaerythritol tetrakis (3-mercapto propionate), and tetra ethylene glycol bis (3- mercapto propio) Nate), dipentaerythritol hexakis (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-2, 4,6 (1H, 3H, 5H) -trione is preferred.

As a compound which has two or more mercapto groups in 1 molecule of a thiol compound, the compound represented by following formula (13)-following formula (15) can also be used.

In said formula (13), R <^41> is a methylene group or a C2-C20 alkylene group. R <^42> is a methylene group or a C2-C6 linear or branched alkylene group. k is an integer of 1-20.

In said formula (14), R <^43> -R <^46> is group represented by a hydrogen atom, a hydroxyl group, or following formula (15) each independently. However, at least 1 of R <^43> -R <^46> is group represented by following formula (15).

In said formula (15), R ⁴⁷ is a methylene group or a C2-C6 linear or branched alkylene group.

A thiol compound can be used individually or in mixture of 2 or more types. As a content rate of the thiol compound in a radiation sensitive resin composition, 1 mass part-20 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 5 mass parts-15 mass parts are more preferable. By making the content rate of a thiol compound into the said specific range, the storage stability of a radiation sensitive resin composition and low temperature hardening can be compatible at a higher level.

[Block Isocyanate Compound]

The blocked polyisocyanate compound is made to be inert at room temperature by reacting an isocyanate group with an active hydrogen group-containing compound (blocking agent), and when heated, the blocking polyisocyanate compound has a property of regenerating isocyanate groups. When the radiation-sensitive resin composition contains blocked polyisocyanate, the isocyanate-hydroxyl group crosslinking reaction proceeds as an effective crosslinking agent, so that the storage stability and low-temperature curing of the radiation-sensitive resin composition can be compatible at a high level.

The blocked polyisocyanate compound is obtained by a known reaction of a polyisocyanate derived from aliphatic or alicyclic diisocyanate with a compound (blocking agent) having active hydrogen.

As the diisocyanate, for example, tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, 2,4,4-trimethyl- 1,6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis (isocyanatomethyl) cyclohexane, 4,4-dicyclohexyl methane diisocyanate, norbornene diisocyanate , Tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tridine diisocyanate, xyldine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl diisocyanate, etc. are mentioned.

As a commercial item, for example,

As an isocyanate group blocked with an oxime of methyl ethyl ketone, Duranate (registered trademark) TPA-B80E, copper TPA-B80X, copper E402-B80T, copper MF-B60XN, copper MF-B60X, copper MF-B80M ( Asahi Kasei Kogyo Co., Ltd.);

As an isocyanate group blocked with active methylene, Duranate (registered trademark) MF-K60X (Asahi Kasei Co., Ltd.);

As a block body of the isocyanate compound which has a (meth) acryloyl group, KARENNZ (registered trademark) MOI-BP and CARENS (registered trademark) MOI-BM (above, Showa Denko KK) are mentioned. have. Among these, when duranate (registered trademark) E402-B80T and MF-K60X are used, high flexibility is exhibited, and since the hardness can be freely controlled by using it as a mixing system with another, it is preferable.

As polyisocyanate derived from diisocyanate, isocyanurate type polyisocyanate, biuret type polyisocyanate, urethane type polyisocyanate, allophanate type polyisocyanate, etc. are mentioned, for example. In view of curability, isocyanurate polyisocyanate is preferable.

Examples of the blocking agent include alcohol compounds, phenol compounds, active methylene compounds, mercaptan compounds, acid amide compounds, acid imide compounds, imidazole compounds, pyrazole compounds, urea compounds, and oximes. A compound, an amine compound, an imine compound, a pyridine compound, etc. are mentioned.

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

As a phenol type compound, For example, phenol, cresol, ethyl phenol, butyl phenol, nonyl phenol, dinonyl phenol, styrenated phenol, hydroxy benzoic acid ester, etc .;

As an active methylene compound, For example, dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetic acid, acetylacetone, etc .;

As a mercaptan type compound, For example, butyl mercaptan, dodecyl mercaptan, etc .;

As an acid amide type compound, For example, acetoanilide, amide acetate, (epsilon) -caprolactam, (delta) -valerolactam, (gamma) -butyrolactam, etc .;

As an acid imide type compound, For example, succinic acid imide, maleic acid imide, etc .;

As an imidazole type compound, For example, imidazole, 2-methylimidazole, etc .;

As a pyrazole type compound, 3-methylpyrazole, 3, 5- dimethyl pyrazole, 3, 5- ethyl pyrazole, etc .;

As a urea type compound, For example, urea, thiourea, ethylene urea, etc .;

As an oxime type compound, For example, formaldehyde oxime, aceto aldooxime, aceto oxime, methyl ethyl keto oxime, cyclohexanone oxime, etc .;

As an amine type compound, For example, diphenylamine, aniline, carbazole, etc .;

As an imine type compound, Ethylene imine, a polyethylene imine, etc .;

As a pyridine type compound, 2-hydroxypyridine, 2-hydroxyquinoline, etc. are mentioned, for example.

Block polyisocyanate compounds can be used individually or in mixture of 2 or more types. As a content rate of the block polyisocyanate compound in a radiation sensitive resin composition, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of a block polyisocyanate compound into the said range, the storage stability of a radiation sensitive resin composition and low temperature hardening can be compatible at a higher level.

 [Imidazole ring containing compound]

As an imidazole ring containing compound, at least 1 sort (s) chosen from the group which consists of a compound represented by following formula (16) can be used.

In said Formula (16), A <^5> , A <^6> , A <^7> and R <^48> are C1-C20 linear, branched or cyclic hydrocarbon group which may respectively independently have a hydrogen atom or a substituent. A ⁶ and A ⁷ may be connected to each other to form a ring.

As a C1-C20 linear, branched, or cyclic hydrocarbon group represented by A <^5> , A <^6> , A <^7> and R <^{48>, it} is, for example,

Methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n -Octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n- C1-C20 alkyl groups, such as a heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-eicosyl group;

C3-C20 cycloalkyl groups, such as a cyclopentyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group;

C6-C20 aryl groups, such as a phenyl group, toluyl group, benzyl group, methyl benzyl group, xylyl group, mesityl group, naphthyl group, and anthryl group;

Condensed alicyclic hydrocarbon groups having 6 to 20 carbon atoms such as norbornyl group, tricyclodecanyl group, tetracyclododecyl group, adamantyl group, methyl adamantyl group, ethyl adamantyl group, and butyl adamantyl group Can be mentioned.

The hydrocarbon group may be substituted, and as a specific example of this substituent,

Hydroxyl group;

Carboxyl groups;

Hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group C1-C4 hydroxyalkyl groups, such as a 3-hydroxybutyl group and 4-hydroxybutyl group;

C1-C4 alkoxyl groups, such as a methoxyl group, an ethoxyl group, n-propoxyl group, i-propoxyl group, n-butoxyl group, 2-methylpropoxyl group, 1-methylpropoxyl group, t-butoxyl group, etc. ;

Cyano;

Cyanoalkyl groups having 2 to 5 carbon atoms such as cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, and 4-cyanobutyl group;

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

Alkoxycarbonylalkoxy groups having 3 to 6 carbon atoms, such as a methoxycarbonyl methoxyl group, an ethoxycarbonyl methoxyl group, and a t-butoxycarbonyl methoxyl group;

Halogen atoms such as fluorine and chlorine;

Fluoroalkyl groups, such as a fluoromethyl group, a trifluoromethyl group, and a pentafluoroethyl group, etc. are mentioned.

As said ring which A <^6> and A <^7> mutually connect and form, Preferably, an aromatic ring and the C2-C20 saturated or unsaturated nitrogen containing heterocycle are mentioned. As an imidazole ring containing compound in the case where the ring which A <^6> and A <^7> connects and mutually forms is a benzene ring, the compound represented by following formula (17) is mentioned.

In said formula (17), R <^48> and A <^5> is synonymous with said formula (16). R ⁴⁹ to R ⁵² are each independently a linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. Moreover, as a hydrocarbon group represented by R <^49> -R <^52> , the thing similar to the hydrocarbon group in said Formula (16) is mentioned.

As an imidazole ring containing compound, 2-phenyl benzimidazole, 2-methylimidazole, and 2-methylbenzimidazole are preferable. The imidazole ring-containing compounds may be used alone or in admixture of two or more. As a content rate of an imidazole ring containing compound, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.5 mass part-5 mass parts are more preferable. By making the content rate of an imidazole ring containing compound into the said specific range, the storage stability and low temperature hardening of a radiation sensitive resin composition can be compatible at a higher level.

&Lt; Other optional components >

The radiation sensitive resin composition of this embodiment used for formation of the insulating film of the array substrate of this embodiment is, in addition to said [A] alkali-soluble resin, [B] polymeric compound, and [C] polymerization initiator, D] In addition to the compounding agent (curing agent), other optional components such as surfactants, storage stabilizers, adhesion aids, heat resistance enhancers and the like may be contained as necessary within a range that does not impair the effects of the present invention. These arbitrary components may be used independently, or may mix and use 2 or more types. Hereinafter, each component is explained in full detail.

[Surfactants]

Surfactant can be used in order to improve the coating film formability of a radiation sensitive resin composition further. As surfactant, a fluorochemical surfactant, silicone type surfactant, and other surfactant are mentioned, for example.

As a fluorine type surfactant, the compound which has a fluoroalkyl group and / or a fluoroalkylene group in at least any part of a terminal, a main chain, and a side chain is preferable.

As a commercial item of a fluorine-type surfactant, For example, FTERGENT (registered trademark) FT-100, copper-110, copper-140A, copper-150, copper-250, copper-251, copper-300, copper- 310, copper-400S, aftergent (registered trademark) FTX-218, copper-251 (above, Neos), etc. are mentioned.

As a commercial item of a silicone type surfactant, Toray silicon (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, DC-190 (above, Torre Dow Corning Silicon Co., Ltd.), etc. are mentioned.

As the usage-amount of surfactant, 1.0 mass part or less is preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 0.8 mass part or less is more preferable. When the usage-amount of surfactant exceeds 1.0 mass part, it will become easy to produce the film nonuniformity of a coating film.

[Storage Stabilizer]

As a storage stabilizer, sulfur, quinones, hydroquinones, a polyoxy compound, an amine, a nitroso compound, etc. are mentioned, for example, 4-methoxyphenol, N-nitroso-N- Phenyl hydroxyl amine aluminum etc. are mentioned.

As the usage-amount of a storage stabilizer, 3.0 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 1.0 mass part or less is more preferable. When the compounding quantity of a storage stabilizer exceeds 3.0 mass parts, a sensitivity may fall and a pattern shape may deteriorate.

[Adhesive preparation]

An adhesion | attachment adjuvant can be used in order to improve the adhesiveness of the insulating film obtained and the layer, board | substrate, etc. which are under it further. As an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group, is preferable, For example, trimethoxysilyl benzoic acid, (gamma)-methacryloxypropyl Trimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, and the like.

As the usage-amount of an adhesion | attachment adjuvant, 20 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 15 mass parts or less are more preferable. When the usage-amount of an adhesion | attachment adjuvant exceeds 20 mass parts, there exists a tendency which becomes easy to generate | occur | produce a developing residue.

[Heat resistance improver]

As a heat resistance improving agent, an N- (alkoxymethyl) glycoluril compound, an N- (alkoxymethyl) melamine compound, etc. are mentioned, for example.

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

As the N- (alkoxymethyl) melamine compound, for example, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine, N, N, N ', N', N " , N "-hexa (ethoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-propoxymethyl) melamine, N, N, N ', N', N" , N "-hexa (i-propoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-butoxymethyl) melamine, N, N, N ', N', N ", N" -hexa (t-butoxymethyl) melamine, etc. are mentioned. Among these N- (alkoxymethyl) melamine compounds, N, N, N ', N', N ", N" -hexa (methoxymethyl) melamine is preferable. As a commercial item, Nikarak (NICALAC) N-2702, the copper MW-30M (above, Sanwa Chemical Co., Ltd.), etc. are mentioned, for example.

As a usage-amount of a heat resistant improving agent, 50 mass parts or less are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 30 mass parts or less are more preferable. When the compounding quantity of a heat resistance improving agent exceeds 50 mass parts, the sensitivity of a radiation sensitive resin composition may fall and a pattern shape may deteriorate.

<Preparation method of a radiation sensitive resin composition>

The radiation sensitive resin composition of this embodiment used for formation of the insulating film of the array substrate of this embodiment is [A] alkali-soluble resin, [B] polymeric compound, and [C] polymerization initiator, D] It is prepared by mixing uniformly a compound (hardening | curing agent) and other arbitrary components added as needed. This radiation sensitive resin composition is preferably dissolved in a suitable solvent and used in a solution state. A solvent can be used individually or in mixture of 2 or more types.

As a solvent used for preparation of a radiation sensitive resin composition, what melt | dissolves an essential component and arbitrary components uniformly, and does not react with each component is used. As such a solvent, the same thing as what was illustrated as a solvent which can be used for manufacturing above-mentioned [A] alkali-soluble resin is mentioned.

For example, in such a solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene from the viewpoint of solubility of each component, reactivity with each component, ease of coating film formation, and the like. 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;

Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexan-2-one Ketones such as these;

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;

Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl acetate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate , N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, hydroxy Ethyl acetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pirbate, ethyl pirbate, n-propyl pirbate, Other esters such as methyl acetoacetic acid, ethyl acetoacetic acid, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate and ethyl 2-oxobutylate;

Aromatic hydrocarbons such as toluene and xylene;

Amides such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and the like.

Among these solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, from the viewpoint of solubility, pigment dispersibility, coating properties, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol Diacetate, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, Preference is given to formic acid n-amyl, i-amyl acetate, n-butyl propionate, ethyl butylate, i-propyl butyrate, n-butyl butyrate and ethyl pirate. The solvent may be used alone or in combination of two or more.

In addition, with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, oxalic acid di High boiling point solvents, such as ethyl, diethyl maleate, (gamma) -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together. The said high boiling point solvent can use individual or 2 types or more.

Although it does not limit as content of a solvent, The quantity which the total concentration of each component except the solvent of a radiation sensitive resin composition becomes 5 mass%-50 mass% from a viewpoint of applicability | paintability, stability, etc. of the radiation sensitive resin composition obtained It is preferable and the quantity used as 10 mass%-40 mass% is more preferable. In the case where the radiation-sensitive resin composition is prepared in a solution state, the solid content concentration (components other than the solvent occupied in the composition solution) is any concentration (for example, 5% by mass to 1) depending on the purpose of use or the value of the desired film thickness. 50 mass%). Although more preferable solid content concentration changes with the formation method of the coating film on a board | substrate, it mentions later. The composition solution thus prepared can be used for use after filtering using a Millipore filter or the like having a pore size of about 0.5 µm.

The radiation sensitive resin composition by the above components and a preparation method can form the insulating film with a contact hole by low temperature hardening. Specifically, an insulating film having good reliability in solvent resistance and the like can be obtained at a curing temperature of 200 ° C. or lower, and further, an insulating film having good reliability in solvent resistance and the like can be obtained even at a curing temperature of 180 ° C. or lower. And the array substrate of this embodiment can be provided by low temperature hardening.

Next, the array substrate of this embodiment can have the alignment film which controls the orientation of a liquid crystal. The alignment film formed on the array substrate of this embodiment is formed using the liquid crystal aligning agent of this embodiment. Therefore, especially the main component about the orientation treatment agent of this embodiment is demonstrated below.

<Liquid crystal aligning agent>

The liquid crystal aligning agent of this embodiment which forms an orientation film on the array substrate of this embodiment contains [L] radiation-sensitive polymer which has a photo-alignment group, or [M] polyimide which does not have a photo-alignment group as a main component. It is a liquid crystal aligning agent to say. All of these can form an oriented film in low temperature heating temperature, such as 200 degrees C or less, for example. In particular, the liquid crystal aligning agent containing the [L] radiation sensitive polymer which has a photo-alignment group is possible, and the formation of the orientation film in low temperature is preferable. Thus, since the liquid crystal aligning agent of this embodiment can form the oriented film by a low temperature heating process, the oriented film can be formed without exposing the insulating film by low temperature hardening in a lower layer to the state of high temperature heating. .

In addition, the liquid crystal aligning agent of this embodiment which forms an alignment film on the array substrate of this embodiment can contain [N] other components, unless the effect of this invention is impaired. Hereinafter, these components are demonstrated.

[[L] Radiation Polymer]

The [L] radiation sensitive polymer contained in the liquid crystal aligning agent of this embodiment is a polymer which has a photo-alignment group. The photo-alignment group which this [L] radiation-sensitive polymer has is an functional group which gives anisotropy to a film | membrane by light irradiation, and in this embodiment, in particular, this film is anisotropic to a film | membrane by generating at least any one of a photoisomerization reaction and a photoduplexing reaction. It is a group to give.

Specific examples of the photo-alignment group include azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole, benzylidene phthalimidine, coumarin, diphenylaceryl It is group which has a structure derived from at least 1 compound chosen from the group which consists of a rene and anthracene. As said photo-alignment group, group which has a structure derived from cinnamic acid among these is especially preferable.

As a [L] radiation sensitive polymer which has a photo-alignment group, it is preferable that it is a polymer in which the above-mentioned photo-alignment group was couple | bonded directly or through the coupling group. Examples of such a polymer include those in which the above-described photoalignment group is bonded to at least one polymer of polyamic acid and polyimide, and those in which the above-described photoalignment group is bonded to a polymer different from the polyamic acid and polyimide. In the latter case, examples of the basic skeleton of the polymer having a photo-alignment group include poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, polyolefin, polyorganosiloxane and the like.

As a radiation sensitive polymer, it is preferable to use polyamic acid, polyimide, or polyorganosiloxane as a basic skeleton. Moreover, polyorganosiloxane is especially preferable among these, For example, it can obtain by the method of international publication (WO) 2009/025386.

[[M] polyimide]

[M] polyimide contained in the liquid crystal aligning agent of this embodiment is a polyimide which does not have a photo-alignment group.

[M] polyimide which does not have such a photo-alignment group can be obtained by dehydrating and ring-closing polyamic acid which does not have a photo-alignment group, and imidizing it. These polyamic acids can be obtained by reacting tetracarboxylic dianhydride and diamine, for example, and can be obtained as described in Unexamined-Japanese-Patent No. 2010-97188.

[M] The polyimide may be a complete imide obtained by dehydrating and closing all the dark acid structures possessed by the polyamic acid as a precursor thereof. It may be a dehydrate. It is preferable that the imidation ratio of [M] polyimide is 30% or more, It is more preferable that it is 50%-99%, It is more preferable that it is 65%-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, and can be obtained as described, for example, in JP 2010-97188 A.

[[N] OTHER COMPONENTS]

The liquid crystal aligning agent of this embodiment can contain [N] other components other than the polyimide which does not have a radiation sensitive polymer which has a photo-alignment group, and a photo-alignment group. [N] As other components, for example, [L] radiation-sensitive polymer which has a photo-alignment group, and polymers other than [M] polyimide which does not have a photo-alignment group, a hardening | curing agent, a curing catalyst, a hardening accelerator, an epoxy compound, and a functional Silane compounds, surfactants, photosensitizers and the like.

As mentioned above, although the main component of the array substrate of this embodiment was demonstrated, the manufacturing method of the array substrate of this embodiment is demonstrated next.

<Method for manufacturing insulating film, alignment film, and array substrate>

In manufacture of the array substrate of this embodiment, the process of manufacturing an insulating film from the radiation sensitive resin composition of this embodiment mentioned above is included as a main process. By the manufacturing process of this insulating film, the insulating film in which the contact hole was formed is formed. And in order to form an oriented film on the array substrate of this embodiment, the process of forming an oriented film from the liquid crystal aligning agent of this embodiment mentioned above is included as a manufacturing process. Hereinafter, the manufacturing method of the array substrate of this embodiment which has an insulating film and an orientation film is demonstrated.

In the manufacturing method of the array substrate of this embodiment, it is preferable that an insulating film is formed on a board | substrate and includes at least the following process [1]-process [4] in the following procedure. And in order to form an oriented film on an array substrate, it is preferable to include process [5] also after process [4].

[1] The coating film of the radiation-sensitive resin composition includes a switching active element and an electrode (meaning a source electrode, a drain electrode, a gate electrode, a source wiring, a gate wiring, etc., sometimes referred to collectively as an electrode) Process to form on the formed substrate (hereinafter, may be referred to as "[1] process")

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

[3] [2] Process of developing coating film irradiated with radiation (hereinafter, sometimes referred to as "[6] process")

[4] A step of curing the coating film developed in the step [3] at 200 ° C. or lower to form an insulating film (hereinafter sometimes referred to as “[4] step”).

[5] The process of forming the coating film of a liquid crystal aligning agent in the board | substrate which has the insulating film hardened | cured at the [4] process, and heating the coating film at 200 degrees C or less (formerly, "[5] process" hereafter). Is available)

And it is preferable to have a process of forming a transparent electrode on the insulating film formed in the process [4] between the said [4] process and the [5] process.

The insulating film provided with a contact hole on the board | substrate with which the switching active element, an electrode, etc. were formed using the radiation sensitive resin composition of this embodiment by the manufacturing method of the array substrate of this embodiment including each said process. Can be formed. And an alignment film can be formed on a board | substrate using the liquid crystal aligning agent of this embodiment. As a result, the array substrate of this embodiment can be formed by the manufacturing method of the array substrate of this embodiment which has the insulating film formed in the desired position of the contact hole of a desired size, and has the insulating film formed at low temperature.

The array substrate manufactured as described above becomes an array substrate suitable even when a lowering of the heating step is desired from the viewpoint of energy saving.

Hereinafter, each process is explained in full detail.

[[1] process]

In this process, the coating film of the radiation sensitive resin composition of this embodiment is formed on a board | substrate. In this 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. These switching active elements are formed by a well-known method, such as repeating normal semiconductor film film formation, well-known insulating film film formation, and etching by the photolithographic method on a board | substrate.

After apply | coating a radiation sensitive resin composition to formation surfaces, such as a switching active element of this board | substrate, prebaking is performed and the solvent is evaporated and a coating film is formed.

As the material of the substrate, for example, glass such as soda lime glass or alkali free glass, silicone, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, aromatic polyamide, polyamideimide, polyimide and the like Can be mentioned. In addition, these substrates may optionally 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 method or vacuum deposition.

As a coating method of a radiation sensitive resin composition, for example, spraying method, roll coating method, rotary coating method (sometimes called spin coating method or spinner method), slit coating method (slit die coating method), bar coating Appropriate methods, such as a method and the inkjet coating method, can be employ | adopted. Among these, a spin coating method or a slit coating method is preferable.

As conditions of the above-mentioned prebaking, although it changes with kinds, compounding ratio, etc. of each component, 70 degreeC-120 degreeC is preferable and it is about 1 minute-about 15 minutes. 0.5 micrometer-10 micrometers are preferable, and, as for the film thickness after prebaking of a coating film, about 1.0 micrometer-about 7.0 micrometers are more preferable.

[[2] process]

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

Examples of the radiation used for the irradiation include visible light, ultraviolet light, and far ultraviolet light. Among these, the radiation whose wavelength is in the range of 200 nm-550 nm is preferable, and the radiation which contains the ultraviolet-ray of 365 nm is more preferable.

The radiation dose (exposure dose) is a value measured by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.) at a wavelength of 365 nm of radiation to be irradiated, and is 10 J / m 2 to 10,000 J / m 2 and is 100 J / M <2> -5,000J / m <2> is preferable and 200J / m <2> -3,000J / m <2> is more preferable.

The radiation sensitive resin composition used for formation of the insulating film of the array substrate of this embodiment has a high radiation sensitivity compared with the composition of the insulation film formation conventionally known, and the said radiation dose is 700 J / m <2> or less, Furthermore, 600 J / m <2> or less Even if it has a desired film thickness, favorable shape, excellent adhesiveness, and the high hardness, the insulating film has the advantage of being able to be obtained.

[[3] process]

Next, by developing the coating film after irradiation, an unnecessary part is removed, and the coating film which has a predetermined shape and formed the desired contact hole is obtained.

As a developing solution used for image development, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, choline, 1,8 Aqueous solutions of alkaline compounds such as -diazabicyclo- [5.4.0] -7-undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene can be used. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, can also be used for the aqueous solution of the above-mentioned alkaline compound. Moreover, surfactant can also be used only by adding it suitably, while adding the water-soluble organic solvent mentioned above.

The developing method may be any of a puddle method, a dipping method, a shower method, a spray method, and the like, and the developing time is 5 seconds to 300 seconds at room temperature, and preferably about 10 seconds to 180 seconds at room temperature. After the development treatment, for example, the desired pattern is obtained by performing dry water washing for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen.

[[4] process]

Subsequently, the insulating film is obtained as a cured film by hardening | curing (also called a postbaking) the coating film obtained by the process [3] with suitable heating apparatuses, such as a hotplate and oven. Contact holes of a desired arrangement are formed in the insulating film. As hardening temperature, 200 degrees C or less is preferable. And even if it is 180 degrees C or less, the insulating film of sufficient characteristic is obtained. Specifically, 100 degreeC-200 degreeC is preferable, and when it is going to make both low temperature hardening and reliability performance high level, 150 degreeC-180 degreeC is more preferable. As hardening time, for example, 5 minutes-30 minutes on a hotplate, and 30 minutes-180 minutes in an oven are preferable. Since a radiation sensitive resin composition contains the compound [D] as mentioned above, it can implement | achieve such low low temperature hardening. In addition, it realizes storage stability and has sufficient radiation sensitivity and resolution.

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

And after forming an insulating film in the process [4], it is preferable to have a process of forming a transparent electrode on this insulating film. For example, a transparent conductive layer made of ITO can be formed on the insulating film by using a sputtering method or the like. Subsequently, this transparent conductive layer can be etched using the photolithography method to form a transparent electrode on the insulating film. The transparent electrode constitutes a pixel electrode and enables electrical connection with a switching active element on the substrate by interposing a contact hole of the insulating film. In addition, a transparent electrode can be comprised using the transparent material which has high transmittance | permeability and electroconductivity with respect to visible light other than ITO. For example, it can comprise using IZO (Indium Zinc Oxide), ZnO (zinc oxide), a tin oxide, etc.

[5] Process

[4] After using the substrate with an insulating film obtained in the step, a transparent electrode is formed on the insulating film as described above, the liquid crystal aligning agent of the present embodiment is coated on the transparent electrode. As a coating method, the appropriate coating methods, such as the roll coater method, the spinner method, the printing method, the inkjet method, can be used, for example. Subsequently, the coated substrate of a liquid crystal aligning agent is prebaked, and then post-baking, a coating film is formed and an array substrate is manufactured. As prebaking conditions, they are 0.1 minute-5 minutes at 40 degreeC-120 degreeC, for example. As the postbaking condition, Preferably it is 120 degreeC-230 degreeC, More preferably, it is 150 degreeC-200 degreeC, More preferably, it is 150 degreeC-180 degreeC, Preferably it is 5 minutes-200 minutes, More preferably, 10 minutes It is ～ 100 minutes. The film thickness of the coating film after postbaking becomes like this. Preferably it is 0.001 micrometer-1 micrometer, More preferably, it is 0.005 micrometer-0.5 micrometer.

Solid content concentration of the liquid crystal aligning agent used when apply | coating a liquid crystal aligning agent (the ratio which the total mass of components other than the solvent of a liquid crystal aligning agent occupies in the total mass of a liquid crystal aligning agent) selects suitably in consideration of viscosity, volatility, etc. Although it is preferable, it is the range of 1 mass%-10 mass% preferably.

When using the liquid crystal aligning agent containing the [L] radiation-sensitive polymer which has a photo-alignment group as a liquid crystal aligning agent, liquid crystal aligning by irradiating linearly or partially polarized radiation or non-polarization radiation to the above-mentioned coating film. Grants ability. The irradiation of such polarized radiation corresponds to the alignment treatment of the alignment film. Here, as the radiation, for example, ultraviolet rays and visible rays containing light having a wavelength of 150 nm to 800 nm can be used. Especially as ultraviolet radiation, the ultraviolet-ray containing the light of the wavelength of 300 nm-400 nm is preferable. When the radiation to be used is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an inclined direction in order to give a pretilt angle, or may be performed in combination. When irradiating non-polarized radiation, the direction of irradiation needs to be inclined direction.

As an irradiation amount of radiation, Preferably it is 1J / m <2> or less than 10,000J / m <2>, More preferably, it is 10J / m <2> -3,000J / m <2>.

As a liquid crystal aligning agent, when using the liquid crystal aligning agent containing [M] polyimide which does not have a photo-alignment group, the coating film after postbaking can be used as an oriented film as it is. Then, if necessary, the coating film after the postbaking can be subjected to a treatment (rubbing treatment) of rubbing in a predetermined direction with a roll wound around a cloth made of fibers such as nylon, rayon, cotton, and the like, thereby providing liquid crystal alignment ability. Do.

As described above, when the alignment film is formed on the array substrate, it is possible to form the alignment film at a heating temperature of 200 ° C. or lower and a heating temperature of 180 ° C. or lower using the above-mentioned liquid crystal aligning agent. Therefore, it can avoid that the insulating film formed in the above-mentioned [1]-[4] process is exposed to a high temperature state in the formation process of an oriented film. And the array substrate of this embodiment can have an insulating film and an orientation film, and can manufacture by low temperature hardening of 200 degrees C or less.

[Example]

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described based on an Example, this invention is not limitedly interpreted by this Example.

<Preparation of radiation sensitive resin composition>

Example 1

[[A] Synthesis of Alkali Soluble Resin (A-I)]

In a flask equipped with a cooling tube and a stirrer, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethylmethyl ether were placed. 16 parts by mass of methacrylic acid, 16 parts by mass of tricyclo [5.2.1.0 ^2,6 ] decane-8-yl methacrylate, 38 parts by mass of methyl methacrylate, 10 parts by mass of styrene, glycidyl 20 methacrylic acid After adding a mass part and carrying out nitrogen substitution, while stirring gently, the temperature of the solution was raised to 70 degreeC, this temperature was preserve | saved for 4 hours, and superposition | polymerization was obtained, and the solution containing copolymer (AI) was obtained (solid content concentration = 34.4 mass%, Mw = 8,000, Mw / Mn = 2.3). In addition, solid content concentration means the ratio of the copolymer mass to the total mass of a copolymer solution.

Example 2

[Preparation of radiation sensitive resin composition]

[A] 100 parts by mass of dipentaerythritol hexaacrylate as the [B] polymerizable compound with respect to 100 parts by mass of the copolymer (AI) obtained in Example 1 which is an alkali-soluble resin, and ethanone as the [C] polymerization initiator. -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irugacure (IRUGACURE) OXE02, Chiba Specialty Chemical Co., Ltd.) 5 parts by mass of Shikisha) and 4,4'-diaminodiphenyl sulfone as a [D] compound are mixed, and 5 parts by mass of? -Glycidoxypropyltrimethoxysilane as an adhesion aid, and a surfactant ( 0.5 parts by mass of FTX-218 and 0.5 parts by mass of 4-methoxyphenol as a preservation stabilizer were added, and propylene glycol monomethyl ether acetate was added so that the solid content concentration was 30% by mass, and then the pore size was 0.5 µm. The radiation sensitive resin composition was prepared by filtering by the Millipore filter.

<Formation and Evaluation of Insulating Film>

Example 3

[Formation of insulating film]

After apply | coating the solution of the radiation sensitive resin composition prepared in Example 2 with the spinner on the alkali free glass substrate, the coating film of 4.0 micrometers in thickness was formed by prebaking on 100 degreeC hotplate for 2 minutes. Subsequently, the obtained coating film was irradiated with an exposure amount of 700 J / m 2 using a high pressure mercury lamp. Subsequently, the insulating film was formed by post-baking in 180 degreeC hardening temperature and 30 minute hardening time in oven.

Example 4

Evaluation of Preservation Stability

The insulating film was formed from the radiation sensitive resin composition of Example 2 immediately after preparation by the formation method of Example 3, and the film thickness was measured (it is called "film thickness immediately after preparation" in the following formula). In addition, after preparing by the method of Example 2, the radiation-sensitive resin composition solution was preserve | saved at 25 degreeC for 5 days, and the film thickness of the insulating film formed similarly after 5 days was measured (in the following formula, "5 days Later film thickness). The film thickness increase rate (%) was computed from the following formula.

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

The film thickness increase rate was 3% or less, and it judged that storage stability was favorable.

Evaluation of light resistance

About the insulating film by the formation method of Example 3, 800,000 J / m <2> of irradiance of 130mW was irradiated with UV irradiation apparatus (UVX-02516S1JS01, Ushio Denki Co., Ltd.), and the amount of film | membrane decrease was investigated. The film reduction amount was 2% or less, and judged that light resistance was favorable.

Evaluation of heat resistance

The insulating film by the formation method of Example 3 was further heated in an oven at 230 ° C. for 20 minutes, and the film thickness before and after the heating was tactile film thickness meter (alpha step (ALPHA-STEP)). IQ, KLA Tenco Corporation). And the residual film ratio ((film thickness after processing / film thickness before processing)) * 100 was calculated, and this residual film ratio was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Evaluation of chemical resistance

About the insulating film by the formation method of Example 3, it immersed for 15 minutes in the aligning-film peeling liquid CHEMICLEAN TS-204 (Sanyo Chemical Co., Ltd.) heated to 60 degreeC, and further wash | cleaned in water, and also in oven. And dried at 120 ° C. for 15 minutes. The film thickness before and after this treatment was measured with a stylus type film thickness gauge (Alphastep IQ, KLA Tenco Co., Ltd.) to calculate the residual film ratio ((film thickness after treatment / film thickness before treatment) × 100) to obtain this residual film ratio. Made chemical resistance. The residual film ratio was 99%, and the chemical resistance was judged to be good.

Evaluation of the resolution

After apply | coating the solution of the radiation sensitive resin composition prepared in Example 2 with the spinner on the alkali free glass substrate, the coating film of 4.0 micrometers in thickness was formed by prebaking on 100 degreeC hotplate for 2 minutes. Subsequently, irradiation was carried out using a high-pressure mercury lamp with a exposure amount of 700 J / m 2 through a photomask having a plurality of annular residue patterns of different sizes having a diameter ranging from 6 µm to 15 µm to the obtained coating film. . Then, after developing by the puddle method at 25 degreeC using the 0.40 mass% tetramethylammonium hydroxide aqueous solution, pure water washing was performed for 1 minute. Furthermore, the insulating film was formed as a pattern-shaped cured film by post-baking in 180 degreeC hardening temperature and 30 minute hardening time in oven. As a result of evaluating the formed insulating film, it confirmed that the pattern was formed in the photomask of 8 micrometers or less, and judged that the resolution was favorable.

<Production of Array Substrate>

Example 4

Using the solution of the radiation sensitive resin composition obtained by Example 2, it applied on the board | substrate with a switching active element, an electrode, etc. with the slit die coater. In this 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. These switching active elements are formed by a well-known method by repeating normal semiconductor film film formation, well-known insulating film film formation, and etching by the photolithography method on a board | substrate.

Next, it prebaked at 90 degreeC for 5 minutes on the hotplate, and formed the coating film. Subsequently, the obtained coating film was irradiated with the exposure amount of 700 J / m <2> using the high pressure mercury lamp through the photomask which has a pattern. Then, after developing by the puddle method at 25 degreeC using the 0.40 mass% tetramethylammonium hydroxide aqueous solution, pure water washing was performed for 1 minute. By developing, the unnecessary part was removed and the coating film of the predetermined shape in which the contact hole was formed was formed. Furthermore, it heat-processed at 180 degreeC for 60 minutes in oven, and formed the insulating film of 4.0 micrometers in film thickness.

Next, the transparent conductive layer which consists of ITO was formed on the insulating film with respect to the board | substrate with which the insulating film was formed using the sputtering method. Subsequently, the transparent conductive layer was etched using the photolithography method, and the transparent electrode was formed on the insulating film.

As described above, the array substrate of the present example was manufactured. In the obtained array substrate of the present embodiment, contact holes having a desired size were formed at desired positions of the insulating film, and electrical connection between the transparent electrode and the drain electrode was realized.

Example 5

[Production of Array Substrate with Photoalignment Film]

In the present Example, the photo-alignment film is formed using the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group using the array substrate obtained in Example 4.

First, as a liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group on the transparent electrode of the array substrate of Example 4, the liquid crystal aligning agent A- of description of Example 6 of WO 2009/025386. 1 is applied by a spinner. Subsequently, after prebaking was performed for 1 minute on the 80 degreeC hotplate, it heated at 180 degreeC for 1 hour in the oven which carried out the nitrogen substitution inside, and formed the coating film of 80 nm in thickness. Subsequently, the coating film surface was irradiated with a polarized ultraviolet ray of 200 J / m 2 containing 313 nm of bright lines using a Hg-Xe lamp and a glan taylor prism from a direction inclined at 40 ° with respect to the direction perpendicular to the substrate surface. An array substrate having an alignment film was produced.

Example 6

[Manufacture of Array Substrate Having a Vertical Alignment Film]

In the present Example, a vertical alignment film is formed using the liquid crystal aligning agent containing the polyimide which does not have a photo-alignment group using the array substrate obtained in Example 4.

First, as a liquid crystal aligning agent containing the polyimide which does not have a photo-alignment group, on top of the transparent electrode of the array substrate of Example 4, AL60101 (made by JSR Corporation) for vertical alignment film formation was apply | coated with the spinner. Subsequently, after prebaking for 1 minute on an 80 degreeC hotplate, the inside was heated at 180 degreeC for 1 hour in the oven which carried out the nitrogen substitution, the coating film of 80 nm thickness was formed, and the array substrate which has a vertical alignment film was manufactured. .

<Manufacture of Liquid Crystal Display Element>

Example 7

The array substrate obtained in Example 5 was used. And the color filter board | substrate manufactured by the well-known method was prepared. In this color filter substrate, three small colored patterns of red, green and blue colors and a black matrix are arranged in a lattice shape on the transparent substrate, and a transparent common electrode is disposed on the colored pattern. And the same photo-alignment film as what was formed on the array substrate in Example 5 was formed on the common electrode of the color filter board | substrate, and it was set as the opposing board | substrate with which the oriented film was formed. The TN liquid crystal layer was sandwiched using these pair of board | substrates, and the color liquid crystal display element was manufactured. The liquid crystal display element of this embodiment has the same structure as the liquid crystal display element shown in FIG. 3 mentioned above. The liquid crystal display element of this Example showed the outstanding operating characteristic, display characteristic, and reliable performance.

In addition, this invention is not limited to each said embodiment, In the range which does not deviate from the meaning of this invention, various deformation | transformation can be implemented. For example, the structure formed from the structural unit formed from at least 1 sort (s) chosen from the group which consists of unsaturated carbonic acid and unsaturated carbonic anhydride which comprise the negative radiation sensitive resin composition of this embodiment, and an epoxy group containing unsaturated compound. A positive radiation sensitive resin composition is formed together with a radiation sensitive acid generating compound such as a quinonediazide compound using a copolymer including a unit, and an insulating film having a contact hole can be formed by low temperature curing. Thus, it is possible to provide an array substrate. Low temperature curing of the insulating film using the positive radiation-sensitive resin composition becomes possible, and the insulating film formation of a desired array substrate becomes possible.

The array substrate of this invention can be manufactured easily by low temperature hardening, and has high reliability. Therefore, the array substrate of this invention can be used suitably for the large size liquid crystal television etc. which require the outstanding display quality and reliability.

1: array board
4, 11: substrate
5: source electrode
6: drain electrode
7: gate electrode
8: switching active element
9: transparent electrode
10: alignment 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: polarizing plate

Claims (10)

Switching active elements,
An insulating film disposed on the switching active element;
A contact hole formed in the insulating film;
An array substrate for a liquid crystal display element having a pixel electrode electrically connected to the switching active element via the contact hole,
The said insulating film is negative radiation sensitive containing the copolymer containing the structural unit formed from the structural unit formed from the at least 1 sort (s) chosen from the group which consists of unsaturated carbonic acid and unsaturated carbonic anhydride, and an epoxy-group-containing unsaturated compound. An array substrate, which is formed of a resin composition. The method of claim 1,
The said radiation sensitive resin composition is a compound represented by following formula (1), the compound represented by 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 And at least one compound selected from the group consisting of imidazole ring-containing compounds:

(Formula (1) of, R ¹ ~ R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group; However, R ¹ ~ R ⁶ at least one of which is an electron-withdrawing group, and R ¹ ~ R ⁶ At least one of which is an amino group, wherein all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;
In formula (2), R <^7> -R <^16> is respectively 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; Moreover, all or one part of hydrogen atoms may be substituted by the C2-C6 alkylene group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; However, all or part of the hydrogen atom may be substituted by the cyano group, the halogen atom, or the fluoroalkyl group in the said methylene group and the alkylene group). The method according to claim 1 or 2,
And the insulating film is formed at a curing temperature of 200 ° C. or less. The method according to claim 1 or 2,
An alignment film obtained by using any of a liquid crystal aligning agent containing a polyimide which has a transparent electrode on the said insulating film and has a photosensitive group which has a transparent electrode on the said transparent electrode, and a photo-alignment group, and a polyimide which does not have a photo-aligning group An array substrate having a. 5. The method of claim 4,
The said alignment film is an alignment film obtained using the liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group. The array substrate of Claim 1 or 2 is provided, The liquid crystal display element characterized by the above-mentioned. [1] Negative radiation-sensitive resin containing a copolymer comprising a structural unit formed of at least one member selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and structural units formed of epoxy group-containing unsaturated compounds Forming a coating film of the composition on the formed substrate of the switching active element,
[2] irradiating at least a portion of the coating film of the radiation-sensitive resin composition with radiation;
[3] a step of developing the coating film to which the radiation is irradiated in step [2] to obtain a coating film with contact holes; and
[4] A method for producing an array substrate, comprising the step of curing the coating film obtained in the step [3] at 200 ° C. or lower to form an insulating film. The method of claim 7, wherein
The said radiation sensitive resin composition is a compound represented by following formula (1), the compound represented by 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 And at least one compound selected from the group consisting of imidazole ring-containing compounds.

(Formula (1) of, R ¹ ~ R ⁶ are each independently a hydrogen atom, an electron withdrawing group or an amino group; However, R ¹ ~ R ⁶ at least one of which is an electron-withdrawing group, and R ¹ ~ R ⁶ At least one of which is an amino group, wherein all or part of the hydrogen atoms may be substituted with an alkyl group having 1 to 6 carbon atoms;
In formula (2), R <^7> -R <^16> is respectively 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; Moreover, all or one part of hydrogen atoms may be substituted by the C2-C6 alkylene group of the said amino group; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonyl methylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms; However, all or part of the hydrogen atom may be substituted by the cyano group, the halogen atom, or the fluoroalkyl group in the said methylene group and the alkylene group). 9. The method according to claim 7 or 8,
The manufacturing method of the array substrate which further has a process of forming an oriented film at 200 degrees C or less. 10. The method of claim 9,
The step of forming the alignment film at 200 ° C. or less may include forming the alignment film using any one of a liquid crystal alignment agent containing a radiation-sensitive polymer having a photoalignment group and a liquid crystal alignment agent including a polyimide having no photoalignment group. The manufacturing method of the array substrate characterized by the above-mentioned.

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