TWI531828B - Array substrate, liquid crystal display device, and method for producing array substrate - Google Patents

Description

Array substrate, liquid crystal display element, and method of manufacturing array substrate

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

The liquid crystal display element is configured by sandwiching a liquid crystal, for example, on a pair of substrates such as a glass substrate. An alignment film for controlling the alignment of the liquid crystal may be provided on the surface of the pair of substrates. The liquid crystal display element functions as a fine shutter for light emitted from a light source such as a backlight or external light, and partially transmits light or shields light to display. The liquid crystal display element is characterized by being thin, lightweight, and the like.

The liquid crystal display element was originally developed as a display element of a calculator or a clock centered on a character display or the like. Thereafter, due to the development of the simple matrix method, the dot matrix display becomes easy and the use is expanded to display elements of a notebook computer or the like. In addition, due to the development of the active matrix type, it is possible to achieve good image quality with excellent contrast ratio and response performance, and overcome the problems of high definition, colorization, and viewing angle expansion, thereby expanding the use to display applications for desktop computers. Wait. Recently, a wider viewing angle, a high-speed response of a liquid crystal, an improvement in display quality, and the like have been realized, and it has been used as a display element for a large-sized thin television.

Further, the liquid crystal display element requires further improvement in image quality or brightness.

In an active matrix type liquid crystal display element, a pair of liquid crystals are sandwiched The gate wiring and the signal wiring are arranged in a lattice shape on one of the substrates, and a switching active element such as a thin film transistor (TFT) is provided at an intersection of the gate wiring and the signal wiring to constitute an array substrate. On the array substrate, the pixel electrode is disposed in a region surrounded by the gate wiring and the signal wiring, and the pixel electrode constitutes a pixel as a display unit.

In the liquid crystal display device, in order to achieve an improvement in luminance, it is effective to increase the pixel electrode. The numerical aperture can be increased by making the area of the pixel electrode as large as possible, thereby increasing the luminance. In this case, for example, as disclosed in Patent Document 1, a technique in which a pixel electrode is overlapped with a gate wiring or a signal wiring to increase a numerical aperture is known. Patent Document 1 discloses a liquid crystal display device in which a thick insulating film containing an organic material is provided between a wiring and a pixel electrode, thereby suppressing an increase in coupling capacitance between a pixel electrode and a wiring. And increase the numerical aperture. Further, Patent Document 2 discloses a resin composition suitable for forming an insulating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-264798

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2004-264623

When a thick insulating film containing an organic material is provided between the wiring and the pixel electrode in the array substrate as in the case of the liquid crystal display device described in Patent Document 1, the electrical connection between the switching element such as a TFT and the pixel electrode can be used for the insulation. The contact hole provided on the film is realized.

Effective when forming contact holes on an insulating film containing an organic material It is the use of lithography. In this case, as described in Patent Document 2, as a material for forming an insulating film, a radiation-sensitive resin composition (hereinafter referred to as a radiation-sensitive resin composition) is preferably used. Moreover, a so-called positive type is widely used, in particular, a radiation sensitive resin composition.

In the insulating film using the positive-type radiation-sensitive resin composition, if radiation is induced, the solubility in the developer is increased, and the sensing portion is removed. Therefore, when a positive-type radiation-sensitive resin composition is used, a desired contact hole can be formed relatively easily by irradiating a portion where the contact hole of the insulating film is irradiated with radiation. Further, in the present invention, the term "radiation" is a concept including visible light rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like. With such a positive-type radiation-sensitive resin composition, in order to form a contact hole in a desired shape at a desired position in the manufactured insulating film, it is required to have high radiation sensitivity and excellent patterning can be realized. performance.

Moreover, when the insulating film having a contact hole is manufactured using the radiation sensitive resin composition, the expansion and contraction of the insulating film in the manufacturing process becomes a problem.

In other words, when an insulating film having a contact hole is produced using the radiation sensitive resin composition of the prior art, it is necessary to use about 230 ° C to 260 ° C after irradiation of radiation (hereinafter referred to as "exposure") and development. The insulating film is hardened by heating at a high temperature. Therefore, in the insulating film of the prior art using the photolithography technique, there is a concern that dimensional changes such as thermal expansion or shrinkage occur in the manufacturing steps. The contact hole in the insulating film strictly requires management of the arrangement position and size. When the dimensional change of the insulating film exceeds the allowable range, a problem may occur in the formation of the contact hole.

From the above, it is desirable to use the radiation sensitive resin composition to manufacture an insulating film on an array substrate, and to suppress thermal expansion or contraction to form a desired contact hole. Therefore, the radiation sensitive resin composition which can be hardened at a temperature lower than the prior art becomes effective. For example, a radiation sensitive resin composition which can be cured at a heating temperature of 220 ° C or lower which is lower than the temperature of the prior art is preferable, and a radiation sensitive resin composition which can be cured at a heating temperature of 200 ° C or lower is particularly preferable. The radiation-sensitive resin composition having such a hardening property can provide an insulating film which is an insulating film which is produced by heat-hardening after patterning by exposure and development, and has desired properties.

Moreover, recently, from the viewpoint of energy saving, it has been demanded to lower the heating step in manufacturing a liquid crystal display element having an array substrate. In other words, in the production of the array substrate and the liquid crystal display element using the array substrate, it is required to lower the temperature of the step of heating such as the hardening step of each constituent element to save energy.

In light of the above, it is strongly desired to realize a radiation-sensitive resin composition having a high radiation sensitivity and capable of forming an insulating film having a contact hole by hardening at a lower temperature than the prior art.

Moreover, it is strongly desired to use such a radiation sensitive resin composition to realize an array substrate having an insulating film produced by a manufacturing process at a temperature lower than that of the prior art. In addition, it is strongly desired to realize a liquid crystal display element constructed using such an array substrate.

The present invention has been made in view of the above problems. That is, the purpose of the present invention An insulating film is provided by using a radiation-sensitive resin composition having high radiation sensitivity and hardenable at a temperature lower than that of the prior art, and an array substrate including the insulating film and a method of manufacturing the same are provided.

Moreover, another object of the present invention is to provide an insulating film using a radiation sensitive resin composition having high radiation sensitivity, which can be hardened at a temperature lower than that of the prior art, and providing an array substrate including the insulating film. Liquid crystal display element.

A first aspect of the invention relates to an array substrate for a liquid crystal display device, comprising: a switching active device, an insulating film disposed on the switching active device, a contact hole formed on the insulating film, via the contact hole a pixel electrode electrically connected to the switch active device via the contact hole, and an alignment film formed on the pixel electrode, wherein the array substrate is characterized in that the insulating film is formed of a radiation-sensitive resin composition containing the following components Insulating film: [A] a polymer having a structural unit containing a group represented by the following formula (1) and a structural unit containing an epoxy group in the same or different polymer molecules, and [B] a photoacid generator The alignment film is an alignment film obtained by using any one of a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group and a liquid crystal alignment agent containing a polyimide having no photo-alignment group;

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these alkyl groups, cycloalkyl groups or aryl groups may be substituted. Wherein, in the case where R ¹ and R ² are each a hydrogen atom; R ³ is a group represented by an alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group or -M(R ⁴ ) ₃ , and these groups A part or all of the hydrogen atom may be substituted by a substituent, wherein M is Si, Ge or Sn, and R ⁴ is an alkyl group; and R ¹ and R ³ may be bonded to form a cyclic ether.

In a first aspect of the invention, it is preferred that the [B] photoacid generator comprises an oxime sulfonate group represented by the following formula (2);

In the formula (2), R ^B1 is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the first aspect of the invention, it is preferable that the radiation sensitive resin composition contains [C] selected from the group consisting of a compound represented by the following formula (C-1), a phosphonium salt, a thiol compound, and a blocked isocyanate compound. At least one compound of the group;

In the formula (C-1), R ⁷ to R ¹⁶ each independently represent a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and further, the hydrogen atom of the above amine group All or part of it may be substituted by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or a carbon number. It is an alkylene group of 2 to 6; wherein all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

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

A second aspect of the invention relates to a liquid crystal display element characterized in The array substrate comprising the first aspect of the invention.

A third aspect of the invention relates to a method of manufacturing an array substrate, comprising the steps of: [1] forming a coating film of a radiation sensitive resin composition containing a compound on a substrate on which a switching active element is formed; : [A] a polymer having a structural unit containing a group represented by the following formula (1) and a structural unit containing an epoxy group in the same or different polymer molecules, and [B] a photoacid generator; [2] a step of irradiating at least a part of the coating film of the radiation sensitive resin composition with radiation; [3] a step of developing a coating film irradiated with radiation in the step [2] to obtain a coating film having a contact hole formed thereon And [4] a step of hardening the coating film obtained in the step [3] to form an insulating film;

In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these alkyl groups, cycloalkyl groups or aryl groups may be substituted. Wherein, in the case where R ¹ and R ² are each a hydrogen atom; R ³ is a group represented by an alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group or -M(R ⁴ ) ₃ , and these groups A part or all of the hydrogen atom may be substituted by a substituent, wherein M is Si, Ge or Sn, and R ⁴ is an alkyl group; and R ¹ and R ³ may be bonded to form a cyclic ether.

In a third aspect of the invention, it is preferred that the [B] photoacid generator comprises an oxime sulfonate group represented by the following formula (2).

In the formula (2), R ^B1 is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

In a third aspect of the invention, it is preferable that the radiation sensitive resin composition contains [C] which is selected from the group consisting of a compound represented by the following formula (C-1), a phosphonium salt, a thiol compound, and a blocked isocyanate compound. At least one compound of the group; [Chemical 6]

In the formula (C-1), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; moreover, the hydrogen of the above amine group All or part of an atom may also be substituted by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or a carbon. The alkyl group having 2 to 6 carbon atoms; wherein all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

In the third aspect of the invention, it is preferable to further comprise the step of forming an alignment film at 200 ° C or lower.

In the third aspect of the present invention, the step of forming the alignment film preferably at 200 ° C or lower is to use a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group and a polyimide having a photo-alignment group. Any of the liquid crystal alignment agents forms an alignment film.

According to the present invention, there is provided an insulating film formed of a radiation sensitive resin composition having high radiation sensitivity and which can be cured at a low temperature, and an array substrate including the insulating film and a method of manufacturing the same are provided.

Moreover, according to the present invention, there is provided a radiation sensitization having high An insulating film formed of a radiation sensitive resin composition which can be cured at a low temperature, and a liquid crystal display element including an array substrate having the insulating film.

The array substrate and the liquid crystal display element of the embodiment of the present invention will be described.

<Liquid crystal display element>

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

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

Fig. 1 is a schematic cross-sectional view showing a configuration of a main part of an array substrate of the embodiment.

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

The array substrate 1 shown in Fig. 1 is an example of the array substrate of the present embodiment. A switching active element 8 is disposed on one surface of the transparent substrate 4. Further, a source 5, a drain 6, and a gate 7 connected to the switching active element 8 are disposed. An insulating film 12 is disposed on the switching active device 8 on the insulating film 12 A transparent electrode 9 as a pixel electrode is disposed thereon.

The transparent electrode 9 is formed of a transparent conductive film containing indium tin oxide (ITO) doped with tin or the like. An alignment film 10 for controlling the alignment of the liquid crystal can be disposed on the transparent electrode 9 as shown. The recessed portion provided to penetrate the insulating film 12 is a contact hole 17 through which the transparent electrode 9 and the drain 6 are electrically connected. As a result, electrical connection between the transparent electrode 9 as a pixel electrode and the switching active element 8 can be performed.

Further, as shown in FIG. 2, the source wiring 18 and the gate wiring 19 are arranged in a matrix on the array substrate 1. A switching active device 8 including a source 5, a drain 6 and a gate 7 is provided in the vicinity of an intersection of the source wiring 18 and the gate wiring 19. The source 5 is connected to the source wiring 18, and the gate 7 is connected to the gate wiring 19. The divided pixels are formed on the array substrate 1 as described above.

As will be described later, in the array substrate 1 of the present embodiment, the insulating film 12 is formed by applying the radiation-sensitive resin composition of the present embodiment to the substrate 4 on which the electrode such as the source electrode 5 and the switching active device 8 are formed. After the necessary patterning of the contact hole 17 or the like, it is formed by hardening. The radiation sensitive resin composition of the present embodiment used for forming the insulating film 12 can be, for example, a positive type.

The radiation sensitive resin composition of the present embodiment has a characteristic of having high radiation sensitivity, and after patterning, the insulating film 12 can be formed by curing at a temperature lower than that of the prior art. The insulating film 12 can be formed, for example, by heat hardening at a temperature of 220 ° C or lower. Further, by optimizing the composition of the radiation sensitive resin composition, it is also possible to form an insulating film by heat hardening at a temperature lower than 200 ° C. 12. Therefore, the insulating film 12 can suppress the dimensional variation in the hardening step, and can form the contact hole 17 of the desired arrangement position and size. Further, the array substrate 1 of the present embodiment can be formed by, for example, curing at 220 ° C or lower, and further, curing at a lower temperature of 200 ° C or lower to form the insulating film 12, which can be made lower than in the prior art. Manufactured by heating at temperature.

Further, in the array substrate 1 of the present embodiment, after the transparent electrode 9 is formed, the alignment film 10 for liquid crystal alignment control can be provided. The alignment film 10 can be formed using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group or a liquid crystal alignment agent containing a polyimide having no photo-alignment group, as will be described later. In this case, it becomes possible to form the alignment film 10 at a low temperature heating temperature, for example, it becomes possible to form the alignment film 10 at a heating temperature of 200 ° C or lower. Therefore, in the array substrate 1 of the present embodiment, for example, the insulating film 12 can be formed by low-temperature heating of 200 ° C or lower, and the alignment film 10 can be formed by, for example, heating at a low temperature of 200 ° C or lower. Therefore, the array substrate 1 of the present embodiment has the alignment film 10 and can be manufactured by heating at a lower temperature than the prior art.

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

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

The liquid crystal display element 21 shown in FIG. 3 is a color liquid crystal display element including the array substrate 1 and the color filter substrate 22, and is an example of the liquid crystal display element of the present embodiment. The liquid crystal display element 21 is, for example, a thin film transistor type twisted nematic (TN) mode liquid crystal display element, and has the array substrate 1 and the color filter of the present embodiment shown in FIG. The substrate 22 has a structure in which the liquid crystal layer 23 including the TN liquid crystal is opposed to each other.

As shown in FIG. 3, the array substrate 1 has a structure in which a source electrode 5, a drain electrode 6, a gate electrode 7, a switching active element 8, and an insulating film 12 are disposed on a surface of the transparent substrate 4 on the liquid crystal layer 23 side. Further, a transparent electrode 9 as a pixel electrode is provided on the insulating film 12. A contact hole 17 penetrating the insulating film 12 is provided on the insulating film 12, and the transparent electrode 9 and the drain 6 are electrically connected via the portion. As a result, electrical connection between the transparent electrode 9 as a pixel electrode and the switching active element 8 can be performed. The alignment film 10 for liquid crystal alignment control is provided on the transparent electrode 9.

On the color filter substrate 22, a minute color pattern 15 of red, green, and blue and a black matrix 13 are disposed on the surface of the transparent substrate 11 on the liquid crystal layer 23 side. The red, green, and blue color patterns 15 are arranged in a regular shape such as a lattice shape. Further, the color of the colored pattern 15 is not limited to the above three colors of red, green, and blue, and may be selected from other colors or further added with yellow to form a four-color colored pattern. Further, a color filter pattern of each color can be arranged to form a color filter substrate.

A transparent common electrode 14 is provided on the coloring pattern 15 and the black matrix 13. The alignment film 10 similar to the array substrate 1 is provided on the surface of the color filter substrate 22 that is 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 alignment treatment if necessary, thereby achieving uniform alignment of the liquid crystal layer 23 sandwiched between the array substrate 1 and the color filter substrate 22.

Further, the distance between the array substrate 1 and the color filter substrate 22 opposed to each other via the liquid crystal layer 23 can be maintained by a spacer (not shown), and usually It is 2 μm~10 μm. 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, a polarizing plate 28 is disposed on the side opposite to the side in contact with the liquid crystal layer 23, respectively.

In FIG. 3, reference numeral 27 is backlight light that is irradiated to the liquid crystal layer 23 from a backlight unit (not shown) that is a light source of the liquid crystal display element 21. As the backlight unit, for example, a backlight unit having a structure in which a fluorescent tube such as a Cold Cathode Fluorescent Lamp (CCFL) or a diffusion plate is combined can be used. Moreover, a backlight unit using a white LED as a light source can also be used. Examples of the white LED include a white LED that uses a red LED having an independent spectrum, a green LED, and a blue LED to obtain white light, and a white LED that combines a red LED, a green LED, and a blue LED to obtain white light by color mixing. A blue LED, a red LED, and a green phosphor are combined to obtain a white LED by mixing colors, and a blue LED, a red illuminating phosphor, and a green luminescent phosphor are combined to obtain white light by color mixing. White LED, which is a white LED with white light by mixing blue LEDs and YAG phosphors, and combines blue LEDs, orange luminescent phosphors, and green luminescent phosphors to obtain white light by color mixing. The white LED is a white LED that combines an ultraviolet LED, a red illuminating phosphor, a green illuminating phosphor, and a blue illuminating phosphor to obtain white light by color mixing.

The liquid crystal mode of the liquid crystal display element 21 of the present embodiment may be a super twisted nematic (STN) or a coplanar switching (In-Planes Switching) in addition to the TN mode described above. Liquid crystal mode such as IPS), Vertical Alignment (VA) or Optically Compensated Birefringence (OCB). In this case, in particular, with respect to the alignment film 10, an alignment film which realizes the alignment which is most suitable for the liquid crystal layer 23 of each liquid crystal mode is selected. For example, when the liquid crystal display element 21 of the present embodiment is a VA mode liquid crystal display element, the alignment film 10 is a vertical alignment type alignment film.

As described above, the liquid crystal display element 21 of the present embodiment includes the array substrate 1 of the present embodiment. In the array substrate 1, the transparent electrode 9 and the drain 6 are electrically connected via the contact hole 17 provided in the insulating film 12. The insulating film 12 of the array substrate 1 can be formed by using a radiation-sensitive resin composition of the present embodiment and heat-hardening at a low temperature of, for example, 200 ° C or lower. Therefore, in the liquid crystal display element 21 of the present embodiment, in the array substrate 1, the transparent electrode 9 and the drain 6 can be electrically connected by the contact hole 17 of a desired arrangement position and size.

Next, the main constituent elements of the array substrate of the liquid crystal display element of the present embodiment can be described in detail by the formation of an insulating film which is cured by heating at a temperature lower than that of the prior art. In particular, the insulating film of the array substrate of the present embodiment can be formed by using the radiation sensitive resin composition of the present embodiment, and the radiation sensitive resin composition of the present embodiment will be described in detail below.

<Inductive Radiation Resin Composition>

The radiation sensitive resin composition used in the production of the insulating film of the array substrate of the present embodiment contains: [A] a specific polymer (hereinafter also simply referred to as "[A] polymer") and [B] photoacid Agent. Moreover, it may further contain The compound [C] detailed later. Further, in addition to the [A] component ([A] polymer) and the [B] component ([B] photoacid generator), and the further [C] component ([C] compound), as long as the present invention is not damaged The effects of the invention may also contain other optional components. The radiation sensitive resin composition of the present embodiment having the above composition can be used as a positive radiation sensitive resin composition. Hereinafter, each component contained in the radiation sensitive resin composition of the present embodiment will be described.

<[A]polymer>

[A] The polymer has a structural unit (hereinafter also simply referred to as "structural unit (1)") containing a group represented by the following formula (1) and a structural unit containing an epoxy group in the same or different polymer molecules, Other structural units are also available as needed. The aspect of the [A] polymer is not particularly limited, and examples thereof include (i) two structural units having a structural unit (1) and a structural unit containing an epoxy group in the same polymer molecule, and [A] a case where one polymer molecule is present in a polymer; (ii) has a structural unit (1) in a polymer molecule, and has a structural unit containing an epoxy group in a polymer molecule different therefrom, and [A] a case where two kinds of polymer molecules are present in a polymer; (iii) two structural units having a structural unit (1) and a structural unit containing an epoxy group in a polymer molecule, having a polymer molecule different therefrom The structural unit (1) has a structural unit containing an epoxy group in a polymer molecule further different from these molecules, and three polymer molecules are present in the [A] polymer; (iv) except (i) In addition to the polymer molecules specified in ~(iii), When the [A] polymer further contains another one or two or more kinds of polymer molecules, and the like.

In the above formula (1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these alkyl groups, cycloalkyl groups or aryl groups may be substituted. A base substitution (wherein, there is no case where both R ¹ and R ² are hydrogen atoms). R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group or a group represented by -M(R ⁴ ) ₃ (M is Si, Ge or Sn, and R ⁴ is an alkyl group), and a part of these hydrogen atoms or All may also be substituted by a substituent. R ¹ and R ³ may also be bonded to form a cyclic ether.

<Structural unit (1)>

The structural unit (1) contains the group represented by the above formula (1). The group represented by the above formula (1) has an acetal structure or a ketal structure, and is a group which is relatively stable to a base and which is dissociated in the presence of an acid to form a polar group (hereinafter also referred to as "acid dissociation". base"). Therefore, in the structural unit (1), the acid dissociable group is dissociated by the acid generated by the [B] photoacid generator described later by irradiation with radiation. As a result, the [A] polymer having the structural unit (1) and being alkali-insoluble is alkali-soluble. Below, for the structural unit (1) The group represented by the above formula (1) contained in the above will be described in more detail.

In the above formula (1), the alkyl group represented by R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 30 carbon atoms, and the alkyl chain may have an oxygen atom or a sulfur atom. Nitrogen atom. Specific examples of the above alkyl group include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-octyl, n-dodecyl, n-tetradecyl, n-octadecane. A linear alkyl group such as an alkyl group, a branched alkyl group such as an isopropyl group, an isobutyl group, a tert-butyl group, a neopentyl group, a 2-hexyl group or a 3-hexyl group.

In the above formula (1), the cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 3 to 20 carbon atoms, a polycyclic ring or an oxygen atom in the ring. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a borneol group, a norbornyl group, and an adamantyl group.

In the above formula (1), the aryl group represented by R ¹ and R ² is preferably an aryl group having a carbon number of 6 to 14, and may be a single ring or a single ring-bonded structure or a condensation. ring. Specific examples of the above aryl group include a phenyl group and a naphthyl group.

In the above formula (1), part or all of the hydrogen atoms of R ¹ and R ² may be substituted with a substituent. Examples of such a substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (the cycloalkyl group can be suitably used as described above), and an aryl group (the aryl group may be suitably used). The description of the above aryl group is used, and an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms) may, for example, be a methoxy group, an ethoxy group, a propoxy group, a n-butoxy group or a pentyloxy group. a hexyloxy group, a heptyloxy group, an octyloxy group, etc., and a fluorenyl group (preferably a fluorenyl group having 2 to 20 carbon atoms, for example, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl group, an isobutyl group, etc.), a decyloxy group. (preferably an anthraceneoxy group having 2 to 10 carbon atoms, and examples thereof include an ethyl methoxy group, an ethoxy group, a butoxy group, a third butyloxy group, a third pentyloxy group, etc.), an alkoxy group. a carbonyl group (preferably, an alkoxycarbonyl group having 2 to 20 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, etc.), a haloalkyl group (hydrogen of the above alkyl group or a cycloalkyl group) Examples of the group in which a part or all of the atom is substituted by a halogen atom include, for example, a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, a fluorocyclobutyl group or the like. Examples of the cyclic structure in the aryl group, the cycloalkyl group and the like include the above alkyl group as a further substituent.

In the above formula (1), the alkyl group, the cycloalkyl group and the aryl group represented by R ³ may be as described in R ¹ and R ² . In the above formula (1), the aralkyl group represented by R ³ is preferably an aralkyl group having 7 to 20 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, and a naphthylethyl group. In the above formula (1), R -M ³ is (R ⁴⁾ ₃ group represented, for example, include alkyl trimethyl silicon, germanium, trimethyl alkyl group. The substituent which may be substituted with a part or all of the hydrogen atom of the aralkyl group represented by R ³ or the group represented by -M(R ⁴ ) ₃ may be suitably used as well as the above R ¹ and R ^{2 .} A substituent in which a part or all of a hydrogen atom is substituted.

In the above formula (1), R ¹ and R ³ may be bonded to each other to form a cyclic ether. Examples of such a cyclic ether include a 2-epoxypropane group, a 2-tetrahydrofuranyl group, a 2-tetrahydropyranyl group, and a 2-dioxanyl group. A part or all of the hydrogen atom of the cyclic ether may be substituted with the above substituent.

The structural unit (1) may have the acetal knot because it has a functional group which has an acetal structure or a ketal structure by bonding to a carbon atom. Structure or ketal structure.

The functional group which should become an acetal structure by bonding to the above other carbon atoms may, for example, be 1-methoxyethoxy, 1-ethoxyethoxy or 1-n-propoxyethoxy , 1-isopropoxyethoxy, 1-n-butoxyethoxy, 1-isobutoxyethoxy, 1-second butoxyethoxy, 1-tert-butoxy Ethoxy, 1-cyclopentyloxyethoxy, 1-cyclohexyloxyethoxy, 1-norbornyloxyethoxy, 1-bornelipyloxyethoxy, 1-phenoxy Ethoxy, 1-(1-naphthyloxy)ethoxy, 1-benzyloxyethoxy, 1-phenylethoxyethoxy, (cyclohexyl)(methoxy)methoxy, Cyclohexyl)(ethoxy)methoxy, (cyclohexyl)(n-propoxy)methoxy, (cyclohexyl)(isopropoxy)methoxy, (cyclohexyl)(cyclohexyloxy) Methoxy, (cyclohexyl)(phenoxy)methoxy, (cyclohexyl)(benzyloxy)methoxy, (phenyl)(methoxy)methoxy, (phenyl)(ethoxy) Methoxy, (phenyl) (n-propoxy) methoxy, (phenyl) (isopropoxy) methoxy, (phenyl) (cyclohexyloxy) methoxy, (benzene (phenoxy)methoxy, (phenyl)(benzyloxy)methoxy, (benzyl) (methoxy)methoxy, (benzyl)(ethoxy)methoxy, (benzyl)(n-propoxy)methoxy, (benzyl)(isopropoxy)methoxy, (benzyl)(cyclohexyloxy)methoxy, (benzyl)(phenoxy)methoxy, (benzyl)(benzyloxy)methoxy, 2-tetrahydrofuranyloxy, 2-tetra Hydropyranyloxy, 1-trimethyldecyloxyethoxy, 1-trimethyldecyloxyethoxy, and the like.

Among these, a 1-ethoxyethoxy group, a 1-cyclohexyloxyethoxy group, a 2-tetrahydropyranyloxy group, and a 1-n-propoxyethoxy group are mentioned as a preferable group.

Examples of the functional group having a ketal structure by bonding with the above other carbon atoms include 1-methyl-1-methoxyethoxy group and 1-methyl-1-ethoxy group. Ethyloxy, 1-methyl-1-n-propoxyethoxy, 1-methyl-1-isopropoxyethoxy, 1-methyl-1-n-butoxyethoxy, 1-methyl-1-isobutoxyethoxy, 1-methyl-1-butoxyethoxy, 1-methyl-1-butoxyethoxy, 1-methyl -1-cyclopentyloxyethoxy, 1-methyl-1-cyclohexyloxyethoxy, 1-methyl-1-norbornyloxyethoxy, 1-methyl-1- Borneol oxyethoxy, 1-methyl-1-phenoxyethoxy, 1-methyl-1-(1-naphthalenyloxy)ethoxy, 1-methyl-1-benzyloxy Ethoxy, 1-methyl-1-phenylethoxyethoxy, 1-cyclohexyl-1-methoxyethoxy, 1-cyclohexyl-1-ethoxyethoxy, 1-ring Hexyl-1-n-propoxyethoxy, 1-cyclohexyl-1-isopropoxyethoxy, 1-cyclohexyl-1-cyclohexyloxyethoxy, 1-cyclohexyl-1-benzene Oxyethoxy, 1-cyclohexyl-1-benzyloxyethoxy, 1-phenyl-1-methoxyethoxy, 1-phenyl-1-ethoxyethoxy, 1- Phenyl-1-n-propoxyethoxy, 1-phenyl-1-isopropoxyethoxy, 1-phenyl-1-cyclohexyloxyethoxy, 1-phenyl-1- Phenoxyethoxy, 1-phenyl-1-benzyloxyethoxy 1-benzyl-1-methoxyethoxy, 1-benzyl-1-ethoxyethoxy, 1-benzyl-1-n-propoxyethoxy, 1-benzyl-1- Isopropoxyethoxy, 1-benzyl-1-cyclohexyloxyethoxy, 1-benzyl-1-phenoxyethoxy, 1-benzyl-1-benzyloxyethoxy , 2-(2-methyl-tetrahydrofuranyl)oxy, 2-(2-methyl-tetrahydropyranyl)oxy, 1-methoxy-cyclopentyloxy, 1-methoxy-cyclic Hexyloxy and the like.

Among these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group are mentioned as a preferable group.

Specific examples of the structural unit (1) having an acetal structure or a ketal structure include, for example, structural units represented by the following formulas (1-1) to (1-3).

In the above formula (1-1) and formula (1-3), R' is a hydrogen atom or a methyl group. R ¹ , R ² and R ^{3 are} synonymous with the description of the above formula (1).

The monomer having a radical polymerizable property (hereinafter also simply referred to as "a monomer having an acetal structure") of the structural unit (1) represented by the above formula (1-1) to formula (1-3), for example, may be mentioned : (meth)acrylic acid-1-alkoxyalkyl ester, (meth)acrylic acid-1-(cycloalkoxy)alkyl ester, (meth)acrylic acid-1-(haloalkoxy)alkyl ester (meth)acrylic acid esters such as (meth)acrylic acid-1-(aralkyloxy)alkyl ester and (meth)acrylic acid tetrahydropyranyl ester containing acetal structure; 2,3- Bis(1-(trialkylsulfonyloxy)alkoxy)carbonyl)-5-norbornene, 2,3-bis(1-(trialkylsulfonyloxy)alkoxy)carbonyl) -5-norbornene, 2,3-bis(1-alkoxyalkoxycarbonyl)-5-norbornene, 2,3-bis(1-(cycloalkoxy)alkoxycarbonyl)- 5-norbornene, 2,3-bis(1-(aralkyloxy)alkoxycarbonyl)-5-norbornene and the like norbornene-containing monomer having an acetal structure; 1-alkoxy alkane Styrenes such as oxystyrene, 1-(haloalkoxy)alkoxystyrene, 1-(aralkyloxy)alkoxystyrene, tetrahydropyranyloxystyrene, etc. containing an acetal structure monomer.

Among these compounds, (meth)acrylic acid-1-alkoxyalkyl ester, (A) Tetrahydropyranyl acrylate, 1-alkoxyalkoxystyrene, tetrahydropyranyloxystyrene, more preferably 1-alkyloxyalkyl (meth)acrylate.

Specific examples of the acetal structure-containing monomer which provides the above structural unit (1) include, for example, 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, and methacrylic acid. 1-n-butoxyethyl ester, 1-isobutoxyethyl methacrylate, 1-tert-butoxyethyl methacrylate, 1-(2-chloroethoxy) methacrylate Ethyl ester, 1-(2-ethylhexyloxy)ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, methacrylic acid 1-(2-cyclohexylethoxy)ethyl ester, 1-benzyloxyethyl methacrylate, 2-tetrahydropyranyl methacrylate; 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-isobutoxyethyl acrylate, 1-tert-butoxyethyl acrylate, Acrylic-1-(2) -Chloroethoxy)ethyl ester, 1-(2-ethylhexyloxy)ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, Acrylic acid-1 -(2-cyclohexylethoxy)ethyl ester, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate; 2,3-di(1-(tri-) Nonyloxy)ethoxy)carbonyl)-5-norbornene, 2,3-bis(1-(trimethyldecyloxy)ethoxy)carbonyl)-5-norbornene, 2 , 3-bis(1-methoxyethoxycarbonyl)-5-norbornene, 2,3-bis(1-(cyclohexyloxy)ethoxycarbonyl)-5-norbornene, 2, 3-bis(1-(benzyloxy)ethoxycarbonyl)-5-norbornene; p- or m-ethoxyethoxy styrene, p- or m--1-methoxyethoxy Styrene, p- or m--1-n-butoxyethoxystyrene, p- or m--1-isobutoxyethoxystyrene, p- or m-(1,1-dimethyl B Oxygen) Styrene, p- or m-(2-chloroethoxy)ethoxystyrene, p- or m-(2-ethylhexyloxy)ethoxystyrene, p- or m--1 - n-propoxyethoxystyrene, p- or m-hexacyclohexyloxyethoxystyrene, p- or m-(2-cyclohexylethoxy)ethoxystyrene, or Between 1-benzyloxyethoxystyrene and the like.

The above structural unit (1) may be used alone or in combination of two or more.

Among the monomers containing the acetal structure of the above structural unit (1), 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, and 2-tetrahydro methacrylate are preferable. Pyranyl ester, 1-benzyloxyethyl methacrylate.

A commercially available compound can be used as the monomer having the acetal structure of the structural unit (1), and a compound synthesized by a known method can also be used. For example, the monomer containing the acetal structure of the structural unit (1) represented by the above formula (1-1) can be reacted with vinyl ether by the (meth)acrylic acid in the presence of an acid catalyst as described below. synthesis.

(In the formula, R ', R ¹ and R ³ respectively in the above formula (1-1) R', R ¹ and R ³ corresponds, R ⁵ and R ⁶ as a ^{-CH (R 5) (R 6} ) And corresponds to R ² in the above formula (1-1))

The content of the structural unit (1) in the [A] polymer is not particularly limited as long as the [A] polymer exhibits alkali solubility due to an acid and exhibits desired heat resistance of the cured film. When the structural unit (1) and the structural unit containing an epoxy group are contained in the molecule, it is preferably 5% by mass based on the monomer input ratio with respect to all the structural units contained in the [A] polymer. ~70% by mass, more preferably 10% by mass to 60% by mass, particularly preferably 20% by mass to 50% by mass.

Further, in the case where the polymer unit has the structural unit (1) and the other polymer molecule has the structural unit containing the epoxy group, the structure in a polymer molecule having the structural unit (1) The content of the unit (1) is preferably 40% by mass to 99% by mass, and more preferably 50% by mass to 98% by mass based on the monomer input ratio of all the structural units contained in the polymer molecule. The mass% or less is particularly preferably from 55% by mass to 95% by mass.

<Structural unit containing an epoxy group>

The [A] polymer has the above structural unit (1) and a structural unit containing an epoxy group. The structural unit containing an epoxy group is a structural unit derived from an epoxy group-containing monomer having a radical polymerizable property, and contains an epoxy group. Examples of the epoxy group include an oxiranyl group (1,2-epoxy structure) and an propylene oxide group (1,3-epoxy structure). When the [A] polymer has a structural unit containing an oxirane group or an oxypropylene group in the molecule, the hardness of the insulating film obtained by the radiation sensitive resin composition of the present embodiment can be further improved. Heat resistance.

Specific examples of the epoxy group-containing monomer which provides the epoxy group-containing structural unit include, for example, glycidyl acrylate, glycidyl methacrylate, 3,4-epoxybutyl acrylate, and methacrylic acid. -3,4-epoxybutyl ester, 3-methyl-3,4-epoxybutyl acrylate, 3-ethyl-3,4-epoxybutyl methacrylate, acrylic acid-5 , 6-epoxyhexyl ester, 5,6-epoxyhexyl methacrylate, 5-methyl-5,6-epoxyhexyl methacrylate, 5-ethyl-5 methacrylate, 6-epoxyhexyl ester, acrylate-6,7-epoxyheptyl ester, -6,7-epoxyheptyl methacrylate; 3,4-epoxycyclohexyl methacrylate, methacrylic acid -3,4-epoxycyclohexylmethyl ester, 3,4-epoxycyclohexylethyl methacrylate, 3,4-epoxycyclohexyl propyl methacrylate, methacrylic acid-3,4- Epoxy cyclohexyl butyl acrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3,4-epoxycyclohexyl methyl acrylate, acrylic acid-3 , 4-epoxycyclohexylethyl ester, 3,4-epoxycyclohexyl propyl acrylate, 3,4-epoxycyclohexyl butyl acrylate, C An oxiranyl group-containing (meth)acrylic compound such as acid-3,4-epoxycyclohexylhexyl ester; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl Glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, etc. Glycidyl ethers; vinyl vinyl glycidyl ethers such as o-vinylphenyl glycidyl ether, m-vinylphenyl glycidyl ether, p-vinylphenyl glycidyl ether; 3-(acryloyloxymethyl) Propylene oxide, 3-(acryloxymethyl)-3-methyl propylene oxide, 3-(acryloxymethyl)-3-ethyl propylene oxide, 3-(propyl Benzeneoxymethyl)-3-phenyl propylene oxide, 3-(2-propenyloxyethyl) propylene oxide, 3-(2-propenyloxyethyl)-3-ethyl ring Oxypropane, 3-(2-propenyloxyethyl)-3-ethyl propylene oxide, 3-(2-propenyloxyethyl)-3-phenyl propylene oxide; 3-(methyl Propylene methoxymethyl) propylene oxide, 3-(methacryloxymethyl)-3-methyl propylene oxide, 3-(methacryloxymethyl)-3-ethyl ring Oxypropane, 3-(methacryloxymethyl)-3-phenyl propylene oxide, 3-(2-methylpropenyloxyethyl) propylene oxide, 3-(2-methyl propylene醯oxyethyl)-3-ethyl propylene oxide, 3-(2-methylpropenyloxyethyl)-3-ethyl propylene oxide, 3-(2-methacryloxyloxyethyl) 3-phenylpropene oxide; 2-(acryloxymethyl) propylene oxide, 2-(acryloxymethyl)-2-methyl propylene oxide, 2-(propylene oxime) Methyl)-2-ethyl propylene oxide, 2-(acryloxymethyl)-2-phenyl propylene oxide, 2-(2-propenyl methoxyethyl) propylene oxide, 2- (2-propenyloxyethyl)-2-ethyl propylene oxide, 2-(2-propenyl methoxyethyl)-2-phenyl propylene oxide; -(methacryloxymethyl) propylene oxide, 2-(methacryloxymethyl)-2-methyl propylene oxide, 2-(methacryloxymethyl)-2 -ethyl propylene oxide, 2-(methacryloxymethyl)-2-phenyl propylene oxide, 2-(2-methylpropenyloxyethyl) propylene oxide, 2-(2 -Methyl propylene methoxyethyl)-2-ethyl propylene oxide, 2-(2-methylpropenyloxyethyl)-2-ethyl propylene oxide, 2-(2-methyl propylene A (meth)acrylic compound containing an oxypropylene group such as methoxyethyl)-2-phenyl propylene oxide. The above epoxy group-containing structural unit may be used singly or in combination of two or more.

Self-coupling reactivity with other radical polymerizable monomers, and sensing From the viewpoint of good developability of the radioactive resin composition, among the above epoxy group-containing monomers, glycidyl methacrylate, -2-methylglycidyl methacrylate, and methacrylic acid-3,4- are preferable. Epoxycyclohexyl ester, 3,4-epoxycyclohexylmethyl methacrylate, 3-(methacryloxymethyl)-3-methyl propylene oxide, 3-(methacryl oxime) Oxymethyl)-3-ethyl propylene oxide.

The content of the epoxy group-containing structural unit in the [A] polymer is not particularly limited as long as the desired heat resistance of the insulating film is exhibited, and the structural unit (1) and the containing ring are contained in one polymer molecule. In the case of the structural unit of the oxy group, it is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass based on the monomer input ratio of all the structural units contained in the [A] polymer. % or more is 55% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less.

On the other hand, in the case of having a structural unit (1) in one polymer molecule and having a structural unit containing an epoxy group in another polymer molecule, as a polymerization in a structural unit having an epoxy group The content of the epoxy group-containing structural unit contained in the molecule is preferably 10% by mass or more and 80% by mass or less, more preferably 20% by mass or more and 70% by mass based on the monomer input ratio. Hereinafter, it is particularly preferably 25% by mass or more and 60% by mass or less.

<Other structural units>

Examples of the radical polymerizable monomer which provides another structural unit include a radical polymerizable monomer having a carboxyl group or a derivative thereof and a hydroxyl group.

The above radical polymerizable monomer having a carboxyl group or a derivative thereof may, for example, be acrylic acid, methacrylic acid, crotonic acid or 2-propenyloxyethyl amber. Monocarboxylic acid such as acid, 2-methylpropenyloxyethyl succinic acid, 2-propenyloxyethylhexahydrophthalic acid, 2-methylpropenyloxyethylhexahydrophthalic acid a dicarboxylic acid such as maleic acid, fumaric acid, citraconic acid, mesaconic acid or itaconic acid; an acid anhydride of the above dicarboxylic acid;

Examples of the radical polymerizable monomer having a hydroxyl group include 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxymethylcyclohexyl methyl acrylate, and the like. Hydroxyalkyl acrylate; 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, methacrylic acid a hydroxyalkyl methacrylate such as -6-hydroxyhexyl ester or 4-hydroxymethyl-cyclohexylmethyl methacrylate.

Among these radically polymerizable monomers having a hydroxyl group, 2-hydroxyethyl acrylate and acrylic acid-3 are preferable from the viewpoints of copolymerization reactivity with other radical polymerizable monomers and heat resistance of the obtained interlayer insulating film. -hydroxypropyl ester, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 4-hydroxymethyl-cyclohexyl methyl acrylate, methacrylic acid - 4-hydroxymethyl-cyclohexylmethyl ester.

Examples of the other radical polymerizable monomer include alkyl acrylates such as methyl acrylate and isopropyl acrylate; methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, and dimethyl methacrylate. Ethyl methacrylate such as ester, butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo[5.1.02.5 ^2,6 ]decane-8-yl acrylate Acrylic cycloalkyl acrylate such as 2-(tricyclo[5.2.1.0 ^2,6 ]decane-8-yloxy)ethyl acrylate or isobornyl acrylate; cyclohexyl methacrylate, methyl 2-methylcyclohexyl acrylate, tricyclo[5.1.02.5 ^2,6 ]decane-8-yl methacrylate, 2-(tricyclo[5.2.1.0 ^2,6 ]decane methacrylate An alicyclic alkyl methacrylate such as -8-yloxy)ethyl ester or isobornyl methacrylate; an aryl ester of acrylic acid such as phenyl acrylate or benzyl acrylate; and an aralkyl ester of acrylic acid; An aryl methacrylate such as phenyl acrylate or benzyl methacrylate; and an aralkyl ester of methacrylic acid; diethyl maleate, diethyl fumarate, diethyl itaconate, etc. Dialkyl carboxylic acid; tetrahydrofurfuryl methacrylate, tetrahydrofuranyl methacrylate, tetrahydropyran-2-methyl methacrylate, etc., unsaturated five-membered heterocyclic ring containing one oxygen atom Acrylate and unsaturated six-membered heterocyclic methacrylate; 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropene醯oxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-cyclohexyl-1,3-dioxolane 4-methylpropenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methylpropenyloxymethyl-2-methyl-2-iso Unsaturated five-membered heterocyclic methacrylate containing two oxygen atoms, such as butyl-1,3-dioxolane; 4-propenyloxymethyl-2,2-dimethyl-1,3- Dioxolane, 4-propenyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxymethyl-2,2-diethyl- 1,3-dioxolan, 4-propenyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolan, 4-propenyloxymethyl-2-cyclo Pentyl-1,3-dioxolan, 4-propenyloxymethyl-2-cyclohexyl-1,3-dioxolan, 4-propene oxime Ethylethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-propenyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane , 4-propenyloxybutyl-2-methyl-2-ethyl-1,3-dioxolan and the like, unsaturated 5-membered heterocyclic acrylate containing 2 oxygen atoms; styrene, α-A Vinyl aromatic compounds such as styrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol; N-phenylmaleimide, N-cyclohexyl Maleidin, N-benzylmaleimide, N-ammonium imino-3-maleimide benzoate, N-ammonium imino-4-malayiya Aminobutyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridine Substituted maleimide such as maleimide, maleimide, conjugated diene such as 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene Class of compounds; other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate.

From the viewpoints of good copolymerization reactivity with the above-mentioned radically polymerizable monomer having a reactive functional group and developability of the radiation sensitive resin composition, styrene and 4- are preferable among these other radical polymerizable monomers. Isopropenylphenol, tricyclo[cyclopropyl] methacrylate [5.2.1.0 ^2,6 ]decane-8-yl ester, tetrahydrofurfuryl methacrylate, 1,3-butadiene, 4-propenyloxy group Alkyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, benzyl methacrylate, and the like.

[A] GPC (gel permeation chromatography) of a polymer The polystyrene-converted mass average molecular weight (hereinafter referred to as "Mw") is preferably 2.0 × 10 ³ to 1.0 × 10 ⁵ , more preferably 5.0 × 10 ³ ~ 5.0×10 ⁴ . By setting the Mw of the [A] polymer to the above range, the radiation sensitivity and alkali developability of the radiation sensitive resin composition of the present embodiment can be improved.

Further, the GPC (gel permeation chromatography) polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") of the [A] polymer is preferably 2.0 × 10 ³ to 1.0 × 10 ⁵ , more preferably 5.0 × 10 ³ ~ 5.0 × 10 ⁴ . When the Mn of the copolymer is in the above range, the curing reactivity of the radiation-sensitive resin composition of the present embodiment at the time of curing of the coating film can be improved.

Further, the molecular weight distribution "Mw/Mn" of the [A] polymer is preferably 3.0 or less, and more preferably 2.6 or less. By setting the Mw/Mn of the [A] polymer to 3.0 or less, the developability of the obtained insulating film or the like can be improved. The radiation sensitive resin composition containing the [A] polymer can easily form a desired pattern shape without developing residue at the time of development.

<[A] Method for Producing Polymer>

[A] The polymer can be produced by radical copolymerization of a monomer having an acetal structure, a monomer having an epoxy group, and a monomer providing another structural unit. In the case of producing a [A] polymer comprising both the structural unit (1) and the structural unit containing an epoxy group in the same polymer molecule, a monomer containing at least an acetal structure and an epoxy group are used. The mixture of monomers can be copolymerized. On the other hand, in the case of the [A] polymer having a structural unit (1) in a polymer molecule and having a structural unit containing an epoxy group in a polymer molecule different therefrom, at least it is included in advance. Acetal The polymerizable solution of the monomer of the structure is subjected to radical polymerization to obtain a polymer molecule having the structural unit (1), and a polymerizable solution containing at least a monomer having an epoxy group is subjected to radical polymerization to obtain an epoxy group-containing compound. The polymer molecules of the structural unit of the group are finally mixed to form the [A] polymer.

Examples of the solvent used in the polymerization for producing the [A] polymer include alcohols, ethers, glycol ethers, ethylene glycol alkyl ether acetates, diethylene glycol alkyl ethers, and propylene glycol monoalkanes. Alkyl ether, propylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether propionate, aromatic hydrocarbons, ketones, other esters, and the like.

As the polymerization initiator used in the polymerization for producing the [A] polymer, a compound known as a radical polymerization initiator can be used. Examples of the radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis(methyl 2-methylpropionate), and 2,2'-azobis-( Azo compounds such as 2,4-dimethylvaleronitrile), 2,2'-azobis-(4-methoxy-2,4-dimethylvaleronitrile); benzamidine peroxide, peroxidation An organic peroxide such as laurel, third butyl peroxypivalate, 1,1'-bis-(t-butylperoxy)cyclohexane; and hydrogen peroxide.

<[B] Photoacid generator>

[B] A photoacid generator is a compound which can generate an acid by irradiating radiation. For example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, or the like can be used as described above. The radiation sensitive resin composition of the present embodiment can be used as a positive radiation sensitive resin composition by exhibiting a positive radiation sensitivity characteristic by containing a [B] photoacid generator. [B] The photoacid generator is not particularly limited as long as it is a compound capable of generating an acid (for example, a carboxylic acid, a sulfonic acid, or the like) by irradiation with radiation. As a [B] photoacid generator in the sense The form of the radioactive resin composition may be in the form of a photoacid generator (hereinafter also referred to as "[B] photoacid generator") of a compound described later, or may be a polymer [A] or other polymerization. The form of the photoacid group introduced into a part of the substance may be in the form of both of them.

The [B] photoacid generator may, for example, be an oxime sulfonate compound or a sulfonium imide compound, and among them, an oxime sulfonate compound is preferred.

<肟sulfonate compound>

The oxime sulfonate compound is preferably a compound containing an oxime sulfonate group represented by the following formula (2).

In the above formula (2), R ^B1 is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent.

In the above formula (2), the alkyl group of R ^B1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ^B1 may also be an alkoxy group or an alicyclic group having a carbon number of 1 to 10 (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably Substituted by a bicycloalkyl group or the like. The aryl group of R ^B1 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group. The aryl group of R ^B1 may also be substituted by an alkyl group, an alkoxy group or a halogen atom having 1 to 5 carbon atoms.

The above compound containing the oxime sulfonate group represented by the above formula (2) is more preferably an oxime sulfonate compound represented by the following formula (3).

In the formula (3), R ^{B1 is} synonymous with the description of R ^B1 in the formula (2). X is an alkyl group, an alkoxy group or a halogen atom. m is an integer from 0 to 3. When m is 2 or 3, a plurality of Xs may be the same or different. The alkyl group as X is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

In the formula (3), the alkoxy group as X is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom as X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. Particularly preferably, in the formula (3), m is 1, and X is a methyl group, and a compound having a substitution position of X is an ortho position.

Specific examples of the oxime sulfonate compound represented by the above formula (3) include a compound (3-i) and a compound (3-ii) represented by the following formula (3-i) to formula (3-v), respectively. ), the compound (3-iii), the compound (3-iv), and the compound (3-v).

[化12]

These compounds may be used singly or in combination of two or more kinds thereof, or may be used in combination with other photoacid generators as the component [B]. The above compound (3-i) [(5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-A Phenyl)acetonitrile], compound (3-ii) [(5H-octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], compound (3-iii) [(camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], compound (3-iv) [(5-p-toluene) Sulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile] and compound (3-v)[(5-octylsulfonyloxyimino) )-(4-Methoxyphenyl)acetonitrile] is available in the form of a commercial product.

<sulfonimide compound>

Examples of the sulfonimide compound which is preferred as the [B] photoacid generator include N-(trifluoromethylsulfonyloxy) succinimide, N-(camphorsulfonyloxy) succinimide, N-(4-methylphenylsulfonyloxy) succinimide, N-(2-trifluoromethylphenylsulfonyloxy) succinimide, N-(4-fluorophenylsulfonate) Oxy) succinimide, N-(trifluoromethylsulfonyloxy) phthalimide, N-(camphorsulfonyloxy) phthalimide, N-(2- Trifluoromethylphenylsulfonyloxy)phthalimide, N-(2-fluorophenylsulfonyloxy)phthalic imine, N-(trifluoromethylsulfonate) Diphenylmaleimide, N-(camphorsulfonyloxy)diphenylmaleimide, 4-(methylphenylsulfonyloxy)diphenylmaleimide, N-(2-trifluoromethylphenylsulfonyloxy)diphenylmaleimide, N-(4-fluorophenylsulfonyloxy)diphenylmaleimide, N-( Phenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-(trifluoromethanesulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyanthracene Amine, N-(nonafluorobutylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenine, N-(camphorsulfonyloxy)bicyclo[2.2.1 G-8-ene-2,3-dicarboxylate Basear imine, N-(camphorsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(trifluoromethylsulfonate) Oxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-methylphenylsulfonyloxy)bicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2- Trifluoromethylphenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-fluorophenylsulfonyloxy) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-fluorophenylsulfonyloxy)-7-oxabicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(trifluoromethylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxy quinone imine , N-(camphorsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyindenine, N-(4-methylphenylsulfonyloxy) Bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)bicyclo[2.2.1]heptane -5,6-oxy-2,3- Carboxylimine, N-(4-fluorophenylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboxyarmine, N-(trifluoromethyl) Alkyl sulfonyloxy)naphthyldicarboxy quinone imine, N-(camphorsulfonyloxy)naphthyldicarboxy quinone imine, N-(4-methylphenylsulfonyloxy)naphthyldicarboxyanthracene Imine, N-(phenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(2-trifluoromethylphenylsulfonyloxy)naphthyldicarboxy quinone imine, N-(4- Fluorophenylsulfonyloxy)naphthyldicarboxyanilide, N-(pentafluoroethylsulfonyloxy)naphthyldicarboxyarsenine, N-(heptafluoropropylsulfonyloxy)naphthalene Dicarboxy quinone imine, N-(nonafluorobutylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(ethylsulfonyloxy)naphthyl dicarboxy quinone imine, N-(propyl Sulfosulfonyloxy)naphthyldicarboxyanilide, N-(butyl Sulfomethoxy)naphthyldicarboxy quinone imine, N-(pentylsulfonyloxy)naphthyldicarboxy quinone imine, N-(hexylsulfonyloxy)naphthyldicarboxy quinone imine, N- (heptylsulfonyloxy)naphthyldicarboxy quinone imine, N-(octylsulfonyloxy)naphthyldicarboxy quinone imine, N-(fluorenylsulfonyloxy)naphthyldicarboxy fluorene Amines, etc.

In the above-mentioned [B] photoacid generator, from the viewpoint of improving the radiation sensitivity and the solubility, it is preferably an oxime sulfonate compound as described above, and more preferably contains the formula (2). The compound of the oxime sulfonate group is more preferably an oxime sulfonate compound represented by the formula (3). Among them, [(5-propylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], [(5H) which can be obtained as a commercial product is particularly preferable. -octylsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile], [(5-p-toluenesulfonyloxyimino-5H-) Thiophen-2-ylidene)-(2-methylphenyl)acetonitrile], [(camphorsulfonyloxyimino-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile ], [(5-octylsulfonyloxyimino)-(4-methoxyphenyl)acetonitrile].

[B] The photoacid generator may be used singly or in combination of two or more. The content of the [B] photoacid generator in the radiation sensitive resin composition of the present embodiment is preferably 0.1 parts by mass to 10 parts by mass, more preferably 1 mass, per 100 parts by mass of the [A] polymer. ~5 parts by mass. When the content of the [B] photoacid generator is in the above range, the radiation sensitivity of the radiation sensitive resin composition can be optimized, and the transparency can be maintained to form an insulating film.

<[C] compound>

The radiation sensitive resin composition of the present embodiment used in the production of the insulating film of the array substrate of the present embodiment may contain the [C] compound. [C] A compound is a compound that functions as a hardener, that is, it promotes The hardening of the coating film formed by the radiation sensitive resin composition. Therefore, for convenience, it is also referred to as a [C] compound (hardener) or a [C] hardener or the like. The compound [C] is at least one compound selected from the group consisting of a compound represented by the following formula (C-1), a phosphonium salt, a thiol compound, and a blocked isocyanate compound. The radiation sensitive resin composition contains the compound [C] selected from the group of the specific compounds, so that the hardening temperature of the insulating film can be more effectively lowered. By including the [C] compound in the radiation sensitive resin composition of the present embodiment, the insulating film can be produced by, for example, a curing temperature of 200 ° C or lower, such as 180 ° C to 200 ° C. Hereinafter, each compound which is a compound of [C] will be described in detail.

[Compound represented by formula (C-1)]

The compound [C] is preferably at least one compound selected from the group consisting of compounds represented by the following formula (C-1). As the [C] compound, by selecting the above specific compound having an amine group and an electron deficient group, the hardening temperature of the insulating film can be more effectively lowered.

In the above formula (C-1), R ⁷ to R ¹⁶ each independently represent a hydrogen atom, an electron withdrawing group or an amine group. Among them, at least one of R ⁷ to R ¹⁶ is an amine group. Further, all or a part of the hydrogen atom of the amine group may be substituted by an alkylene group having 2 to 6 carbon atoms. A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or an alkylene group having 2 to 6 carbon atoms. Here, all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group.

Examples of the electron withdrawing group represented by R ⁷ to R ^{16 in} the above formula (C-1) include a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, a carboxyl group, a decyl group, an alkylsulfonyl group, and an alkoxy group. Sulfonyl, dicyanovinyl, tricyanovinyl, sulfonyl and the like. Among these, a nitro group, an alkoxysulfonyl group, and a trifluoromethyl group are preferable. The group represented by A is preferably a sulfonyl group or a methylene group which may be substituted by a fluoroalkyl group.

The compound represented by the above formula (C-1) is preferably 2,2-bis(4-aminophenyl)hexafluoropropane or 2,3-bis(4-aminophenyl)succinonitrile, 4, 4'-Diaminobenzophenone, 4,4'-diaminophenyl benzoate, 4,4'-diaminodiphenylanthracene, more preferably 4,4'-diaminodiphenyl Base, 2,2-bis(4-aminophenyl)hexafluoropropane.

The compounds represented by the above formula (C-1) may be used singly or in combination of two or more. The content ratio of the compound represented by the above formula (C-1) is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.2 parts by mass to 10 parts by mass, per 100 parts by mass of the [A] polymer. By setting the content ratio of the compound represented by the above formula (C-1) to the above range, the hardening of the insulating film formed of the radiation sensitive resin composition can be effectively promoted.

[鏻盐]

The onium salt can be formed using a compound selected from the group consisting of the following formula (4) At least one of the group formed.

In the above formula (4), A ¹ is a phosphorus atom. R ²¹ to R ²⁴ 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. Among them, some or all of the hydrogen atoms of these groups may be substituted. Q ^- is a monovalent anion.

The alkyl group having 1 to 20 carbon atoms represented by R ²¹ to R ²⁴ in the above formula (4) may, for example, be a linear or branched methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group. , heptyl, octyl, decyl, decyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nineteen Alkyl, eicosyl, and the like.

Examples of the aryl group having 6 to 18 carbon atoms represented by R ²¹ to R ²⁴ in the above formula (4) include a phenyl group and a naphthyl group.

The aralkyl group having 7 to 30 carbon atoms represented by R ²¹ to R ²⁴ in the above formula (4) may, for example, be a benzyl group or a phenethyl group.

Examples of the monovalent anion represented by Q ^- in the above formula (4) include a chloride ion, a bromide ion, an iodide ion, a cyanide ion, a nitrate ion, a nitrite ion, a hypochlorite ion, and a chlorine. Acid ion, chlorate ion, perchlorate ion, permanganate ion, hydrogencarbonate ion, dihydrogen phosphate ion, hydrogen sulfide ion, thiocyanate ion, carboxylate ion, sulfonate ion, phenoxy ion , tetrafluoroborate ion, tetraaryl borate ion, hexafluoroantimonate ion, and the like.

Examples of the phosphonium salt include tetraphenylphosphonium. Tetraphenylborate, tetraphenylphosphonium. Tetrakis(p-tolyl)borate, tetraphenylphosphonium. Tetrakis(p-ethylphenyl)borate, tetraphenylphosphonium. Tetrakis(p-methoxyphenyl)borate, tetraphenylphosphonium. Tetrakis(p-ethoxyphenyl)borate, tetraphenylphosphonium. Tetrakis(p-tert-butoxyphenyl)borate, tetraphenylphosphonium. Tetra(m-tolyl)borate, tetraphenylphosphonium. Tetra(m-methoxyphenyl)borate, tris(p-tolyl)phenylhydrazine. Tetrakis(p-tolyl)borate, tetra (p-tolyl) oxime. Tetrakis(p-tolyl)borate, tris(p-methoxyphenyl)phenylhydrazine. Tetra(p-tolyl)borate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, methyltriphenylphosphonium thiocyanate, p-tolyltriphenylsulfonium thiocyanate Salt and so on.

Among these onium salts, butyltriphenylphosphonium thiocyanate is preferred. The onium salts may be used singly or in combination of two or more.

The content ratio of the onium salt in the radiation-sensitive resin composition is preferably 0.05 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] polymer. By setting the content ratio of the onium salt to the above specific range, the hardening promotion of the radiation sensitive resin composition can be achieved.

[thiol compound]

The thiol compound is a compound having two or more mercapto groups in one molecule.

The thiol compound is not particularly limited as long as it has two or more thiol groups in one molecule, and at least one selected from the group consisting of compounds represented by the following formula (5) can be used.

In the above formula (5), R ³¹ is a methylene group and an alkylene group having 2 to 10 carbon atoms. Among them, some or all of the hydrogen atoms of these groups may be substituted with an alkyl group. Y ¹ is a single bond, -CO- or -O-CO- ^* . Among them, the key with ^* is bonded to R ³¹ . n is an integer from 2 to 10. A ² is an n-valent hydrocarbon group having 2 to 70 carbon atoms which may have one or more ether bonds, or a group represented by the following formula (6) when n is 3.

In the above formula (6), R ³² to R ³⁴ are each independently a methylene group or an alkylene group having 2 to 6 carbon atoms. " ^* " indicates the key.

As the compound represented by the above formula (5), an esterified product of a mercaptocarboxylic acid and a polyhydric alcohol can be typically used. Examples of the mercaptocarboxylic acid constituting the ester compound include thioacetic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercaptovaleric acid, and the like. Further, examples of the polyhydric alcohol constituting the ester compound include ethylene glycol, propylene glycol, trimethylolpropane, tetraethylene glycol, dipentaerythritol, 1,4-butanediol, and pentaerythritol.

The compound represented by the above formula (5) is preferably trimethylolpropane tris(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(3-mercaptopropionic acid) ester, and tetraethylene glycol bis(3-mercaptopropionate) ester. Dipentaerythritol hexa(3-mercaptopropionic acid) ester, pentaerythritol tetrakis(mercaptoacetic acid) ester, 1,4-bis(3-mercaptobutyloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), pentaerythritol Tetrakis(3-mercaptovalerate), 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)- Triketone.

As the compound having two or more mercapto groups in one molecule of the thiol compound, a compound represented by the following formula (7) to the following formula (9) can also be used.

[化18]

In the above formula (7), R ⁴¹ is a methylene group or an alkylene group having 2 to 20 carbon atoms. R ⁴² is a methylene group or a linear or branched alkyl group having 2 to 6 carbon atoms. k is an integer from 1 to 20.

In the above formula (8), R ⁴³ to R ⁴⁶ each independently represent a hydrogen atom, a hydroxyl group or a group represented by the following formula (9). However, at least one of R ⁴³ to R ⁴⁶ is a group represented by the following formula (9).

In the above formula (9), R ⁴⁷ is a methylene group or a linear or branched alkyl group having a carbon number of 2 to 6.

The thiol compound may be used singly or in combination of two or more. The content ratio of the thiol compound in the radiation-sensitive resin composition is preferably 1 part by mass to 20 parts by mass, more preferably 5 parts by mass to 15 parts by mass, per 100 parts by mass of the [A] polymer. By setting the content ratio of the thiol compound to the above specific range, the hardening acceleration of the radiation sensitive resin composition can be achieved.

[Block isocyanate compound]

The blocked polyisocyanate compound is a compound which reacts with an active hydrogen group-containing compound (blocking agent) and is inert at normal temperature, and has a property that if it is heated, the blocking agent dissociates and regenerates Isocyanate group. By allowing the radiation-sensitive resin composition to contain a block polyisocyanate, the isocyanate-hydroxyl crosslinking reaction can be carried out as an effective crosslinking agent, thereby achieving the hardening acceleration of the radiation sensitive resin composition.

The blocked polyisocyanate compound can be obtained by a known reaction of a polyisocyanate derived from an aliphatic or alicyclic diisocyanate with a compound (blocker) having an active hydrogen.

Examples of the diisocyanate include tetramethylene diisocyanate, pentane diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4-trimethyl-1,6-diisocyanatohexane, and 2 , 4,4-trimethyl-1,6-diisocyanatohexane, lysine diisocyanate, isophorone diisocyanate (IPDI), 1,3-bis(isocyanatemethyl)cyclohexane Alkane, 4,4-dicyclohexylmethane diisocyanate, norbornene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, Xylidine isocyanate, 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5- Trimethylcyclohexyl diisocyanate or the like.

As a commercially available product, for example, a compound which blocks an isocyanate group with a hydrazine of methyl ethyl ketone can be exemplified by Duranate (registered trademark) TPA-B80E, Duranate TPA-B80X, Duranate E402-B80T, Duranate MF-B60XN, Duranate MF-B60X, Duranate MF. -B80M (above manufactured by Asahi Kasei Industrial Co., Ltd.); compounds which block isocyanate groups with active methylene groups For example, Dranate (registered trademark) MF-K60X (Asahi Kasei Kogyo Co., Ltd.); a block of an isocyanate compound having a (meth) acrylonitrile group; Karenz (registered trademark) MOI-BP, Karenz (registered trademark) MOI-BM ( The above is manufactured by Showa Denko.)

Among these commercial products, when using Duranat (registered trademark) E402-B80T or Duranate MF-B60X, it exhibits high flexibility, and it can be used by mixing with other compounds, and it can control freely. Hardness is therefore preferred.

Examples of the polyisocyanate derived from the diisocyanate include a hetero-cyanate type polyisocyanate, a biuret type polyisocyanate, a urethane type polyisocyanate, and an allophanate type polyisocyanate. From the viewpoint of hardenability, a isocyanurate type polyisocyanate is preferred.

Examples of the blocking agent include an alcohol compound, a phenol compound, an active methylene compound, a thiol compound, a guanamine compound, a quinone compound, an imidazole compound, a pyrazole compound, a urea compound, and the like. An anthracene compound, an amine compound, an imine compound, a pyridine compound or the like.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, 2-ethylhexanol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, cyclohexanol, and the like; phenolic compounds; Examples thereof include phenol, cresol, ethylphenol, butylphenol, nonylphenol, dinonylphenol, styrenated phenol, and hydroxybenzoic acid ester; and examples of the active methylene-based compound include malonic acid Methyl ester, diethyl malonate, methyl ethyl acetate, ethyl acetate, ethyl acetate, etc.; Examples of the thiol compound include butyl thiol and dodecyl thiol; and examples of the guanamine compound include acetanilide, acetamide, ε-caprolactam, δ-valeroinamide, and γ. - butylidene and the like; examples of the quinone imine compound include succinimide and maleimide; examples of the imidazole compound include imidazole and 2-methylimidazole; and pyrazole compounds include, for example, 3 -methylpyrazole, 3,5-dimethylpyrazole, 3,5-ethylpyrazole, etc.; examples of the urea compound include urea, thiourea, and ethyl urea; and examples of the hydrazine compound include formaldehyde. Examples thereof include hydrazine, acetaldoxime, acetone oxime, butanone oxime, cyclohexanone oxime, and the like; and examples of the amine compound include diphenylamine, aniline, carbazole, and the like; and the imine compound is exemplified by exoethylenimine and poly Examples of the pyridine compound include 2-hydroxypyridine and 2-hydroxyquinoline.

The block polyisocyanate compounds may be used singly or in combination of two or more. The content ratio of the block polyisocyanate compound in the radiation sensitive resin composition is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.5 parts by mass to 5 parts by mass, per 100 parts by mass of the [A] polymer. . By setting the content ratio of the block polyisocyanate compound to the above range, the curing of the radiation sensitive resin composition can be promoted.

<Other optional ingredients>

Used in the formation of the insulating film of the array substrate of the present embodiment. The radiation sensitive resin composition of the present embodiment may contain a [C] compound (curing agent) in addition to the above [A] polymer and [B] photoacid generator, and may not detract from the present invention. In the range of the effect, other optional components such as an antioxidant, a surfactant, a adhesion aid, a basic compound, a quinonediazide compound, and a plasticizer may be contained as needed. These optional components may be used alone or in combination of two or more.

<Modulation of Radiation-Linear Resin Composition>

The radiation sensitive resin composition of the present embodiment used for forming the insulating film of the array substrate of the present embodiment can be further mixed by the addition of the above [A] polymer and [B] photoacid generator [C] The compound (hardener) and any components added as needed are prepared. Further, the radiation sensitive resin composition of the present embodiment can be used as a positive radiation sensitive resin composition. The radiation sensitive resin composition of the present embodiment is preferably used in a state of being dissolved or dispersed in a suitable solvent. For example, [A] component ([A] polymer), [B] component ([B] photoacid generator), [C] component ([C] compound), and [D] as an optional component in a solvent The components are mixed at a predetermined ratio, whereby the radiation sensitive resin composition can be modulated.

The solid content concentration of the radiation sensitive resin composition of the present embodiment (refers to the ratio of the mass of the polymer contained in the polymer solution to the total mass of the polymer solution) may be depending on the purpose of use or the desired film. The thickness is arbitrarily set, and is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 40% by mass, still more preferably 15% by mass to 35% by mass.

<solvent>

As a modulation of the radiation sensitive resin composition which can be used in the present embodiment As the solvent used in the production, as described above, a solvent which uniformly dissolves or disperses each component and does not react with each component is suitably used. Examples of such a solvent include alcohols, ethers, diethylene glycol alkyl ethers, ethylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, and propylene glycol monoalkanes. Alkyl ether propionates, aromatic hydrocarbons, ketones, esters, and the like.

Examples of such a solvent include benzyl alcohol and diacetone alcohol; and examples of the ether include tetrahydrofuran or diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether, and the like. Examples of the dialkyl ethers such as n-hexyl ether; and examples of the diethylene glycol alkyl ethers include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether. And diethylene glycol methyl ether and the like; and examples of the ethylene glycol alkyl ether acetates include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and B. Examples of the propylene glycol monoether ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether; and propylene glycol monoalkyl ether acetates include, for example, propylene glycol. Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, etc.; propylene glycol monoalkyl ether propionate, for example, propylene glycol monomethyl ether propionate Propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionic acid Examples of the aromatic hydrocarbons include toluene and xylene; and examples of the ketones include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 2-heptanone, and 4-hydroxy-4-methyl-2- Pentanone Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, and 2-hydroxyl group. Ethyl 2-methylpropionate, methyl hydroxyacetate, ethyl hydroxyacetate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3 - ethyl hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, Propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, C Ethyl oxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, 2- Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2- Ethyl ethoxypropionate and the like.

Among these solvents, ethers such as dialkyl ethers, diethylene glycol alkyl ethers, and ethylene glycol alkane are preferred from the viewpoints of excellent solubility and dispersibility, non-reactivity with each component, and easy formation of a coating film. Ethyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates, ketones and esters, particularly preferably diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, methyl cellosolve B Acid ester, ethyl cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, propyl acetate, isopropyl acetate, acetic acid Butyl ester, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropanoate, ethyl 2-hydroxy-2-methylpropionate, methyl lactate, ethyl lactate, propyl lactate, lactic acid Butyl ester, methyl 2-methoxypropionate, 2- Ethyl methoxypropionate. These solvents may be used singly or in combination of two or more.

Further, among these solvents, an ether such as a dialkyl ether such as diisopropyl ether, di-n-butyl ether, di-n-pentyl ether, diisoamyl ether or di-n-hexyl ether is preferable, and diisoamyl ether is most preferable. By using such a solvent, when the radiation sensitive resin composition of the present embodiment is applied to, for example, a large glass substrate by a slit coating method, the drying step time is shortened, and the coating property is further improved (suppression coating) Uneven).

In addition to the above solvents, benzyl ethyl ether, dihexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, acetone acetone, and isophor may be further used as needed. Ketone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, carbonic acid A high boiling point solvent such as ethylene diester, propylene carbonate, phenyl cellosolve acetate or carbitol acetate.

The radiation sensitive resin composition obtained by the above components and the preparation method can form an insulating film having contact holes by low temperature hardening. For example, an insulating film having good reliability such as solvent resistance can be obtained by a curing temperature lower than that of the prior art such as 180 ° C to 200 ° C. Further, the array substrate of the present embodiment can be provided by low temperature curing.

Next, the array substrate of the present embodiment may include an alignment film that controls the alignment of the liquid crystal. The alignment film formed on the array substrate of the present embodiment can be formed by using the liquid crystal alignment agent of the present embodiment. Therefore, the alignment treatment agent of the present embodiment, in particular, the main components thereof will be described below.

<Liquid alignment agent>

The liquid crystal alignment agent of the present embodiment in which the alignment film is formed on the array substrate of the present embodiment is a [L] sensitizing radioactive polymer having a photoalignment group or a [M] polyimine having no photoalignment group. A liquid crystal alignment agent as a main component. These components can form an alignment film at a low temperature of, for example, 200 ° C or lower. In particular, a liquid crystal alignment agent containing a [L] radiation-sensitive polymer having a photo-alignment group can form an alignment film at a lower temperature, and is a more preferable liquid crystal alignment agent. As described above, since the liquid crystal alignment agent of the present embodiment can form the alignment film by the low-temperature heating step, the alignment film can be formed without exposing the insulating film provided on the lower layer to a high-temperature heating state.

Further, the liquid crystal alignment agent of the present embodiment in which the alignment film is formed on the array substrate of the present embodiment may contain [N] other components as long as the effects of the present invention are not impaired. These components are described below.

[[L] Sense Radiation Polymer]

The [L] radiation sensitive polymer contained in the liquid crystal alignment agent of the present embodiment is a polymer having a photoalignment group. The photoalignment group of the [L] radiation sensitive polymer is a functional group that imparts anisotropy to the film by light irradiation. In the present embodiment, in particular, photoisomerization reaction and photodimerization are produced. At least one of the reactions imparts an anisotropic substrate to the film.

The photo-alignment group is specifically derived from the group consisting of azobenzene, anthracene, α -imido-β-ketoester, spiropyran, spirooxazine, cinnamic acid, chalcone, carbazole, A group having a structure of at least one compound of the group consisting of benzylidene phthalimide, coumarin, diphenylacetylene, and hydrazine. As the photo-alignment group, those having a structure derived from cinnamic acid are particularly preferable.

The [L] radiation-sensitive polymer having a photo-alignment group is preferably a polymer in which the above-mentioned photo-alignment group is bonded directly or via a linking group. Examples of such a polymer include a compound obtained by bonding the above photo-alignment group to at least any polymer of polyglycine and polyimine; and different from poly-proline and polyimine. A compound in which the above photo-alignment group is bonded to the polymer. In the latter case, examples of the basic skeleton of the polymer having a photo-alignment group include poly(meth)acrylate, poly(meth)acrylamide, polyvinyl ether, polyolefin, polyorganosiloxane, and the like. .

As the radiation sensitive polymer, a radiation sensitive polymer having polyacetamide, polyamidimide or polyorganosiloxane as a basic skeleton is preferable. Further, among these, a polyorganosiloxane is particularly preferable, and it can be obtained, for example, by the method described in the specification of WO 2009/025386.

[[M]polyimine]

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

Such a [M] polyimine which does not have a photo-alignment group can be obtained by hydrazine imidization by dehydration of a poly-proline which does not have a photo-alignment group. Such a poly-proline acid having no photo-alignment group can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine, and can be obtained by the method described in JP-A-2010-97188.

[M] Polyimine may be a complete hydrazine imide formed by dehydration ring closure of the proline structure of polyglycine as its precursor, or may be only a part of the guanylate structure dehydration ring closure, Proline structure and 醯亚 A portion of the quinone imide that coexists with the amine ring structure. The [M] polyimine has a quinone imidization ratio of preferably 30% or more, more preferably 50% to 99%, still more preferably 65% to 99%. The ruthenium imidization ratio is a ratio of the number of quinone ring structures to the total number of guanidine structures and the number of quinone ring structures of the polyimine. Here, a part of the quinone ring may be an isoindole ring, and is obtained, for example, as described in JP-A-2010-97188.

[[N]Other ingredients]

The liquid crystal alignment agent of the present embodiment may contain a radiation sensitive polymer having a photoalignment group and [N] other components other than the polyimide having no photoalignment group. Examples of the [N] other component include a [L] radiation-sensitive polymer having a photo-alignment group and a polymer other than the [M] poly-imine having no photo-alignment group, a curing agent, a curing catalyst, and a curing accelerator. An epoxy compound, a functional decane compound, a surfactant, a photosensitizer, and the like.

The main constituent elements of the array substrate of the present embodiment have been described above, and the method of manufacturing the array substrate of the present embodiment will be described next.

<Method for Manufacturing Insulating Film, Aligning Film, and Array Substrate>

In the production of the array substrate of the present embodiment, the step of producing the insulating film from the radiation sensitive resin composition of the present embodiment is mainly the main step. An insulating film formed with a contact hole can be formed by the manufacturing process of the insulating film. Further, in order to form an alignment film on the array substrate of the present embodiment, a step of forming an alignment film by the liquid crystal alignment agent of the above-described embodiment is used as a production step. Hereinafter, the present invention has an insulating film and an alignment film A method of manufacturing an array substrate of the embodiment will be described.

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

[1] Forming a radiation-sensitive resin composition on a substrate on which a switching active device, an electrode, or the like (a source, a drain, a gate, a source wiring, and a gate wiring, etc., which are collectively referred to as electrodes, etc.) are formed. The step of the membrane (hereinafter sometimes referred to as "step [1]").

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

[3] A step of developing a coating film irradiated with radiation in the step [2] (hereinafter sometimes referred to as "step [3]").

[4] A step of forming an insulating film by heat-hardening the coating film developed in the step [3] (hereinafter sometimes referred to as "step [4]").

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

Further, between the above steps [4] and [5], it is preferable to include a step of providing a transparent electrode on the insulating film formed in the step [4].

The radiation-sensitive resin composition of the present embodiment can be used to form a contact-containing hole on a substrate on which a switching active device, an electrode, or the like is formed, by using the method for manufacturing an array substrate of the present embodiment including the above steps. Insulating film. Further, an alignment film can be formed on the substrate by using the liquid crystal alignment agent of the present embodiment. As a result, the array substrate of the present embodiment can be formed by the method for manufacturing an array substrate of the present embodiment, and includes an insulating film having a contact hole having a desired size at a desired position, and is included in the prior art. An insulating film formed at a temperature.

The array substrate manufactured as described above is also an appropriate array substrate from the viewpoint of energy saving, in the case where it is desired to lower the temperature of the heating step.

Hereinafter, each step will be described in detail.

[step 1]]

In this step, a coating film of the radiation sensitive resin composition of the present embodiment is formed on the substrate. A switching active device, a source, a drain, a gate, a source wiring, a gate wiring, and the like are formed on the substrate. These switching active elements and the like are formed by repeating a conventional semiconductor film formation, a known insulating layer formation, etching by photolithography, or the like on a substrate by a known method.

After coating the radiation sensitive resin composition on the forming surface of the switching active device or the like of the substrate, it is preferable to perform heating (also referred to as prebaking) to remove the solvent to form a coating film.

Examples of the material of the substrate include glass such as soda lime glass or alkali-free glass, quartz, rhodium, and resin. Specific examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, aromatic polyamine, polyamidimide, polyimine, A ring-opening polymer of a cyclic olefin, a hydride thereof, or the like. Moreover, these substrates can also be pre-positioned as needed. An appropriate pretreatment such as a chemical treatment such as a decane coupling agent, a plasma treatment, ion plating, sputtering, a gas phase reaction method, or a vacuum vapor deposition is carried out.

The coating method of the radiation sensitive resin composition can be, for example, a spray method, a roll coating method, a spin coating method (also sometimes referred to as a spin coating method or a rotator method), a slit coating method (slit die coating method), or the like. A suitable method such as a bar coating method or an inkjet coating method. Among these methods, a spin coating method or a slit coating method is preferred.

The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, and are preferably from 70 ° C to 120 ° C, and may be from about 1 minute to 10 minutes.

[Step [2]]

Next, in the step [2], at least a part of the coating film formed in the step [1] is irradiated with radiation. At this time, when only a part of the coating film is irradiated, for example, a method of irradiating with a photomask that forms a mask pattern corresponding to a desired contact hole can be performed.

The radiation used in the irradiation is preferably a radiation used for the photoacid generator. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm is particularly preferable.

The radiation exposure amount (exposure amount) is a value obtained by measuring the intensity at a wavelength of 365 nm of the irradiated radiation by an illuminometer (OAI model 356, manufactured by Optical Associates Inc.), and is preferably 100 J/m ² to 3,000 J/ m ^{2 is} more preferably 500 J/m ² to 2,000 J/m ² .

[Step [3]]

Next, in the step [3], the coating film after the radiation irradiation is developed, and the unnecessary portion (irradiated portion of the radiation) is removed, thereby obtaining A coating film having a predetermined shape and having a desired contact hole is formed.

The developing solution used in the development is preferably an alkaline aqueous solution. Examples of the base to be contained include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Wait.

Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkaline aqueous solution. The concentration of the alkali in the alkaline aqueous solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. The developing method can be, for example, a suitable method such as a liquid coating method, a dipping method, a shaking dipping method, or a shower method. The development time varies depending on the composition of the radiation sensitive resin composition, and is preferably from about 10 seconds to about 180 seconds. After such development treatment, for example, a running water cleaning is performed for 30 seconds to 90 seconds, and then air-dried, for example, with compressed air or compressed nitrogen gas, whereby a desired pattern can be formed.

[Step [4]]

Next, in the step [4], the patterned film may be heated (also referred to as post-baking) using a heating means such as a hot plate or an oven, thereby promoting the [A] contained in the radiation-sensitive resin composition. The hardening reaction of the polymer produces a cured film having desired characteristics to obtain an insulating film. The heating temperature in this step is, for example, preferably from 120 ° C to 220 ° C. In the case where the radiation sensitive resin composition of the present embodiment comprising the above-mentioned [C] component is used, the heating temperature in this step is preferably, for example, 120 ° C to 200 ° C, and more preferably Low temperature of 120 ° C ~ 180 ° C.

The heating time varies depending on the type of heating machine, for example on a hot plate In the case of the heating step, it can be set to 5 minutes to 30 minutes, and when the heating step is performed in an oven, it can be set to 30 minutes to 90 minutes. A step-by-step baking method or the like which performs two or more heating steps may also be used. As described above, an insulating film having a contact hole to be targeted can be formed on the substrate. The film thickness of the formed insulating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, still more preferably 0.1 μm to 4 μm.

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

Further, it is preferable to include a step of providing a transparent electrode on the insulating film after the insulating film is formed in the step [4]. For example, a transparent conductive layer containing ITO can be formed on the insulating film by a sputtering method or the like. Next, the transparent conductive layer can be etched by photolithography to form a transparent electrode on the insulating film. The transparent electrode constitutes a pixel electrode, and is electrically connected to the switching active element on the substrate via a contact hole of the insulating film. Further, the transparent electrode can be formed using a transparent material having high transmittance and conductivity for visible light in addition to ITO. For example, indium zinc oxide (Indium Zinc Oxide, IZO), ZnO (zinc oxide), tin oxide, or the like can be used.

[Step [5]]

Using the insulating film-attached substrate obtained in the step [4], a transparent electrode was formed on the insulating film as described above, and then the liquid crystal alignment agent of the present embodiment was applied onto the transparent electrode. As the coating method, for example, a suitable coating method such as a roll coating method, a spin coating method, a printing method, or an inkjet method can be used. Next, the substrate coated with the liquid crystal alignment agent is prebaked, and then post-baked to form a coating film. The array substrate is fabricated. The prebaking conditions are, for example, from 0.1 to 5 minutes at 40 to 120 °C. The post-baking conditions are preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes, at from 120 ° C to 230 ° C, preferably from 150 ° C to 200 ° C, more preferably from 150 ° C to 180 ° C. The film thickness of the coating film after post-baking is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

The solid content concentration of the liquid crystal alignment agent used in the liquid crystal alignment agent (the ratio of the total weight of the components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) can be considered in terms of viscosity, volatility, and the like. Suitably, it is preferably in the range of 1% by weight to 10% by weight.

When a liquid crystal alignment agent containing a [L] radiation sensitive polymer having a photoalignment group is used as the liquid crystal alignment agent, the coating film is irradiated with linearly polarized or partially polarized radiation or non-polarized radiation. Controls the liquid crystal alignment ability of liquid crystal alignment. Such polarized radiation irradiation corresponds to the alignment treatment of the alignment film. Here, as the radiation, for example, ultraviolet rays and visible rays including wavelengths of light of 150 nm to 800 nm can be used. It is particularly preferable to use ultraviolet rays containing light having a wavelength of 300 nm to 400 nm as radiation. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from a diagonal direction to impart a pretilt angle to the liquid crystal, or these methods may be combined. In the case of irradiating non-polarized radiation, the irradiation direction must be an oblique direction.

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

In the liquid crystal alignment agent, [M] polyazide containing no photo-alignment group is used. In the case of an amine liquid crystal alignment agent, the post-baking coating film can also be used as an alignment film as it is. Further, the post-baking coating film may be subjected to a rubbing treatment (friction treatment) in a fixing direction by, for example, a roll wound with a cloth comprising fibers such as nylon, rayon, or cotton, to impart liquid crystal alignment ability.

When the alignment film is formed on the array substrate as described above, the alignment film can be formed at a heating temperature of 200 ° C or lower and a heating temperature of 180 ° C or lower using the liquid crystal alignment agent. Therefore, the insulating film formed in the above steps [1] to [4] can be prevented from being exposed to a high temperature in the step of forming the alignment film. Further, the array substrate of the present embodiment may include an insulating film and an alignment film having contact holes of a desired configuration and size, and may be fabricated by heating at a temperature lower than that of the prior art.

[Example]

Hereinafter, the embodiments of the present invention will be described in detail based on examples, but the present invention is not limited by the examples.

In the following, the mass average molecular weight (Mw) and the number average molecular weight (Mn) of the polymer can be determined by gel permeation chromatography (GPC) according to the following conditions.

Device: GPC-101 (made by Showa Denko Co., Ltd.)

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

Mobile phase: tetrahydrofuran

Column temperature: 40 ° C

Flow rate: 1.0 mL/min

Sample concentration: 1.0% by mass

Sample injection amount: 100 μL

Detector: differential refractometer

Reference material: monodisperse polystyrene

<[A] Synthesis of Polymers> [Synthesis Example 1]

In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed. Next, 5 parts by mass of methacrylic acid, 40 parts by mass of 2-tetrahydropyranyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, and 2-hydroxyethyl methacrylate were charged. After 10 parts by mass and 3 parts by mass of the α-methylstyrene dimer and nitrogen substitution, the stirring was gradually started. The temperature of the solution was raised to 70 ° C, and the temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-1). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (A-1) was 9,000. Further, the solid solution concentration of the polymer solution obtained here was 31.3% by mass.

[Synthesis Example 2]

In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate were placed. Next, 85 parts by mass of 2-tetrahydropyranyl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, and 8 parts by mass of methacrylic acid were placed and replaced with nitrogen, and then stirring was gradually started. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (a-1). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (a-1) was 10,000. Moreover, the solid solution of the polymer solution obtained here The concentration of the substance was 29.2% by mass.

[Synthesis Example 3]

In a flask equipped with a condenser and a stirrer, 7 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol methyl ethyl ether were placed. Next, 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl methacrylate were added and replaced with nitrogen, and then stirring was gradually started. The temperature of the solution was raised to 80 ° C, and the temperature was maintained for 6 hours to obtain a polymer solution containing the copolymer (aa-1). The polystyrene-equivalent mass average molecular weight (Mw) of the copolymer (aa-1) was 10,000. Further, the solid solution concentration of the polymer solution obtained here was 32.3% by mass.

<Modulation of Radiation-Linear Resin Composition> [Example 1]

In the solution containing the copolymer (A-1) obtained in Synthesis Example 1 (corresponding to the amount of the copolymer (A-1) in an amount of 100 parts by mass (solid matter)), [( camphorsulfonamide) was mixed as the component [B]. 4 parts by mass of oxyiminoimido-5H-thiophene-2-ylidene)-(2-methylphenyl)acetonitrile] ("CGI1380" manufactured by BASF Corporation), which is an antioxidant as a component [D] Tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate ("Adekastab AO-20" manufactured by ADEKA Co., Ltd.) 1 part by mass, as a component of [D] 0.20 parts by mass of ketone surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning Co., Ltd.), 3.0 parts by mass of γ-glycidoxypropyltrimethoxydecane as the component [D], and a pore diameter of 0.2 μm. The membrane filter was filtered to thereby modulate the radiation sensitive resin composition (S-1).

[Example 2]

A solution containing the copolymer (a-1) and the copolymer (aa-1) obtained in Synthesis Example 2 and Synthesis Example 3 (corresponding to 50% of copolymer (a-1) and copolymer (aa-1)) [(5-propylsulfonyloxyimino-5H-thiophene-[(5-propylsulfonyloxyimino)-5H-thiophene] as a component [B] in a mass ratio (solid content) in a total of 100 parts by mass in a ratio of 1 to 1) 4-methylene)-(2-methylphenyl)acetonitrile] ("IRGACURE PAG 103" manufactured by BASF Corporation) 4 parts by mass of 4,4'-diaminodiphenylphosphonium as component [C] A mass fraction of tris-(3,5-di-t-butyl-4-hydroxybenzyl)-isocyanurate which is an antioxidant in the [D] component (Adekastab AO-20, manufactured by ADEKA) "1" by mass of an anthrone-based surfactant ("SH 8400 FLUID" manufactured by Toray Dow Corning Co., Ltd.) as a component [D], 0.20 parts by mass, γ-glycidoxypropyl group as a component [D] 3.0 parts by mass of methoxymethoxysilane was filtered using a membrane filter having a pore size of 0.2 μm to prepare a radiation sensitive resin composition (S-2).

<Feature evaluation> [Example 3]

Using the radiation sensitive resin composition (S-1, S-2) prepared by the example 1 and the example 2, the characteristics were evaluated as described below, and the coating film formed of these radiation sensitive resin compositions or The insulating film obtained as the cured film thereof evaluated various characteristics.

(1) Evaluation of radiation sensitivity

Hexamethyldioxane (HMDS) was applied to a 550 mm × 650 mm chromium film-forming glass and heated at 60 ° C for 1 minute (hereinafter also referred to as "HMDS treatment"). On the HMDS-treated chromium film-forming glass, the radiation-sensitive resin composition S-1 prepared in Example 1 was applied using a slit die coater "TR632105-CL", and the arrival pressure was set to 100 Pa. The solvent was removed under vacuum. Thereafter, prebaking was further carried out at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. Then, using a MPA-600FA exposure machine manufactured by Canon Inc., a mask having a mask pattern of 60 μm line and gap (10 to 1) was interposed, and the exposure amount was set as a variable to irradiate the coating film with radiation. The development was carried out by a coating method at a concentration of 0.40% by mass in a tetramethylammonium hydroxide aqueous solution at 25 °C. Here, the development time was set to 80 seconds. Next, the water was washed with ultrapure water for 1 minute, and then dried, whereby a pattern was formed on the chrome-crystallized glass substrate after the HMDS treatment. At this time, the amount of exposure necessary for completely dissolving the 6 μm interval pattern was examined and evaluated. When the value is 500 J/m ² or less, it can be judged that the sensitivity is good. In the pattern formed by using the radiation sensitive resin composition S-1, the value is 500 J/m ² or less, and it is understood that the radiation sensitivity of the radiation sensitive resin composition S-1 is good.

Next, using the radiation sensitive resin composition S-2 prepared in Example 2, the radiation sensitivity was evaluated in the same manner as described above. In the pattern formed by using the radiation sensitive resin composition S-2, the above value is 500 J/m ² or less, and it is understood that the radiation sensitivity of the radiation sensitive linear resin composition S-2 is good.

(2) Evaluation of light resistance

The radiation sensitive resin composition S-1 prepared in Example 1 was applied onto a glass substrate using a spinner, and then prebaked on a hot plate at 90 ° C for 2 minutes to form a coating film having a film thickness of 3.0 μm. . The glass substrate was post-baked in a clean oven at 220 ° C for 1 hour to form a cured film to obtain an insulating film. The insulating film was irradiated with 800,000 J/m ^{2 with} an illumination of 130 mW using a UV irradiation device ("UVX-02516S1JS01" manufactured by Ushio Co., Ltd.).

When the amount of film reduction of the film thickness after irradiation is 2% or less, it can be judged that the light resistance of the film formation is good, compared with the film thickness before irradiation. In the insulating film formed by using the radiation sensitive resin composition S-1, the film reduction amount was 2% or less, and it was found to have good light resistance.

Next, an insulating film was formed in the same manner as described above except that the temperature of the post-baking performed in the clean oven was 180 ° C using the radiation-sensitive resin composition S-2 prepared in Example 2. Next, the light resistance of the obtained insulating film was evaluated in the same manner as above. The amount of film reduction of the insulating film formed by using the radiation sensitive resin composition S-2 was 2% or less, and it was found to have good light resistance.

Further, in the evaluation of the above light resistance, the formed film was not required to be patterned, and thus the development step was omitted, and only the coating film forming step, the light resistance test, and the heating step were performed and evaluated.

(3) Evaluation of heat resistance

The radiation-sensitive resin composition S-1 prepared in Example 1 was used in the same manner as the evaluation of the light resistance described above to form a coating film on the ruthenium substrate. The tantalum substrate was heated in a clean oven at 220 ° C for 1 hour to obtain a cured film to obtain an insulating film. Next, the film thickness (T1) of the obtained insulating film was measured. Next, the tantalum substrate on which the insulating film was formed was additionally baked in a clean oven at 240 ° C for 1 hour, and then the insulation after additional baking was measured. The film thickness (t1) of the film was calculated as a film thickness change rate {| t1 - T1 | / T1} × 100 [%] due to additional baking. When the film thickness change rate is 3% or less, it can be judged that the heat resistance is good. In the insulating film formed by using the radiation sensitive resin composition S-1, the film thickness change rate is 3% or less, and it is understood that the film has good heat resistance.

Next, an insulating film was formed in the same manner as above except that the radiation-sensitive resin composition S-2 prepared in Example 2 was used, and the heating temperature in the clean oven was set to 180 °C. In addition, after the film thickness of the obtained insulating film was measured, it was subjected to additional baking in a clean oven at 240 ° C for 1 hour, and the heat resistance of the obtained insulating film was evaluated in the same manner as described above. The film thickness change rate of the insulating film formed using the radiation sensitive resin composition S-2 was 3% or less, and it was found that the heat resistance was excellent.

(4) Evaluation of transmittance

The radiation-sensitive resin composition S-1 prepared in Example 1 was used in the same manner as the above evaluation of light resistance to form a coating film on the ruthenium substrate. The tantalum substrate was heated in a clean oven at 220 ° C for 1 hour to obtain a cured film to obtain an insulating film. The transmittance at a wavelength of 400 nm was measured using a spectrophotometer ("150-20 type double beam" manufactured by Hitachi, Ltd.) and evaluated. At this time, when the transmittance at a wavelength of 400 nm is less than 90%, it is judged that the transparency is poor. In the insulating film formed using the radiation sensitive resin composition S-1, the transmittance at a wavelength of 400 nm is 90% or more, and it is understood that the transparency is excellent and the transmittance characteristics are excellent.

Next, the composition of the radiation-sensitive resin prepared in Example 2 was used. In the object S-2, an insulating film was formed in the same manner as described above except that the heating temperature in the clean oven was 180 °C. Further, the heat resistance of the obtained insulating film was evaluated in the same manner as above. The transmittance of the insulating film formed using the radiation sensitive resin composition S-2 at a wavelength of 400 nm was 90% or more, and it was found that the insulating film was excellent in transparency and had excellent transmittance characteristics.

(5) Evaluation of voltage retention rate

Using the radiation sensitive resin composition S-1 prepared in Example 1, it was spin-coated on the surface to form an SiO ₂ film for preventing elution of sodium ions, and further, the ITO electrode was vapor-deposited on a soda glass substrate having a predetermined shape. Next, prebaking was performed in a clean oven at 90 ° C for 10 minutes to form a coating film having a film thickness of 2.0 μm.

Next, the coating film was exposed at an exposure amount of 500 J/m ² without interposing the photomask. Thereafter, post-baking was performed in a clean oven at 220 ° C for 30 minutes to cure the coating film to form a permanent cured film to form an insulating film.

Then, the substrate on which the pixel was formed was bonded to a substrate on which only the ITO electrode was vapor-deposited into a predetermined shape, and then injected into a liquid crystal MLC6608 (trade name) manufactured by Merck. Liquid crystal cell.

Next, the liquid crystal cell was placed in a constant temperature layer at 60 ° C, and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage retention ratio measurement system ("VHR-1A type" manufactured by Toyo Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio is (the potential difference of the liquid crystal cell after 16.7 milliseconds) / (the voltage applied at 0 milliseconds)} Value. When the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level within 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned, and the afterimage of the liquid crystal display element is defective. The possibility of "burn marks" is high.

The liquid crystal cell having the insulating film formed using the radiation sensitive resin composition S-1 has a voltage holding ratio of more than 90%, and it is known that it has excellent voltage holding ratio characteristics.

Next, using the radiation sensitive resin composition S-2 prepared in Example 2, the temperature of the post-baking performed in the clean oven was set to 180 ° C, and an insulating film was formed in the same manner as described above. The liquid crystal cell in which the insulating film was formed was produced to evaluate the voltage holding ratio. The liquid crystal cell having the insulating film formed using the radiation sensitive resin composition S-2 has a voltage holding ratio of more than 90%, and it is known that it has excellent voltage holding ratio characteristics.

According to the above evaluation results, it is understood that the radiation sensitive resin composition S-1 of Example 1 and the radiation sensitive resin composition S-2 of Example 2 have excellent radiation sensitivity. Further, it is understood that the insulating film formed by using the radiation sensitive resin composition S-1 of Example 1 and the radiation sensitive resin composition S-2 of Example 2 is excellent in light resistance, heat resistance, and transparency, and can constitute a voltage retention. A liquid crystal cell with good characteristics.

<Manufacture of Array Substrate> [Example 4]

The radiation sensitive resin composition S-1 obtained in Example 1 was applied onto a substrate on which a switching active element or an electrode or the like was formed using a spinner. A switching active component, a source, a drain, and a gate are formed on the substrate Pole, source wiring, and gate wiring. These switching active elements and the like are elements formed by a conventional method in which a normal semiconductor film is formed on a substrate, a known insulating layer is formed, and etching by photolithography is performed.

Next, pre-baking was performed in a clean oven at 90 ° C for 10 minutes to form a coating film. Next, using a exposure machine (high-pressure mercury lamp), a photomask having a desired pattern such as a contact hole pattern was interposed, and the obtained coating film was irradiated with radiation by setting the exposure amount to 500 J/m ² . Thereafter, development was carried out by a coating method at 25° C. using a 0.40% by mass aqueous solution of tetramethylammonium hydroxide, followed by washing with pure water for 1 minute. An unnecessary portion is removed by development, and a coating film having a predetermined shape in which a contact hole is formed is formed. Further, it was post-baked in an oven at 220 ° C for 1 hour to be hardened to form an insulating film having a film thickness of 3.0 μm.

Next, a transparent conductive layer containing ITO was formed on the insulating film by a sputtering method on the substrate on which the insulating film was formed. Next, the transparent conductive layer is etched by photolithography to form a transparent electrode on the insulating film.

The array substrate of the present example was fabricated as described above. In the obtained array substrate of the present example, a contact hole of a desired size is formed at a desired position of the insulating film, and electrical connection between the transparent electrode and the drain is realized.

[Example 5]

An insulating film was formed on the substrate in the same manner as in Example 4 except that the temperature of the post-baking treatment performed in the oven was set to 180 ° C using the radiation-sensitive resin composition S-2 prepared in Example 2. The transparent electrode is formed to fabricate the array substrate. In the obtained array substrate of the present example, a desired size is formed at a desired position of the insulating film. The contact hole realizes an electrical connection between the transparent electrode and the drain electrode as the pixel electrode.

[Example 6] (Manufacture of array substrate with photoalignment film)

In the present example, using the array substrate obtained in Example 4, a photo-alignment film was formed using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group.

First, on the transparent electrode of the array substrate of Example 4, Example 6 of the specification of International Publication (WO) 2009/025386, which is a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group, was coated by a rotator. The liquid crystal alignment agent A-1 described in the above. Next, after prebaking for 1 minute on a hot plate at 80 ° C, it was heated in an oven which was internally purged with nitrogen at 180 ° C for 1 hour to form a coating film having a film thickness of 80 nm. Next, using Hg-Xe lamp and a Glan - Taylor prism, autocorrelation vertical direction is inclined 40 ° in terms of the direction of the surface of the substrate, / m ² comprising a bright line of 313 nm of the polarized light irradiating the surface of the coating film 200 J Ultraviolet rays are used to manufacture an array substrate having a photo-alignment film.

[Example 7] (Manufacture of array substrate with photoalignment film)

In the present example, using the array substrate obtained in Example 5, a liquid alignment film containing a radiation-sensitive polymer having a photo-alignment group was used in the same manner as in Example 6 to form a photo-alignment film, and an array substrate having a photo-alignment film was produced. .

[Example 8] (Manufacture of array substrate with vertical alignment film)

In the present example, using the array substrate obtained in Example 4, a vertical alignment film was formed using a liquid crystal alignment agent containing a polyimide having no photo-alignment group.

First, on the transparent electrode of the array substrate of Example 4, AL60101 (manufactured by JSR Corporation) for vertical alignment film formation as a liquid crystal alignment agent containing a polyimide having no photo-alignment group was applied by a spinner. Next, after prebaking on a hot plate at 80 ° C for 1 minute, the film was heated at 180 ° C for 1 hour in an oven which was internally purged with nitrogen to form a coating film having a film thickness of 80 nm, and was manufactured to have a vertical shape. An array substrate of an alignment film.

[Example 9] (Manufacture of array substrate with vertical alignment film)

In the present example, using the array substrate obtained in Example 5, a liquid crystal alignment agent containing a polyimide having no photo-alignment group was used to form a vertical alignment film in the same manner as in Example 8, and an array substrate having a vertical alignment film was produced.

<Manufacture of liquid crystal display element> [Example 10]

The array substrate obtained in Example 7 was used. Further, a color filter substrate manufactured by a known method is prepared. In the color filter substrate, a minute color pattern of three colors of red, green, and blue and a black matrix are arranged in a lattice shape on a transparent substrate, and a transparent common electrode is disposed on the coloring pattern. Further, a light alignment film which is the same as that formed on the array substrate in Example 6 was formed on the common electrode of the color filter substrate to form an opposite substrate on which the alignment film was formed. Use these pair of substrates and use a sealant After bonding, a TN liquid crystal was injected to sandwich a liquid crystal layer between the substrates to produce a color liquid crystal display element. The liquid crystal display element of this example has the same structure as the liquid crystal display element shown in Fig. 3 described above. The liquid crystal display element of this example exhibited excellent operational characteristics and display characteristics and reliability.

The present invention is not limited to the embodiments described above, and various modifications can be made without departing from the spirit and scope of the invention.

[Industrial availability]

The array substrate of the present invention can be manufactured by a heating step at a lower temperature than the prior art, and has high reliability. Therefore, the array substrate of the present invention can be suitably used in a large-sized liquid crystal television application or the like which requires excellent display quality and reliability.

1‧‧‧Array substrate

4, 11‧‧‧ substrate

5‧‧‧ source

6‧‧‧汲polar

7‧‧‧ gate

8‧‧‧Switching active components

9‧‧‧Transparent electrode

10‧‧‧Alignment film

12‧‧‧Insulation film

13‧‧‧Black matrix

14‧‧‧Common electrode

15‧‧‧Coloring pattern

17‧‧‧Contact hole

18‧‧‧Source wiring

19‧‧ ‧ gate wiring

21‧‧‧Liquid display components

22‧‧‧Color filter substrate

23‧‧‧Liquid layer

27‧‧‧Backlight light

28‧‧‧Polar plate

Fig. 1 is a schematic cross-sectional view showing a configuration of a main part of an array substrate of the embodiment.

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

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

1‧‧‧Array substrate

4‧‧‧Substrate

5‧‧‧ source

6‧‧‧汲polar

7‧‧‧ gate

8‧‧‧Switching active components

9‧‧‧Transparent electrode

10‧‧‧Alignment film

12‧‧‧Insulation film

17‧‧‧Contact hole

Claims (8)

An array substrate for a liquid crystal display device, comprising: a switching active device, an insulating film disposed on the switching active device, a contact hole formed on the insulating film, and a contact hole via the contact hole a pixel electrode electrically connected to the switching active device, and an alignment film formed on the pixel electrode, wherein the array substrate is characterized in that the insulating film is formed of a radiation-sensitive resin composition containing the following components. Insulating film: [A] a polymer having a structural unit including a group represented by the following formula (1) and a structural unit containing an epoxy group in the same or different polymer molecules, [B] a photoacid generator, and [C] at least one compound selected from the group consisting of a compound represented by the following formula (C-1), a phosphonium salt, a thiol compound, and a blocked isocyanate compound; the alignment film is used to have a photoalignment An alignment film obtained by any one of a liquid crystal alignment agent of a radiation-sensitive polymer of a base group and a liquid crystal alignment agent containing a polyimide having no photo-alignment group; [Chemical Formula 1] In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these alkyl groups, cycloalkyl groups or aryl groups may be substituted. Wherein, in the case where R ¹ and R ² are each a hydrogen atom; R ³ is a group represented by an alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group or -M(R ⁴ ) ₃ , and these groups A part or all of the hydrogen atom may be substituted by a substituent, wherein M is Si, Ge or Sn, and R ⁴ is an alkyl group; and R ¹ and R ³ may be bonded to form a cyclic ether; In the formula (C-1), R ⁷ to R ¹⁶ each independently represent a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; and further, the hydrogen atom of the above amine group All or part of it may be substituted by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or a carbon number. It is an alkylene group of 2 to 6; wherein all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group. The array substrate according to claim 1, wherein the [B] photoacid generator comprises an oxime sulfonate group represented by the following formula (2); In the formula (2), R ^B1 is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent. The array substrate according to claim 1 or 2, wherein the alignment film is an alignment film obtained by using a liquid crystal alignment agent containing a radiation-sensitive polymer having a photo-alignment group. A liquid crystal display element comprising the array substrate according to any one of claims 1 to 3. A method of manufacturing an array substrate, comprising: [1] a step of forming a coating film containing a radiation sensitive resin composition of the following composition on a substrate on which a switching active element is formed: [A] in the same or different polymer a polymer having a structural unit containing a group represented by the following formula (1) and a structural unit containing an epoxy group in the molecule, [B] a photoacid generator, and [C] are selected from the following formula (C-1) At least one compound of the group consisting of the compound, the onium salt, the thiol compound, and the blocked isocyanate compound; [2] the step of irradiating at least a part of the coating film of the radiation sensitive resin composition with radiation [3] developing the coating film irradiated with radiation in the step [2] to obtain a coating film having a contact hole formed; and [4] performing the coating film obtained in the step [3] a step of hardening to form an insulating film; In the formula (1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these alkyl groups, cycloalkyl groups or aryl groups may be substituted. Wherein, in the case where R ¹ and R ² are each a hydrogen atom; R ³ is a group represented by an alkyl group, a cycloalkyl group, an arylalkyl group, an aryl group or -M(R ⁴ ) ₃ , and these groups A part or all of the hydrogen atom may be substituted by a substituent, wherein M is Si, Ge or Sn, and R ⁴ is an alkyl group; and R ¹ and R ³ may be bonded to form a cyclic ether; In the formula (C-1), R ⁷ to R ¹⁶ are each independently a hydrogen atom, an electron withdrawing group or an amine group; wherein at least one of R ⁷ to R ¹⁶ is an amine group; moreover, the hydrogen of the above amine group All or part of an atom may also be substituted by an alkylene group having 2 to 6 carbon atoms; A is a single bond, a carbonyl group, a carbonyloxy group, a carbonylmethylene group, a sulfinyl group, a sulfonyl group, a methylene group or a carbon. The alkyl group having 2 to 6 carbon atoms; wherein all or a part of the hydrogen atom of the above methylene group and alkylene group may be substituted by a cyano group, a halogen atom or a fluoroalkyl group. The method for producing an array substrate according to claim 5, wherein the [B] photoacid generator comprises an oxime sulfonate group represented by the following formula (2). In the formula (2), R ^B1 is an alkyl group, a cycloalkyl group or an aryl group, and some or all of the hydrogen atoms of these groups may be substituted with a substituent. The method for producing an array substrate according to claim 5, wherein the method further comprises the step of forming an alignment film at 200 ° C or lower. The method for producing an array substrate according to claim 7, wherein the step of forming the alignment film at 200 ° C or lower is to use a liquid crystal alignment agent comprising a radiation-sensitive polymer having a photo-alignment group, and comprising The alignment film is formed of any one of the photoalignment-based polyimine liquid crystal alignment agents.