KR20130110000A - Array substrate, liquid crystal display device, radiation-sensitive resin composition, and process for producing the array substrate - Google Patents

Abstract

PURPOSE: An array substrate, a liquid crystal display device, a radiation-sensitive resin composition, and a process for producing the array substrate are provided to improve reliability by forming a pixel structure suitable for high brightness. CONSTITUTION: An active circuit element is formed in a substrate. An insulating layer (12) is formed on the substrate. A common electrode (14) is arranged on the insulating layer. An interlayer dielectric (33) and a pixel electrode (9) are arranged on the insulating layer. The interlayer dielectric is made of a radiation-sensitive resin composition.

Description

ARRAY SUBSTRATE, LIQUID CRYSTAL DISPLAY DEVICE, RADIATION-SENSITIVE RESIN COMPOSITION, AND PROCESS FOR PRODUCING THE ARRAY SUBSTRATE}

This invention relates to an array substrate, a liquid crystal display element, a radiation sensitive resin composition, and a manufacturing method of an array substrate.

The liquid crystal display element has a structure in which liquid crystal is sandwiched between a pair of substrates. An alignment film is formed on the surface of these substrates for the purpose of controlling alignment of the liquid crystal. When an electric field is applied between the substrates, an orientation change occurs in the liquid crystal and partially transmits or blocks light. In a liquid crystal display element, an image is displayed using these characteristics. Such a liquid crystal display element has the advantage of being thinner and lighter than the conventional CRT display device.

The liquid crystal display element of the beginning of development was used as a display element of an electronic calculator and a clock centering on a character display etc. Since then, the development of the simple matrix system has facilitated the dot matrix display, thereby expanding its use to display elements of notebook PCs and the like. Subsequently, the development of the active matrix system enables realization of good image quality with excellent contrast ratio and response performance, and also overcomes the problems of high definition, colorization, and viewing angle expansion, and so on, for desktop monitors and the like. Has become available. In recent years, wider viewing angles, high-speed response of liquid crystals, improvement of display quality, and the like have been realized, and have been used as display devices for large-sized and thin televisions.

In a liquid crystal display device, various liquid crystal modes in which an initial alignment state of liquid crystal and an orientation change operation are different are known. For example, a liquid crystal mode such as Twisted Nematic (TN), Super Twisted Nematic (STN), In-Planes Switching (IPS), Vertical Alignment (FFS), or Optically Compensated Birefringence have.

Among the liquid crystal modes, the IPS mode is one of the modes which have been particularly noticed recently in view of having a wide viewing angle, a fast response speed, and a high contrast ratio. In addition, the IPS mode as referred to in the present specification refers to a liquid crystal mode in which the liquid crystal switches in the plane of the substrate on which the liquid crystal is held, as described later, and uses a gradient electric field in addition to the so-called transverse electric field system. The concept also includes the FFS mode, which realizes in-plane switching.

In the liquid crystal display element of the IPS mode (hereinafter simply referred to as IPS mode) including the FFS mode, the initial alignment state of the liquid crystal is controlled so that the liquid crystal sandwiched between the pair of substrates is substantially parallel to the substrate. By applying a voltage between the pixel electrode disposed on one of these substrates and the common electrode, an electric field (so-called a transverse electric field or a gradient electric field) mainly composed of components parallel to the substrate plane is formed, and the alignment state of the liquid crystal changes. do. Therefore, in the IPS mode, as for the orientation change of the liquid crystal by electric field application, rotation of the liquid crystal molecule in the plane parallel to a board | substrate plane is a main thing, as the name.

In this respect, in the IPS mode, the change in the tilt angle of the liquid crystal with respect to the substrate sandwiching the liquid crystal is small, unlike the TN mode in which the liquid crystal oriented in parallel performs a rising operation by application of an electric field. Therefore, in the IPS mode liquid crystal display element, the change in the effective value of the retardation accompanying the voltage application becomes small, and a high-quality image can be displayed with a wide viewing angle.

In the IPS mode liquid crystal display device as described above, an inorganic insulating film made of an inorganic material is laminated on a transparent plate-shaped electrode (for example, a common electrode), and a comb-shaped electrode (for example, a pixel electrode) is placed thereon. The development of the electrode structure to superimpose is advanced (for example, refer patent document 1 or patent document 2). According to this structure, the aperture ratio of the pixel is improved, and image display at high luminance is realized.

Japanese Laid-Open Patent Publication No. 2011-48394 Japanese Laid-Open Patent Publication No. 2011-59314

With respect to the IPS mode liquid crystal display element, in recent years, higher image quality, particularly, higher definition has been required in order to cope with the display of a moving image or a display of a portable electronic device such as a smart phone requiring high density display.

In the IPS mode liquid crystal display element, an active element for switching a thin film transistor (TFT) or the like is disposed on one of a pair of substrates sandwiching the liquid crystal. Then, pixel electrodes, common electrodes, wirings to be connected to them, and the like are arranged, and an array substrate is constituted. For this reason, in IPS mode liquid crystal display, the structural member arrange | positioned on an array board | substrate increases, and the electrode structure and wiring arrangement structure on an array board | substrate become complicated compared with other liquid crystal modes, such as TN mode. From this point of view, if further high definition is to be advanced, there is a concern that the area of the pixel electrode in the pixel is reduced, the aperture ratio of the pixel is lowered, and the brightness of the display is lowered.

Patent Document 2 discloses a pixel electrode (hereinafter also referred to as a comb-tooth shaped pixel electrode) having a portion formed in a comb-tooth shape on a flat common electrode through an insulating film made of an inorganic material (hereinafter also referred to as an inorganic insulating film). In an array substrate to be arranged, a technique of forming an insulating film (hereinafter also referred to as an organic insulating film) made of an organic material between a common electrode and a wiring is disclosed. According to this, it is considered that the aperture ratio can be improved while suppressing an increase in the coupling capacitance between the pixel electrode and the wiring.

However, in the case of the structure of patent document 2, peeling between each film laminated | stacked on an array substrate becomes a problem. Specifically, an organic insulating film is formed on the array substrate, and a common electrode made of, for example, ITO (Indium Tin Oxide) is formed on the array substrate. Subsequently, an inorganic insulating film is formed by a manufacturing process such as CVD (Chemical Vapor Deposition) so as to cover the common electrode, and a pixel electrode is further formed thereon. As described above, when the common electrode, the inorganic insulating film, and the pixel electrode are laminated on the organic insulating film in this order and formed, when the peeling occurs between the inorganic insulating film and the common electrode in the heating step in forming the pixel electrode. There is.

Since the peeling of the film on such an array substrate reduces the reliability of the IPS mode liquid crystal display element using the same, and further reduces the image quality of the liquid crystal display element, in the array substrate and the IPS liquid crystal display mode liquid crystal display element using the same, The development of the interlayer insulation film between electrodes which is hard to produce peeling is calculated | required.

In that case, the interlayer insulation film which is difficult to peel off can be easily formed using, for example, a coating method or the like, without requiring a manufacturing process using CVD or the like, thereby improving the productivity of the array substrate and the liquid crystal display element. It is desirable to have.

On the other hand, from the viewpoint of energy saving, it is required to lower the temperature of the heat treatment in the manufacturing process of the liquid crystal display element. For this reason, also in the manufacturing process of the array substrate, it is required to set the curing process of the constituent members at a low temperature.

This invention is made | formed in view of the above subjects. That is, an object of the present invention is to provide an array substrate having an insulating film which is effective for increasing the high aperture ratio of a pixel and where peeling hardly occurs. An object of the present invention is to provide a liquid crystal display device having a pixel structure suitable for high luminance and having high reliability.

Moreover, it is providing the radiation sensitive resin composition used for forming the insulating film.

Also. An object of the present invention is to provide a method for producing an array substrate having an insulating film which is less likely to cause peeling.

The first aspect of the present invention is an active element,

A first insulating film formed on the active element,

An array substrate having a common electrode and a pixel electrode formed on the first insulating film,

An array substrate having a second insulating film between the common electrode and the pixel electrode, wherein the second insulating film is an organic insulating film.

In the first aspect of the present invention, the second insulating film is

[X] polymers,

[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,

[Z] polyfunctional acrylate,

[W] radiation sensitive polymerization initiator

It is preferable that it is formed using a radiation sensitive resin composition containing.

In the first aspect of the present invention, the oxide particles are preferably particles of titanate salts.

In the first aspect of the present invention, the polymer [X] is preferably a polymer containing a structural unit having a (X1) aromatic ring and a structural unit having a (X2) (meth) acryloyloxy group.

In the 1st aspect of this invention, it is preferable that content of the structural unit which has a (X1) aromatic ring in [X] polymer is 20 mol%-90 mol% of the whole [X] polymer.

In the first aspect of the present invention, the common electrode and the pixel electrode are formed in this order on the first insulating film,

It is preferable that the pixel electrode has a comb-tooth shape and is electrically connected to the active element via a contact hole formed in the first insulating film.

In the first aspect of the present invention, the second insulating film preferably has a refractive index of 1.55 to 1.85 at a wavelength of 633 nm.

In the first aspect of the present invention, the second insulating film preferably has a light transmittance of 85% or more at a wavelength of 400 nm.

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

The 3rd aspect of this invention is a radiation sensitive resin composition used for formation of the 2nd insulating film of the array substrate of the 1st aspect of this invention,

[X] polymers

[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,

[Z] polyfunctional acrylate,

[W] radiation sensitive polymerization initiator

It relates to a radiation sensitive resin composition characterized by containing.

In the third aspect of the present invention, the oxide particles are preferably particles of titanate salts.

According to a fourth aspect of the present invention, an active element is provided.

A first insulating film formed over the active element,

Manufacture of an array substrate having a first electrode and a second electrode, one of which is a common electrode and the other of which is a pixel electrode, on the first insulating film, and a second insulating film disposed between the first electrode and the second electrode. As a method,

The process of forming a 1st insulating film has at least the following process [1]-process [4],

The process of forming a 2nd insulating film relates to the manufacturing method of the array substrate characterized by having the following process [5]-process [7] at least.

[1] a step of forming a coating film of a first radiation-sensitive resin composition containing a polymer containing a structural unit having a carboxyl group and a structural unit having a polymerizable group on a substrate on which an active element is formed;

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

[3] forming a contact hole by developing a coating film irradiated with radiation in step [2];

[4] a step of thermosetting the coating film obtained in step [3];

[5] On a substrate having a first insulating film formed using step [1] to step [4],

[X] A polymer comprising a structural unit having a (X1) aromatic ring, a structural unit having a (X2) (meth) acryloyloxy group,

[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,

[Z] polyfunctional acrylates, and

[W] forming a coating film of the second radiation-sensitive resin composition containing a radiation-sensitive polymerization initiator,

[6] a step of irradiating at least a portion of the coating film of the second radiation-sensitive resin composition formed in the step [5];

[7] A step of developing a coating film irradiated with radiation in step [6].

In the fourth aspect of the present invention, the oxide particles are preferably particles of titanate salts.

In the 4th aspect of this invention, it is preferable that a 1st radiation sensitive resin composition contains a thermal acid generator.

According to the first aspect of the present invention, an array substrate having an insulating film effective for increasing the high aperture ratio of a pixel and hardly causing peeling is obtained.

According to the 2nd aspect of this invention, the liquid crystal display element which has the pixel structure suitable for high luminance, and has high reliability is obtained.

According to the 3rd aspect of this invention, the radiation sensitive resin composition for forming the insulating film which is hard to produce peeling in an array substrate is obtained.

According to the 4th aspect of this invention, the manufacturing method of the array substrate which has an insulating film which is effective for high aperture ratio of a pixel, and hard to produce peeling is obtained. Moreover, according to this aspect, it is possible to make the heat processing process of an insulating film into 200 degrees C or less.

1 is a plan view schematically showing a pixel portion of the array substrate of this embodiment.
2 is a cross-sectional view taken along line A-A 'in Fig.
3 is a schematic cross-sectional view of the liquid crystal display element of the present embodiment.

(Mode for carrying out the invention)

The organic insulating film of the IPS mode liquid crystal display element of patent document 2 is formed with the photosensitive acrylic resin etc. The common electrode disposed on the organic insulating film is made of ITO, and the inorganic insulating film disposed on the organic insulating film and the common electrode is made of silicon nitride (SiN) or the like. In this case, the thermal expansion coefficient is different from the organic insulating film and the inorganic insulating film formed thereon. For this reason, if an organic insulating film is formed on an array substrate, and a common electrode, an inorganic insulating film, and a pixel electrode are laminated | stacked on it in order, and it forms, it is large in a common electrode or an inorganic insulating film in the heating process at the time of pixel electrode formation. Stress is applied

Here, since the common electrode disposed on the organic insulating film is made of ITO as described above, the adhesive force between the organic insulating film and the organic insulating film is strong, and peeling between them is unlikely to occur. However, since the adhesive force between the inorganic insulating film and the ITO film is weak, peeling occurs between the inorganic insulating film and the common electrode due to the stress described above.

Therefore, the present inventor develops an organic insulating film (hereinafter, simply referred to as a first insulating film) made of an organic material having a small expansion and contraction by heating, and forms a common electrode or the like on the first insulating film, thereby applying it to a common electrode or the like. We plan to reduce stress. In this embodiment, the 1st insulating film which consists of this organic material is formed using a 1st radiation sensitive resin composition. The first radiation-sensitive resin composition is radiation sensitive, and either positive or negative type can be used, but both positive and negative types have a polymer including a structural unit having a carboxyl group and a structural unit having a polymerizable group. After irradiating the coating film formed from the first radiation-sensitive resin composition to form a pattern, and further curing by heating, the resins having a polymerizable group crosslinked by the polymerizable group reacting with heating to form a highly crosslinked network. A cured film can be formed. Even when the cured film is further heated after that, since the expansion and contraction of the film is small, stress applied to the film formed thereon can be minimized.

In addition, the present inventor uses an organic insulating film (hereinafter also referred to as a second insulating film) using an organic material in place of the conventional inorganic insulating film. And it arrange | positions between a common electrode and a pixel electrode, and comprises an array substrate and a liquid crystal display element. The second insulating film using the organic material has the same thermal expansion characteristics as the insulating film made of the organic material described above, and has a strong adhesive force with a common electrode made of ITO or the like, and hardly causes peeling between the second insulating film and the common electrode. can do.

At this time, it is preferable that the 2nd insulating film using this organic material is a coating type interlayer insulation film which can be formed into a film by a coating method, regardless of a film forming method, such as CVD. By doing so, the throughput of the film forming process can be improved, and the productivity of the array substrate and the liquid crystal display element can be improved.

Moreover, it is preferable that the 2nd insulating film using this organic material contains the component for high refractive index, and can adjust refractive index, and it has a high refractive index compared with the organic film using the conventional organic material. When the second insulating film of the array substrate of the present embodiment has such a refractive index characteristic, in a liquid crystal display element using the same, the so-called "skeletal visible" problem in which an electrode stands out on the screen can be reduced.

Hereinafter, the array substrate and the liquid crystal display element formed using the said 1st insulating film and a 2nd insulating film, the radiation sensitive resin composition suitable for formation of a 1st insulating film and a 2nd insulating film, and those radiation sensitive resin compositions are used The manufacturing method of the array substrate which forms and manufactures the said 1st insulating film and a 2nd insulating film is demonstrated.

First, the array substrate of embodiment of this invention and the liquid crystal display element comprised using it are demonstrated.

In the present invention, "radiation" irradiated at the time of exposure includes visible rays, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams, and the like.

<Liquid crystal display element>

The liquid crystal display element of the present embodiment is a color liquid crystal display element of the IPS mode using the array substrate of the present embodiment.

This liquid crystal display element can be a color liquid crystal display element of an active matrix type IPS mode.

In addition, the liquid crystal display element can have a structure in which an array substrate on which an active element, an electrode, an insulating film, or the like used for switching is formed, and a color filter substrate configured with a coloring pattern face each other via a liquid crystal layer. Then, a plurality of pixels have display areas arranged in a dot matrix form.

FIG. 1 is a plan view schematically showing a main structure of a pixel portion of the array substrate of the present embodiment.

FIG. 2 is a diagram schematically showing a cross-sectional structure along the line AA ′ of FIG. 1.

1 and 2, the array substrate 1 has a structure in which the active element 8 is disposed on one surface of the transparent substrate 4. The active element 8 includes a gate electrode 7a that forms part of the scan signal line 7 disposed on the substrate 4, and a semiconductor layer disposed on the gate electrode 7a via the gate insulating film 31. 8a, the first source-drain electrode 6 connected to the semiconductor layer 8a, and the second source-drain electrode 5a forming part of the image signal line 5 and connected to the semiconductor layer 8a. And a TFT (Thin Film Transistor) element as a whole. The semiconductor layer 8a can be formed using, for example, a-Si (amorphous-silicon) or microcrystalline silicon. Disposed so as to cover the gate electrode (7a), gate insulating film 31 is, for example, can be formed of a metal nitride such as a metal oxide, such as SiO ₂ or SiN.

On the active element 8, the inorganic insulating film 32 which is a 3rd insulating film different from the 1st insulating film and the 2nd insulating film mentioned later is formed so that the active element 8 may be coat | covered. The inorganic insulating film 32 can be formed of, for example, a metal oxide such as SiO ₂ or a metal nitride such as SiN. The inorganic insulating film 32 is formed to prevent the semiconductor layer 8a from being affected by humidity. In the array substrate of the present embodiment, the inorganic insulating film 32 serving as the third insulating film is not formed, and the insulating film 12 serving as the first insulating film described later is disposed on the active element 8. It is possible.

The insulating film 12 which is a 1st insulating film is arrange | positioned on the active element 8 so that the inorganic insulating film 32 may be covered. The insulating film 12 is an insulating film formed using the 1st radiation sensitive resin composition of embodiment of this invention mentioned later, and is an organic insulating film formed using an organic material. It is preferable that the insulating film 12 has a function as a planarization film, and is formed thick from this viewpoint. For example, in the case of the active element 8 having a general structure, the insulating film 12 can be formed with a film thickness of 1 µm to 6 µm.

A contact hole 17 penetrating the insulating film 12 is formed in the insulating film 12 to connect the pixel electrode 9 and the first source-drain electrode 6 to be described later. The contact hole 17 is also formed so as to penetrate the inorganic insulating film 32 underlying the insulating film 12 as well. The insulating film 12 is formed using the 1st radiation sensitive resin composition of embodiment of this invention which is a radiation sensitive resin composition. Thus, for example, after the radiation is irradiated to the insulating film 12 to form a through hole, the contact hole 17 is formed by dry etching the inorganic insulating film 32 using the insulating film 12 as a mask. can do. In the case where the array substrate 1 does not have the inorganic insulating film 32, the through hole formed by irradiating the insulating film 12 with the radiation becomes the contact hole 17.

The upper surface of the insulating film 12 is flat and the common electrode 14 is formed thereon. The common electrode 14 is disposed to avoid the contact hole 17.

The common electrode 14 forms a film which consists of transparent conductive materials, such as ITO, for example using the sputtering method. Then, patterning is performed by photolithography or the like, and an opening is formed so as to surround the contact hole 17. Thus, the common electrode 14 having the structure of FIG. 2 can be formed.

On the insulating film 12 and the common electrode 14, the interlayer insulating film 33 using the organic material as a 2nd insulating film is formed so that these may be coat | covered. The interlayer insulating film 33 has an opening at the same position as the contact hole 17 of the insulating film 12. For this reason, the contact hole 17 of the insulating film 12 is not blocked by the interlayer insulating film 33, and is connected to the pixel electrode 9 on the interlayer insulating film 33, which will be described later, and the semiconductor layer 8a. This enables electrical connection with one source-drain electrode 6. At this time, the contact hole 17 should be kept in a state where the top and bottom portions of the contact hole 17 penetrate through the insulating film 12, and at least a part of the inner wall of the contact hole 17 is formed in the interlayer insulating film 33. It may be coat | covered by.

The interlayer insulating film 33 is a film formed using an organic material. The interlayer insulating film 33 forms a coating film by application | coating using the 2nd radiation sensitive resin composition of embodiment of this invention mentioned later, and the coating type interlayer which predetermined patterning was performed using the photolithographic method etc. It is an insulating film. As for the 2nd radiation sensitive resin composition of embodiment of this invention, in the interlayer insulation film 33 of the array substrate 1 of this embodiment, composition is optimized so that a desired refractive index characteristic may be implement | achieved. The interlayer insulating film 33 is patterned so as not to block the contact hole 17 of the insulating film 12, and is disposed to cover the common electrode 14.

In addition, the photolithography method includes a step of forming a resist film by applying a resist composition to a surface of a substrate subjected to processing or processing, an exposure step of forming a resist pattern latent image by exposing a predetermined resist pattern by irradiating light or electron beams; The process of heat processing as needed, the development process of developing this and forming a desired fine pattern, and the process of performing an etching etc. with respect to a board | substrate using this fine pattern as a mask are included.

The pixel electrode 9 is formed on the interlayer insulating film 33. The pixel electrode 9 has a portion formed in the shape of a comb teeth as a transparent electrode (hereinafter, simply referred to as "comb teeth" or "comb teeth"). The pixel electrode 9 of the comb-tooth shaped shape (henceforth simply referred to as a comb-tooth shape) is the first source-drain electrode 6 connected to the semiconductor layer 8a via the contact hole 17. Connect with. By setting it as such a structure, the aperture ratio of a pixel can be improved and a pixel structure of high luminance can be realized, and the luminance of a liquid crystal display element using the array substrate 1 can be realized.

The pixel electrode 9 may be formed as follows. For example, a film made of a transparent conductive material such as ITO (Indium Tin Oxide: indium oxide doped with tin) is formed by sputtering or the like. Subsequently, patterning is performed using a photolithography method or the like to form a comb-tooth shaped electrode.

On the pixel electrode 9, the alignment film 10 can be formed so as to cover the pixel electrode 9. The alignment film 10 controls the alignment of the liquid crystal layer. More specifically, the alignment film 10 controls the alignment of the liquid crystal molecules constituting the liquid crystal layer, and further controls the alignment of the liquid crystal layer.

In the array substrate 1, the video signal line 5 and the scanning signal line 7 are arranged in a matrix. The active element 8 is formed near the intersection of the video signal line 5 and the scan signal line 7, and they constitute each pixel partitioned on the array substrate 1.

The insulating film 12 which is the 1st insulating film of the array substrate 1 of this embodiment is the 1st radiation sensitive resin of this embodiment on the board | substrate 4 in which the video signal line 5 etc. and the active element 8 were formed. After apply | coating a composition and making necessary patterning, such as formation of the contact hole 17, it forms by heat-hardening.

The 1st radiation sensitive resin composition of this embodiment used for formation of the insulating film 12 can also be any of a positive type and a negative type. For example, in the insulating film 12 using the positive 1st radiation sensitive resin composition, when it responds to radiation, the solubility to a developing solution increases and a sensitive part is removed. Therefore, in the case of using the positive first radiation-sensitive resin composition, the desired contact hole can be formed relatively easily by irradiating the radiation-sensitive radiation to the contact hole formation portion of the insulating film 12.

In the insulating film 12 using the negative 1st radiation sensitive resin composition, since the solubility to a developing solution falls when sensitive to radiation, an insensitive part is removed. Therefore, when using a negative radiation sensitive resin composition, a desired contact hole can be formed by irradiating radiation other than the formation part of the contact hole of the insulating film 12. FIG. Compared with the positive type, there is a disadvantage in that it is difficult to control the shape of the contact hole, but there are advantages in terms of transparency and heat resistance of the insulating film 12 obtained.

The 1st radiation-sensitive resin composition of this embodiment has alkali-soluble resin of the point which is a polymer containing the structural unit which has a positive type and a negative type, and the structural unit which has a carboxyl group. After irradiating the coating film formed from the first radiation-sensitive resin composition to form a pattern, and further curing by heating, the resins having a polymerizable group crosslinked by the polymerizable group reacting with heating to form a highly crosslinked network. A cured film can be formed. Even if the cured film is further heated after that, since the expansion and contraction of the film is small, stress applied to the film formed thereon can be minimized. Therefore, even if the insulating film 12 is further subjected to the heat treatment in the curing process of other films formed thereon after the insulating film 12 is formed, the fluctuation in the size of the insulating film 12 due to the heat treatment can be minimized. As a result, the stress applied to the common electrode 14 and the interlayer insulating film 33 on the insulating film 12 can be reduced.

Due to the small expansion and contraction of the film due to the heating of the insulating film 12, even if the adhesive force between the common electrode 14 made of ITO or the like and the interlayer insulating film 33 disposed thereon may be weak, the common electrode 14 and Peeling can be prevented from occurring between the interlayer insulating film 33.

The 1st radiation sensitive resin composition of this embodiment can be hardened by the low temperature heating of 200 degrees C or less by optimizing the composition. Therefore, low-temperature heat treatment in the manufacturing process of the array substrate can be made possible, and an insulating film suitable for energy saving can also be formed.

Moreover, the component composition of the 2nd radiation sensitive resin composition of this embodiment used for formation of the interlayer insulation film 33 which is a 2nd insulation film of the array substrate 1 of this embodiment is a thing of the interlayer insulation film 33. It is optimized for forming. In particular, in the interlayer insulating film 33, the second radiation-sensitive resin composition of the present embodiment includes aluminum, zirconium, titanium, zinc, indium, tin, antimony, and the like as the high refractive index particles so that high refractive index can be realized. It is comprised by containing the oxide particle of the metal which is at least 1 sort (s) chosen from the group which consists of cerium. In addition, the second radiation-sensitive resin composition is designed to be optimal for other components so as to realize excellent patterning properties. The 2nd radiation sensitive resin composition of this embodiment is demonstrated in detail later.

As a result, in the array substrate 1, the refractive index of the interlayer insulating film 33 is adjusted so that the problem of visible skeleton in the liquid crystal display element can be reduced. It is preferable that the refractive index of the interlayer insulation film 33 is considered to be within the range of 1.55-1.85, respectively. In consideration of both the reduction of skeleton visibility and the patterning performance, the refractive index of the interlayer insulating film 33 is more preferably considered to be within the range of 1.60 to 1.80, respectively. In addition, in consideration of the reduction in skeletal visibility and a higher level of compatibility between patterning properties, the refractive index of the interlayer insulating film 33 is more preferably considered to be within the range of 1.65 to 1.75, respectively.

Although the film thickness of the interlayer insulation film 33 is not specifically limited, While ensuring the insulation between the common electrode 14 and the pixel electrode 9, the problem of the visible skeleton in the array substrate 1 is reduced. It is preferred that it is a suitable thickness. The film thickness of the interlayer insulating film 33 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. The interlayer insulating film 33 formed of the second radiation-sensitive resin composition of the present embodiment has transparency and adhesiveness, as apparent from the examples described later.

In addition, the interlayer insulating film 33 is a component constituting the array substrate 1 similarly to the insulating film 12, the common electrode 14, and the pixel electrode 9, and requires excellent visible light transmittance. It is preferable that the transmittance | permeability of the light in wavelength 400nm is 85% or more, and, as for the interlayer insulation film 33, it is more preferable that it is 90% or more.

Furthermore, in the array substrate 1 of this embodiment, after forming the pixel electrode 9, it is possible to form the alignment film 10 for liquid crystal orientation. As described later, the alignment layer 10 is formed by using a liquid crystal aligning agent containing (1) a radiation-sensitive polymer having a photo-aligning group, or (2) a liquid crystal aligning agent containing a polyimide having no photo- Can be obtained. Although the resin composition of (1) differs from the 1st radiation sensitive resin composition used for formation of the insulating film 12, and the 2nd radiation sensitive resin composition used for formation of the interlayer insulation film 33, 200 degrees C or less It is hardened by low temperature heat treatment of. In addition, (2) is a solvent-soluble polyimide, and it hardens by the heat processing of 200 degrees C or less similarly to (1). Therefore, by forming the alignment film 10 from these materials, the stretching of the insulating film 12 caused by the heating in the forming process of the alignment film 10 can be minimized. Further, since heat treatment at 200 DEG C or lower is possible, a method of manufacturing an array substrate which is preferable from the viewpoint of energy saving can be provided.

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

As shown in FIG. 3, the liquid crystal display element 41 is a color liquid crystal display element of the active matrix type | mold IPS mode which consists of the array substrate 1 and the color filter substrate 22 shown in FIG. 1 and FIG. . The liquid crystal display element 41 has a structure in which the array substrate 1 and the color filter substrate 22 face each other via a liquid crystal layer 23 that is aligned in parallel with the substrate 4 and the substrate 11. .

As shown in FIG. 3, the array substrate 1 has an active element 8 used for switching on the surface of the transparent substrate 4 on the side of the liquid crystal layer 23. As described above, the active element 8 includes the gate electrode 7a, the gate insulating film 31, the semiconductor layer 8a, the first source-drain electrode 6, and the second source-drain electrode. It has (5a) and comprises a TFT element as a whole. 3) connected to the second source-drain electrode 5a and the scanning signal line 7 (not shown in Fig. 3) connected to the gate electrode 7a are formed on the array substrate 1 Not shown in Fig. 3) are arranged in a matrix. The active element 8 is formed in the vicinity of the intersection of the video signal line 5 and the scanning signal line 7, and constitutes each pixel partitioned on the array substrate 1 by them.

On the active element 8, the inorganic insulating film 32 which is a 3rd insulating film can be formed, and the insulating film 12 which is a 1st insulating film is arrange | positioned so that the inorganic insulating film 32 may be covered. The insulating film 12 is formed using the 1st radiation sensitive resin composition of this embodiment mentioned above, and is thickly formed so that it may also have a function as a planarization film.

The common electrode 14 is disposed on the insulating film 12, avoiding the contact hole 17. On the common electrode 14 and the insulating film 12, the interlayer insulating film 33 which is a 2nd insulating film is arrange | positioned.

On the interlayer insulating film 33, a pixel electrode 9 having a portion formed in the shape of a comb teeth is disposed as a transparent electrode. A contact hole 17 penetrating the insulating film 12 and penetrating the underlying inorganic insulating film 32 is also formed in the insulating film 12. The pixel electrode 9 is connected to the first source-drain electrode 6 connected to the semiconductor layer 8a via the contact hole 17. On the pixel electrode 9, an alignment film 10 for controlling the alignment of the liquid crystal layer 23 is formed.

The color filter substrate 22 is formed on the surface of the liquid crystal layer 23 of the transparent substrate 11. In addition, the color filter board | substrate 22 is comprised by the coloring pattern 15 and the black matrix 13 arrange | positioned. In the coloring pattern 15, minute patterns of red, green, and blue are arranged in a regular shape such as a lattice shape. In addition, about the color of the coloring pattern 15, it is not limited to said three colors of red, green, and blue, It is also possible to select other colors, or to add other yellow and set it as a four-color coloring pattern. These color patterns can be arranged to constitute a color filter substrate.

On the surface of the color filter substrate 22 that is in contact with the liquid crystal layer 23, an alignment film 10 similar to the array substrate 1 is formed. It is also possible to form a planarization film between the alignment film 10 and the color filter substrate 22 for the purpose of planarizing the irregularities on the surface of the color filter substrate 22. [

As described above, in the present embodiment, the alignment film 10 is formed on the surface in contact with each liquid crystal layer 23 of the array substrate 1 and the color filter substrate 22. When necessary, the alignment film 10 is subjected to an alignment process such as rubbing to realize uniform parallel alignment of the liquid crystal layer 23 sandwiched between the array substrate 1 and the color filter substrate 22.

The distance between the array substrate 1 and the color filter substrate 22, which face each other via the liquid crystal layer 23, is kept at a predetermined value by a spacer (not shown), and is usually 2 m. 10 micrometers. Further, the array substrate 1 and the color filter substrate 22 are fixed to each other by a sealing material (not shown) formed in these peripheral portions.

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

In FIG. 3, reference numeral 27 denotes backlight light irradiated toward the liquid crystal layer 23 from a backlight unit (not shown) serving as a light source of the liquid crystal display element 41.

As the backlight unit, for example, one having a structure in which a fluorescent tube such as a cold cathode fluorescent lamp (CCFL) and a scattering plate are combined can be used. It is also possible to use a backlight unit having a white LED as a light source. Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by mixing colors, white LEDs that combine blue LEDs with red LEDs and green phosphors to obtain white light by mixing colors, A white LED for obtaining a white light by mixing color of a red light emitting phosphor and a green light emitting phosphor, a white LED for obtaining white light by mixing with a blue LED and a YAG-base phosphor, a blue LED and an isochromatic light emitting phosphor combined with a green light emitting phosphor A white LED that obtains white light by mixing color, a white LED that combines an ultraviolet LED and a red light emitting phosphor, a green light emitting phosphor and a blue light emitting phosphor to obtain white light by mixing color.

As described above, the liquid crystal display element 41 of the present embodiment has a structure in which the liquid crystal layer 23 is sandwiched by the array substrate 1 and the color filter substrate 22 of the present embodiment. In the array substrate 1, the electrical connection between the pixel electrode 9 and the first source-drain electrode 6 is made through the contact hole 17 formed through the insulating film 12 and the inorganic insulating film 32. Is realized. A signal voltage of the video signal line 5 is applied to the pixel electrode 9 and the liquid crystal molecules of the liquid crystal layer 23 are applied to the substrate 4 , 11) in a plane parallel to the plane of the substrate. Using this, the liquid crystal display element 41 controls the light transmission characteristics of the liquid crystal layer 23 for each pixel to form an image. Here, the liquid crystal display element 41 is an element of the IPS mode, and the operation of the liquid crystal molecules differs from the conventional TN mode and the like. Therefore, the liquid crystal display element 41 has a small change in the tilt angle of the liquid crystal molecules with respect to the substrates 4 and 11 holding the liquid crystal layer therebetween. Therefore, a wide visual characteristic is realized and image display of high quality is attained.

In the liquid crystal display element 41 of this embodiment, the interlayer insulating film 33 is formed on the common electrode 14, and the comb-shaped pixel electrode 9 is further disposed on the interlayer insulating film 33. Has a structure. According to this structure, the aperture ratio of the pixel is improved, and image display at high luminance is realized.

Moreover, in the liquid crystal display element 41, the insulating film 12 is formed using the 1st radiation sensitive resin composition of this embodiment mentioned later. For this reason, since the insulating film 12 is formed by heat-hardening after radiation irradiation and may be heated further, since the thermal contraction rate is small, it is equipped with the characteristic that the expansion-contraction rate of a film is small. Therefore, even after the formation of the insulating film 12, even if there is a heating step for forming other constituent members, for example, since the variation in the size of the insulating film 12 due to heating is small, it is common on the insulating film 12. The stress applied to the electrode 14 or the interlayer insulating film 33 can be minimized.

As mentioned above, in the liquid crystal display element 41 of this embodiment, even when the adhesive force between the common electrode 14 which consists of ITO etc., and the interlayer insulation film 33 arrange | positioned on it is weak, the common electrode 14 is carried out. Peeling can be prevented from occurring between the inorganic insulating film 33 and the inorganic insulating film 33. Thereby, it can be set as the liquid crystal display element 41 which has the pixel structure which can be made high, and has high reliability.

And in the liquid crystal display element 41, the interlayer insulation film 33 is a coating type interlayer insulation film which consists of organic materials formed using the 2nd radiation sensitive resin composition of this embodiment mentioned later later. That is, the interlayer insulating film 33 has a strong adhesive force with a common electrode made of ITO or the like, and can make it difficult to cause peeling therebetween. The interlayer insulating film 33 can be formed only by formation of a coating film by a coating method and by patterning using a photolithography method, and enables high throughput film formation and high productivity. In addition, in the interlayer insulating film 33 using an organic material, the liquid crystal display device 41 has a component design for increasing the refractive index, so that the problem of visible skeleton can be reduced.

As mentioned above, although the liquid crystal display element of this embodiment has the outstanding image quality and high reliability, in the realization of such performance, the insulating film which is a 1st insulating film which is a main component of the array substrate of this embodiment, and 2nd The characteristics of the interlayer insulating film as the insulating film become important. That is, in the array substrate of this embodiment, the insulating film formed using the 1st radiation-sensitive resin composition of this embodiment is arrange | positioned between an electrode and wiring, and the 2nd radiation-sensitive property of this embodiment is between electrodes. Although the interlayer insulation film formed using the resin composition is arrange | positioned, this insulation film and an interlayer insulation film greatly contribute to the realization of the outstanding image quality and high reliability of the liquid crystal display element of this embodiment. Although the insulating film formed using said 1st radiation sensitive resin composition is comprised using the organic material, even if it receives a thermal history after becoming a film, it has a characteristic that the stretch rate of a film is small. The interlayer insulating film formed by using the second radiation-sensitive resin composition is composed of an organic material, has excellent adhesive force with an electrode made of ITO, and the like, and has a feature of having desirable refractive index characteristics.

Next, the 1st radiation sensitive resin composition of this embodiment for forming an insulating film is demonstrated in detail.

<1st radiation sensitive resin composition>

In the array substrate of the present embodiment, the first radiation-sensitive resin composition used in the production of the insulating film, which is one of its constituent members, has a positive type and a negative type of [A] alkali-soluble resin as an essential component, and is positive In the case of the radiation sensitive resin composition, the [B] quinonediazide compound is further contained as an essential component, and in the case of the negative radiation sensitive resin composition, the [C] polymerizable compound and the [D] radiation sensitive property It contains a polymerization initiator.

Both a positive type and a negative type can contain a [E] thermal acid generator, and a 1st radiation sensitive resin composition can also contain the [F] hardening accelerator mentioned later. In addition, as long as the effect of the present invention is not impaired, other optional components may be contained.

Hereinafter, each component contained in the 1st radiation sensitive resin composition of this embodiment is demonstrated.

<[A] alkali-soluble resin>

[A] Alkali-soluble resin will not be limited, if it is resin which has alkali developability. And as for [A] alkali-soluble resin, resin containing the structural unit which has a carboxyl group, the structural unit which has a polymeric group, or polyimide resin obtained by dehydrating and ring-closing polyamic acid is imidated.

Below, first, the acrylic resin containing the structural unit which has a carboxyl group, and the structural unit which has a polymeric group which is an example of [A] alkali-soluble resin is demonstrated.

About acrylic resin containing the structural unit which has a carboxyl group, and the structural unit which has a polymeric group, the structural unit which has a polymeric group is selected from the group which consists of the structural unit which has an epoxy group, and the structural unit which has a (meth) acryloyloxy group. It is preferable that it is at least 1 type of structural unit. When alkali-soluble resin (A) contains the said specific structural unit, the cured film which has the outstanding surface curability and deep part curability, ie, the insulating film of this embodiment can be formed.

As for the structural unit which has a (meth) acryloyloxy group mentioned above, the method of making (meth) acrylic acid react with the epoxy group in a copolymer, the method of making the (meth) acrylic acid ester which has an epoxy group in the carboxyl group in a copolymer react, for example. And the (meth) acrylic acid ester which has an isocyanate group in the hydroxyl group in a copolymer, the method of making (meth) acrylic acid react with the acid anhydride site | part in a copolymer, etc. can be formed. Among these, the method of making the (meth) acrylic acid ester which has an epoxy group react with the carboxyl group in a copolymer is preferable.

[A] alkali-soluble resin containing the structural unit which has a carboxyl group, and the structural unit which has an epoxy group as a polymerizable group is at least 1 sort (s) chosen from the group which consists of (A1) unsaturated carbonic acid and unsaturated carbonic anhydride (hereinafter, "( A1) compound "and (A2) epoxy group containing unsaturated compound (henceforth" the (A2) compound ") can be copolymerized and synthesize | combined. In this case, the [A] alkali-soluble resin is a copolymer comprising a constituent unit formed of at least one kind selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carbonic anhydride and a constituent unit formed from an epoxy group-containing unsaturated compound .

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

[(A1) Compound]

Examples of the compound (A1) include unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, anhydrides of unsaturated dicarboxylic acid, and mono [(meth) acryloyloxyalkyl] esters of polyhydric carbonic acid.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid.

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

The anhydrides of the unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the dicarboxylic acids.

Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ] And the like.

Among these (A1) compounds, acrylic acid, methacrylic acid and maleic anhydride are preferred, and acrylic acid, methacrylic acid and maleic anhydride are more preferable from copolymerization reactivity, solubility in aqueous alkali solution and ease of obtaining.

These (A1) compounds may be used independently and may be used in mixture of 2 or more type.

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

[(A2) Compound]

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

Examples of the unsaturated compound having oxiranyl include glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl acrylate, and 3,4-epoxy methacrylate. Butyl, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, methacrylic acid 3,4-epoxycyclohexylmethyl, etc. are mentioned. Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, methacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylic acid, 3,4-epoxycyclohexyl acrylate, etc. are preferable from the viewpoint of improvement of copolymerization reactivity and solvent resistance, such as an insulating film.

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

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

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

Among these (A2) compounds, methacrylic acid glycidyl, methacrylic acid 3,4-epoxycyclohexyl, and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable. These (A2) compounds may be used independently and may be used in mixture of 2 or more type.

The use ratio of the compound (A2) is preferably 5% by mass to 60% by mass based on the total of the compound (A1) and the compound (A2) (optional (A3) compound and (A4) compound, if necessary). 10 mass%-50 mass% are more preferable. (A2) compound is used in an amount of 5% by mass to 60% by mass, a cured film having excellent curability, that is, the insulating film of the present embodiment can be formed.

[(A3) Compound]

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

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

As methacrylic acid ester which has a hydroxyl group, 2-hydroxyethyl methacrylic acid, 3-hydroxypropyl methacrylic acid, 4-hydroxybutyl methacrylic acid, 5-hydroxypentyl methacrylic acid, methacrylic acid 6- Hydroxyhexyl, and the like.

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

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

The use ratio of the compound (A3) is preferably 1% by mass to 30% by mass, based on the total of the compound (A1), the compound (A2) and the compound (A3) (optional (A4), if necessary). 5 mass%-25 mass% are more preferable.

[(A4) Compound]

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

As methacrylic acid linear alkylester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate Isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

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

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

As the acrylic acid cyclic alkyl ester, for example, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, acrylic acid tricyclo [5.2.1.0 ^2,6 ] Decan-8-yloxyethyl, isoboroyl acrylate, and the like.

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

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

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

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

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

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

As an unsaturated compound containing a tetrahydrofuran skeleton, methacrylic acid tetrahydrofurfuryl, 2-methacryloyloxy- propionic acid tetrahydrofurfuryl ester, 3- (meth) acryloyloxy tetrahydrofuran 2-one, etc. are mentioned.

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

Among these (A4) compounds, methacrylic acid chain alkyl esters, methacrylic acid cyclic alkyl esters, methacrylic acid aryl esters, maleimide compounds, tetrahydrofuran skeletons, unsaturated aromatic compounds, and acrylic acid cyclic alkyl esters are preferable. Among these, in particular, styrene, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, benzyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl , p-methoxystyrene, 2-methylcyclohexyl acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, and tetrahydrofurfuryl methacrylate are preferable in terms of copolymerization reactivity and solubility in aqueous alkali solution.

These (A4) compounds may be used independently and may be used in mixture of 2 or more type.

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

<The synthesis method 1 of [A] alkali-soluble resin containing the structural unit which has a carboxyl group, and the structural unit which has an epoxy group as a polymerizable group>

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

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

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

In the polymerization reaction for producing the [A] alkali-soluble resin, a molecular weight regulator can be used for the purpose of adjusting the molecular weight.

Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

(A) 1,000-30,000 are preferable and, as for the weight average molecular weight (Mw) of alkali-soluble resin, 5,000-20,000 are more preferable. By making Mw of alkali-soluble resin into the said range, the sensitivity and developability with respect to the radiation of a 1st radiation sensitive resin composition can be improved. The Mw and the number average molecular weight (Mn) of the polymer in the present specification were measured by gel permeation chromatography (GPC) under the following conditions.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

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

Mobile phase: tetrahydrofuran

Column temperature: 40 DEG C

Flow rate: 1.0 mL / min

Sample concentration: 1.0 mass%

Sample injection amount: 100 μL

Detector: differential refractometer

Standard material: monodisperse polystyrene

<The synthesis method 2 of the [A] alkali-soluble resin containing the structural unit which has a methacryl group as a structural unit which has a carboxyl group, and a polymeric group>

(A) Alkali-soluble resin reacts the copolymer (henceforth called a "specific copolymer") and the said (A2) compound which can be synthesize | combined using one or more types of above-mentioned (A1) compounds, for example. Can be synthesized. According to such a synthesis method, a copolymer containing a constituent unit having at least a (meth) acryloyloxy group can be synthesized.

[A] The structural unit having a (meth) acryloyloxy group contained in the alkali-soluble resin is obtained by reacting a (meth) acrylic acid ester having an epoxy group with a carboxyl group in a copolymer, and a structure having a (meth) acryl group after the reaction A unit is represented by following formula (1). This structural unit is obtained by reacting the carboxyl group in the specific copolymer derived from the compound (A1) with the epoxy group of the compound (A2) to form an ester bond.

In said formula (1), R <^10> and R <^11> is a hydrogen atom or a methyl group each independently. c is an integer of 1-6. R <^12> is a bivalent group represented by following formula (2-1) or following formula (2-2).

In said formula (2-1), R <^13> is a hydrogen atom or a methyl group. In said formula (2-1) and said formula (2-2), * represents the site | part couple | bonded with an oxygen atom.

About the structural unit represented by the said Formula (1), for example, the copolymer which has a carboxyl group reacted with compounds, such as glycidyl methacrylate and 2-methylglycidyl methacrylate, as (A2) compound In this case, R ¹² in formula (1) becomes formula (2-1). On the other hand, when compounds, such as methacrylic acid 3, 4- epoxycyclohexylmethyl, are made to react as a (A2) compound, R <^12> in Formula (1) becomes Formula (2-2).

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

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

As a radical polymerization initiator, the thing similar to what was illustrated by the term of the above-mentioned [A] alkali-soluble resin is mentioned. The amount of the radical polymerization initiator to be used is usually 0.1% by mass to 50% by mass, preferably 0.1% by mass to 20% by mass, based on 100% by mass of the polymerizable unsaturated compound.

A specific copolymer may be provided for manufacture of [A] alkali-soluble resin as a polymerization reaction solution, and may be used for manufacture of [A] alkali-soluble resin after separating a copolymer from a solution once.

The molecular weight distribution (Mw / Mn) of the specific copolymer is preferably 5.0 or less, more preferably 3.0 or less.

By making molecular weight distribution (Mw / Mn) into 5.0 or less, the shape of the pattern obtained can be kept favorable. In addition, an insulating film containing a specific copolymer having a molecular weight distribution (Mw / Mn) in the above specific range has a high developing property. That is, in the developing step, a predetermined pattern can be easily formed without generating development residue.

5 mass%-60 mass% are preferable, as for the content rate of the structural unit derived from the (A1) compound of a specific copolymer, 7 mass%-50 mass% are more preferable, 8 mass%-40 mass% are especially preferable. Do.

The content rate of structural units derived from compounds, such as a compound (A3) other than the (A1) compound of a specific copolymer, is 10 mass%-90 mass%, 20 mass%-80 mass%.

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

5 mass%-99 mass% are preferable with respect to the carboxyl group derived from the (A1) compound in a copolymer, and, as for the usage ratio of (A2) compound, 10 mass%-97 mass% are more preferable. By setting the ratio of the compound (A2) to within the above range, the reactivity with the copolymer, the curability of the insulating film, and the like are further improved. (A2) may be used alone or in admixture of two or more.

Next, polyimide resin (henceforth simply a polyimide) which is [A] alkali-soluble resin is demonstrated.

A polyimide is obtained by imidating by dehydrating and closing polyamic acid. Such polyamic acid can be obtained, for example, by reacting tetracarboxylic dianhydride and diamine, and specifically, it can be obtained according to the method described in Unexamined-Japanese-Patent No. 2010-97188.

(A) The polyimide which is alkali-soluble resin may be the complete imide which dehydrated and closed all the dark acid structures which the polyamic acid which is its precursor has, and dehydrates and closes only a part of the dark acid structure, and the acidic structure and the imide ring structure The partial imide which coexists may be sufficient.

It is preferable that the imidation ratio of polyimide which is (A) alkali-soluble resin is 30% or more, It is more preferable that it is 50%-99%, It is still more preferable that it is 65%-99%. However, the imidation ratio in this case shows the ratio which the number of the imide ring structures to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, a part of the imide ring may be an isoimide ring, and this can be obtained by, for example, being disclosed in Japanese Unexamined Patent Publication No. 2010-97188.

<[B] quinonediazide compound>

While the 1st radiation sensitive resin composition of this embodiment contains [A] alkali-soluble resin as an essential component, it can contain a [B] quinonediazide compound. Thereby, it can be used as a positive 1st radiation sensitive resin composition.

[B] The quinonediazide compound is a quinonediazide compound which generates a carboxylic acid by irradiation of radiation. As the [B] quinone diazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter referred to as "mother nucleus") and 1,2-naphthoquinone diazidesulfonic acid halide can be used.

Examples of the above-mentioned mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, other mother nucleus and the like.

As trihydroxy benzophenone, 2,3, 4- trihydroxy benzophenone, 2 4, 6- trihydroxy benzophenone, etc. are mentioned, for example.

As tetrahydroxy benzophenone, it is 2,2 ', 4,4'- tetrahydroxy benzophenone, 2,3,4,3'- tetrahydroxy benzophenone, 2,3,4,4', for example. -Tetrahydroxybenzophenone, 2,3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone, etc. are mentioned. Can be.

As pentahydroxy benzophenone, 2,3,4,2 ', 6'- pentahydroxy benzophenone etc. are mentioned, for example.

As hexahydroxy benzophenone, it is 2,4,6,3 ', 4', 5'-hexahydroxy benzophenone, 3,4,5,3 ', 4', 5'-hexahydroxy, for example. Benzophenone etc. are mentioned.

(P-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1, 2-dihydroxyphenyl) methane, Tris (p-hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 3-tris (2,5-dimethyl-4-hydroxyphenyl) -3-phenylpropane, 4,4 '- [1- [4- [1- [4- hydroxyphenyl] ] Ethylidene] bisphenol, bis (2,5-dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3 ' 5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl-7,2 ', 4'-trihydroxyflavone and the like.

Examples of the other parent nuclei include 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7- - (1- (4-hydroxyphenyl) -1-methylethyl} -4,6-dihydroxyphenyl) -1-methylethyl] -3- (4-hydroxyphenyl) -1-methylethyl} -1, 4-dihydroxyphenyl) Dihydroxybenzene, and the like.

Among these nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tris (p-hydroxyphenyl) ethane, 4,4 '- [1- [4- [1- [ 4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferably used.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazide sulfonic acid chloride is preferable. As 1, 2- naphthoquinone diazide sulfonic-acid chloride, a 1, 2- naphthoquinone diazide- 4-sulfonic acid chloride, a 1, 2- naphthoquinone diazide-5-sulfonic acid chloride, etc. are mentioned, for example. have. Among these, 1,2-naphthoquinone diazide-5-sulfonic acid chloride is more preferable.

In the condensation reaction of a phenolic compound or an alcoholic compound (parent nucleus) with 1,2-naphthoquinonediazidesulfonic acid halide, the molar ratio of the OH group in the phenolic compound or the alcoholic compound is preferably 30 mol% to 85 mol. %, More preferably, 1, 2- naphthoquinone diazide sulfonic-acid halide corresponding to 50 mol%-70 mol% can be used. Condensation reaction can be performed by a well-known method.

As the [B] quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the above-described parent nucleus is changed to an amide bond, for example, 2,3,4-trimano Benzophenone-1,2-naphthoquinone diazide-4-sulfonic acid amide etc. are also used suitably.

These [B] quinone diazide compounds may be used alone or in combination of two or more. As for the use ratio of the quinone diazide compound in the 1st radiation sensitive resin composition of this embodiment, 5 mass parts-100 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, 10 mass parts-50 A mass part is more preferable. By making the use ratio of a quinone diazide compound into the said range, the difference of the solubility of the irradiation part and the unirradiation part of the radiation with respect to the alkaline aqueous solution used as a developing solution can be enlarged, and patterning performance can be improved. In addition, the solvent resistance of the insulating film obtained using the radiation-sensitive resin composition may be good.

<[C] polymerizable compound>

The 1st radiation-sensitive resin composition of this embodiment contains [A] alkali-soluble resin as an essential component, and replaces the above-mentioned [B] quinonediazide compound, [C] polymeric compound, and later It can contain the radiation sensitive polymerization initiator [D]. Thereby, it can be used as a negative 1st radiation sensitive resin composition.

As the [C] polymerizable compound contained in the first radiation-sensitive resin composition of the present embodiment, for example, ω-carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1,6 -Hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylic Laterate, bisphenoxyethanol fluorenedi (meth) acrylate, dimethylol tricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- ( 2'-vinyloxyethoxy) ethyl (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meta) acrylic In addition to dihydrate, dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, etc. Urethane obtained by reacting a compound having a linear alkylene group and an alicyclic structure and having at least two isocyanate groups with a compound having at least one hydroxyl group in the molecule and having 3 to 5 (meth) acryloyloxy groups (meth) ) Acrylate compound and the like.

[C] The polymerizable compounds may be used alone or in combination of two or more.

As for the content rate of the [C] polymeric compound in a 1st radiation sensitive resin composition, 20 mass parts-200 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and 40 mass parts-160 mass parts more desirable. By setting the ratio of the [C] polymerizable compound within the above range, a cured film having excellent adhesiveness and having sufficient hardness even at a low exposure dose, that is, an insulating film can be obtained.

<[D] radiation sensitive polymerization initiator>

The radiation sensitive polymerization initiator [D] contained in the first radiation sensitive resin composition of the present embodiment together with the [C] polymerizable compound is capable of initiating polymerization of the [C] polymerizable compound in response to radiation. It is a component that generates active species. As such a [D] radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned. These compounds may be used independently and may mix and use 2 or more types.

As the O-acyl oxime compound, for example, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1 -Onoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethane-1-onoxime-O-benzoate, 1- [9 -n-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2 -Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4 -Tetrahydropyranylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyl Benzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) Can.

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

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

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

Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropane-1-one and 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane -1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, and the like.

As an acetophenone compound, (alpha)-amino ketone compound is preferable, and 2-benzyl- 2-dimethylamino- 1- (4-morpholinophenyl) -butan- 1-one, 2-dimethylamino- 2- ( 4-Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1- On is preferred.

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2,2'-, for example. Bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole or 2,2'-bis (2,4,6-trichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferable, among which 2,2'-bis (2,4-dichlorophenyl) -4,4', 5, 5'-tetraphenyl-1,2'-biimidazole is more preferable.

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

<[E] thermal acid generator>

The 1st radiation sensitive resin composition of this embodiment can contain a [E] thermal acid generator. Here, the [E] thermal acid generator is defined as a compound capable of releasing an acidic active substance that acts as a catalyst when curing the [A] alkali-soluble resin by applying heat. Using such a thermal acid generator [E] is especially suitable at the point which enables the hardening temperature of 200 degrees C or less. That is, the cured film excellent in surface hardness and heat resistance by further promoting hardening reaction of [A] alkali-soluble resin in the heating process after image development of a 1st radiation sensitive resin composition by use of a [E] thermal acid generator. That is, the insulating film of this embodiment can be formed. Therefore, even if a thermal history is received in a later step, the expansion ratio of the film can be reduced. Such an effect becomes easy to be expressed by the combination with [F] company mentioned later.

The thermal acid generator (E) includes an ionic compound and a nonionic compound.

It is preferable that an ionic compound does not contain a heavy metal or a halogen ion.

Examples of the ionic thermal acid generator include triphenylsulfonium, 1-dimethylthionaphthalene, 1-dimethylthio-4-hydroxynaphthalene, 1-dimethylthio-4,7-dihydroxynaphthalene and 4-hydride. Hydroxyphenyldimethylsulfonium, benzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-hydroxyphenylmethylsulfonium, 2-methylbenzyl-4-acetylphenylmethylsulfonium, 2-methylbenzyl-4 -Benzoyloxyphenyl methyl sulfonium, these methanesulfonic acid salts, trifluoromethanesulfonic acid salt, camphorsulfonic acid salt, p-toluenesulfonic acid salt, hexafluorophosphonic acid salt, etc. are mentioned.

As a nonionic [E] thermal acid generator, a halogen containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a phosphate ester compound, a sulfonimide compound, a sulfone benzotriazole compound, for example Etc. can be mentioned. Of these, a sulfonimide compound is particularly preferable.

Examples of the sulfone imide compound include N- (trifluoromethylsulfonyloxy) succinimide (trade name: SI-105, Midori Kagakusha), N- (camphorsulfonyloxy) succinimide (Trade name: SI-106, Midorikagakusha), N- (4-methylphenylsulfonyloxy) succinimide N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) (2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide (trade name: N- (Phenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenyl) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) Phenyloxy) diphenylmaleimide, N- ( (Phenylsulfonyloxy) bicyclo [2.2.1] hept-5- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- 2,3-dicarboxyimide (trade name "NDI-100", Midori Kagakusha), N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept- Dicarboxylic imide (trade name "NDI-101", Midori Kagakusha), N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide NDI-109 ", Midori Kagakusha), N- (nonafluorobutanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide NDI-106, Midori Kagakusha), N (N, N-dimethylaminopropyl) carbodiimide - (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (trifluoromethylsulfonyloxy) ) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hepto- , 3-dicarboxyimide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hepto-5-ene-2,3-dicarboxylimide, N- 2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 2,1-hept-5-ene-2,3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [ 2,1-hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2. Heptane-5,6-oxy-2,3-dicarboxylic imide, N- (camphorsulfonyloxy) bicyclo [2.2.1] - (4-methylphenylsulfonyloxy) bicyclo [ 2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2, 3-dicarboxyimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxyimide, N- (trifluoromethylsulfonyl Oxy) naphthyl dicarboxyl imide (brand name "NAI-105", Midorika Gakusha), N- (camphor sulfonyloxy) naphthyl dicarboxyl imide (brand name "NAI-106", Midorika Gakusha), N- (4-methylphenylmethylsulfonyloxy) naphthyldicarboxylimide (brand name "NAI-101", Midorika Gakusha), N- (phenylsulfonyloxy) naphthyldicarboxylimide (brand name "NAI-100", Midori Kagakusha), N- (2-trifluoromethylphenylsulfonyloxy) naphthyldicarboxyimide, N- (4-fluorophenylsulfonyloxy) naphthyldicarboxyimide, N- (pentafluoroethylsul Ponyloxy) naphthyldicarboxyimide, N- (heptafluoropropylsulfo Oxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxyimide (brand name "NAI-109", Midorika Gakusha), N- (ethylsulfonyloxy) naphthyldicarboxyl Mid, N- (propylsulfonyloxy) naphthyldicarboxylimide, N- (butylsulfonyloxy) naphthyldicarboxyimide (brand name "NAI-1004", Midorika Gakusha), N- (pentylsulfonyloxy Naphthyldicarboxyimide, N- (hexylsulfonyloxy) naphthyldicarboxylimide, N- (heptylsulfonyloxy) naphthyldicarboxyimide, N- (octylsulfonyloxy) naphthyldicarboxyimide, N -(Nonylsulfonyloxy) naphthyl dicarboxyimide, etc. are mentioned.

As other [E] thermal acid generators, for example, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiopheniumtrifluoromethanesulfonate and 1- (4,7-dibutoxy Tetrahydrothiophenium salts, such as the 1-naphthalenyl) tetrahydrothiophenium trifluoromethane sulfonate, are mentioned.

Among these [E] thermal acid generators, in view of the catalysis of the curing reaction of the [A] alkali-soluble resin, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate and 1- (4,7-dibutoxy- 1-naphthalenyl) tetrahydrothiopheniumtrifluoromethanesulfonate and N- (trifluoromethylsulfonyloxy) naphthyldicarboxyimide are more preferable.

0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of [A] alkali-soluble resin, and, as for the usage-amount of the thermal acid generator (E), 1 mass part-5 mass parts are more preferable. By setting the usage-amount of the thermal acid generator (E) to the said range, the cured film with a high surface hardness, ie, an insulating film, can be formed, optimizing the sensitivity of a 1st radiation sensitive resin composition, and maintaining transparency.

<[F] Curing Accelerator>

The 1st radiation sensitive resin composition of this embodiment can contain a [F] hardening accelerator. [F] A hardening accelerator is a compound which fulfills the function which accelerates hardening, and is suitable at the point of realizing low temperature hardening of 200 degrees C or less.

[F] the curing accelerator is 4,4'-diaminodiphenylsulfone, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (trifluoromethyl) benzidine, 3- It has an electron-withdrawing group and an amino group in molecules, such as ethylaminobenzenesulfonic acid ethyl, 3, 5-bistrifluoromethyl- 1, 2-diaminobenzene, 4-aminonitrobenzene, N, N- dimethyl- 4-nitroaniline, etc. It is at least 1 compound chosen from the group which consists of a compound, a tertiary amine compound, an amide compound, a thiol compound, a block isocyanate compound, and an imidazole ring containing compound.

By the 1st radiation sensitive resin composition containing [F] hardening accelerator chosen from the specific compound group, hardening of a 1st radiation sensitive resin composition is accelerated | stimulated and the low temperature hardening of an insulating film, specifically 200 degrees C or less Can be achieved. This makes it possible to reduce the rate of expansion and contraction of the film even when the thermal history is received in a later step. Such an effect is likely to be expressed in combination with the [E] thermal acid generator. Moreover, the storage stability of a 1st radiation sensitive resin composition can also be improved by using a [F] hardening accelerator.

&Lt; Other optional components >

The 1st radiation sensitive resin composition of this embodiment is [A] alkali-soluble resin and [B] quinone diazide compound, or [A] alkali-soluble resin, [C] polymeric compound, and [D] radiation sensitive polymerization In addition to the initiator, in addition to the [E] thermal acid generator or the [F] curing accelerator, other optional agents such as a surfactant, a storage stabilizer, an adhesion aid, and a heat resistance enhancer, as necessary, within a range that does not impair the effects of the present invention. It may contain components. Each of these optional components may be used independently, and may mix and use 2 or more types. Hereinafter, each component is described.

[Surfactants]

A surfactant can be used for the purpose of further improving the coating film formability of a 1st radiation sensitive resin composition. As surfactant, a fluorine-type surfactant, silicone type surfactant, and other surfactant which can be used for the 2nd radiation sensitive resin composition mentioned later are mentioned, for example.

[Storage stabilizer]

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

[Adhesion preparation]

An adhesion | attachment adjuvant can be used for the purpose of further improving adhesiveness with the insulating film obtained from the 1st radiation sensitive resin composition of this embodiment, a layer, a board | substrate, etc. under it. As an adhesion | attachment adjuvant, the functional silane coupling agent which has reactive functional groups, such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, an oxiranyl group, is used preferably, For example, trimethoxy silyl benzoic acid, (gamma)- Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclo Hexyl) ethyl trimethoxysilane etc. are mentioned.

<Preparation method of a 1st radiation sensitive resin composition>

The 1st radiation sensitive resin composition of this embodiment is [E] other than [A] alkali-soluble resin, [B] quinonediazide compound or [C] polymerizable compound, and [D] radiation sensitive polymerization initiator. It is prepared by uniformly mixing a thermal acid generator, a [F] hardening accelerator, or other optional components added as necessary. This first radiation-sensitive resin composition is preferably dissolved in an appropriate solvent and used in a solution form. A solvent can be used individually or in mixture of 2 or more types.

As a solvent used for preparation of the 1st radiation sensitive resin composition of this embodiment, an essential component and arbitrary components are melt | dissolved uniformly, and what does not react with each component is used. Examples of such a solvent include the same solvents exemplified as the usable solvents for producing the above-described [A] alkali-soluble resin.

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the 1st radiation sensitive resin composition obtained, the total concentration of each component except the solvent of a 1st radiation sensitive resin composition is 5 mass%-50 The amount used as mass% is preferable, and the amount used as 10 mass%-40 mass% is more preferable. When preparing the solution of a 1st radiation sensitive resin composition, actually, in the said concentration range, solid content concentration (components other than the solvent which occupies in a composition solution) according to a use purpose, a desired film thickness value, etc. are set. More preferably, it is set according to the method of forming the coating film on the substrate, which will be described later.

The solution-like composition thus prepared is preferably used for forming an insulating film after filtration using a Millipore filter having a pore size of about 0.5 μm or the like.

According to the 1st radiation sensitive resin composition obtained by said component and the adjustment method, the insulating film with a small expansion ratio after a thermal history can be formed. In addition, this 1st radiation sensitive resin composition can form such an insulating film in low temperature effect, specifically, the hardening temperature of 200 degrees C or less. In some cases, it is possible to form an insulating film even at a curing temperature of 180 DEG C or less, which is suitable for formation on a resin substrate.

Next, the 2nd radiation sensitive resin composition of this embodiment for forming the interlayer insulation film of the array substrate and liquid crystal display element of this embodiment is demonstrated in detail.

<2nd radiation sensitive resin composition>

As described above, the interlayer insulating film of the array substrate of the embodiment of the present invention is a coating type interlayer insulating film made of an organic material, and is disposed between the common electrode and the pixel electrode. The 2nd radiation sensitive resin composition of embodiment of this invention is a radiation sensitive resin composition suitable for formation of this interlayer insulation film.

The second radiation-sensitive resin composition according to the embodiment of the present invention is an oxide of at least one metal selected from the group consisting of [X] polymer, [Y] aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium. It consists of particle | grains, a [Z] polyfunctional acrylate, and a [W] radiation sensitive polymerization initiator.

As the polymer [X], the acrylic resin or the polyimide described in the above-mentioned first radiation-sensitive resin composition can be used. And the polymer [X] can be made into the polymer containing the structural unit which has a (X1) aromatic ring and the structural unit which has (X2) (meth) acryloyloxy group especially among them.

Moreover, the 2nd radiation sensitive resin composition which is embodiment of this invention may contain other arbitrary components, unless the effect of this invention is impaired.

Hereinafter, each component contained in the 2nd radiation sensitive resin composition of this embodiment is demonstrated.

<[X] polymer>

The polymer [X] can be made into the polymer containing the structural unit which has a (X1) aromatic ring, and the structural unit which has a (X2) (meth) acryloyloxy group as mentioned above. [X] The polymer is an alkali-soluble resin which is soluble in alkali. Here, especially [X] polymer which is a polymer containing the structural unit which has a (X1) aromatic ring, and the structural unit which has a (X2) (meth) acryloyloxy group is demonstrated.

The structural unit which has an (X1) aromatic ring is a structural unit represented by following formula (3). By including the structural unit which has a (X1) aromatic ring, the refractive index of the cured film obtained can be improved, and the heat resistance of a cured film can also be improved.

In said formula (3), R <^21> represents a C1-C12 alkyl group, a hydroxyl group, a C1-C12 alkoxyl group, and a halogen. R <^22> represents a single bond, a methylene group, and a C2-C6 alkylene group. R ²³ represents a single bond or an ester bond. R ²⁴ represents a hydrogen atom or a methyl group.

The following are mentioned as a specific polymeric compound for forming the structural unit which has a (X1) aromatic ring.

Styrene, p-hydroxystyrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-chlorostyrene, p-methoxystyrene, p- (t-butoxy) styrene,

Phenyl acrylate, phenyl methacrylate, 4-hydroxyphenyl acrylate, 4-hydroxyphenyl methacrylate, benzyl acrylate, benzyl methacrylate, phenethyl acrylate, phenethyl methacrylate and the like.

Among these, styrene, benzyl acrylate and benzyl methacrylate are preferable from the viewpoint of polymerizability.

It is preferable that content of the structural unit which has the (X1) aromatic ring in [X] polymer is 20 mol% or more and 90 mol% or less in the [X] polymer whole component, More preferably, it is 50 mol% or more and 80 mol It is% or less.

In the case of content less than 20 mol%, it is difficult to fully improve the refractive index of the protective film obtained, and heat resistance is also not enough. Moreover, in the case of content exceeding 90 mol%, it will become a cause of the image development defect at the time of image development, and a image development residue will become easy to generate | occur | produce.

(X2) The structural unit which has a (meth) acryloyloxy group is obtained by making the carboxyl group in a polymer react with the (meth) acrylic acid ester which has an epoxy group. The structural unit which has a (meth) acryl group after reaction is (meth) acryl represented by said formula (1) which [A] alkali-soluble resin contained in the 1st radiation sensitive resin composition of this embodiment may have. It is preferable that it is the same structural unit as the structural unit which has a monooxy group.

In the reaction with an unsaturated compound such as a (meth) acrylic acid ester having a carboxyl group and an epoxy group in the polymer described above, in the presence of a suitable catalyst, if necessary, the epoxy group is preferably added to a solution of a polymer containing a polymerization inhibitor. The unsaturated compound which has is thrown in, and it stirred for a predetermined time under heating. As said catalyst, tetrabutylammonium bromide etc. are mentioned, for example. As said polymerization inhibitor, p-methoxy phenol etc. are mentioned, for example. As for reaction temperature, 70 degreeC-100 degreeC is preferable. As for reaction time, 8 hours-12 hours are preferable.

It is preferable that content of the structural unit which has the (X2) (meth) acryloyloxy group in [X] polymer is 10 mol%-70 mol% in the [X] polymer all components, and it is 20 mol%-50 mol It is more preferable that it is%.

(X2) When content of the structural unit which has a (meth) acryloyloxy group is less than 10 mol%, there exists a tendency for the sensitivity to the radiation of a 2nd radiation sensitive resin composition to fall, and the heat resistance of the cured film obtained is also not enough. not. Moreover, when it contains more than 70 mol%, it will become a cause of the image development defect at the time of image development, and development residue will become easy to generate | occur | produce.

The carboxyl group in a polymer can be introduce | transduced by superposing | polymerizing the unsaturated monomer which has a carboxyl group shown below.

Examples of such unsaturated monomers include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, anhydrides of unsaturated dicarboxylic acids, and mono [(meth) acryloyloxyalkyl] esters of polyvalent carbonic acids.

Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, and crotonic acid. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, and the like. The anhydrides of the unsaturated dicarboxylic acids include, for example, anhydrides of the compounds exemplified as the dicarboxylic acids.

Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl ] And the like.

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferred, and acrylic acid, methacrylic acid and maleic anhydride are more preferable from the copolymerization reactivity, solubility in aqueous alkali solution and ease of obtaining. These compounds may be used alone or in combination of two or more thereof.

It is preferable that the use ratio is 5 mol%-20 mol% more than the use ratio of the structural unit which has a (X2) (meth) acryloyloxy group. It is because developability with respect to alkaline developing solution will be impaired when all of a carboxyl group is made to react with the (meth) acrylic acid ester which has an epoxy group. Therefore, it is preferable that it is the range of 5 mol% or more and 90 mol% or less, and it is more preferable that it is the range which is 15 mol% or more and 70 mol% or less.

[X] The polymer is a structural unit having a (X1) aromatic ring (hereinafter, may be simply referred to as a (X1) structural unit), or a structural unit having a (X2) (meth) acryloyloxy group (hereinafter, simply ( In addition to the X2) structural unit) and the structural unit which has the above-mentioned carboxyl group (henceforth a (X3) structural unit), the structural unit derived from the following unsaturated monomers (henceforth a (X4) structural unit) You may have

As a (X4) structural unit, the structural unit which has the following oxetanyl group, etc. are mentioned.

As an unsaturated monomer which forms the structural unit which has an oxetanyl group, for example,

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

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

As an unsaturated monomer which forms the structural unit which has an alkyl group which is (X4) a structural unit, it is, for example,

As methacrylic acid linear alkylester, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate Isodecyl methacrylate, n-lauryl methacrylate, tridecyl methacrylate, n-stearyl methacrylate, and the like.

Moreover, as methacrylic acid cyclic alkyl ester, methacrylic acid cyclohexyl, methacrylic acid 2-methylcyclohexyl, methacrylic acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yl, methacrylic acid are mentioned, for example. Acid tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl, isobornyl methacrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, 2-acrylate Ethylhexyl, isodecyl acrylate, n-lauryl acrylate, tridecyl acrylate, n-stearyl acrylate, cyclohexyl acrylate, 2-methylcyclohexyl acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8- And tricyclo [5.2.1.0 ^2,6 ] decane-8-yloxyethyl acrylate, isobornyl acrylate, and the like.

As an unsaturated monomer which forms the structural unit which has a maleimide skeleton which is (X4) a structural unit,

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

As an unsaturated monomer which forms the structural unit containing a tetrahydrofuran frame | skeleton, methacrylic acid tetrahydrofurfuryl, 2-methacryloyloxy- propionic acid tetrahydrofurfuryl ester, 3- (meth) acrylo, for example Iloxy tetrahydrofuran-2-one etc. are mentioned.

Of the unsaturated monomers constituting the (X4) structural unit, methyl methacrylate, t-butyl methacrylate, n-lauryl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl , Acrylic acid-2-methylcyclohexyl, N-phenylmaleimide, N-cyclohexylmaleimide, and methacrylic acid tetrahydrofurfuryl are preferable in terms of copolymerization reactivity and solubility in aqueous alkali solution.

These compounds may be used independently and may mix and use 2 or more types.

As a use ratio, 10 mass%-80 mass% are preferable based on the sum total with the (X1) structural unit, the (X2) structural unit, the structural unit which has a carboxyl group ((X3) structural unit), and (X4) structural unit. Do.

[X] The polymer is, for example, a compound for forming the above-mentioned (X1) structural unit in the presence of a polymerization initiator (hereinafter also referred to as a (X1) compound) and a compound for forming the (X2) structural unit. (Hereinafter also referred to as (X2) compound) (compound to form any (X3) structural unit as needed (hereinafter also referred to as (X3) compound)) Unsaturated monomer for forming the compound and (X4) structural unit ( Hereinafter, it can manufacture by copolymerizing (it is also called a (X4) compound).

Examples of the solvent used in the polymerization reaction for producing the polymer [X] include alcohol, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol monoalkyl ether, diethylene glycol dialkyl ether, and dipropylene glycol dialkyl. Ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol monoalkyl ether propionate, methyl-3-methoxy propionate, ketone, ester and the like.

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

In the polymerization reaction for producing the polymer [X], a molecular weight modifier can be used for the purpose of adjusting the molecular weight.

Examples of the molecular weight regulator include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan and thioglycolic acid; Azetidine derivatives such as dimethylzantogen sulfide and diisopropylzantogen disulfide; Terpinolene, (alpha) -methylstyrene dimer, etc. are mentioned.

1000-30000 are preferable and, as for the weight average molecular weight (Mw) of [X] polymer, 5000-20000 are more preferable. By making Mw of a polymer [X] into the said range, the sensitivity and developability with respect to the radiation of a 2nd radiation sensitive resin composition can be improved. In addition, Mw and number average molecular weight (Mn) of polymer [X] were measured by the gel permeation chromatography (GPC) by the conditions mentioned above.

<[Y] metal oxide particles>

The oxide particle of metal [Y] (henceforth simply a metal oxide particle) is contained in the 2nd radiation sensitive resin composition of this embodiment, and can improve the refractive index of the interlayer insulation film obtained.

[Y] The metal oxide particles are oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium, among which oxide particles of zirconium, titanium or zinc are preferred. And, oxide particles of zirconium or titanium are more preferable. And it is also possible to use a titanate salt.

These metal oxide particles can be used individually by 1 type or in combination of 2 or more types. Moreover, as [Y] metal oxide particle, the complex oxide particle of the metal of the said illustration may be sufficient. As this composite oxide particle, ATO (Antimony-Tin Oxide), ITO, IZO (Indium-Zinc Oxide), etc. are mentioned, for example. As these metal oxide particles, commercially available ones can be used. For example, Nanotech (NANO TEK) by Seaikasei Co., Ltd. can be used. And particle | grains of a titanate salt can also be used.

[Y] The shape of the metal oxide particles is not particularly limited, and may be spherical or irregular, or may be hollow particles, porous particles, core-shell particles, or the like.

Moreover, 5 nm or more and 200 nm or less are preferable, as for the number average particle diameter of [Y] metal oxide particle calculated | required by the dynamic light scattering method, 5 nm or more and 100 nm or less are more preferable, 10 nm or more and 80 nm or less are more preferable. . If the number average particle diameter of the [Y] metal oxide particles is less than 5 nm, the hardness of the cured film may be lowered, and if it exceeds 200 nm, the haze of the cured film may be increased.

[Y] When the oxide of zirconium or titanium which is a more preferable metal is used in a metal oxide particle, even higher refractive index can be obtained. Although it is not certain that the refractive index becomes higher by using zirconium or titanium, the polarization in the particle is high due to the low degree of electronegativity, and as a result, the refractive index can be considered to be improved. Therefore, as the [Y] metal oxide particles, oxide particles of metals having an electronegativity of 1.7 or less are preferable, and oxide particles of metals having an electronegativity of 1.6 or less are more preferable.

In addition, when using the particle | grains of a titanate salt, a titanate salt is preferable at the point which can achieve high dielectric constant in addition to high refractive index formation. Examples of such titanate salts include potassium titanate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, lead titanate, aluminum titanate, and lithium titanate. Among them, barium titanate and strontium titanate are particularly preferable from the viewpoint of high dielectric constant.

It is preferable to disperse | distribute [Y] metal oxide particle to a dispersion medium with a dispersing agent, and to use for a 2nd radiation sensitive resin composition as a metal oxide particle dispersion liquid. By doing in this way, it is possible to uniformly disperse the [Y] metal oxide particles by containing a dispersing agent, to improve applicability, to increase the adhesiveness of the resulting cured film, and to increase the refractive index without causing bias.

As a dispersing agent, a nonionic dispersing agent, a cationic dispersing agent, an anionic dispersing agent, etc. are mentioned, A nonionic dispersing agent is preferable from a viewpoint of positive radiation sensitive characteristic and patterning property improvement. As this nonionic dispersing agent, polyoxyethylene alkyl phosphate ester, the amide amine salt of high molecular weight polycarboxylic acid, ethylene diamine PO-EO condensate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, alkyl glucoside, polyoxy Preference is given to ethylene fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or fatty acid alkanolamides.

As a dispersion medium, if [Y] metal oxide particle can be disperse | distributed uniformly, it will not specifically limit. A dispersion medium can function a dispersing agent effectively, and can disperse | distribute a [Y] metal oxide particle uniformly.

As a dispersion medium, Alcohol, such as methanol, ethanol, isopropanol, butanol, and octanol; Esters such as ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monobutyl ether and diethylene glycol methyl ethyl ether; Esters such as propylene glycol monomethyl ether acetate and methyl-3-methoxypropionate; Amides such as dimethylformamide, N, N-dimethylacetoacetamide and N-methylpyrrolidone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene can be used. Especially, acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene, xylene, methanol, isopropyl alcohol and propylene glycol monomethyl ether are preferable, and methyl ethyl ketone, propylene glycol monomethyl ether and diethylene glycol methyl Ethyl ether, propylene glycol monomethyl ether acetate, and methyl-3-methoxy propionate are more preferable. A dispersion medium can be used 1 type or in mixture of 2 or more types.

The metal oxide particles of the dispersion are preferably 5% to 50%, more preferably 10% to 40%.

Although it does not specifically limit as a compounding quantity of [Y] metal oxide particle, 0.1 mass part-1500 mass parts are preferable with respect to 100 mass parts of [X] polymers, and 1 mass part-1000 mass parts are more preferable. When the compounding quantity of [Y] metal oxide particle is less than 0.1 mass part, the effect of improving the refractive index of the cured film obtained cannot fully be acquired. On the contrary, when the compounding quantity of a metal oxide particle exceeds 1500 mass parts, the applicability | paintability of a 2nd radiation sensitive resin composition may fall, and there exists a possibility that the haze of the cured film obtained may become high.

The specific surface area (based on the BET specific surface area measurement method using nitrogen) of the metal oxide particles [Y] is preferably 10 m 2 / g to 1000 m 2 / g, and more preferably 100 m 2 / g to 500 m 2 / g. In addition, when a polymerizable group having high cationically polymerizable properties such as oxiranyl is present in the [X] polymer, the [Y] metal oxide particles are irradiated with radiation such as ultraviolet rays by using the above ones for the [Y] metal oxide particles. The surface of may act photocatalytically and may catalyze the crosslinking reaction of [X] polymer catalytically. In that case, the specific surface area of the [Y] metal oxide particle is in the said range, the said photocatalytic effect is expressed effectively, and high desired radiation characteristic is exhibited.

<[Z] polyfunctional acrylate>

The second radiation-sensitive resin composition of the present embodiment contains a polymerizable compound having a plurality of (meth) acryloyl groups in a molecule as a polyfunctional acrylate. As one of the functions of this polymeric compound, when the 2nd radiation sensitive resin composition is irradiated with the radiation which is radiation, what superposes | polymerizes and what forms a crosslinked structure is mentioned. By containing such a polymeric compound, the whole coating film of a 2nd radiation sensitive resin composition can be hardened. And the contrast of a light irradiation part and the part which is not is improved, and prevention of peeling at the time of image development, and formation of a residue can be suppressed.

In addition, here, "(meth) acryloyl group" refers to an acryloyl group or a methacryloyl group, and "having a some (meth) acryloyl group in a molecule" means the acryloyl group which exists in the molecule | numerator. And a total of methacryloyl groups are two or more. In that case, the total number of these groups should just be 2 or more, and neither acryloyl group nor methacryloyl group may exist.

The following are mentioned as an example of the polymeric compound which has a some (meth) acryloyl group in a molecule | numerator.

As a polymeric compound which has two (meth) acryloyl groups in a molecule | numerator, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol di (meth) acrylate, and 1, 6- hexanediol di (meth) ) Acrylate, 1,10-decanedioldi (meth) acrylate, neopentylglycoldi (meth) acrylate, 2,4-dimethyl-1,5-pentanedioldi (meth) acrylate, butylethylpropanediol (Meth) acrylate, ethoxylated cyclohexanemethanol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (Meth) acrylate, oligoethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 2-ethyl-2-butyl-butanediol di (meth) acrylic Laterate, fluorenedi (meth) acrylic , Hydroxypivalic acid neopentyl glycol di (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, oligopropylene glycol di (meth) acrylate, 2- Ethyl-2-butyl-propanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, propoxylated ethoxylated bisphenol A di (meth) acrylate, tricyclodecanedi (meth) acrylic Elate, bis (2-hydroxyethyl) isocyanurate di (meth) acrylate, etc. are mentioned.

As a polymeric compound which has three (meth) acryloyl groups in a molecule | numerator, the alkylene oxide modified tri (meth) acryl of trimethylol propane tri (meth) acrylate, trimethylol ethane tri (meth) acrylate, and trimethylol propane Rate, pentaerythritol tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, trimethylolpropane tri ((meth) acryloyloxypropyl) ether, glycerin tri (meth) acrylate, tris (2 -Hydroxyethyl) isocyanurate tri (meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, propionic acid dipentaerythritol tri (meth) acrylate, tri ((meth) acrylo Yloxyethyl) isocyanurate, hydroxypivalaldehyde-modified dimethylol propane tri (meth) acrylate, sorbitol tri (meth) acrylate, pro And the like ethoxylated trimethylolpropane tri (meth) acrylate, ethoxylated glycerin tri (meth) acrylate.

As a polymeric compound which has four (meth) acryloyl groups in a molecule | numerator, pentaerythritol tetra (meth) acrylate, sorbitol tetra (meth) acrylate, ditrimethylol propane tetra (meth) acrylate, and propionic acid dipentaerytes Lithol tetra (meth) acrylate, an ethoxylated pentaerythritol tetra (meth) acrylate, a succinic acid modified pentaerythritol tri (meth) acrylate, etc. are mentioned.

As a polymeric compound which has five (meth) acryloyl groups in a molecule | numerator, sorbitol penta (meth) acrylate and dipentaerythritol penta (meth) acrylate are mentioned.

As a polymeric compound which has six (meth) acryloyl groups in a molecule | numerator, dipentaerythritol hexa (meth) acrylate, sorbitol hexa (meth) acrylate, the alkylene oxide modified hexa (meth) acrylate of phosphazene, Caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

[Z] The polyfunctional acrylate may be a polymerizable compound having seven or more (meth) acryloyl groups. Moreover, the (Z) polyfunctional acrylate may be the (meth) acrylate which has a hydroxyl group among the above-mentioned polymeric compounds, and the poly (meth) acrylate of the ethylene oxide or the propylene oxide addition product to these hydroxyl groups. Moreover, as a [Z] polyfunctional acrylate, if it is a compound which has two or more (meth) acryloyl groups, oligoester (meth) acrylates, oligoether (meth) acrylates, and oligoepoxy (meth) acrylate And the like can be used.

As the [Z] polyfunctional acrylate, among these, pentaerythritol tri (meth) acrylate, fluorenedi (meth) acrylate, and oligoester (meth) acrylate (dendrimer (meth) acrylate) are polymerized. It is more preferable at the point which is excellent in property.

About the commercial item of the polymeric compound illustrated as [Z] polyfunctional acrylate above, Toagose Corporation ARONIX (trademark) M-400, M-404, M-408 , M-450, M-305, M-309, M-310, M-313, M-315, M-320, M-350, M-360, M-208, M-210, M-215, M -220, M-225, M-233, M-240, M-245, M-260, M-270, M-1100, M-1200, M-1210, M-1310, M-1600, M-221 , M-203, TO-924, TO-1270, TO-1231, TO-595, TO-756, TO-1343, TO-902, TO-904, TO-905, TO-1330, TO-1450, TO -1382, Nippon Kayaku Co., Ltd.KAYARAD (registered trademark) D-310, D-330, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, SR -295, SR-355, SR-399 E, SR-494, SR-9041, SR-368, SR-415, SR-444, SR-454, SR-492, SR-499, SR-502, SR- 9020, SR-9035, SR-111, SR-212, SR-213, SR-230, SR-259, SR-268, SR-272, SR-344, SR-349, SR-601, SR-602, SR-610, SR-9003, PET-30, T-1420, GPO-303, TC-120 S, HDDA, NPGDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-551, R-712 , R-167, R-526, R-551, Light acrylate (manufactured by R-712, R-604, R-684, TMPTA, THE-330, TPA-320, TPA-330, KS-HDDA, KS-TPGDA, KS-TMPTA, Kyoeisha Kagaku LIGHT ACRYLATE) PE-4A, DPE-6A, DTMP-4A, VISCOAT # 802, manufactured by Osaka Yuki Chemical Co., Ltd .; And mixtures of tripentaerythritol octaacrylate and tripentaerythritol hepacrylate.

As for content of the [Z] polyfunctional acrylate in the 2nd radiation sensitive resin composition of this embodiment, 1 mass%-20 mass% are preferable with respect to the whole 2nd radiation sensitive resin composition. In addition, when the 2nd radiation sensitive resin composition of this embodiment contains an organic solvent, content of the [Z] polyfunctional acrylate polymerizable compound in a 2nd radiation sensitive resin composition removes an organic solvent. It is preferable to carry out in the range of 5 mass%-50 mass% or less with respect to the sum total of a component, and it is more preferable to exist in the range which is 10 mass%-40 mass%. By containing [Z] polyfunctional acrylate in the said range, the cured film of high hardness can be obtained from a 2nd radiation sensitive resin composition.

<[W] radiation sensitive polymerization initiator>

The 2nd radiation sensitive resin composition of this embodiment contains a [W] radiation sensitive polymerization initiator with [Z] polyfunctional acrylate. [W] The radiation sensitive polymerization initiator is a component that generates active species capable of initiating polymerization of the [Z] polyfunctional acrylate in response to radiation. [W] The radiation sensitive polymerization initiator is, for example, an optical radical polymerization initiator. As such a [W] radiation sensitive polymerization initiator, an O-acyl oxime compound, an acetophenone compound, a biimidazole compound, etc. are mentioned, [C] superposition | polymerization to the 1st radiation sensitive resin composition of this embodiment mentioned above The same thing as the [D] radiation sensitive polymerization initiator contained with a soluble compound is mentioned. These compounds may be used independently and may mix and use 2 or more types.

A radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types.

[W] 1 mass part-40 mass parts are preferable with respect to 100 mass parts of [X] polymers, and, as for content of a radiation sensitive polymerization initiator, 5 mass parts-30 mass parts are more preferable. [W] By setting the content of the radiation sensitive polymerization initiator to 1 part by mass to 40 parts by mass, the second radiation sensitive resin composition can form an interlayer insulating film having high solvent resistance, high hardness, and high adhesion even at a low exposure amount. have.

<Optional ingredients>

In addition to the [X] polymer, [Y] metal oxide particle, [Z] polyfunctional acrylate, and [W] radiation sensitive polymerization initiator, the 2nd radiation sensitive resin composition of this embodiment is a [Y] metal oxide particle. In addition to the dispersant and the dispersion medium used together with, other optional components such as surfactants may be contained, if necessary, within a range that does not impair the effects of the present invention. You may use arbitrary components in mixture of 2 or more types. Hereinafter, each component is described.

[Surfactants]

The surfactant contained in the second radiation-sensitive resin composition of the present embodiment can be added in order to improve the applicability of the second radiation-sensitive resin composition, to reduce the coating unevenness, and to improve the developability of the radiation irradiation part. As an example of a preferable surfactant, a fluorochemical surfactant and silicone type surfactant are mentioned.

As the fluorine-based surfactant, for example, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether , Octaethylene glycol di (1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1 Fluoro ethers such as 1,2,2-tetrafluorobutyl) ether and hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether; Sodium perfluorododecylsulfonate; Fluoroalkanes such as 1,1,2,2,8,8,9,9,10,10-decafluorododecane and 1,1,2,2,3,3-hexafluorodecane; Sodium fluoroalkylbenzenesulfonic acid; Fluoroalkyloxyethylene ethers; Fluoroalkylammonium iodides; Fluoroalkyl polyoxyethylene ethers; Perfluoroalkyl polyoxyethanols; Perfluoroalkylalkoxylates; Fluorine-based alkyl esters and the like.

Commercially available products of these fluorine-based surfactants include EFTOP (registered trademark) EF301, 303, and 352 (manufactured by Shin-Akita Kasei Co., Ltd.), Mega Pack (MEGAFACE) (registered trademark) F171, 172, and 173 (DIC Corporation). Kaisha), Fluorad (FLUORAD) FC430, 431 (manufactured by Sumitomo 3M Co., Ltd.), Asahi GUARD AG (registered trademark) 710, SURFLON (registered trademark) S-382, SC-101 , 102, 103, 104, 105, 106 (manufactured by Asahi Glass Co., Ltd.), FTX-218 (manufactured by Neos Co., Ltd.), and the like.

As an example of silicone type surfactant, SH200-100cs, SH28PA, SH30PA, ST89PA, SH190, SH8400 FLUID (made by Toray Dow Corning Silicone Co., Ltd.), organosiloxane polymer KP341 (Shin-Etsu Chemical Co., Ltd.) is a commercial brand name. Production).

When using surfactant as an arbitrary component, the content becomes like this. Preferably it is 0.01 mass part or more and 10 mass parts or less, More preferably, it is 0.05 mass part or more and 5 mass parts or less with respect to 100 mass parts of [X] polymers. By making the usage-amount of surfactant into 0.01 mass part or more and 10 mass parts or less, the coating property of a 2nd radiation sensitive resin composition can be optimized.

<Preparation of 2nd radiation sensitive resin composition>

The 2nd radiation sensitive resin composition of this embodiment mixes [X] polymer, [Y] metal oxide particle, [Z] polyfunctional acrylate, [W] radiation sensitive polymerization initiator, and surfactant as needed. It is prepared by. At this time, an organic solvent can be used in order to prepare the 2nd radiation sensitive resin composition of a dispersion state. An organic solvent can be used individually or in mixture of 2 or more types.

As a function of an organic solvent, the viscosity of a 2nd radiation sensitive resin composition is adjusted, for example, improving applicability | paintability to a board | substrate etc., etc., and improving operability, moldability, etc. are mentioned. As a viscosity of the 2nd radiation sensitive resin composition implemented by containing organic solvent etc., 0.1 mPa * s-500000 mPa * s (25 degreeC) are preferable, for example, More preferably, it is 0.5 mPa * s- It is 10000 mPa * s (25 degreeC).

As an organic solvent which can be used for a 2nd radiation sensitive resin composition, what melt | dissolves or disperse | distributes another containing component and does not react with another containing component is mentioned.

Examples thereof include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactoate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and methyl-3-methoxypropionate; Ethers such as polyoxyethylene lauryl ether, ethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol methyl ethyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like.

Content of the organic solvent used in the 2nd radiation sensitive resin composition of this embodiment can be suitably determined considering a viscosity etc.

As a dispersion method at the time of preparing the 2nd radiation sensitive resin composition of a dispersion state, using a paint shaker, an SC mill, an annular type mill, a pin type mill, etc., it is a circumferential speed of 5 m / s-15 m / s, and the fall of a particle size It may be carried out by the method of continuing until it is not observed. This duration is usually several hours. In addition, it is preferable to use dispersion beads, such as glass beads and zirconia beads, at the time of this dispersion. The bead diameter is not particularly limited, but is preferably 0.05 mm to 0.5 mm, more preferably 0.08 mm to 0.5 mm, and still more preferably 0.08 mm to 0.2 mm.

Next, the alignment film applicable to the array substrate of this embodiment is demonstrated. This alignment film is formed using the liquid crystal aligning agent of the present embodiment. Then, this main component is demonstrated especially the main component below.

<Liquid Crystal Aligner>

In the liquid crystal aligning agent of the present embodiment,

An [L] radiation-sensitive polymer having a photo-orientable group,

[M] polyimides without photoalignment groups

It is contained as a main ingredient. All of these can be hardened by low temperature heating, such as 200 degrees C or less, for example. In particular, the liquid crystal aligning agent containing the [L] radiation sensitive polymer which has a photo-alignment group can form alignment film at low temperature.

Thus, since the liquid crystal aligning agent of this embodiment can form the oriented film by low temperature heating, it is not necessary to provide thermal history at high temperature with respect to the lower insulating film and interlayer insulation film.

The liquid crystal aligning agent of this embodiment may contain [N] other components as long as the effect of the present invention is not impaired. Hereinafter, these components will be described.

[[L] Radiation Polymer]

[L] The radiation sensitive polymer may be contained in the liquid crystal aligning agent of the present embodiment as a polymer having a photo aligning group. The photo-alignment group of the [L] radiation-sensitive polymer is a functional group which imparts anisotropy to the film by irradiation with light, and in the present embodiment, particularly, at least one of the photoisomerization reaction and the photo-duplexing reaction gives the film anisotropy. It is a flag.

Specific examples of the photo-alignment group include azobenzene, stilbene, α-imino-β-ketoester, spiropyran, spiroxazine, cinnamic acid, chalcone, stilazole, benzylidene futalimidine, coumarin, diphenylaceryl It is group which has a structure derived from at least 1 compound chosen from the group which consists of a rene and anthracene. Of these, groups having a structure derived from cinnamic acid are particularly preferable as photo-aligning groups.

[L] The radiation sensitive polymer is preferably a polymer in which the above-described photoalignment group is bonded directly or through a linking group. As such a polymer, the thing which the above-mentioned photoalignment group couple | bonded with the polymer of at least one of polyamic acid and a polyimide, and the thing which the said photo-alignment group couple | bonded with the polymer different from polyamic acid and a polyimide are mentioned, for example. In the latter case, examples of the basic skeleton of the polymer having a photo-orientable group include poly (meth) acrylic acid ester, poly (meth) acrylamide, polyvinyl ether, polyolefin, and polyorganosiloxane.

The radiation-sensitive polymer preferably has a basic skeleton of polyamic acid, polyimide or polyorganosiloxane. Among these, polyorganosiloxane is especially preferable, and this can be obtained by the method as described, for example, in WO 2009/025386 pamphlet.

[[M] polyimide]

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

[M] A polyimide is obtained by dehydrating and ring-closing polyamic acid which does not have a photo-alignment group, and imidizing it. Such polyamic acid can be obtained, for example, by making tetracarboxylic dianhydride and diamine react, and can be specifically obtained by the method of Unexamined-Japanese-Patent No. 2010-97188.

[M] The polyimide may be a complete imide product obtained by dehydrating and closing all of the dark acid structures possessed by the polyamic acid as the precursor thereof, or by dehydrating and closing only a part of the dark acid structures to partially coexist with the dark acid structure and the imide ring structure. It may be de cargo.

It is preferable that the imidation ratio of [M] polyimide is 30% or more, It is more preferable that it is 50%-99%, It is still more preferable that it is 65%-99%. However, the imidation ratio in this case shows the ratio which the number of the imide ring structures to the sum of the number of the dark acid structures of a polyimide, and the number of imide ring structures occupies as a percentage. Here, a part of the imide ring may be an isoimide ring, and this can be obtained by, for example, being disclosed in Japanese Unexamined Patent Publication No. 2010-97188.

[[N] other ingredients]

The liquid crystal aligning agent of the present embodiment may contain other components than the radiation sensitive polymer having a photo aligning group and the polyimide having no photo aligning group. [N] As other components, for example, [L] radiation-sensitive polymer which has a photo-alignment group, and polymers other than [M] polyimide which does not have a photo-alignment group, a hardening | curing agent, a curing catalyst, a hardening accelerator, an epoxy compound, and a functional Silane compounds, surfactants, photosensitizers and the like.

Next, the manufacturing method of the insulating film, the oriented film, and the array substrate of this embodiment is demonstrated.

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

In the manufacturing process of the array substrate of this embodiment, the process of forming an insulating film using the 1st radiation sensitive resin composition of this embodiment mentioned above, and the 2nd radiation sensitive resin composition of this embodiment are used, The process of forming an interlayer insulation film is included as a main process. In the step of forming the insulating film, a contact hole is formed in the insulating film. In addition, in the formation process of an interlayer insulation film, patterning of an interlayer insulation film is performed.

The manufacturing process of the array substrate according to the present embodiment includes a step of forming an alignment film with the liquid crystal aligning agent of the present embodiment described above in order to form an alignment film on the array substrate. Hereinafter, the manufacturing method of the array substrate of this embodiment which has an insulation film, an interlayer insulation film, and an orientation film is demonstrated.

In the method for manufacturing an array substrate according to the present embodiment, it is preferable to include at least the following steps [1] to [4] in the following order so that an insulating film is formed on the substrate. The following steps [5] to [7] are preferably included in the following order so that the interlayer insulating film is formed between the common electrode and the pixel electrode on the substrate on which the insulating film is formed. Moreover, in order to form an alignment film on an array substrate, it is preferable to include process [8] after process [7]. Process [1]-process [8] are as follows.

[1] a step of forming a coating film of a first radiation-sensitive resin composition containing a polymer comprising a structural unit having a carboxyl group and a structural unit having a polymerizable group on a substrate having an active element used for switching (hereinafter, It may be called "process [1]". An electrode or the like may be formed on the substrate. Hereinafter, the active element and the electrode (the semiconductor layer, the gate electrode, the gate insulating film, the source-drain electrode, the image signal line, the scan signal line, etc., which have already been described) may be collectively referred to as "active element," or the like.

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

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

[4] A step of curing the coating film developed in Step [3] to form an insulating film (hereinafter sometimes referred to as "step [4]").

[5] A step of forming the coating film of the second radiation-sensitive resin composition of the embodiment of the present invention on a substrate having an insulating film formed through steps [1] to [4] (hereinafter, referred to as "step [5]"). May be called).

[6] A step of irradiating at least a portion of the coating film formed in step [5] (hereinafter sometimes referred to as "step [6]").

[7] A step of developing the coating film irradiated with radiation in step [6] (hereinafter sometimes referred to as "step [7]").

[8] A coating film of the liquid crystal aligning agent is formed on a substrate having an insulating film formed through steps [1] to [4] and an insulating film formed through steps [5] to Step [7], and the coating film is 200 ° C. The process of heating and forming an oriented film below (henceforth, it may be called "process [8]").

It is preferable to have a process of forming a common electrode on the insulating film formed in process [4] between the said process [4] and the process [5]. And it is preferable to have a process of forming the comb-tooth shaped pixel electrode on the interlayer insulation film formed in the process [7] between the said process [7] and the process [8]. In each of these steps [4] and [5] and between the steps [7] and [8], a common electrode and a pixel electrode can be formed using a known technique.

According to process [1]-process [4], the insulating film can be formed on the board | substrate with which the active element etc. were formed using the 1st radiation sensitive resin composition of this embodiment. The insulating film formed on the substrate has a contact hole. In addition, the insulating film has a reduced expansion / contraction ratio of the film due to the subsequent heat treatment.

And according to process [5]-process [7], the interlayer insulation film can be formed on the board | substrate with which the insulating film, the common electrode, etc., such as an active element, were formed using the 2nd radiation sensitive resin composition of this embodiment. . The formed interlayer insulating film is a coating type interlayer insulating film which can be easily formed by a coating method or the like. The interlayer insulating film is formed by using an organic material and exhibits excellent adhesion between a common electrode made of ITO and the like.

Moreover, according to process [8], the alignment film can be formed on a board | substrate by low temperature hardening using the liquid crystal aligning agent of this embodiment.

Therefore, according to the process [1]-the process [8], the contact hole was formed in the predetermined position, the insulating film which the expansion ratio of the film | membrane reduced by heating, and the coating type interlayer insulation film excellent in the adhesive force comprised using the organic material are An array substrate of this embodiment having a structure is manufactured. This manufacturing method of the array substrate is suitable for the case where the lowering of the heating step is desired from the viewpoint of energy saving, since the insulating film, the interlayer insulating film and the alignment film can be formed by low temperature heating.

Hereinafter, the above-mentioned process [1]-process [4], process [5]-process [7], and process [8] are demonstrated in detail.

[Process [1]]

In this process, the coating film of the 1st radiation sensitive resin composition of this embodiment is formed on a board | substrate. In this substrate, active elements, electrodes, and the like for switching are formed. These active elements and the like are formed in accordance with a known method such as normal semiconductor film deposition, known insulating layer formation, and the like by repeating etching by a photolithography method on a substrate. As the substrate, for example, an inorganic insulating film made of a metal oxide such as SiO ₂ or a metal nitride such as SiN can be used on the switching active element or the like.

In the said board | substrate, after apply | coating a 1st radiation sensitive resin composition to the surface in which the active element etc. were formed, prebaking is performed and the solvent is evaporated and a coating film is formed.

As a material of a board | substrate, glass substrates, such as a soda-lime glass and an alkali free glass, a silicon substrate, or a polyethylene terephthalate, a polybutylene terephthalate, a polyether sulfone, a polycarbonate, an aromatic polyamide, a polyamideimide, for example And resin substrates such as polyimide. In addition, these substrates may be subjected to pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like as desired.

As a coating method of a 1st radiation sensitive resin composition, for example, a spray method, a roll coating method, a rotary coating method (also called a spin coating method or a spinner method), a slit coating method (slit die coating method), a bar Appropriate methods, such as a coating method and the inkjet coating method, can be employ | adopted. Among them, the spin coating method or the slit coating method is preferable in that a film having a uniform thickness can be formed.

Although the conditions of said prebaking differ according to the kind, compounding ratio, etc. of each component which comprise a 1st radiation sensitive resin composition, it is preferable to carry out at the temperature of 70 degreeC-120 degreeC, and time is a hotplate or oven. Although it changes with heating apparatuses, such as these, it is about 1 minute-about 15 minutes. The thickness of the coating film after pre-baking is preferably 0.5 to 10 mu m, more preferably 1.0 to 7.0 mu m.

[Process [2]]

Subsequently, at least a part of the coating film formed in step [1] is irradiated with radiation. At this time, in order to irradiate only a part of the coating film, for example, a photomask having a pattern corresponding to the formation of a desired contact hole is performed.

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

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

The 1st radiation sensitive resin composition of this embodiment has a high radiation sensitivity compared with the composition for insulating film formation known conventionally. For example, even if the said irradiation amount is 700 J / m <2> or less and further 600 J / m <2> or less, the insulating film of desired film thickness, favorable shape, excellent adhesiveness, and high hardness can be obtained.

[Process [3]]

Next, the coating film after irradiation of the process [2] is developed, an unnecessary part is removed, and the coating film in which the contact hole of the predetermined shape was formed is obtained.

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

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

[Process [4]]

Subsequently, the coating film obtained in process [3] is hardened | cured (it is also called post-baking) with suitable heating apparatuses, such as a hotplate and oven. Thereby, the insulating film of this embodiment as a cured film is obtained. The film thickness of the insulating film after curing is preferably 1 m to 5 m. In the insulating film, contact holes arranged at desired positions are formed by the process [3].

According to the 1st radiation sensitive resin composition of this embodiment, it is possible to make hardening temperature 200 degrees C or less. Moreover, the insulating film of sufficient characteristic is obtained even if it is 180 degrees C or less suitable by formation on a resin substrate. Specifically, the curing temperature is preferably set to 100 ° C to 200 ° C, and more preferably 150 ° C to 180 ° C when both low temperature curing and heat resistance are to be achieved at a high level. It is preferable to make hardening time into 5 minutes-30 minutes on a hotplate, for example, and it is preferable to set it as 30 minutes-180 minutes in oven.

Said low-temperature hardening can advance because a 1st radiation sensitive resin composition contains the above-mentioned [E] thermal acid generator and a [F] hardening accelerator. This is also effective for reducing film stretching that occurs when heat treatment is performed on the film after curing. Moreover, by containing these compounds, storage stability improves and sufficient radiation sensitivity and resolution are obtained.

After forming an insulating film in process [4], it is preferable to have a process of forming the common electrode which is a transparent electrode as a 1st electrode on an insulating film. For example, a transparent conductive layer made of ITO can be formed on the insulating film by using a sputtering method or the like. Subsequently, this transparent conductive layer is etched using the photolithography method to form a common electrode having a uniform shape as a transparent electrode in a region where contact holes on the insulating film are not arranged.

[Process [5]]

In this process, the 2nd radiation sensitive resin composition of this embodiment is apply | coated on the board | substrate using the board | substrate with an insulating film obtained in process [4]. Subsequently, Preferably, a coating surface is heated (prebaked), and when a solvent is contained in a coating film, the solvent is removed and a coating film is formed.

It does not specifically limit as a coating method of a 2nd radiation sensitive resin composition. For example, a suitable method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or an inkjet method can be adopted. Among these coating methods, a spin coating method or a slit die coating method is particularly preferable. The conditions of the prebaking may vary depending on the kind of each component, the mixing ratio, etc., and preferably from 70 to 120 占 폚 for 1 minute to 10 minutes.

[Process [6]]

Next, in this step, at least a part of the coating film on the substrate formed in step [5] is irradiated with radiation. In this case, when irradiating a part of coating film with radiation, it is preferable to carry out through the photomask which has a predetermined pattern. As radiation used for irradiation of radiation, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, etc. can be used, for example. Among these radiation, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays of 365 nm in particular is preferable.

The irradiation dose of radiation in the step [6] is a value obtained by measuring the intensity at the wavelength of 365 nm of the radiation with an illuminometer (OAI model356, manufactured by OAI Optical Associates Inc.), and preferably 100J / m 2 to 10000J. / M 2, more preferably 500 J / m 2 to 6000 J / m 2.

[Process [7]]

Subsequently, in this process, by developing the coating film after radiation irradiation obtained in process [6], an unnecessary part (non-irradiation part of radiation when the coating film of a 2nd radiation sensitive resin composition is negative) removes a predetermined pattern, To form.

As a developing solution used for the developing process of process [6], it is preferable to use the alkaline developing solution which consists of aqueous solution of alkali (basic compound). Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; Quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide, and the like.

In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to such an alkaline developer. The concentration of alkali in the alkaline developer is preferably 0.1% by mass or more and 5% by mass or less from the viewpoint of obtaining appropriate developability. As the developing method, for example, suitable methods such as puddle method, dipping method, oscillating dipping method, and shower method can be used. Although image development time changes with the composition of a 2nd radiation sensitive resin composition, Preferably it is about 10 second-180 second. Following this developing treatment, for example, water washing is carried out for 30 seconds to 90 seconds, followed by air drying with compressed air or compressed nitrogen, for example, to form a desired pattern.

As mentioned above, the interlayer insulation film on the board | substrate formed by process [5]-process [7] has high transparency, and has high refractive index. Although the interlayer insulation film formed from the 2nd radiation sensitive resin composition of this embodiment differs according to the compounding ratio of each component, etc., it has a high refractive index of 1.50 or more, Furthermore, 1.55 or more.

As the film thickness of an interlayer insulation film, Preferably it is 0.1 micrometer-8 micrometers, More preferably, they are 0.1 micrometer-6 micrometers, More preferably, they are 0.1 micrometer-4 micrometers. The interlayer insulating film formed from the second radiation-sensitive resin composition of the present embodiment is coated and has transparency and adhesiveness, as apparent from the examples described later.

As mentioned above, after forming an interlayer insulation film, it is preferable to have a process of forming a comb-tooth shaped pixel electrode as a 2nd electrode on the said interlayer insulation film. For example, a transparent conductive layer made of ITO can be formed on the interlayer insulating film using a sputtering method or the like. Subsequently, this transparent conductive layer can be etched using the photolithography method to form a comb-tooth shaped pixel electrode as a transparent electrode on the interlayer insulating film described above. The pixel electrode enables electrical connection with the switching active element on the substrate through the contact hole of the insulating film.

In addition to the ITO, the common electrode and the pixel electrode can be formed using a transparent material having high transmittance and conductivity to visible light. For example, it can comprise using IZO (Indium Zinc Oxide), ZnO (zinc oxide), a tin oxide, etc.

[Process [8]]

After forming a pixel electrode on the interlayer insulation film on a common electrode using the board | substrate with an insulating film and interlayer insulation film obtained at the process [7], the liquid crystal aligning agent of this embodiment is apply | coated on a pixel electrode. . Examples of the application method include a roll coater method, a spinner method, a printing method, and an ink jet method.

Subsequently, the substrate coated with the liquid crystal aligning agent is pre-baked, and then baked to form a coating film.

The prebaking condition is, for example, from 40 to 120 DEG C for 0.1 to 5 minutes. The temperature of postbaking conditions becomes like this. Preferably it is 120 degreeC-230 degreeC, More preferably, it is 150 degreeC-200 degreeC, More preferably, it is 150 degreeC-180 degreeC. The post baking time varies depending on a heating apparatus such as a hot plate or an oven, but is usually from 5 minutes to 200 minutes, and more preferably from 10 minutes to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 mu m to 1 mu m, more preferably 0.005 mu m to 0.5 mu m.

The solid content concentration (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) of the liquid crystal aligning agent used when applying the liquid crystal aligning agent is appropriately selected in consideration of viscosity, volatility, and the like. Preferably, they are 1 mass%-10 mass%.

When using the liquid crystal aligning agent containing the [L] radiation-sensitive polymer which has a photo-alignment group as a liquid crystal aligning agent, by irradiating linearly or partially polarized radiation or non-polarized radiation to the above-mentioned coating film, It gives a liquid crystal aligning ability. The irradiation of the polarized radiation corresponds to the alignment treatment of the alignment film.

As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 nm to 800 nm can be used. In particular, it is 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, irradiation may be performed from a direction perpendicular to the substrate surface, or may be performed from an inclined direction in order to give a pretilt angle, or may be performed in combination. When irradiating non-polarized radiation, the direction of irradiation needs to be inclined direction.

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

When using the liquid crystal aligning agent containing [M] polyimide which does not have a photo-alignment group as a liquid crystal aligning agent, it is also possible to use the coating film after postbaking as an oriented film. Then, if necessary, the coating film after the postbaking is subjected to a rubbing treatment (rubbing treatment) in a predetermined direction with a roll wound with a cloth made of fibers such as nylon, rayon, cotton, and the like to impart liquid crystal alignment capability. It is possible.

As described above, in the case of forming the alignment film on the array substrate, using the above-described liquid crystal aligning agent, the alignment film at a heating temperature of 200 ° C. or lower, and optionally 180 ° C. or lower by forming on the resin substrate. It is possible to form By setting the curing temperature in the alignment film forming step to such a low temperature, the insulating film formed in the above-described steps [1] to [4] and the interlayer insulating film formed in the steps [5] to [7] are subjected to a high temperature in the forming step of the alignment film. Exposure to the condition can be avoided.

[Example]

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

<Preparation of a 1st radiation sensitive resin composition>

Synthesis Example 1

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

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 13 parts by mass of methacrylic acid, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of α-methyl-p-hydroxystyrene, 10 parts by mass of styrene, 12 parts by mass of tetrahydrofurfuryl methacrylate, and N- 15 parts by mass of cyclohexyl maleimide and 10 parts by mass of n-lauryl methacrylate were added, and after nitrogen-substituting, the temperature of the solution was raised to 70 ° C. with gentle stirring, and the temperature was maintained for 5 hours to polymerize. And the solution containing copolymer (A-I) were obtained. Solid content concentration of the obtained polymer solution was 31.9 mass%, Mw of the copolymer (A-I) was 8,000 and molecular weight distribution (Mw / Mn) was 2.3. In addition, solid content concentration means the ratio of the copolymer mass to the total mass of a polymer solution.

Synthesis Example 2

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

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 300 parts by mass of diethylene glycol methylethyl ether were added, followed by 23 parts by mass of methacrylic acid, 10 parts by mass of styrene, and meta 32 mass parts of benzyl acrylate, 35 mass parts of methyl methacrylates, and 2.7 mass parts of (alpha) -methylstyrene dimers as a molecular weight regulator are put, and the temperature of a solution is raised to 80 degreeC, stirring gently, and this temperature is preserve | saved for 4 hours. After hold | maintaining, it heated up at 100 degreeC, preserve | saved and maintained this temperature for 1 hour, and obtained the solution containing a copolymer (solid content concentration = 24.9 mass%). The Mw of the obtained copolymer was 12,500. Subsequently, 1.1 mass part of tetrabutylammonium bromide and 0.05 mass part of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and after stirring for 30 minutes at 90 degreeC under air atmosphere, glycidyl methacrylate. The copolymer (A-II) was obtained by making 16 mass parts and reacting for 10 hours with 90 degreeC (solid content concentration = 29.0 mass%). Mw of the copolymer (A-II) was 14,200.

Synthesis Example 3

[Synthesis of alkali-soluble resin (a-I) having no polymerizable group]

In order to use for the comparative example mentioned later, alkali-soluble resin (a-I) which does not have a polymeric group was synthesize | combined as follows.

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 220 parts by mass of diethylene glycol methyl ethyl ether were placed. Subsequently, 20 mass parts of methacrylic acid, 50 mass parts of benzyl methacrylate, 20 mass parts of methyl methacrylate, and 10 mass parts of styrene are put, and after nitrogen-substituting, the temperature of a solution is raised to 80 degreeC, stirring gently. The solution containing the copolymer (a-I) was obtained by preserving and polymerizing this temperature for 5 hours. Solid content concentration of the obtained polymer solution was 31.0 mass%, Mw of the copolymer (a-I) was 10,000, and molecular weight distribution (Mw / Mn) was 2.2.

Example 1

[Preparation of Positive First Radiation-Resistant Resin Composition]

[A] Component (alkali-soluble resin), the amount of the solution containing the copolymer (A-I) of Synthesis Example 1 in an amount corresponding to 100 parts by mass of the copolymer (solid content) and the component [B] (quinonediazide) 30 mass parts of 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) as a compound), and [E] component ( 2 parts by mass of benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate as a thermal acid generator) was dissolved in diethylene glycol ethyl methyl ether so that the solid content concentration was 30% by mass, and then Millipore having a pore diameter of 0.2 µm. It filtered by the filter and prepared the 1st radiation sensitive resin composition.

Example 2

[Preparation of Negative First Radiation-Resistant Resin Composition]

As component [A], the solution containing the copolymer (A-I) of the synthesis example 1 contains the copolymer (A-II) of the synthesis example 2 in the quantity corresponded to 10 mass parts (solid content) of a copolymer. The solution was used in an amount corresponding to 100 parts by mass of a copolymer (solid content) and a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate as the component [C] (polymerizable compound) (KAYARAD (registered trademark)). 100 parts by mass of DPHA (above Nippon Kayaku Co., Ltd.) and ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carrha as a component (D) (radiation-sensitive polymerization initiator) 5 parts by mass of bazol-3-yl] -1- (O-acetyloxime) (IRUGACURE OXE02, BASF) and 4,4'-diaminodi as the [F] component (curing accelerator) After mixing phenyl sulfone and adding propylene glycol monomethyl ether acetate so that solid content concentration may be 30 mass%, respectively, it is filtered by the millipore filter of 0.5 micrometer of pore diameters, and a 1st prison cell A diagonal resin composition was prepared.

Comparative Example 1

[Preparation of negative radiation sensitive resin composition]

An amount corresponding to 100 parts by mass of the copolymer (a solid content) of the solution containing the copolymer (a-I) of Synthesis Example 3, which is an alkali-soluble resin having no polymerizable group, as the component [A] and the component [C] 100 parts by mass of a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD® DPHA (above, Nippon Kayaku Co., Ltd.) and ethanone-1- as [D] component 5 parts by mass of [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (irgacure OXE02, BASF Co.), Propylene glycol monomethyl ether acetate was added so that it might become 30 mass%, and the radiation sensitive resin composition which is a comparative example was prepared by filtering by the millipore filter of 0.5 micrometer of pore diameters.

<Formation and Evaluation of Insulating Film>

Example 3

[Insulating Film Formed with Positive First Radiation-Resistant Resin Composition]

On the alkali free glass substrate, after apply | coating the 1st radiation sensitive resin composition prepared in Example 1 with the spinner, the coating film of 4.0 micrometers in thickness was formed by prebaking on 100 degreeC hotplate for 2 minutes. Subsequently, the obtained coating film was irradiated with an exposure amount of 1000 J / m <2> using the high pressure mercury lamp, and image development was performed for 25 second and 80 second in 0.4 mass% of tetramethylammonium hydroxide aqueous solution. Subsequently, post-baking was performed in an oven at a curing temperature of 230 DEG C and a curing time of 30 minutes to form an insulating film.

Example 4

[Insulating Film Formed with Negative First Radiation Resin Composition]

After apply | coating the solution of the 1st radiation sensitive resin composition prepared in Example 2 with the spinner on the alkali free glass substrate, the coating film of 4.0 micrometers in thickness was formed by prebaking on 90 degreeC hotplate for 2 minutes. Subsequently, the resulting coating film was irradiated with a high-pressure mercury lamp at an exposure dose of 700 J / m 2, and a 0.40 mass% aqueous potassium hydroxide solution at 23 캜 was developed with a developing solution. Subsequently, post baking was performed in an oven at a curing temperature of 180 캜 and a curing time of 30 minutes to form an insulating film.

Comparative Example 2

[Insulator film formed of negative radiation sensitive resin composition]

A solution of the radiation sensitive resin composition prepared in Comparative Example 1 was coated on a non-alkali glass substrate by a spinner and prebaked on a hot plate at 90 캜 for 2 minutes to form a coating film having a film thickness of 4.0 탆. Subsequently, the obtained coating film was irradiated with an exposure amount of 1200 J / m <2> using a high pressure mercury lamp, and image development was performed using the 23 degreeC 0.40 mass% potassium hydroxide aqueous solution as a developing solution. Next, the insulating film was formed by post-baking in 230 degreeC hardening temperature and 60 minute hardening time in oven.

Example 5

[Evaluation of heat resistance]

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

Similarly, about the insulating film by the formation method of Example 4, it heats further at 230 degreeC in oven for 20 minutes, and measures the film thickness before and behind this heating with a stylus film thickness meter (alpha step IQ, KLA Tencor company). did. And the residual film ratio ((film thickness after processing / film thickness before processing)) * 100 was calculated, and this residual film ratio was made into heat resistance. The residual film ratio was 99%, and the heat resistance was judged to be good.

Similarly, about the insulating film by the formation method of the comparative example 2, it heats at 230 degreeC for 20 minutes further in oven, and measures the film thickness before and behind this heating with a stylus film thickness meter (alpha step IQ, KLA Tencor company). did. And the residual film ratio ((film thickness after processing / film thickness before processing)) * 100 was calculated, and this residual film ratio was made into heat resistance. The residual film ratio was 80%, and the heat resistance was judged to be defective.

Example 6

[Evaluation of Light Resistance]

About the insulating film by the formation method of Example 3, 800,000J / m <2> ultraviolet-rays were irradiated with the irradiance of 130mW using UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation) further, and the film | membrane reduction amount after irradiation was Investigated. The film reduction amount was 2% or less, and judged that light resistance was favorable.

Similarly, the insulating film by the formation method of Example 4 was further irradiated with ultraviolet light of 800,000 J / m 2 at an illuminance of 130 mW using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), and the film after irradiation The amount of reduction was investigated. The film reduction amount was 2% or less, and judged that light resistance was favorable.

Similarly, about the insulating film by the formation method of the comparative example 2, 800,000J / m <2> ultraviolet-rays were irradiated with 130mW illuminance using a UV irradiation apparatus (UVX-02516S1JS01, Ushio Corporation), and the film reduction amount after irradiation Investigated. It was judged that the film reduction amount was 5% or more and the light resistance was bad.

From the above evaluation results, it turned out that the insulating film manufactured using the 1st radiation sensitive resin composition prepared in Example 1 and Example 2 can be used suitably as an insulating film of the array substrate of a liquid crystal display element.

<Preparation of 2nd radiation sensitive resin composition>

Synthesis Example 4

[Synthesis of Copolymer (α)]

The synthesis | combination of the copolymer ((alpha)) which is a [X] polymer used as a component of a 2nd radiation sensitive resin composition was performed as follows.

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were added, followed by 55 parts by mass of methacrylic acid and 45 parts by mass of benzyl methacrylate. Part, and 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator were added and the temperature of the solution was raised to 80 ° C. while gently stirring, and the temperature was maintained at 4 ° C. for 4 hours, and then the temperature was raised to 100 ° C. The solution containing a copolymer was obtained by hold | maintaining and polymerizing for 1 hour. Subsequently, 1.1 mass part of tetrabutylammonium bromide and 0.05 mass part of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and after stirring for 30 minutes at 90 degreeC under air atmosphere, glycidyl methacrylate. The copolymer ((alpha)) was obtained by making 74 mass parts and reacting for 10 hours with 90 degreeC (solid content concentration = 35.0 mass%). Mw of the copolymer (α) was 9000.

At this time, the content of the above (X1) structural unit in the copolymer (α) obtained from the ¹ H-NMR, FT-IR has been 37.5㏖%.

Synthesis Example 5

[Synthesis of Copolymer (β)]

The synthesis | combination of the copolymer ((beta)) which is [X] polymer was performed as follows.

In a flask equipped with a cooling tube and a stirrer, 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate were added, followed by 85 parts by mass of methacrylic acid and 15 parts by mass of benzyl methacrylate. Part, and 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator were added and the temperature of the solution was raised to 80 ° C. while gently stirring, and the temperature was maintained at 4 ° C. for 4 hours, and then the temperature was raised to 100 ° C. The solution containing a copolymer was obtained by hold | maintaining and polymerizing for 1 hour. Subsequently, 1.1 mass part of tetrabutylammonium bromide and 0.05 mass part of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and after stirring for 30 minutes at 90 degreeC under air atmosphere, glycidyl methacrylate. The copolymer (β) was obtained by making 74 mass parts and reacting for 90 hours with 90 degreeC (solid content concentration = 35.5 mass%). Mw of the copolymer (β) was 10000.

At this time, the content of (X1) structural unit in the copolymer (β) determined from the ¹ H-NMR, FT-IR has been 8.5㏖%.

Synthesis Example 6

[Synthesis of Resin (γ) Having Epoxy Group]

In order to comprise a comparative example, the synthesis | combination of the copolymer ((gamma)) which is resin which has an epoxy group was performed as follows.

In a flask equipped with a cooling tube and a stirrer, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 220 parts by mass of diethylene glycol methylethyl ether were placed. Subsequently, 10 mass parts of methacrylic acid, 40 mass parts of glycidyl methacrylate, and 50 mass parts of methyl methacrylates were put, and after nitrogen-substituting, the temperature of a solution was raised to 70 degreeC, stirring gently, and this temperature The solution containing the copolymer ((gamma)) was obtained by hold | maintaining and polymerizing for 5 hours. Solid content concentration of the obtained polymer solution was 31.9 mass%, Mw of the copolymer ((gamma)) was 9000, and molecular weight distribution (Mw / Mn) was 2.3.

Example 7

[Preparation of 2nd radiation sensitive resin composition]

3 parts by mass of polyoxyethylene alkyl phosphate ester as a dispersant and 90 parts by mass of methyl ethyl ketone as a dispersion medium were mixed, and 7 parts by mass of zirconium oxide particles (ZrO ₂ particles) as the [Y] component (metal oxide particles) while stirring with a homogenizer. It was added slowly over about 10 minutes. After the addition of the zirconium oxide particles, the mixture was stirred for about 15 minutes. The obtained slurry was dispersed using an SC mill to obtain a ZrO ₂ particle dispersion.

[415] 415 parts by mass of the ZrO ₂ particle dispersion and [Z] component in a solution (amount corresponding to 100 parts by mass of a copolymer (solid content)) containing a copolymer (α) synthesized in Synthesis Example 4 as the polymer [X] 100 mass parts of succinic acid modified pentaerythritol triacrylate ("Aronix (trademark) TO-756" by Toagosei Co., Ltd.) as polyfunctional acrylate 1 which is polyfunctional acrylate), [W] component (persimmon 3 mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (made by Chiba Specialty Chemicals, Irgacure (registered trademark) 907) as a radiation polymerization initiator) Subsequently, 0.3 mass part of SH8400 FLUID (made by Toray Dow Corning Silicone Co., Ltd.) was added as silicone type surfactant, and the 2nd radiation sensitive resin composition was prepared.

Example 8

[Preparation of 2nd radiation sensitive resin composition]

In Example 8, the TiO ₂ particle dispersion was adjusted in the same manner as in Example 7, except that TiO ₂ particles were used in place of the zirconium oxide particles (ZrO ₂ particles) as the [Y] component (metal oxide particles). . Subsequently, using this TiO ₂ particle dispersion, MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.) as polyfunctional acrylate 2 was used as the [Z] component (polyfunctional acrylate). It was made to prepare the 2nd radiation sensitive resin composition.

Example 9

[Preparation of 2nd radiation sensitive resin composition]

In the ninth embodiment, in the same manner as in [Y] component (metal oxide particles) embodiment except for using barium titanate particles in place of the zirconium oxide particles (ZrO ₂ particles), as in Example 7 was adjusted barium titanate particle dispersion . Subsequently, using this barium titanate particle dispersion, MAX-3510 (manufactured by Nippon Kayaku Co., Ltd.) as polyfunctional acrylate 2 was used as the [Z] component (polyfunctional acrylate). It was made to prepare the 2nd radiation sensitive resin composition.

Example 10

[Preparation of 2nd radiation sensitive resin composition]

In Example 10, a ZrO ₂ particle dispersion obtained in the same manner as in Example 7 was used.

[415] 415 parts by mass of the ZrO ₂ particle dispersion and [Z] component in a solution (amount equivalent to 100 parts by mass of a copolymer (solid content)) containing a copolymer (β) synthesized in Synthesis Example 5 as the polymer [X] 100 mass parts of MAX-3510 (made by Nippon Kayaku Co., Ltd.) as polyfunctional acrylate 2 which is polyfunctional acrylate), and 2-methyl-1- (4-methyl as a [W] component (radiation-sensitive polymerization initiator) Thiophenyl) -2-morpholinopropane-1-one (made by Chiba Specialty Chemicals Co., Ltd., Irgacure (registered trademark) 907) 3 parts by mass, a surfactant of the silicone-based SH8400 FLUID (Torda Dou Corning Silicone Co., Ltd.) 0.3 mass parts) was prepared, and the 2nd radiation sensitive resin composition was prepared.

Comparative Example 3

[Preparation of radiation sensitive resin composition]

In this comparative example 3, the ZrO ₂ particle dispersion liquid obtained by the method similar to Example 7 was used.

415 parts by mass of the ZrO ₂ particle dispersion and the [Z] component (in an amount corresponding to 100 parts by mass of the copolymer (solid content)) containing the copolymer (γ) synthesized in Synthesis Example 6 as the polymer [X] 100 mass parts of succinic acid modified pentaerythritol triacrylate ("Aronix (trademark) TO-756" by Toagosei Co., Ltd.) as polyfunctional acrylate 1 which is polyfunctional acrylate), [W] component (persimmon 3 mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (made by Chiba Specialty Chemicals, Irgacure (registered trademark) 907) as a radiation polymerization initiator) In addition, 0.3 mass part of SH8400 FLUID (made by Toray Dow Corning Silicone Co., Ltd.) was added as silicone type surfactant, and the radiation sensitive resin composition which is a comparative example was prepared.

Comparative Example 4

[Preparation of radiation sensitive resin composition]

In this comparative example 4, the radiation sensitive resin composition was prepared without containing the [Y] component (metal oxide particle).

Polyfunctional acrylic which is a [Z] component (polyfunctional acrylate) in the solution (quantity equivalent to 100 mass parts (solid content) of a copolymer) containing the copolymer (alpha) synthesize | combined by the synthesis example 4 as a [X] polymer. As a rate 1, 100 mass parts of succinic acid modified pentaerythritol triacrylate ("Aronix (trademark) TO-756" by Toagosei Co., Ltd.), 2-methyl as a [W] component (radiation-sensitive polymerization initiator) SH8400 FLUID as 3 parts by mass of -1- (4-methylthiophenyl) -2-morpholinopropane-1-one (manufactured by Chiba Specialty Chemicals, Irgacure (registered trademark) 907) and a silicone-based surfactant (Trade Dow Corning Silicone Co., Ltd. product) 0.3 mass part was added, and the radiation sensitive resin composition which is a comparative example was prepared.

Example 11

[Evaluation of Curing Film]

Using the 2nd radiation sensitive resin composition prepared in Examples 7-10, and the radiation sensitive resin composition prepared in Comparative Examples 3-4, the cured film was formed as follows and the characteristic was evaluated.

(Evaluation of transmittance)

The radiation sensitive property prepared by the 2nd radiation sensitive resin composition prepared in Examples 6-9 by the glass substrate ("CORNING (trademark) 7059" (made by Corning Corporation)), and the comparative examples 3-4. After apply | coating a resin composition using a spinner, it prebaked at 90 degreeC for 2 minutes on the hotplate, and formed the coating film. Subsequently, irradiation (hereinafter also referred to as "exposure") was carried out using a Canon® PLA (registered trademark) -501F exposure machine (ultra-high pressure mercury lamp), and development was carried out using an aqueous potassium hydroxide solution having a concentration of 0.05% by mass. . After drying, the light transmittance of the wavelength of 400 nm-800 nm was measured about the glass substrate in which this cured film was formed using the spectrophotometer "150-20 type double beam" (made by Hitachi Seisakusho Co., Ltd.), About each glass substrate, the lowest value (it is also called minimum light transmittance) of the light transmittance of the range of 400 nm-800 nm of wavelengths was evaluated. And when the light transmittance in wavelength 400nm was made into the criteria of evaluation, and the light transmittance in wavelength 400nm is 85% or more, it was judged that the light transmittance characteristic was especially favorable. The evaluation result was put together in Table 1 mentioned later as "transmittance (%) of a cured film".

As for the cured film obtained using the 2nd radiation sensitive resin composition prepared in Examples 7-10, and the radiation sensitive resin composition prepared in Comparative Example 4, the light transmittance in wavelength 400nm is 90% or more, and the light transmittance The characteristic was especially good. In the cured film obtained using the radiation sensitive resin composition prepared in Comparative Example 3, the light transmittance at a wavelength of 400 nm was 83%, and good light transmittance characteristics could not be obtained.

(Evaluation of refractive index)

In the method described above (evaluation of transmittance), using the second radiation-sensitive resin composition prepared in Examples 7 to 10 and the radiation-sensitive resin composition prepared in Comparative Examples 3 to 4 using an Abbe refractometer. Therefore, the refractive index in 25 degreeC and the 633 nm light beam of the obtained cured film was measured. The evaluation result was put together in Table 1 shown later as "the refractive index of a hardened film (633 nm)."

(Evaluation of Patterning)

Using the second radiation-sensitive resin composition prepared in Examples 7 to 10 and the radiation-sensitive resin composition prepared in Comparative Examples 3 to 4, each of the coating films in the same manner as described above (evaluation of transmittance) Formed. Subsequently, exposure was performed with respect to the coating film obtained on the obtained glass substrate through the mask which has a pattern of 5 cm x 8 cm using Canon Co., Ltd. PLA (trademark) -501F exposure machine (ultra high pressure mercury lamp). Then, it developed in 25 degreeC and 60 second in 0.05 mass% of potassium hydroxide aqueous solution. Subsequently, flowing water was washed with ultrapure water for 1 minute to form a patterned cured film.

The end part of each patterned cured film was observed with the optical microscope, and it was judged that patterning property was favorable when there was no image development residue and a pattern was formed in linear form.

On the other hand, when there existed image development residue in the edge part of a pattern, it judged that it was poor patterning property. The evaluation result was put together in Table 1 shown later as "patterning property". In addition, in Table 1, when it judged that patterning property was favorable, (circle) mark was attached | subjected and when it judged that it was defective, the x mark was attached.

(Evaluation of dielectric constant)

Using the second radiation-sensitive resin composition prepared in Examples 7 to 10 and the radiation-sensitive resin composition prepared in Comparative Examples 3 to 4, curing was performed on the SUS substrate by the method described above (evaluation of transmittance). A film was produced and the electrode was further produced by aluminum evaporation thereon. The dielectric constant was measured with the LCR meter using the board | substrate with an electrode. The evaluation result was put together in Table 1 shown later as "dielectric constant of cured film (1kHz)."

Table 1 shows the compositions of the second radiation-sensitive resin composition prepared in Examples 7 to 10 and the radiation-sensitive resin composition prepared in Comparative Examples 3 to 4, and the evaluation results of the cured films produced using them. Are summarized. In addition, "-" in the composition column of Table 1 shows that the corresponding component was not used.

As shown in Table 1, the cured film manufactured using the 2nd radiation sensitive resin composition prepared in Examples 7-10, and the radiation sensitive resin composition prepared in Comparative Example 4 has the outstanding patterning property, respectively. On the other hand, the cured film manufactured using the radiation sensitive resin composition prepared in the comparative example 3 was inferior in patterning property.

In addition, the cured film manufactured using the 2nd radiation-sensitive resin composition prepared in Examples 7-10, and the radiation-sensitive resin composition prepared in Comparative Example 3 all showed high refractive index of 1.6 or more. In the cured film manufactured using the radiation sensitive resin composition prepared in the comparative example 4, the refractive index exceeding 1.55 was not able to be obtained.

As mentioned above, it turned out that the cured film manufactured using the 2nd radiation sensitive resin composition prepared in Examples 7-10 can be used suitably as an interlayer insulation film of the array substrate of a liquid crystal display element.

<Production of Array Substrate>

Example 12

The solution of the 1st radiation sensitive resin composition obtained by Example 1 was apply | coated with the slit die coater on the board | substrate with which the active element, an electrode, etc. were formed.

An active element or the like (semiconductor layer, gate electrode, gate insulating film, source-drain electrode, video signal line, scan signal line, etc.) is formed on the substrate. These active elements and the like are formed in accordance with a known method, such as normal semiconductor film deposition, known insulating layer formation, etc., and etching by a photolithography method are repeated on a substrate.

Next, by the formation method of Example 3, the insulating film in which the contact hole was formed was formed.

Next, the sputtering method was used for the board | substrate with an insulating film, and the transparent conductive layer which consists of ITO was formed on the insulating film. Next, the transparent conductive layer was etched using the photolithography method to form a common electrode of uniform shape on the insulating film.

Then, using the 2nd radiation sensitive resin composition prepared in Example 7, it is the same as that of the cured film of Example 11 mentioned above on the surface of the board | substrate with which the common electrode of the uniform shape was formed on the insulating film. The coating film was formed in accordance with the method. Subsequently, the coating film on the obtained board | substrate was exposed through the mask which has a predetermined | prescribed pattern using Canon (trademark) PLA-501F exposure machine (ultra high pressure mercury lamp) by a Canon Corporation. Then, it developed in 25 degreeC and 60 second in 0.05 mass% of potassium hydroxide aqueous solution. Subsequently, flowing water was washed for 1 minute with ultrapure water, and a patterned interlayer insulating film was formed on the surface of the substrate on which the common electrode was formed.

Next, the transparent conductive layer which consists of ITO was formed on the interlayer insulation film using the sputtering method. Subsequently, this transparent conductive layer was etched using the photolithography method, and the comb-tooth shaped pixel electrode was formed on the inorganic insulating film.

Thus, the array substrate of this embodiment was manufactured. In the obtained array substrate of the present embodiment, contact holes having a desired size are formed at desired positions of the insulating film, and electrical connection between the pixel electrode and the source-drain electrode of the active element is realized.

Example 13

The solution of the 1st radiation sensitive resin composition obtained by Example 2 was apply | coated with the slit die coater on the board | substrate with which the active element, electrode, etc. similar to Example 12 were formed.

Next, by the formation method of Example 4, the insulating film in which the contact hole was formed was formed.

Next, the sputtering method was used for the board | substrate with an insulating film, and the transparent conductive layer which consists of ITO was formed on the insulating film. Next, the transparent conductive layer was etched using the photolithography method to form a common electrode of uniform shape on the insulating film.

Thereafter, using the second radiation-sensitive resin composition prepared in Example 7, the surface of the substrate on which the common electrode of uniform shape was formed on the insulating film was the same as that of the cured film of Example 11 described above (evaluation of transmittance). The coating film was formed in accordance with the method. Subsequently, the coating film on the obtained board | substrate was exposed through the mask which has a predetermined | prescribed pattern using Canon (trademark) PLA-501F exposure machine (ultra high pressure mercury lamp) by a Canon Corporation. Then, it developed in 25 degreeC and 60 second in 0.05 mass% of potassium hydroxide aqueous solution. Subsequently, flowing water was washed with ultrapure water for 1 minute to form a patterned interlayer insulating film on the surface of the substrate where the common electrode was formed.

Next, the transparent conductive layer which consists of ITO was formed on the interlayer insulation film using the sputtering method. Subsequently, this transparent conductive layer was etched using the photolithography method, and the comb-tooth shaped pixel electrode was formed on the inorganic insulating film.

Comparative Example 5

Using the solution of the negative radiation sensitive resin composition obtained by the comparative example 1, it apply | coated with the slit die coater on the board | substrate with which switching active element, electrode, etc. similar to Example 12 were formed.

Next, an insulating film in which a contact hole was formed was formed by the forming method of Comparative Example 2.

Next, the sputtering method was used for the board | substrate with an insulating film, and the transparent conductive layer which consists of ITO was formed on the insulating film. Next, the transparent conductive layer was etched using the photolithography method to form a common electrode of uniform shape on the insulating film.

Then, after forming a SiN film by CVD on a common electrode, desired patterning was performed using the photolithographic method etc., and the interlayer insulation film was formed as an inorganic insulation film.

Next, the transparent conductive layer which consists of ITO was formed on the interlayer insulation film using the sputtering method. Subsequently, this transparent conductive layer was etched using the photolithography method, and the comb-tooth shaped pixel electrode was formed on the inorganic insulating film.

As described above, an array substrate was manufactured in the same manner as in Example 12, Example 13, and Comparative Example 5. In all of the obtained array substrates, contact holes having a desired size were formed at desired positions of the insulating film, and electrical connection between the pixel electrode and the source-drain electrode of the switching active element was realized.

Example 14

<Evaluation of Peeling Between Common Electrode and Inorganic Insulating Film on Array Substrate>

After performing the pressure cooker test (120 degreeC, 100% of humidity, 4 hours) with respect to the array board | substrate manufactured by Example 12, Example 13, and the comparative example 5, SEM (scanning electron microscope) of the cross-sectional structure of an array board | substrate. Observed. These array substrates had the structure shown in FIG. 2, and the presence or absence of peeling between the common electrode 14 and the interlayer insulation film 33 shown in FIG. 2 was observed by SEM.

As a result of SEM observation, peeling could not be confirmed in the array substrates of Examples 12 and 13, but peeling was confirmed in the array substrates of Comparative Example 5.

Example 15

[Production (1) of Array Substrate with Photoalignment Film]

Using the array substrate obtained in Example 12, the photoalignment film was formed using the liquid crystal aligning agent containing the radiation sensitive polymer which has a photoalignment group.

First, the liquid crystal aligning agent A as described in Example 6 of the international publication (WO) 2009/025386 pamphlet as a liquid crystal aligning agent containing the radiation sensitive polymer which has a photo-alignment group on the transparent electrode of the array substrate of Example 12. -1 is applied by a spinner. Subsequently, after prebaking was performed for 1 minute on the 80 degreeC hotplate, it heated at 180 degreeC for 1 hour in the oven which carried out the nitrogen substitution inside, and formed the coating film of 80 nm in film thickness. Subsequently, the coating film surface was irradiated with a polarized ultraviolet ray of 200 J / m 2 containing 313 nm of bright lines using a Hg-Xe lamp and a retainer prism in a direction inclined at 40 ° with respect to the direction perpendicular to the substrate surface, so as to provide light. An array substrate having an alignment film was produced.

Example 16

[Production (2) of Array Substrate with Photoalignment Film]

Using the array substrate obtained in Example 13, using a liquid crystal aligning agent containing a radiation sensitive polymer having the same photoalignment group as in Example 15, a photoalignment film was formed in the same manner as in Example 15 to form a photoalignment film. An array substrate having was prepared.

<Manufacture of Liquid Crystal Display Element>

Example 17

First, the color filter substrate manufactured by the well-known method was prepared. In this color filter substrate, a fine color pattern of three colors of red, green and blue and a black matrix are arranged in a lattice shape on the transparent substrate.

Next, on the coloring pattern of a color filter substrate and a black matrix, the same photo-alignment film as what was formed on the array substrate in Example 15 was formed. The liquid crystal layer was sandwiched by the obtained color filter substrate with an optical alignment film and the array substrate obtained in Example 15 to manufacture a color liquid crystal display element. As a liquid crystal layer, what consists of nematic liquid crystals and orientates parallel to a board | substrate surface was used. This liquid crystal display element had the same structure as the liquid crystal display element shown in FIG. 3 mentioned above, and showed the outstanding operating characteristic, display characteristic, and reliability.

Example 18

The same color filter substrate as in Example 17 was prepared. Next, on the coloring pattern of this color filter substrate and the black matrix, the same photo-alignment film as what was formed on the array substrate in Example 16 was formed. By the obtained photo-alignment film color filter substrate and the array substrate obtained in Example 16, the liquid crystal layer was clamped similarly to Example 17, and the color liquid crystal display element was manufactured. This liquid crystal display element had the same structure as the liquid crystal display element shown in FIG. 3 mentioned above similarly to Example 17, and showed the outstanding operation characteristic, display characteristic, and reliability.

In addition, this invention is not limited to each said embodiment, In the range which does not deviate from the meaning of this invention, various deformation | transformation can be implemented.

For example, the array substrate of the present embodiment uses a bottom gate type TFT element as an active element, but is not limited to the bottom gate type, and it is also possible to apply and use a top gate type TFT element.

The array substrate of the present invention can be manufactured by a low-temperature heat treatment, and the liquid crystal display device manufactured using this array substrate has high reliability. Therefore, the array substrate and the liquid crystal display element of the present invention are suitable for use in a large-sized liquid crystal television or the like requiring excellent image quality and reliability.

1: array board
4, 11: substrate
5: Video signal line
5a: a second source-drain electrode
6: first source-drain electrode
7: scanning signal line
7a: gate electrode
8: active element
8a: semiconductor layer
9: pixel electrode
10: Orientation film
12: Insulating film
13: black matrix
15: coloring pattern
14: common electrode
17: Contact hole
22: Color filter substrate
23: liquid crystal layer
27: backlight light
28: polarizing plate
31: gate insulating film
32: inorganic insulating film
33: interlayer insulation film
41 liquid crystal display element

Claims (14)

The active element,
A first insulating film formed on the active element,
An array substrate having a common electrode and a pixel electrode formed on the first insulating film,
An array substrate having a second insulating film between the common electrode and the pixel electrode, wherein the second insulating film is an organic insulating film. The method of claim 1,
The second insulating film,
[X] polymers,
[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,
[Z] polyfunctional acrylate,
[W] radiation sensitive polymerization initiator
It is formed using the radiation sensitive resin composition containing the array substrate. 3. The method of claim 2,
The oxide particles are particles of titanate salts. 3. The method of claim 2,
[X] An array substrate, wherein the polymer is a polymer including a structural unit having a (X1) aromatic ring and a structural unit having a (X2) (meth) acryloyloxy group. 5. The method of claim 4,
Content of the structural unit which has a (X1) aromatic ring in [X] polymer is 20 mol%-90 mol% of the whole [X] polymer, The array substrate characterized by the above-mentioned. The method according to any one of claims 1 to 5,
The common electrode and the pixel electrode are formed in this order on the first insulating film,
And the pixel electrode has a comb-tooth shape and is electrically connected to the active element via a contact hole formed in the first insulating film. The method according to any one of claims 1 to 5,
The second insulating film has an index of refraction of 1.55 to 1.85 at a wavelength of 633 nm. The method according to any one of claims 1 to 5,
The second insulating film has an optical transmittance of 85% or more at a wavelength of 400 nm. It has an array substrate in any one of Claims 1-5, The liquid crystal display element characterized by the above-mentioned. As a radiation sensitive resin composition used for formation of the said 2nd insulating film of the array substrate as described in any one of Claims 1-5,
[X] polymers
[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,
[Z] polyfunctional acrylate,
[W] radiation sensitive polymerization initiator
A radiation-sensitive resin composition comprising a. The method of claim 10,
The said oxide particle is a particle | grain of a titanate salt, The radiation sensitive resin composition characterized by the above-mentioned. The active element,
A first insulating film formed on the active element,
An array substrate having a first electrode and a second electrode, one of which is a common electrode and the other of which is a pixel electrode, on the first insulating film, and a second insulating film disposed between the first electrode and the second electrode. As a manufacturing method of
The step of forming the first insulating film has at least the following steps [1] to Step [4], and the step of forming the second insulating film has at least the following steps [5] to Step [7]. Characterized in that the manufacturing method of the array substrate:
[1] a step of forming a coating film of a first radiation-sensitive resin composition containing a polymer containing a structural unit having a carboxyl group and a structural unit having a polymerizable group on a substrate on which the active element is formed;
[2] irradiating at least a portion of the coating film of the first radiation-sensitive resin composition with radiation;
[3] forming a contact hole by developing a coating film irradiated with radiation in step [2];
[4] a step of thermosetting the coating film obtained in step [3];
[5] On the substrate having the first insulating film formed using Steps [1] to [4],
[X] A polymer comprising a structural unit having a (X1) aromatic ring, a structural unit having a (X2) (meth) acryloyloxy group,
[Y] oxide particles of at least one metal selected from the group consisting of aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium,
[Z] polyfunctional acrylates, and
[W] forming a coating film of the second radiation-sensitive resin composition containing a radiation-sensitive polymerization initiator,
[6] a step of irradiating at least a portion of the coating film of the second radiation sensitive resin composition formed in step [5], and
[7] A step of developing a coating film irradiated with radiation in step [6]. The method of claim 12,
The said oxide particle is a particle | grain of a titanate salt, The manufacturing method of the array substrate characterized by the above-mentioned. The method according to claim 12 or 13,
The said 1st radiation sensitive resin composition contains a thermal acid generator, The manufacturing method of the array substrate characterized by the above-mentioned.

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