JP2022068916A - Liquid crystal display element, liquid crystal display element manufacturing method, and radiation-sensitive resin composition - Google Patents

Abstract

To provide an ADS mode liquid crystal display element that improves display reliability, while reducing light leakage on data wiring.SOLUTION: An ADS (Advanced-super dimension switch) mode liquid crystal display element has a liquid crystal 13 sandwiched between a first substrate 1 and a second substrate 2, in which these substrates are arranged facing each other. The first substrate 1 has a resin transparent structure 16 above data wiring 3, and the second substrate 2 has a color filter 11.SELECTED DRAWING: Figure 4

Description

The present invention relates to a liquid crystal display element, a method for manufacturing a liquid crystal display element, and a radiation-sensitive resin composition.

For liquid crystal displays, especially liquid crystal display panels for large televisions, the viewing angle, transmittance, response time, etc. are important performance indicators. As liquid crystal display modes for improving the values of these performance indicators, PSA (Polymer Sustained Alignment) mode, IPS (In Plane Switching) mode, FFS (Fringe Field Switching) mode, ADS (Advanced-super dimension switch) mode Various modes such as are being developed. At present, large-sized TVs using these liquid crystal display mode technologies are mass-produced.

In recent years, higher-definition 4K (pixels 3840 x 2160) and 8K (pixels 7680 x 4320) are being realized from the conventional high-definition television (pixels 1920 x 1080). However, in a 4K or 8K liquid crystal display panel, the panel transmittance tends to decrease due to an increase in the number of wirings and switching elements. When the panel transmittance decreases, the light utilization efficiency of the backlight decreases, which leads to an increase in power consumption.
The liquid crystal display panel of the lateral electric field drive system such as the IPS mode, the FFS mode, and the ADS mode has a wide viewing angle, a fast response speed, and a high contrast ratio, and is therefore a mode that has attracted particular attention in recent years.

However, due to the structure of the ADS mode element, it is known that an electric field is generated from the data wiring in the vicinity of the data wiring and light leakage occurs, and in order to prevent this display defect, the portion is covered with a black matrix (BM). This is one of the factors that reduce the aperture ratio.

On the other hand, in the ADS mode, a technique is known in which a black post spacer (BPS) is arranged directly above the data wiring to prevent light leakage in the vicinity of the data wiring (see, for example, Non-Patent Document 1). However, since it is necessary to install the BPS, there are problems that the manufacturing process becomes complicated and the display reliability due to the BPS itself.

H. Wang, SID 2019 DIGEST, 711-712

In the ADS mode liquid crystal display element, it has been difficult to realize good display reliability while preventing light leakage in the vicinity of the data wiring. In addition, there is an increasing demand for reducing the complexity of the manufacturing process and achieving high throughput.

The present invention has been made in view of the above problems. That is, an object of the present invention is to provide an ADS mode liquid crystal display element having improved display reliability while reducing light leakage in the vicinity of data wiring.

Further, an object of the present invention is to form a transparent resin film having a thicker film thickness directly above the data wiring and having an opening pattern on some source / drain electrodes in the manufacture of the ADS mode liquid crystal display element. It is an object of the present invention to provide the manufacturing method of the liquid crystal display element.

Another object of the present invention is to provide a radiation-sensitive resin composition used for forming a resin transparent structure above a data wiring in manufacturing the ADS mode liquid crystal display element.

Other objects and advantages of the present invention will become apparent from the description below.

A first aspect of the present invention is an ADS mode liquid crystal display element in which a liquid crystal display is sandwiched between a first substrate and a second substrate arranged to face each other.
The first substrate has a transparent resin structure above the data wiring.
The second substrate relates to an ADS mode liquid crystal display element characterized by having a color filter.

The second aspect of the present invention is
(1) A coating film forming step of forming a coating film of a radiation-sensitive resin composition on the first substrate,
(2) An exposure step of irradiating the coating film with radiation using at least one selected from a halftone mask and a gray tone mask.
It has a developing step of (3) developing the coating film irradiated with the radiation, and (4) a heating step of heating the developed coating film, and the place directly above the data wiring is on the first substrate. The present invention relates to a method for manufacturing a liquid crystal display element in the ADS mode, which is thicker than the film and forms a transparent resin film having an opening pattern on some source / drain electrodes.
Further, from (5) an etching step of etching the substrate having the heated coating film using at least one selected from dry etching and wet etching, and further (6) a halftone and gray tone mask on the substrate. A step of removing a film at a site irradiated with at least one of the selected sites using at least one selected from dry etching and basic chemical treatment.
The present invention relates to a method for manufacturing a liquid crystal display element in the ADS mode, which comprises the above.

A third aspect of the present invention is an ADS mode liquid crystal display element in which a liquid crystal display is sandwiched between a first substrate and a second substrate arranged to face each other.
The first substrate has a transparent resin structure above the data wiring.
The second substrate is a radiation-sensitive resin composition used for forming the resin transparent structure of a liquid crystal display element having a color filter by irradiation with radiation using at least one selected from a halftone mask and a gray tone mask. It ’s a thing,
[A] A polymer containing a structural unit having an acidic group or a protected acidic group, and [B] a radiation-sensitive resin composition comprising a radiation-sensitive compound.

According to the first aspect of the present invention, there is provided an ADS mode liquid crystal display element having improved display reliability while reducing light leakage on data wiring.

According to the second aspect of the present invention, in manufacturing the liquid crystal display element in the ADS mode, a transparent resin having a thicker film thickness directly above the data wiring and having an opening pattern on some source / drain electrodes. A method for manufacturing a liquid crystal display element capable of forming a film is provided.

According to the third aspect of the present invention, there is provided a radiation-sensitive resin composition used for forming a resin transparent structure above a data wiring in manufacturing the liquid crystal display element in the ADS mode.

It is sectional drawing which schematically explains the periphery of the electrode of the liquid crystal display element of a general ADS mode. It is sectional drawing which schematically explains the structure of the conventional ADS element. It is sectional drawing which schematically explains the structure of the ADS element which arranged the black post spacer just above the said data wiring. It is sectional drawing which schematically explains an example of the structure of the liquid crystal display element of 1st Embodiment of this invention. It is a schematic block diagram which shows an example of the manufacturing process of the liquid crystal display element of 2nd Embodiment of this invention.

Hereinafter, a more detailed example of the structure of the liquid crystal display element according to the first embodiment of the present invention will be described with reference to the drawings. Then, a method for manufacturing the liquid crystal display element of the second embodiment of the present invention and the radiation-sensitive resin composition of the third embodiment of the present invention used thereof will be described.

In the present invention, the "radiation" irradiated at the time of exposure includes visible light, ultraviolet rays, far ultraviolet rays, X-rays, charged particle beams and the like.
Embodiment 1.
<Liquid crystal display element>
The liquid crystal display element of the first embodiment of the present invention is an ADS mode liquid crystal display element in which a liquid crystal display is sandwiched between a first substrate and a second substrate arranged to face each other, and is the first substrate. Has a resin transparent structure above the data wiring, and the second substrate has a color filter.

FIG. 1 is a cross-sectional view schematically illustrating the periphery of an electrode of a general ADS mode liquid crystal display element. In the first substrate 1, the common electrode 8 is provided on the glass substrate 7, and the gate electrode 5 is arranged on the upper layer of a part of the common electrode. After covering the present substrate with the gate insulating film 9, a TFT is formed, and further, a data wiring 3 and a source / drain electrode 4 are formed. After the substrate is covered with the passivation film 10, a passivation layer directly above a part of the source / drain electrodes is opened and electrically connected to the pixel electrode 6.

FIG. 2 is a cross-sectional view schematically illustrating the configuration of a conventional ADS element, and FIG. 3 is a cross-sectional view schematically illustrating the configuration of an ADS element in which a black post spacer is arranged directly above the data wiring (here, a common electrode, a pixel electrode, a TFT, Alignment film etc. are omitted). When the ADS element is driven, an electric field 14 is generated from the data wiring 3 to the common electrode, and the liquid crystal 13 in the vicinity of the data wiring is driven, so that light leakage occurs in the vicinity of the data wiring. In order to prevent this light leakage defect, the portion is covered with a black matrix (BM) 12. This is one of the factors that reduce the aperture ratio.
On the other hand, there is known a technique for preventing light leakage in the vicinity of the data wiring by disposing the black post spacer (BPS) 15 directly above the data wiring. However, since it is necessary to install the BPS, there are problems that the manufacturing process becomes complicated and the display reliability due to the BPS itself.

FIG. 4 is a cross-sectional view schematically illustrating an example of the configuration of the liquid crystal display element according to the first embodiment of the present invention. In the configuration of the first embodiment, the resin transparent structure 16 is arranged directly above the data wiring 3 in a general ADS element. The width of this transparent resin structure is wider than the width of the data wiring arranged directly underneath. The width of the transparent resin structure is preferably 3 μm or more and 9 μm or less than the width of the data wiring. More preferably, it has a width of 5 μm or more and 8 μm or less. The height of the transparent resin structure is preferably 1/4 or more of the thickness of the liquid crystal display sandwiched between the first substrate and the second substrate. More preferably, it is a structure having a height of 1/3 or more and 3/4 or less.
Embodiment 2.
<Manufacturing method of liquid crystal display element>
Next, a method for manufacturing the liquid crystal display element according to the second embodiment of the present invention will be described.

In the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention, the liquid crystal display element according to the first embodiment of the present invention described above can be manufactured. That is, the method for manufacturing the liquid crystal display element according to the second embodiment of the present invention is the data of the first substrate 1 of the first substrate 1 and the second substrate 2 arranged to face each other shown in FIG. This is a method for manufacturing a liquid crystal display element having a resin transparent structure 16 directly above the wiring 3 and sandwiching a liquid crystal crystal between the first substrate 1 and the second substrate 2.

As the second substrate, a facing substrate in which a black matrix 12 and a color filter 11 are formed on a glass substrate and an overcoat film or the like is formed so as to cover the color filter 11 can be used. can. Further, according to a known method, a columnar spacer can be formed on at least one substrate selected from the first substrate and the second substrate.

Regarding the method of manufacturing the liquid crystal display element of the second embodiment of the present invention, the method of forming the resin transparent structure directly above the data wiring on the first substrate, that is, directly above the data wiring, with reference to FIG. 5 as appropriate. A method for manufacturing a substrate for an ADS mode liquid crystal display element having a transparent resin structure will be described in detail.
(Manufacturing method of a substrate having a transparent resin structure)
The method for forming a resin transparent structure included in the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention preferably includes the following steps [1] to [4] in this order.

[1] The coating film forming step (hereinafter referred to as "step [1]") for forming the coating film of the radiation-sensitive resin composition of the third embodiment of the present invention, which will be described later, on the substrate to be coated shown below. There is.). Here, the substrate to be coated is a common electrode 8, a gate wiring 5, a gate insulating film 9, an active element TFT, a data wiring 3, and a common electrode 8 on an insulating substrate 7 such as a glass substrate by a known method. The source / drain electrode 4 and the passivation film 10 are laminated.

[2] An exposure step of irradiating the coating film of the radiation-sensitive resin composition formed in the step [1] with radiation using at least one selected from a halftone mask and a gray tone mask (hereinafter, "step [2]]. ".).

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

[4] A heating step of heating the coating film developed in the step [3] (hereinafter, may be referred to as "step [4]").

According to the steps [1] to [4], a pattern having a predetermined shape made of resin can be formed on the first substrate, and directly above the data wiring made of resin having a desired composition on the first substrate. In addition, it is possible to collectively form a resin transparent film having a thicker film thickness than other places and at the same time having an opening pattern on at least one source / drain electrode.

Hereinafter, the above-mentioned steps [1] to [4] will be described in more detail.

[Step [1]]
In this step, the coating film of the radiation-sensitive resin composition of the third embodiment of the present invention, which will be described later, is formed on the substrate to be coated used for producing the first substrate. The radiation-sensitive resin composition of the third embodiment of the present invention to be used will be described in detail later.

After applying the radiation-sensitive resin composition of the third embodiment of the present invention to one surface of this substrate, it is dried under reduced pressure and prebaked to evaporate a solvent such as an organic solvent to form a coating film.

Examples of the material of the base material of the first substrate include glass substrates such as soda lime glass and non-alkali glass, silicon substrates, polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, aromatic polyamide, and polyamideimide. And resin substrates such as polyimide, and if desired, these substrates are subject to chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc. It can also be processed.

Examples of the method for applying the radiation-sensitive resin composition include a spray method, a roll coating method, a rotary coating method (sometimes referred to as a spin coating method or a spinner method), and a slit coating method (slit die coating method). , A suitable method such as a bar coating method or an inkjet coating method can be adopted. Of these, the spin coating method or the slit coating method is preferable because a film having a uniform thickness can be formed.

The above-mentioned conditions for vacuum drying differ depending on the type, blending ratio, etc. of each component constituting the radiation-sensitive resin composition, but it is preferably performed under a reduced pressure of 5 to 200 Pa, and the drying time varies depending on the depressurizing device. It can be about 30 seconds to 3 minutes.
The above-mentioned prebaking conditions vary depending on the type of each component constituting the radiation-sensitive resin composition, the mixing ratio, etc., but are preferably performed at a temperature of 70 ° C to 120 ° C, and the time is set to a hot plate, an oven, or the like. It depends on the heating device, but it can be about 1 to 10 minutes.

[Step [2]]
Next, in this step, a halftone mask made of a semi-transmissive film and a semi-transmissive region by a slit are applied to the coating film on the substrate to be coated used for manufacturing the first substrate formed in the step [1]. Use at least one selected from the group consisting of gray tone masks comprising. By doing so, it becomes possible to suitably produce a resin transparent film containing portions having different film thicknesses, and it is possible to suitably form a resin transparent film in which a thick film pattern is arranged and an opening pattern is formed. ..

The halftone mask or gray tone mask used in this step is provided with a mask pattern corresponding to the shape of the resin transparent film having the thick film pattern and the opening pattern shown in FIG.

When the radiation-sensitive resin composition to be used has a positive radiation-sensitive property, the region in which the thick film pattern of the resin transparent film shown in FIG. 5 is formed is an unexposed region that is not irradiated with radiation. It becomes. Then, as compared with the thick film pattern on the substrate to be coated used for manufacturing the first substrate, the region having a thin film thickness becomes a half-exposed region in which the irradiation amount of radiation is controlled. Further, the region where the opening pattern of the resin transparent film is formed is a full exposure region where radiation is irradiated without controlling the irradiation amount of radiation.

On the other hand, when the radiation-sensitive resin composition to be used has a negative radiation-sensitive property, the region where the thick film pattern of the resin transparent film shown in FIG. 5 is formed does not control the irradiation amount of radiation. It is a full exposure area where radiation is applied. Then, as compared with the thick film pattern on the substrate to be coated used for manufacturing the first substrate, the region having a thin film thickness becomes a half-exposed region in which the irradiation amount of radiation is controlled. Further, the region where the opening pattern of the resin transparent film is formed is an unexposed region that is not irradiated with radiation.

As the radiation used for irradiating the radiation, for example, visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used as described above. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation containing ultraviolet rays having a wavelength of 313 nm or 365 nm is particularly preferable.

The irradiation amount of the radiation in the step [2] is preferably 100 J / m in the above-mentioned full exposure region as a value obtained by measuring the intensity of the radiation at a wavelength of 365 nm with an illuminance meter (OAI model 356, manufactured by OAI Optical Associates Inc.). It is ² to 10000 J / m ² , more preferably 300 J / m ² to 4000 J / m ² .

Then, in the above-mentioned half-exposure region, an irradiation amount having a smaller value, which is more limited than the irradiation amount in these full-exposure regions, is selected and irradiation is performed.

[Step [3]]
Next, in this step, an unnecessary portion is removed by developing the coating film after irradiation obtained in step [2], and a predetermined cured film having a thick film pattern and an opening pattern is provided. The pattern of the resin transparent film is collectively formed. When the coating film of the radiation-sensitive resin composition to be used is a negative type, the non-irradiated portion of radiation becomes an unnecessary portion. Further, when the coating film of the radiation-sensitive resin composition to be used is a positive type, the radiation-irradiated portion becomes an unnecessary portion.

As the developing solution used in the developing step of the step [3], it is preferable to use an alkaline developing solution composed of an aqueous solution of an alkali (basic compound). Examples of alkalis include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and ammonia; and quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. be able to.

Further, a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to such an alkaline developer in an appropriate amount before use. The concentration of alkali in the alkaline developer is preferably 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. As a developing method, for example, an appropriate method such as a liquid filling method, a dipping method, a rocking dipping method, and a shower method can be used. The developing time varies depending on the composition of the radiation-sensitive resin composition, but is preferably about 10 seconds to 180 seconds. Following such a development process, for example, washing with running water for 30 to 90 seconds and then air-drying with compressed air or compressed nitrogen can form a pattern of a resin transparent film having a desired shape. can.

[Step [4]]
Next, in this step, the patterned coating film on the first substrate obtained in step [3] is heated by an appropriate heating device such as a hot plate or an oven to obtain a thick film pattern as a cured film. A resin transparent film having a predetermined shape and having an opening pattern is formed. The heating temperature is preferably 100 ° C to 350 ° C. By setting the heating temperature to 150 ° C. or higher, the coating film can be sufficiently cured. Further, by setting the temperature to 350 ° C. or lower, even if the first substrate 2 is configured by using a resin substrate, its thermal deterioration can be prevented. From the above points, the heating temperature is more preferably 150 ° C to 300 ° C. The curing time is preferably, for example, 5 to 30 minutes on a hot plate and 20 to 120 minutes in an oven.

From the above, the structure shown in FIG. 51) can be obtained.
The method for forming a resin transparent structure included in the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention is required to follow the above steps [1] to [4], followed by the following step "5". It is preferable to perform the step "6" in this order according to the above.

Hereinafter, the above-mentioned steps [5] and [6] will be described in more detail.
[Step [5]]
In this step, by etching the substrate having the resin transparent film obtained in the step [4], the region corresponding to the opening pattern of the resin transparent film is removed from the passivation layer 10, and a part of the source / Expose the drain electrode.

As the etching method, dry etching or wet etching can be used. Examples of the etching gas used in dry etching include O ₂ , N ₂ , CF ₄ , NF ₃ , and SF ₆ . As the etching method, ion etching, plasma etching, or the like can be used.

Examples of the chemical used in wet etching include a mixed aqueous solution of hydrofluoric acid, which is buffered hydrofluoric acid, and ammonium fluoride.

From the above, the structure shown in FIG. 52) can be obtained.
[Step [6]]
In this step, with respect to the substrate to which some source / drain electrodes obtained in step [5] are exposed.
This is a step of removing a film at a site irradiated with radiation using at least one selected from a halftone and a gray tone mask by using at least one selected from dry etching and a basic agent.
Examples of the etching gas used in dry etching include O ₂ , N ₂ , CF ₄ , NF ₃ , and SF ₆ as in step [5]. For the purpose of preferentially removing the resin transparent film, the etching gas used in this step preferably has an O ₂ gas concentration of 60% or more, and more preferably an O ₂ gas concentration of 80% or more.
When removing a predetermined part of the resin transparent film with a basic chemical, an inorganic alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, etc .; tetramethylammonium hydroxide, tetraethylammonium Examples thereof include quaternary ammonium salts such as hydroxide and 2-aminoethanol. These basic agents may be diluted to any concentration with an organic solvent such as water or N-methylpyrrolidone.

From the above, the structure shown in FIG. 53) can be obtained.
(Manufacturing method of liquid crystal display element)
According to the above, in the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention, a first substrate having a transparent resin structure is prepared on the data wiring, and the liquid crystal display element is manufactured.

First, an alignment film for orienting a liquid crystal is formed on each of the above-mentioned first substrate and second substrate according to a known method using a known liquid crystal alignment agent.

Next, for example, an ultraviolet curable sealing material is applied to a predetermined place on one of the first substrate and the second substrate, and further on the alignment film surface according to a known liquid crystal dropping method. After dropping the liquid crystal on several predetermined places, the other substrate is attached so that the liquid crystal alignment film faces each other. Then, the liquid crystal display panel is manufactured by spreading the liquid crystal between the substrates on the entire surface of the substrate and then irradiating the entire surface of the substrate with ultraviolet light to cure the sealant.

It is desirable that the liquid crystal panel manufactured in this manner is further heated to a temperature at which the liquid crystal used is isotropic, and then slowly cooled to room temperature to remove the flow orientation at the time of filling the liquid crystal.

From the above, the liquid crystal display panel is manufactured by arranging and sandwiching the liquid crystal between the first substrate and the second substrate on which the alignment film is formed. At this time, as another well-known method for manufacturing a liquid crystal display panel, the first substrate and the second substrate are arranged facing each other through a gap (cell gap) so that the alignment films face each other. It is also possible to use a method in which the peripheral portions of the substrates are bonded to each other using a sealing agent, the liquid crystal is injected and filled in the surface of the substrate and the space partitioned by the sealing agent, and then the injection holes are sealed.

Then, by adhering the polarizing plate to the outer surface of the obtained liquid crystal panel, the liquid crystal display element of the first embodiment of the present invention can be obtained.

The liquid crystal display element of the first embodiment of the present invention constitutes the liquid crystal display element which is an example of the first embodiment of the present invention by providing a drive circuit, a control circuit 34, a backlight and the like by a known method. Can be done.

Next, the first aspect of the present invention, which is suitably used in the method for manufacturing a liquid crystal display element according to the second embodiment of the present invention, can form a resin transparent structure of the liquid crystal display element according to the first embodiment of the present invention. 3 The radiation-sensitive resin composition of the embodiment will be described.
Embodiment 3.
<Radiation-sensitive resin composition>
The radiation-sensitive resin composition of the third embodiment of the present invention can be suitably used for forming a resin transparent structure above the data wiring in the liquid crystal display element of the first embodiment of the present invention. By using the radiation-sensitive resin composition of the third embodiment of the present invention and using the method for manufacturing the liquid crystal display element of the second embodiment of the present invention described above, the film directly above the data wiring is thicker than other parts and is partially formed. A transparent resin film having an opening pattern can be formed on the source / drain electrodes of the above, and a desired resin transparent structure can be formed above the data wiring by further undergoing an etching step or the like.

At this time, the radiation-sensitive resin composition of the present embodiment can be optionally provided with either positive type or negative type radiation-sensitive resin composition.

The radiation-sensitive resin composition of the third embodiment of the present invention comprises [A] a polymer containing a structural unit having an acidic group or a protected acidic group, and [B] a radiation-sensitive compound. .. The radiation-sensitive resin composition of the present embodiment has radiation-sensitive properties. The radiation-sensitive resin composition of the present embodiment can contain the [C] polymerizable unsaturated compound. In addition, the radiation-sensitive resin composition of the present embodiment may contain other optional components as long as the effects of the present invention are not impaired.

Hereinafter, each component contained in the radiation-sensitive resin composition according to the third embodiment of the present invention will be described.

([A] Polymer containing a structural unit having an acidic group or a protected acidic group)
A polymer containing a structural unit having an acidic group [A] or a protected acidic group contained in the radiation-sensitive resin composition of the third embodiment of the present invention (hereinafter, may be simply referred to as [A] polymer. .)teeth,
(A1) A structural unit having an acidic group or a protected acidic group (hereinafter referred to as "structural unit (A1)"),
(A2) It has a structural unit having a crosslinkable group (hereinafter referred to as “structural unit (A2)”).
And [A] polymer is (A3) a structural unit represented by the following formula (4-1) or the following formula (4-2) (hereinafter referred to as “structural unit (A3)”).
(A4) It may have a structural unit (hereinafter referred to as "structural unit (A4)") other than the above (A1) to (A3).

(In the formula (4-1) and the formula (4-2), ^RA is a hydrogen atom, a methyl group, a hydroxymethyl group, a cyano group or a trifluoromethyl group. R ⁷ and R ⁸ are independent of each other. It is a divalent aromatic ring group or a chain hydrocarbon group. R ¹ is a hydrogen atom, a halogen atom, a hydroxy group, or an alkoxy group having 1 to 6 carbon atoms. R ² and R ³ are, respectively. Independently, it is a hydrogen atom, a halogen atom, a hydroxy group, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a phenyl group.)
^In the above formulas (4-1) and (4-2), the divalent aromatic ring group of ^R7 and R8 may be a substituted or unsubstituted phenylene group or a substituted or unsubstituted naphthalenylene group. preferable. The divalent chain hydrocarbon group is preferably an alkanediyl group having 1 to 6 carbon atoms, and more preferably an alkanediyl group having 1 to 4 carbon atoms.

Among the above, ^R7 and R8 are divalent aromatics ⁱⁿ that a cured film having higher heat resistance, chemical resistance and hardness can be obtained, and the solubility of the exposed portion in an alkaline developer can be increased. It is preferably a ring group, and particularly preferably a substituted or unsubstituted phenylene group.

Specific examples of the structural unit represented by the above formula (4-1) include structural units represented by the following formulas (4-1-1) and (4-1-2). Specific examples of the structural unit represented by the above formula (4-2) include structural units represented by the following formulas (4-2-1) and (4-2-2). Be done.

(In Eqs. (4-1-1), Eqs. (4-1-2), Eqs. (4-2-1) and Eqs. (4-2-2), R ¹¹ and R ¹² are independent of each other. It is an alkyl group having 1 to 4 carbon atoms, R ¹³ is an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms or a hydroxyl group. N3 is an integer of 1 to 4 A ¹ and A ² is independently a halogen atom, a hydroxy group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. N1 is an integer of 0 to 4; n2 is an integer of 0 to 4. It is an integer of 6. However, when n1 is 2 or more, the plurality of A1s are the same group or different groups from each other. When n2 is ² or more, the plurality of ^A2s are the same group or different from each other. ^RA is synonymous with the above equations (4-1) and (4-2).)
The acidic group or protected acidic group of the structural unit (A1) includes a carboxyl group, an acetal ester structure of a carboxyl group, a ketal ester structure of a carboxyl group, a phenolic hydroxyl group, a structural unit derived from maleimide, a phosphoric acid group, and a sulfone. Acid groups can be mentioned.
Examples of the functional group having an acetal structure include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1-n-butoxyethoxy group, and the like. 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxyethoxy group, 1-bol Nyloxyethoxy group, 1-phenyloxyethoxy group, 1- (1-naphthyloxy) ethoxy group, 1-benzyloxyethoxy group, 1-phenethyloxyethoxy group, (cyclohexyl) (methoxy) methoxy group, (cyclohexyl) ( Ethoxy) methoxy group, (cyclohexyl) (n-propoxy) methoxy group, (cyclohexyl) (i-propoxy) methoxy group, (cyclohexyl) (cyclohexyloxy) methoxy group, (cyclohexyl) (phenoxy) methoxy group, (cyclohexyl) ( Benzyloxy) methoxy group, (phenyl) (methoxy) methoxy group, (phenyl) (ethoxy) methoxy group, (phenyl) (n-propoxy) methoxy group, (phenyl) (i-propoxy) methoxy group, (phenyl) ( Cyclohexyloxy) methoxy group, (phenyl) (phenoxy) methoxy group, (phenyl) (benzyloxy) methoxy group, (benzyl) (methoxy) methoxy group, (benzyl) (ethoxy) methoxy group, (benzyl) (n-propoxy) ) Methoxy group, (benzyl) (i-propoxy) methoxy group, (benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group , 2-Tetrahydropyranyloxy group and the like.
Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group and 2-tetrahydropyranyloxy group can be mentioned as preferable ones.
Examples of the functional group having a ketal structure include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n-propoxyethoxy group and 1-methyl-. 1-i-propoxyethoxy group, 1-methyl-1-n-butoxyethoxy group, 1-methyl-1-i-butoxyethoxy group, 1-methyl-1-sec-butoxyethoxy group, 1-methyl-1- t-Butoxyethoxy group, 1-methyl-1-cyclopentyloxyethoxy group, 1-methyl-1-cyclohexyloxyethoxy group, 1-methyl-1-norbornyloxyethoxy group, 1-methyl-1-bornyloxy Ethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-naphthyloxy) ethoxy group, 1-methyl-1-benzylooxyethoxy group, 1-methyl-1-phenethyloxyethoxy Group, 1-cyclohexyl-1-methoxyethoxy group, 1-cyclohexyl-1-ethoxyethoxy group, 1-cyclohexyl-1-n-propoxyethoxy group, 1-cyclohexyl-1-i-propoxyethoxy group, 1-cyclohexyl- 1-Cyclohexyloxyethoxy group, 1-cyclohexyl-1-phenoxyethoxy group, 1-cyclohexyl-1-benzyloxyethoxy group, 1-phenyl-1-methoxyethoxy group, 1-phenyl-1-ethoxyethoxy group, 1- Phenyl-1-n-propoxyethoxy group, 1-phenyl-1-i-propoxyethoxy group, 1-phenyl-1-cyclohexyloxyethoxy group, 1-phenyl-1-phenyloxyethoxy group, 1-phenyl-1- Benzyloxyethoxy group, 1-benzyl-1-methoxyethoxy group, 1-benzyl-1-ethoxyethoxy group, 1-benzyl-1-n-propoxyethoxy group, 1-benzyl-1-i-propoxyethoxy group, 1 -Benzyl-1-cyclohexyloxyethoxy group, 1-benzyl-1-phenyloxyethoxy group, 1-benzyl-1-benzyloxyethoxy group, 2- (2-methyl-tetrahydrofuranyl) oxy group, 2- (2- (2-) Methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like can be mentioned.
Of these, 1-methyl-1-methoxyethoxy group and 1-methyl-1-cyclohexyloxyethoxy group can be mentioned as preferable ones.

The structural unit (A2) is a structural unit having a crosslinkable group. As the crosslinkable group, it is preferable to have at least one selected from the group consisting of an oxetanyl group, an oxynyl group and a (meth) acryloyl group. That is, the structural unit (A2) is a structural unit having at least one selected from the group consisting of an oxetanyl group, an oxynyl group and a (meth) acryloyl group.

The structural unit (A1) is at least one selected from the group consisting of (a1) an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride, and a (meth) acrylic acid ester compound having an acetal or ketal structure (hereinafter referred to as “1”). It is preferably a structural unit derived from "compound (a1)");
The structural unit (A2) is preferably a structural unit derived from (a2) a polymerizable unsaturated compound having an oxylanyl group or an oxetanyl group (hereinafter, referred to as “compound (a2)”);
The structural unit (A3) is preferably a structural unit represented by each of the above formulas (4-1-1) and (4-1-2);
The structural unit (A4) is preferably a structural unit derived from (a4) a polymerizable unsaturated compound (hereinafter referred to as “compound (a4)”) other than the above (a1) to (a3).

Examples of the compound (a1) include monocarboxylic acids, dicarboxylic acids, and anhydrides of dicarboxylic acids. Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethylhexahydrophthalic acid, and 2-methacryloyloxyethylhexa. Hydrophthalic acid etc .;
Examples of the dicarboxylic acid include maleic acid, fumaric acid, citraconic acid and the like;
Examples of the dicarboxylic acid anhydride include the above-mentioned dicarboxylic acid anhydride and the like.

Of these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride are selected from the viewpoints of copolymerizability and solubility of the obtained copolymer in the developing solution. preferable.
Examples of the (meth) acrylic acid ester compound having an acetal or ketal structure include 1-ethoxyethyl (meth) acrylate, tetrahydro-2H-pyran-2-yl (meth) acrylate, and 1- (cyclohexyloxy) ethyl (meth) acrylate. , 1- (2-methylpropoxy) ethyl (meth) acrylate, 1- (1,1-dimethyl-ethoxy) ethyl (meth) acrylate, 1- (cyclohexyloxy) ethyl (meth) acrylate and the like can be mentioned.
Of these, (meth) acrylic acid ester compounds having an acetal or ketal structure are preferable, and 1-ethoxyethyl methacrylate, tetrahydro-2H-pyran-2-yl methacrylate, 1- (cyclohexyloxy) ethyl methacrylate, 1- ( 2-Methylpropoxy) ethyl methacrylate, 1- (1,1-dimethyl-ethoxy) ethyl methacrylate and 1- (cyclohexyloxy) ethyl methacrylate are preferred.

Compound (a1) can be used alone or in admixture of two or more.

The compound (a2) is preferably at least one selected from the group consisting of a polymerizable unsaturated compound having an oxylanyl group and a polymerizable unsaturated compound having an oxetanyl group.

Examples of the polymerizable unsaturated compound having an oxylanyl group include (meth) acrylic acid oxylanyl (cyclo) alkyl ester, α-alkylacrylic acid oxylanyl (cyclo) alkyl ester, and a glycidyl ether compound having a polymerizable unsaturated bond;
As the polymerizable unsaturated compound having an oxetanyl group, for example, a (meth) acrylic acid ester having an oxetanyl group and the like can be mentioned.

Specific examples of the above compound (a2) include
Examples of the (meth) acrylic acid oxylanyl (cyclo) alkyl ester include (meth) acrylic acid glycidyl, (meth) acrylic acid 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylic acid 3,. 4-Epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl, (meth) acrylic acid 3,4-epoxycyclohexylmethyl, 3,4-epoxytricyclo [ 5.2.1.02.6] Decyl (meth) acrylate, etc.;
Examples of the α-alkylacrylic acid oxylanyl (cyclo) alkyl ester include α-ethylacrylic acid glycidyl, α-n-propylacrylic acid glycidyl, α-n-butylacrylic acid glycidyl, and α-ethylacrylic acid 6,7-epoxy. Heptyl, α-ethylacrylic acid 3,4-epoxycyclohexyl, etc.;
Examples of the glycidyl ether compound having a polymerizable unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like;
Examples of the (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxy). Methyl) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyl Examples thereof include oxymethyloxetane and 3-ethyl-3- (meth) acryloyloxymethyloxetane.

Among these specific examples, in particular, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxytricyclo [5.2. 1.02.6] decylmethacrylate, 3,4-epoxytricyclo [5.2.1.02.6] decylacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl-3-methacryloyloxy Methyloxetane or 3-ethyl-3-methacryloyloxymethyloxetane is preferred from the standpoint of polymerizable properties.

The above-mentioned compound (a2) can be used alone or in combination of two or more.

[A] The structural unit having a (meth) acryloyloxy group of a polymer containing a structural unit having an acidic group or a protected acidic group is a (meth) acrylic acid ester having an epoxy group in the carboxyl group in the polymer. Obtained by reacting. The structural unit having a (meth) acryloyloxy group after the reaction is preferably a structural unit represented by the following formula (2).

In the above formula (2), R10 and R11 are independently hydrogen atoms or methyl groups, respectively. c is an integer of 1 to 6. R12 is a divalent group represented by the following formula (2-1) or the following formula (2-2).

In the above formula (2-1), R13 is a hydrogen atom or a methyl group. In the above formula (2-1) and the above formula (2-2), * indicates a site that bonds with an oxygen atom.

Regarding the structural unit represented by the above formula (2), for example, when a compound such as glycidyl methacrylate or 2-methylglycidyl methacrylate is reacted with a copolymer having a carboxyl group, R12 in the formula (2) Is equation (2-1). On the other hand, when a compound such as 3,4-epoxycyclohexylmethyl methacrylate is reacted with the copolymer having a carboxyl group, R12 in the formula (2) becomes the formula (2-2).

In the above-mentioned reaction between a carboxyl group and an unsaturated compound such as an (meth) acrylic acid ester having an epoxy group in the polymer, a weight containing a polymerization inhibitor is preferable in the presence of an appropriate catalyst, if necessary. An unsaturated compound having an epoxy group is added to the combined solution, and the mixture is stirred under heating for a predetermined time. Examples of the catalyst include tetrabutylammonium bromide and the like. Examples of the polymerization inhibitor include p-methoxyphenol and the like. The reaction temperature is preferably 70 ° C to 100 ° C. The reaction time is preferably 8 to 12 hours.
[A] The content of the structural unit having a crosslinkable group in the polymer containing the structural unit having an acidic group or a protected acidic group is 10 mol% to 70 in the total components of the [A] polymer. It is preferably mol%, more preferably 20 mol% to 50 mol%.

(A2) When the content of the structural unit having a crosslinkable group is less than 10 mol%, the sensitivity of the radiation-sensitive resin composition of the present embodiment to radiation tends to decrease, and the heat resistance of the obtained cured film tends to decrease. Is not enough. Further, when the content is more than 70 mol%, it causes a development defect at the time of development, and a development residue is likely to be generated.

Specific examples of the monomer constituting the structural unit (A3) include styryltrimethoxysilane, styryltriethoxysilane, styrylmethyldimethoxysilane, styrylethyldiethoxysilane, styryldimethoxyhydroxysilane, and styryldiethoxyhydroxysilane. (Meta) acryloxiphenyltrimethoxysilane, (meth) acryloxiphenyltriethoxysilane, (meth) acryloxiphenylmethoxydimethoxysilane, (meth) acryloxiphenylethyldiethoxysilane, trimethoxy (4-vinylnaphthyl) silane, Triethoxy (4-vinylnaphthyl) silane, methyldimethoxy (4-vinylnaphthyl) silane, ethyldiethoxy (4-vinylnaphthyl) silane, (meth) acryloxynaphthyltrimethoxysilane, 3- (meth) acryloxipropyltrimethoxy Silane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloxylpropylmethyldimethoxysilane, 3- (meth) acryloxylpropylmethyldiethoxysilane, 4- (meth) acryloxybutyltrimethoxysilane And so on. The monomer constituting the structural unit (A3) can be used alone or in combination of two or more.

Examples of the compound (a4) include (meth) acrylic acid alkyl ester, (meth) acrylic acid cycloalkyl ester, (meth) acrylic acid aryl ester, (meth) acrylic acid aralkyl ester, and unsaturated dicarboxylic acid dialkyl ester. Examples thereof include (meth) acrylic acid esters having oxygen-containing complex 5-membered rings or oxygen-containing complex 6-membered rings, vinyl aromatic compounds, conjugated diene compounds and other polymerizable unsaturated compounds. Specific examples of these include, as (meth) acrylic acid alkyl esters, for example, methyl acrylate, n-propyl (meth) acrylic acid, i-propyl (meth) acrylic acid, n-butyl (meth) acrylic acid, (. Meta) sec-butyl acrylate, t-butyl (meth) acrylate, etc.;
Examples of the (meth) acrylic acid cycloalkyl ester include (meth) acrylic acid cyclohexyl, (meth) acrylic acid 2-methylcyclohexyl, and (meth) acrylic acid tricyclo [5.2.1.02,6] decane-8-. Il, 2- (tricyclo [5.2.1.02,6] decane-8-yloxy) ethyl (meth) acrylate, isoboronyl (meth) acrylate, etc.;
As the (meth) acrylic acid aryl ester, for example, acrylic acid phenyl or the like;
As the (meth) acrylic acid aralkyl ester, for example, benzyl (meth) acrylic acid or the like;
As unsaturated dicarboxylic acid dialkyl esters, for example, diethyl maleate, diethyl fumaric acid, etc.;
Examples of the (meth) acrylic acid ester having an oxygen-containing complex 5-membered ring or an oxygen-containing complex 6-membered ring include (meth) acrylate tetrahydropyran-2-yl, (meth) acrylate tetrahydropyran-2-yl, (meth). ) 2-Methyltetrahydropyran-2-yl acrylate, etc.;
As the vinyl aromatic compound, for example, styrene, α-methylstyrene and the like;
As the conjugated diene compound, for example, 1,3-butadiene, isoprene and the like;
Examples of other polymerizable unsaturated compounds include 2-hydroxyethyl (meth) acrylate, acrylonitrile, methacrylonitrile, acrylamide, and methacrylamide, respectively.

Among the compounds (a4) listed above, n-butyl methacrylate, 2-methylglycidyl methacrylate, benzyl methacrylate, and tricyclo methacrylate [5.2.1.02,6] from the viewpoint of polymerization reactivity. Decane-8-yl, styrene, p-methoxystyrene, methacrylic acid tetrahydrofuran-2-yl, 1,3-butadiene and the like are preferable.

Compound (a4) can be used alone or in admixture of two or more.

The polymer containing the preferred [A] carboxyl group-containing structural unit in the present embodiment is a mixture of polymerizable unsaturated compounds containing the above compounds (a1) to (a4) in the following proportions, respectively. It can be synthesized by polymerization.

Compound (a1): preferably 0.1 mol% to 30 mol%, more preferably 1 mol% to 20 mol%, still more preferably 5 mol% to 15 mol%.
Compound (a2): preferably 1 mol% to 95 mol%, more preferably 10 mol% to 60 mol%, still more preferably 20 mol% to 30 mol%.
Compound (a3): preferably 50 mol% or less, more preferably 1 mol% to 40 mol%, still more preferably 10 mol% to 30 mol%.
Compound (a4): preferably 80 mol% or less, more preferably 1 mol% to 60 mol%, still more preferably 25 mol% to 50 mol%.
It is preferable to use in the range of.

The radiation-sensitive resin composition of the third embodiment of the present invention is obtained by copolymerizing a mixture of polymerizable unsaturated compounds containing each compound in the above range [A] acidic group or protected acidic. By containing a polymer containing a structural unit having a group, high resolution is achieved without impairing good coatability, so that even a high-definition pattern can be cured with a highly balanced characteristic. It is preferable because a film can be provided.

[A] For a polymer containing a structural unit having an acidic group or a protected acidic group, the polystyrene-equivalent weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC) is preferably used. It is 2000 to 100,000, more preferably 5000 to 50000. By using a polymer containing [A] an acidic group having a Mw in this range or a structural unit having a protected acidic group, high resolution is achieved without impairing good coatability, and thus high definition is achieved. It is possible to give a cured film in which the balance of characteristics is highly adjusted even if the pattern is different.

In the radiation-sensitive resin composition of the third embodiment of the present invention, the polymer containing the structural unit having the [A] acidic group or the protected acidic group is preferably a mixture of the polymerizable unsaturated compound as described above. Can be produced by polymerizing in a suitable solvent, preferably in the presence of a radical polymerization initiator.

Examples of the solvent used for the above polymerization include diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, and dipropylene glycol monomethyl. Examples thereof include ether acetate, 3-methoxybutyl acetate, cyclohexanol acetate, benzyl alcohol, 3-methoxybutanol and the like. These solvents can be used alone or in admixture of two or more.

The radical polymerization initiator is not particularly limited, and is, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2. '-Azobis- (4-methoxy-2,4-dimethylvaleronitrile), 4,4'-azobis (4-cyanovaleric acid), dimethyl-2,2'-azobis (2-methylpropionate), 2, Examples thereof include azo compounds such as 2'-azobis (4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators can be used alone or in admixture of two or more.
<[B] Radiation-sensitive compounds>
[B] The radiation-sensitive compound imparts radiation-sensitive properties to the radiation-sensitive composition. This [B] radiation-sensitive compound is a compound that produces a reactive active species upon exposure to radiation. Here, the radiation includes at least visible light, ultraviolet rays, far ultraviolet rays, electron beams (charged particle beams) and X-rays. [B] As the radiation-sensitive compound, (B1) an acid generator, (B2) a polymerization initiator, or a combination thereof is preferable. (B1) When an acid generator is used, it can be made into either a positive type or a negative type radiation-sensitive composition depending on other additive components. When a quinone diazide compound is used, or when a compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation is used, a positive radiation-sensitive composition can be obtained. On the other hand, when the (B2) polymerization initiator is used, a negative type radiation-sensitive composition can be obtained.
((B1) Acid generator)
(B1) The acid generator is a compound that generates an acid by irradiation with radiation. By containing the (B1) acid generator, the radiation-sensitive resin composition of the present embodiment can exhibit positive radiation-sensitive characteristics with respect to, for example, an alkaline developer.

The (B1) acid generator is not particularly limited as long as it is a compound that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. Examples of the acid generator (B1) include an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound, a quinonediazide compound, and pKa by irradiation with radiation. Examples thereof include compounds that generate an acid having a value of 4.0 or less. Of these, quinonediazide compounds and compounds that generate an acid with a pKa of 4.0 or less upon irradiation with radiation are preferable.
(Kinone diazide compound)
The quinonediazide compound generates a carboxylic acid by irradiation with radiation. As the quinone diazide compound, for example, a condensate of a phenolic compound or an alcoholic compound (hereinafter, also referred to as “matrix”) and a 1,2-naphthoquinone diazide sulfonic acid halide can be used.

Examples of the mother nucleus include trihydroxybenzophenone, tetrahydroxybenzophenone, pentahydroxybenzophenone, hexahydroxybenzophenone, (polyhydroxyphenyl) alkane, and other mother nuclei.

Examples of the trihydroxybenzophenone include 2,3,4-trihydroxybenzophenone, 2,4,6-trihydroxybenzophenone and the like.

Examples of the tetrahydroxybenzophenone include 2,2', 4,4'-tetrahydroxybenzophenone, 2,3,4,3'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2, Examples thereof include 3,4,2'-tetrahydroxy-4'-methylbenzophenone, 2,3,4,4'-tetrahydroxy-3'-methoxybenzophenone and the like.

Examples of the pentahydroxybenzophenone include 2,3,4,2', 6'-pentahydroxybenzophenone and the like.

Examples of the hexahydroxybenzophenone include 2,4,6,3', 4', 5'-hexahydroxybenzophenone, 3,4,5,3', 4', 5'-hexahydroxybenzophenone and the like.

Examples of the (polyhydroxyphenyl) alkane include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, and 1,1,1-tri (p-). Hydroxyphenyl) ethane, bis (2,3,4-trihydroxyphenyl) methane, 2,2-bis (2,3,4-trihydroxyphenyl) propane, 1,1,3-tris (2,5-dimethyl) -4-Hydroxyphenyl) -3-phenylpropane, 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol, bis (2,5-) Dimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 3,3,3', 3'-tetramethyl-1,1'-spirobiindene-5,6,7,5', 6', 7' -Hexanol, 2,2,4-trimethyl-7,2', 4'-trihydroxyflaban and the like can be mentioned.

Other mother nuclei include, for example, 2-methyl-2- (2,4-dihydroxyphenyl) -4- (4-hydroxyphenyl) -7-hydroxychroman, 1- [1- {3- (1- [ 4-Hydroxyphenyl] -1-methylethyl) -4,6-dihydroxyphenyl} -1-methylethyl] -3- [1- {3- (1- [4-hydroxyphenyl] -1-methylethyl)- 4,6-Dihydroxyphenyl} -1-methylethyl] benzene, 4,6-bis {1- (4-hydroxyphenyl) -1-methylethyl} -1,3-dihydroxybenzene and the like can be mentioned.

Of these mother nuclei, 2,3,4,4'-tetrahydroxybenzophenone, 1,1,1-tri (p-hydroxyphenyl) ethane, 4,4'-[1- [4- [1- [ 4-Hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol is preferred.

As the 1,2-naphthoquinone diazide sulfonic acid halide, 1,2-naphthoquinone diazido sulfonic acid chloride is preferable. Examples of the 1,2-naphthoquinone diazide sulfonic acid chloride include 1,2-naphthoquinone diazide-4-sulfonic acid chloride, 1,2-naphthoquinone diazide-5-sulfonic acid chloride and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferable.

The synthesis of the quinonediazide compound can be carried out by a known condensation reaction. In this condensation reaction, 1,2-naphthoquinonediazide sulfone corresponding to preferably 30 mol% or more and 85 mol% or less, that is, 30 mol% to 85 mol% with respect to the number of OH groups in the phenolic compound or the alcoholic compound. Acid halides can be used.

Further, as the quinone diazide compound, 1,2-naphthoquinone diazide sulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, for example, 2,3,4-triaminobenzophenone-1,2-naphtho A quinonediazide-4-sulfonic acid amide or the like is also preferably used.

These quinone diazide compounds can be used alone or in admixture of two or more. Further, the quinone diazide compound can also be used in combination with an oxime sulfonate compound, an onium salt, a sulfonimide compound, a halogen-containing compound, a diazomethane compound, a sulfone compound, a sulfonic acid ester compound, a carboxylic acid ester compound and the like.

The lower limit of the content of the quinonediazide compound in the radiation-sensitive resin composition of the present embodiment is preferably 5 parts by mass, more preferably 10 parts by mass, and 20 parts by mass with respect to 100 parts by mass of the polymer [A]. More preferred. On the other hand, as the upper limit, 80 parts by mass is preferable, 60 parts by mass is more preferable, and 40 parts by mass is further preferable. By setting the content of the quinonediazide compound in the above range, the difference in solubility between the irradiated portion and the unirradiated portion of the developing solution can be increased, and the patterning performance can be improved. In addition, the solvent resistance of the cured film can be improved.
(A compound that generates an acid with a pKa of 4.0 or less when irradiated with radiation)
A compound that generates an acid with a pKa of 4.0 or less by irradiation with radiation may generate an acid with a pKa of 4.0 or less by irradiating with radiation such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams. It is a compound that can be produced. The value of pKa of the acid generated by irradiation with radiation is preferably 3.5 or less, and more preferably 3.0 or less. Examples of such compounds include trichloromethyl-s-triazines, diaryliodonium salts, triarylsulfonium salts, quaternary ammonium salts, sulfonic acid esters and the like. Of these, diaryliodonium salts and triarylsulfonium salts are preferable.
Specific examples of these include 2- (3-chlorophenyl) -bis (4,6-trichloromethyl) -s-triazine and 2- (4-methoxyphenyl) -bis as trichloromethyl-s-triazines. (4,6-trichloromethyl) -s-triazine, 2- (4-methylthiophenyl) -bis (4,6-trichloromethyl) -s-triazine, 2- (4-methoxy-β-styryl) -bis ( 4,6-Trichloromethyl) -s-triazine, 2-piperonyl-bis (4,6-trichloromethyl) -s-triazine, 2- [2- (fran-2-yl) ethenyl] -bis (4,6) -Trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine, 2- [2- (4-diethylamino) -2-Methylphenyl) ethenyl] -bis (4,6-trichloromethyl) -s-triazine or 2- (4-methoxynaphthyl) -bis (4,6-trichloromethyl) -s-triazine and the like;
Diaryliodonium salts include diphenyliodonium trifluoroacetate, diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, phenyl, 4- (2'-hydroxy-1). '-Tetradecaoxy) Phenyliodonium Trifluoromethanesulfonate, 4- (2'-Hydroxy-1'-Tetradecaoxy) Phenyliodonium Hexafluoroantimonate, Phenyl, 4- (2'-Hydroxy-1'-Tetradeca Oxy) Phenyliodonium-p-toluenesulfonate, etc .;
As triarylsulfonium salts, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-phenylthiophenyldiphenylsulfonium trifluo Lomethan sulfonate or 4-phenylthiophenyldiphenylsulfonium trifluoroacetate, etc .;
As quaternary ammonium salts, tetramethylammonium butyltris (2,6-difluorophenyl) borate, tetramethylammonium hexyltris (p-chlorophenyl) borate, tetramethylammonium hexyltris (3-trifluoromethylphenyl) borate, benzyl Dimethylphenylammonium butyltris (2,6-difluorophenyl) borate, benzyldimethylphenylammonium hexyltris (p-chlorophenyl) borate, benzyldimethylphenylammonium hexyltris (3-trifluoromethylphenyl) borate, etc .;
Examples of sulfonic acid esters include 2,6-dinitrobenzyl-p-toluene sulfonic acid ester, 2,6-dinitrobenzyl-trifluoromethanesulfonic acid ester, N-hydroxynaphthalimide-p-toluene sulfonic acid ester, and N-hydroxyna. Phthalimide-trifluoromethanesulfonic acid esters can be mentioned respectively.
The amount of the compound that generates an acid having a pKa of 4.0 or less by irradiation with radiation in the present invention is preferably 1 to 40 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of the polymer (A). ~ 20 parts by weight. If this amount is less than 1 part by weight, patterning may be difficult, and the heat resistance and solvent resistance of the obtained cured film may be insufficient. On the other hand, if this amount exceeds 40 parts by weight, patterning may become difficult.
((B2) Polymerization Initiator)
(B2) The polymerization initiator is a component that produces an active species that can initiate the polymerization of a polymerizable compound in response to radiation. By containing (B2) a polymerization initiator, the radiation-sensitive resin composition of the present embodiment can exhibit, for example, negative radiation-sensitive characteristics with respect to an alkaline developer. (B2) Examples of the polymerization initiator include a photoradical polymerization initiator. Examples of the photoradical polymerization initiator include O-acyloxime compounds, acetophenone compounds, biimidazole compounds and the like. These compounds may be used alone or in admixture of two or more.
(O-acyloxime compound)
Examples of the O-acyloxime compound include 1- [4- (phenylthio) -2- (O-benzoyloxime)] and 1,2-octanedione 1- [4- (phenylthio) -2- (O-benzoyl). Oxime)], Etanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-6-benzoyl] -9. H. -Carbazole-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, ethane-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime) and the like can be mentioned.
(Acetophenone compound)
Examples of the acetophenone compound include α-aminoketone compounds and α-hydroxyketone compounds.
(Α-Aminoketone compound)
Examples of the α-aminoketone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and 2-dimethylamino-2- (4-methylbenzyl) -1- (4). -Morpholine-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one and the like can be mentioned.
(Α-Hydroxyketone compound)
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.
(Bimidazole compound)
Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,). 4-Dichlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5, Examples thereof include 5'-tetraphenyl-1,2'-biimidazole.

The content of the (B2) polymerization initiator in the radiation-sensitive resin composition of the present embodiment may be, for example, 1 part by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the polymer [A]. (B2) By setting the content of the polymerization initiator in such a range, the radiation-sensitive resin composition of the present embodiment has high solvent resistance, hardness and adhesion even at a low exposure amount. A cured film can be formed.

[C] Polymerizable unsaturated compound The [C] polymerizable unsaturated compound in the radiation-sensitive resin composition of the third embodiment of the present invention is irradiated with radiation in the presence of the above-mentioned [B] radiation-sensitive compound. It is an unsaturated compound that polymerizes as a result. The [C] polymerizable unsaturated compound is not particularly limited, but for example, a monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid ester has good polymerizable property. Moreover, it is preferable because the strength of the formed cured film is improved.

Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, (2- (meth) acryloyloxyethyl) (2-hydroxypropyl) phthalate, and the like. Examples thereof include ω-carboxypolycaprolactone mono (meth) acrylate. These commercially available products include, for example, Aronix (registered trademark) M-101, M-111, M-114, M-5300 (all manufactured by Toagosei Co., Ltd.); KAYARAD (registered). Trademarks) TC-110S, TC-120S (above, manufactured by Nippon Kayaku Co., Ltd.); Viscort 158, 2311 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and the like.

Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol diacrylate, and tetraethylene glycol di (meth). Examples thereof include acrylate, 1,6-hexanediol di (meth) acrylate, and 1,9-nonanediol di (meth) acrylate. These commercially available products include, for example, Aronix (registered trademark) M-210, M-240, M-6200 (all manufactured by Toagosei Co., Ltd.), KAYARAD (registered trademark) HDDA, and the same. HX-220, R-604 (above, manufactured by Nippon Kayaku Co., Ltd.), Viscort 260, 312, 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), Light Acrylate 1,9-NDA (Kyoeisha) (Made by Chemical Co., Ltd.) and the like.

Examples of the trifunctional or higher (meth) acrylic acid ester include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylate. Dipentaerythritol hexa (meth) acrylate;
Mixture of dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate;
Ethylene oxide-modified dipentaerythritol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, succinic acid-modified pentaerythritol tri (meth) acrylate, succinic acid-modified dipentaerythritol penta (meth) acrylate, tri Pentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, a mixture of isocyanuric acid EO-modified diacrylate and isocyanuric acid EO-modified triacrylate;
A compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and three, four or five (meth) acryloyloxy having one or more hydroxyl groups in the molecule. Examples thereof include a polyfunctional urethane acrylate compound obtained by reacting with a compound having a group.

Commercially available products of the above-mentioned trifunctional or higher (meth) acrylic acid ester are trade names such as Aronix (registered trademark) M-309, M-400, M-405, M-450, and M. -7100, M-8030, M-8060, TO-1450 (all manufactured by Toa Synthetic Co., Ltd.), KAYARAD (registered trademark) TMPTA, DPHA, DPCA-20, DPCA-30, DPCA -60, DPCA-120, DPEA-12 (above, manufactured by Nippon Kayaku Co., Ltd.), Viscort 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.) ), And as commercial products containing polyfunctional urethane acrylate compounds, New Frontier (registered trademark) R-1150 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), KAYARAD (registered trademark) DPHA-40H (Nippon Kayaku) (Made by Co., Ltd.) and the like.

Of these, in particular, ω-carboxypolycaprolactone monoacrylate, 1,9-nonanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate. ;
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate;
Mixture of tripentaerythritol hepta (meth) acrylate and tripentaerythritol octa (meth) acrylate;
Commercially available products containing ethylene oxide-modified dipentaerythritol hexaacrylate, polyfunctional urethane acrylate compounds, succinic acid-modified pentaerythritol triacrylate, and succinic acid-modified dipentaerythritol pentaacrylate are preferable.

The [C] polymerizable unsaturated compound as described above can be used alone or in combination of two or more.

The proportion of the [C] polymerizable unsaturated compound used in the radiation-sensitive resin composition of the third embodiment of the present invention is preferably 30 parts by mass to 250 parts by mass with respect to 100 parts by mass of the [A] polymer. Yes, more preferably 50 parts by mass to 200 parts by mass. [B] By setting the ratio of the polymerizable unsaturated monomer in the above range, it is possible to form a cured film with high resolution without causing a problem of development residue, which is preferable.
(Other optional ingredients)
The radiation-sensitive resin composition of the third embodiment of the present invention is added to or [A] a polymer containing a structural unit having an acidic group or a protected acidic group and [B] a radiation-sensitive compound. ] In addition to polymers containing acidic groups or structural units having protected acidic groups, [B] radiosensitive compounds and [C] polymerizable unsaturated compounds, as required to the extent that the effects of the present invention are not impaired. And other optional ingredients can be contained. Examples of other optional components that can be used here include [D] an adhesive aid, [E] a surfactant, and [F] a polymerization inhibitor. Other optional components may be used as a mixture of two or more. Hereinafter, each optional component will be described.

[D] Adhesive Aid The above [D] Adhesive Aid can be used to further improve the adhesiveness between the cured film to be formed and the substrate. As such [D] adhesion aid, the same as the above compound (a3) can be used, as well as trimethoxysilyl benzoic acid, vinyltriacetoxysilane, vinyltrimethoxysilane, and γ-isoxapropyltriethoxy. Silane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane or the like can be used. The proportion of the [D] adhesive aid used in the radiation-sensitive resin composition of the present embodiment is preferably 20 parts by mass or less, more preferably 1 part by mass or more, based on 100 parts by mass of the [A] polymer. It is 10 parts by mass. [D] By setting the content ratio of the adhesive aid in the above range, the adhesion between the formed cured film and the substrate is effectively improved.

[E] Surfactant Examples of the above-mentioned [E] surfactant include a fluorine-based surfactant and a silicone-based surfactant. The ratio of the [E] surfactant used in the radiation-sensitive resin composition of the present embodiment is preferably 1 part by mass or less, more preferably 0.01 part by mass, with respect to 100 parts by mass of the [A] polymer. Parts to 0.6 parts by mass.

[F] Polymerization inhibitor The above-mentioned [F] polymerization inhibitor cleaves the molecule of the [A] polymer by capturing radicals generated by exposure or heating, or by decomposing the peroxide generated by oxidation. It is a component that suppresses. Since the radiation-sensitive resin composition of the present embodiment contains the [F] polymerization inhibitor, the rupture deterioration of the polymer molecules in the formed cured film is suppressed, so that the cured film obtained can be obtained. For example, light resistance and the like can be improved.

Examples of such [F] polymerization inhibitor include hindered phenol compounds, hindered amine compounds, alkyl phosphite compounds, thioether compounds and the like, and among these, the hindered phenol compound is preferably used. Can be done.

Examples of the hindered phenol compound include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and thiodiethylenebis [3- (3,5-di-tert-). Butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -Isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenylpropionamide)], 3,3', 3', 5', 5'-hex-tert-butyl-a, a', a' -(Mesitylen-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, ethylene bis (Oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] , 1,3,5-Tris [(4-tert-butyl-3-hydroxy-2,6-kisilyl) methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Trion, 2,6-di-tert-butyl-4- [4,6-bis (octylthio) -1,3,5-triazine-2-ylamine] phenol and the like can be mentioned.

Examples of these commercially available products include ADEKA STAB (registered trademark) AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, and AO. -330 (above, manufactured by ADEKA Corporation), sumilizer (registered trademark) GM, GS, MDP-S, BBM-S, WX-R, GA-80 (above, manufactured by Sumitomo Chemical Co., Ltd.) ), IRGANOX (registered trademark) 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 565, IRGAMOD295 (above, BASF). , Yoshinox (registered trademark) BHT, BB, 2246G, 425, 250, 930, SS, TT, 917, 314 (all manufactured by AP Corporation), etc. Can be mentioned.

Examples of the [F] polymerization inhibitor in the present embodiment include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and tris- (3,5-di) among the above. It is preferable to use one or more selected from the group consisting of -tert-butyl-4-hydroxybenzyl) -isocyanurate.

The content ratio of the [F] polymerization inhibitor is preferably 10 parts by mass or less, and more preferably 0.1 parts by mass to 5 parts by mass with respect to 100 parts by mass of the polymer [A]. By setting the content ratio in this range, the cleavage deterioration of the cured film can be effectively suppressed without impairing the effect of the present invention.
(Preparation of radiation-sensitive resin composition)
Next, the preparation of the radiation-sensitive resin composition according to the third embodiment of the present invention will be described.

The radiation-sensitive resin composition of the third embodiment of the present invention is added to or [A] a polymer containing a structural unit having an acidic group or a protected acidic group and [B] a radiation-sensitive compound. ] In addition to polymers containing acidic groups or structural units having protected acidic groups, [B] radiosensitive compounds and [C] polymerizable unsaturated compounds, and if necessary, [E] surfactants and the like. It is prepared by mixing any other components. At this time, an organic solvent can be used to prepare a liquid radiation-sensitive resin composition. The organic solvent can be used alone or in combination of two or more.

Functions of the organic solvent include, for example, improving the applicability to a substrate and the like by adjusting the viscosity of the radiation-sensitive resin composition, and improving operability and moldability. The viscosity of the radiation-sensitive resin composition realized by the inclusion of an organic solvent or the like is preferably, for example, 0.1 mPa · s to 50,000 mPa · s (25 ° C.), and more preferably 0.5 mPa · s to 10,000 mPa ·. s (25 ° C.).

Examples of the organic solvent that can be used in the radiation-sensitive resin composition of the third embodiment of the present invention include those that dissolve or disperse other contained components and do not react with other contained components.

For example, alcohols such as methanol, ethanol, isopropanol, butanol, octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene glycol monomethyl ether acetate, propylene. Esters such as 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; benzene, Aromatic hydrocarbons such as toluene and xylene; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone can be mentioned.

The content of the organic solvent used in the radiation-sensitive resin composition of the third embodiment of the present invention can be appropriately determined in consideration of viscosity and the like.

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

[Synthesis Example 1]
<Synthesis of a polymer ([A] polymer) containing a structural unit having an acidic group or a protected acidic group (1)>
A flask equipped with a cooling tube and a stirrer was charged with 4 parts by mass of 2,2'-azobisisobutyronitrile and 190 parts by mass of propylene glycol monomethyl ether acetate, followed by 55 parts by mass of methacrylic acid and 45 parts by mass of benzyl methacrylate. , And 2 parts by mass of α-methylstyrene dimer as a molecular weight regulator, and while gently stirring, raise the temperature of the solution to 80 ° C., hold this temperature for 4 hours, and then raise it to 100 ° C. A solution containing a copolymer was obtained by polymerizing at a temperature maintained for 1 hour. Next, 1.1 parts by mass of tetrabutylammonium bromide and 0.05 parts by mass of 4-methoxyphenol as a polymerization inhibitor were added to the solution containing this copolymer, and the mixture was stirred at 90 ° C. for 30 minutes under an air atmosphere and then methacrylic acid. A polymer (A-1) was obtained by adding 74 parts by mass of glycidyl acid acid and reacting at 90 ° C. for 10 hours (solid content concentration = 35.0%). The weight average molecular weight Mw of the polymer (A-1) was 9000.

[Synthesis Example 2]
<Synthesis of a polymer ([A] polymer) containing a structural unit having an acidic group or a protected acidic group (2)>
A flask equipped with a cooling tube and a stirrer was charged with 5 parts by mass of 2,2'-azobisisobutyronitrile and 250 parts by mass of 3-methoxybutyl acetate, and further charged with 18 parts by mass of methacrylic acid and tricyclomethacrylate [5.2]. 1.02.6] 25 parts by mass of decane-8-yl, 5 parts by mass of styrene, 20 parts by mass of 3-acryloxypropyltrimethoxysilane and 32 parts by mass of glycidyl methacrylate were charged and replaced with nitrogen, and then gently stirred. At the same time, the temperature of the solution was raised to 80 ° C. By maintaining this temperature for 5 hours and polymerizing, a solution containing 28.8% by mass of the polymer (A-2) was obtained. The Mw of this polymer (A-2) was 12000.

[Synthesis Example 3]
<Synthesis of a polymer ([A] polymer) containing a structural unit having an acidic group or a protected acidic group (3)>
A flask equipped with a cooling tube and a stirrer was charged with 7 parts by weight of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by weight of diethylene glycol ethylmethyl ether. Subsequently, 40 parts by weight of 1- (cyclohexyloxy) ethyl methacrylate, 5 parts by weight of styrene, 45 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer were charged and replaced with nitrogen, and then slowly. Started stirring. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to obtain a polymer solution containing the copolymer (A-3). The polystyrene-equivalent weight average molecular weight (Mw) of the copolymer (A-3) was 11,000. The solid content concentration of the polymer solution obtained here was 31.6% by weight.

[Example 1]
<Preparation of Negative Radiation Sensitive Resin Composition>
[A] The solution containing the polymer (A-1) obtained in Synthesis Example 1 as a polymer is 100 parts by mass in terms of solid content, and [B] the following (B) as a polymerization initiator as a radiation-sensitive compound. B-1) 10 parts by mass and [C] 100 parts by mass of the following (C-1) as a polymerizable unsaturated compound are mixed, and propylene glycol monomethyl ether acetate is used as a solvent so that the solid content concentration becomes 30% by mass. Was added, and the mixture was filtered through a millipore filter having a pore size of 0.5 μm to prepare a radiation-sensitive resin composition of Example 1.

[Example 2]
<Preparation of positive radiation-sensitive resin composition>
[A] A solution containing the polymer (A-2) obtained in Synthesis Example 2 as a polymer is 100 parts by mass in terms of solid content, and [B] a quinonediazide compound as a radiation-sensitive compound is described below (B). -2) 30 parts by mass are mixed, propylene glycol monomethyl ether acetate is added as a solvent so that the solid content concentration becomes 30% by mass, and then the mixture is filtered through a millipore filter having a pore size of 0.5 μm. A radiation-sensitive resin composition was prepared.

[Example 3]
<Preparation of positive radiation-sensitive resin composition>
A solution containing the polymer (A-3) as the component (A) synthesized in Synthesis Example 3 in an amount corresponding to 100 parts by weight (solid content) of the copolymer (A-3) and the component (B). As a result, 5 parts by weight of 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate (B-3) was dissolved in diethylene glycol methyl ethyl ether so that the solid content concentration was 30% by weight. Then, the radiation-sensitive resin composition of Example 3 was prepared by filtering with a millipore filter having a pore size of 0.5 μm.

Details of each component used in Examples 1 to 3 are shown below.

[B] Radiation-sensitive compound B-1: 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)] (Irgacure (registered trademark) OXE01, manufactured by BASF)
B-2: 4,4'-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol (1.0 mol) and 1,2-naphthoquinonediazide-5 -Condensate with sulfonic acid chloride (2.0 mol) [C] Polymerizable unsaturated compound C-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (KAYARAD® DPHA, Japan) Made by Yaku Co., Ltd.)
[Example 4]
After forming a coating film of the radiation-sensitive resin composition on the substrate to be coated using the radiation-sensitive composition prepared in Example 1, the coating film was irradiated with radiation using a halftone mask. Next, the coating film irradiated with radiation is developed, the developed coating film is heated, dry etching is performed with a gas containing CF4 gas, and further etching is performed with a gas containing O2 gas to obtain a predetermined region. , A film in which a transparent resin structure and a penetrating contact hole were formed could be formed.
This can be a structure corresponding to FIG. 53).

[Examples 5 and 6]
By performing the same steps as in Example 4 using the radiation-sensitive composition prepared in Examples 2 and 3, a film in which a resin transparent structure and a penetrating contact hole are formed is formed in a predetermined region. We were able to.
These can be structures corresponding to FIG. 53).

By going through a predetermined process using the composition of this example, a structure suitable for an ADS mode liquid crystal display element having a resin transparent structure above the data wiring can be formed, and data can be formed using this structure. It is possible to obtain an ADS mode liquid crystal display element having a resin transparent structure above the wiring.

1: 1st substrate 2: 2nd substrate 3: Data wiring 4: Source / drain electrode 5: Gate electrode, 6: Pixel electrode, 7: Glass substrate, 8: Shared electrode, 9: Gate insulation Film 10, Passion film, 11: Color filter, 12: Black matrix, 13: Liquid crystal display, 14: Image of generated electric field, 15: Black post spacer, 16: Resin transparent structure

Claims (11)

A liquid crystal display element in ADS (Advanced-superdimination switch) mode in which a liquid crystal display is sandwiched between a first substrate and a second substrate arranged to face each other.
The first substrate has a transparent resin structure above the data wiring.
The second substrate is an ADS mode liquid crystal display element having a color filter. (1) A coating film forming step of forming a coating film of a radiation-sensitive resin composition on the first substrate,
(2) An exposure step of irradiating the coating film with radiation using at least one selected from a halftone mask and a gray tone mask.
It has a developing step of (3) developing the coating film irradiated with the radiation, and (4) a heating step of heating the developed coating film, and is placed on the first substrate and directly above the data wiring. The method for manufacturing an ADS mode liquid crystal display element according to claim 1, wherein a transparent resin film having a thicker film thickness and having an opening pattern on a part of the source / drain electrodes is formed. The liquid crystal display in the ADS mode according to claim 2, further comprising (5) an etching step of etching the substrate having the heated coating film using at least one selected from dry etching and wet etching. Manufacturing method of display element. Further, (6) the film at the site irradiated with at least one selected from the halftone and gray tone masks on the substrate is subjected to the said using at least one selected from dry etching and basic chemical treatment. The process of removing the film at the site,
3. The method for manufacturing a liquid crystal display element in the ADS mode according to claim 3. In the (2) exposure step, radiation is irradiated using at least one selected from the halftone mask and the gray tone mask, and the coating film of the radiation-sensitive resin composition is irradiated with at least two different amounts of the radiation. With two parts,
By the (3) developing step and the (4) heating step, one part of at least two parts of the (2) exposure step forms a resin structure having a thickness thicker than the other parts directly above the data wiring. The ADS according to any one of claims 2 to 4, wherein another portion of at least two portions simultaneously forms an opening pattern on some source / drain electrodes. A method for manufacturing a mode liquid crystal display element. The radiation-sensitive resin composition is
[A] The ADS according to any one of claims 2 to 5, which contains a polymer containing a structural unit having an acidic group or a protected acidic group, and [B] a radiation-sensitive compound. A method for manufacturing a mode liquid crystal display element. [A] The method for producing an ADS mode liquid crystal display element according to claim 6, wherein the polymer containing a structural unit having an acidic group or a protected acidic group further has a crosslinkable group. [B] The method for manufacturing an ADS mode liquid crystal display element according to claim 6 or 7, wherein the radiation-sensitive compound is an acid generator, a polymerization initiator, or a combination thereof. An ADS mode liquid crystal display element in which a liquid crystal display is sandwiched between a first substrate and a second substrate arranged to face each other.
The first substrate has a transparent resin structure above the data wiring.
The second substrate is a radiation-sensitive resin composition used for forming the resin transparent structure of a liquid crystal display element having a color filter by irradiation with radiation using at least one selected from a halftone mask and a gray tone mask. It ’s a thing,
[A] A radiation-sensitive resin composition comprising a polymer containing a structural unit having an acidic group or a protected acidic group, and [B] a radiation-sensitive compound. [A] The radiation-sensitive resin composition according to claim 9, wherein the polymer containing a structural unit having an acidic group or a protected acidic group further has a crosslinkable group. [B] The radiation-sensitive resin composition according to claim 9 or 10, wherein the radiation-sensitive compound is an acid generator, a polymerization initiator, or a combination thereof.

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