JP5967178B2 - Manufacturing method of liquid crystal display element - Google Patents

Description

  The present invention relates to a positive radiation sensitive composition, an interlayer insulating film for a liquid crystal display element, and a method for producing a liquid crystal display element.

  In recent years, liquid crystal display devices have been widely used as television receivers, monitor devices for personal computers, and the like. The liquid crystal display device used for these applications is required to have a wide viewing angle that allows the display screen to be viewed from all directions. As a liquid crystal display device capable of obtaining a wide viewing angle, for example, an apparatus using a MVA (Multi-domain Vertical Alignment) type liquid crystal display element is known. However, such a liquid crystal display device has a disadvantage that the response time of the liquid crystal is not sufficiently short, and the alignment is liable to be disturbed by finger pressing or the like.

  Therefore, in a liquid crystal display element, a polymer orientation that stores a tilt direction of a liquid crystal compound by mixing a monomer that can be polymerized by light or heat into the liquid crystal and polymerizing the monomer in a state where the liquid crystal compound is tilted by applying a voltage. The introduction of a support (PSA: Polymer Sustained Alignment) technology has been studied (see Japanese Patent Application Laid-Open No. 2003-149647). A liquid crystal display element using the PSA technology has a strong alignment regulating force because a polymer film that memorizes the tilt direction of the liquid crystal compound is formed at the interface between the liquid crystal and the alignment film. Therefore, by using this PSA technology, it is possible to realize a liquid crystal display device in which the response time of the liquid crystal is short and the alignment is not easily disturbed by finger pressing or the like.

  In a liquid crystal display device using such PSA technology, a liquid crystal containing a monomer capable of reacting with light or heat is injected between a pair of substrates, and then the entire cell is irradiated with light or heated to polymerize the monomer. It becomes. For this reason, according to this liquid crystal display element, the interlayer insulation film laminated | stacked on the board | substrate may deform | transform by the light or heat for making a liquid crystal react. When the interlayer insulating film is deformed, for example, the voltage holding ratio of the liquid crystal display element is lowered.

  On the other hand, the applicant of the present application uses a positive-type radiation-sensitive composition containing a polymer having a carboxyl group and an epoxy group in one molecule, and thus has a highly crosslinked structure due to a thermosetting reaction between the carboxyl group and the epoxy group. An interlayer insulating film having a high hardness has been developed (see Japanese Patent Application Laid-Open No. 05-165214).

  In this positive-type radiation-sensitive composition, if the content of carboxyl groups and epoxy groups in the polymer is improved, the interlayer insulation is excellent in heat resistance and light resistance and can withstand the production of liquid crystal display elements using PSA technology. It is possible to obtain a membrane. However, when the content of highly reactive carboxyl groups and epoxy groups in the polymer is increased, the storage stability of the radiation-sensitive composition is deteriorated and the productivity of the liquid crystal display device is lowered. is there.

JP 2003-149647 A JP 05-165214 A

  The present invention has been made based on the circumstances as described above, and the object thereof is a method for producing a liquid crystal display element having an interlayer insulating film having excellent heat resistance and light resistance, and having a high voltage holding ratio, and It is an object of the present invention to provide a positive radiation sensitive composition which is excellent in storage stability and suitable for forming the interlayer insulating film.

（式（１）中、Ｒ^０は下記式（１−１）〜（１−６）のいずれかで表される基である。）

The invention made to solve the above problems is
Two substrates placed opposite each other,
An interlayer insulating film laminated on at least one inner surface of the substrate, and a liquid crystal layer disposed between the substrates and formed from a polymerizable liquid crystal composition,
The resin constituting the interlayer insulating film is a liquid crystal display element having a polymer cross-linked portion represented by the following formula (1).

(In Formula (1), R ⁰ is a group represented by any of the following Formulas (1-1) to (1-6).)

  The resin constituting the liquid crystal display element of the present invention includes an interlayer insulating film having a crosslinked portion of the polymer represented by the above formula (1), thereby having excellent heat resistance and light resistance. The liquid crystal display element can have a high voltage holding ratio.

（式（２）中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、アルキル基、シクロアルキル基又はアリール基である。但し、上記アルキル基、シクロアルキル基又はアリール基の水素原子の一部又は全部は置換されていてもよい。また、Ｒ^１及びＲ^２が共に水素原子である場合はない。Ｒ^３は、アルキル基、シクロアルキル基、アラルキル基、アリール基又は−Ｍ（Ｒ^３ｍ）_３で表される基である。上記Ｍは、Ｓｉ、Ｇｅ又はＳｎである。Ｒ^３ｍはアルキル基である。但し、これらの基の水素原子の一部又は全部は置換されていてもよい。また、Ｒ^１とＲ^３とが連結して環状エーテルを形成してもよい。） The interlayer insulating film is
[A] A polymer having a structural unit containing a group represented by the following formula (2) in the same or different polymer molecule (hereinafter also referred to as “structural unit (1)”) and an epoxy group-containing structural unit (hereinafter referred to as “a structural unit”) , Also referred to as “[A] polymer”),
[B] A liquid crystal display device formed using a positive radiation-sensitive composition containing a photoacid generator and [C] an organic solvent.

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, provided that one of the hydrogen atoms of the above-mentioned alkyl group, cycloalkyl group, or aryl group) Part or all may be substituted, and R ¹ and R ² are not both hydrogen atoms, R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M (R ^3m ) is a group represented by _3. above M is, Si, a Ge or Sn .R ^3m is an alkyl group. However, some or all of the hydrogen atoms of these groups may be substituted R ¹ and R ³ may be linked to form a cyclic ether.)

  [A] Since the functional group that reacts with the epoxy group is protected by the structure represented by the above formula (2), the polymer does not react in a normal state and is functional only after being deprotected by an acid. The group and the epoxy group will react. Therefore, this positive radiation-sensitive composition containing the [A] polymer is excellent in storage stability, and the liquid crystal display device has high productivity. In addition, the interlayer insulating film of the liquid crystal display element has excellent heat resistance and light resistance because it is hardened by a cross-linking reaction between the deprotected functional group and the epoxy group. As a result, the liquid crystal display element Can have a high voltage holding ratio.

  The polymerizable liquid crystal composition preferably has photopolymerization or thermal polymerization. Since the polymerizable liquid crystal composition has photopolymerizability or thermal polymerizability, a liquid crystal layer can be formed from the polymerizable liquid crystal composition by light irradiation or heating, and efficient production becomes possible. Further, according to the liquid crystal display element, even when manufactured through such light irradiation or heating, deformation of the interlayer insulating film is suppressed, so that a high voltage holding ratio and excellent productivity are exhibited. Can do.

（式（２）中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、アルキル基、シクロアルキル基又はアリール基である。但し、上記アルキル基、シクロアルキル基又はアリール基の水素原子の一部又は全部は置換されていてもよい。また、Ｒ^１及びＲ^２が共に水素原子である場合はない。Ｒ^３は、アルキル基、シクロアルキル基、アラルキル基、アリール基又は−Ｍ（Ｒ^３ｍ）_３で表される基である。上記Ｍは、Ｓｉ、Ｇｅ又はＳｎである。Ｒ^３ｍはアルキル基である。但し、これらの基の水素原子の一部又は全部は置換されていてもよい。また、Ｒ^１とＲ^３とが連結して環状エーテルを形成してもよい。） The positive radiation-sensitive composition of the present invention is
Two substrates placed opposite each other,
To form an interlayer insulating film of a liquid crystal display device comprising an interlayer insulating film laminated on at least one inner surface side of the substrate, and a liquid crystal layer disposed between the substrates and formed from a polymerizable liquid crystal composition Used for
[A] a polymer having a structural unit containing a group represented by the following formula (2) and an epoxy group-containing structural unit in the same or different polymer molecules;
[B] A positive radiation-sensitive composition containing a photoacid generator and [C] an organic solvent.

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, provided that one of the hydrogen atoms of the above-mentioned alkyl group, cycloalkyl group, or aryl group) Part or all may be substituted, and R ¹ and R ² are not both hydrogen atoms, R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M (R ^3m ) is a group represented by _3. above M is, Si, a Ge or Sn .R ^3m is an alkyl group. However, some or all of the hydrogen atoms of these groups may be substituted R ¹ and R ³ may be linked to form a cyclic ether.)

  [A] As described above, the functional group that reacts with the epoxy group is protected by the structure represented by the above formula (2), so that the polymer does not react in a normal state and is deprotected by an acid. Thus, the epoxy group reacts with the functional group. The cross-linking reaction between the functional group deprotected by irradiation and the epoxy group proceeds and is hardened. Therefore, an interlayer insulating film with excellent heat resistance and light resistance can be obtained, and excellent storage stability. Have Therefore, the composition can suitably form an interlayer insulating film for a liquid crystal display element that forms a liquid crystal layer by heating or light irradiation.

  The composition further contains a [D] surfactant, and the [D] surfactant is preferably a silicone surfactant. The composition can further improve the film thickness uniformity of the interlayer insulating film obtained by further containing a silicone-based surfactant, and as a result, the voltage holding ratio of the obtained liquid crystal display element can be further increased. it can.

The method for forming an interlayer insulating film for a liquid crystal display element of the present invention comprises:
(1) The process of forming the coating film of the said composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3).

  The interlayer insulating film is suitable as a method for forming an interlayer insulating film for a liquid crystal display element in which a liquid crystal layer is formed by heating or light irradiation.

  The interlayer insulation film of the liquid crystal display element of this invention is formed using the said positive radiation sensitive composition. The interlayer insulating film can be suitably used as an interlayer insulating film for a liquid crystal display element that forms a liquid crystal layer by heating or light irradiation as described above.

  The “polymer” of the component [A] referred to in the present specification has the structural unit (1) in one polymer molecule and has an epoxy in a polymer molecule different from the one polymer molecule. It is a concept including the case of having a group-containing structural unit. “Radiation” is a concept including visible light, ultraviolet light, far ultraviolet light, X-rays, charged particle beams, and the like.

  As described above, the method for manufacturing a liquid crystal display element of the present invention can suppress deformation and the like in the manufacturing process because the formed interlayer insulating film has excellent heat resistance and light resistance. As a result, the obtained liquid crystal display element can exhibit excellent voltage holding ability. Moreover, since this positive radiation sensitive composition is excellent in storage stability, the liquid crystal display element has high productivity.

It is typical sectional drawing which shows the state in the middle of manufacture of the liquid crystal display element which concerns on one Embodiment of the liquid crystal display element of this invention.

  The liquid crystal display element of the present invention includes two substrates disposed opposite to each other, an interlayer insulating film laminated on at least one inner surface of the substrate, and a liquid crystal layer disposed between the substrates. Hereinafter, each component will be described in detail.

<Board>
As a board | substrate, what is normally used for a general liquid crystal display element is mentioned. Examples of the material of the substrate include glass, quartz, silicone, and resin. Examples of the resin include polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, polyimide, a ring-opening polymer of a cyclic olefin, and a hydrogenated product thereof. The substrate is not limited to a rigid material, and may be a flexible material such as a plastic film.

  At least one board | substrate arrange | positioned facing is transparent. Through this transparent substrate, the liquid crystal layer and the like can be visually recognized from the outside. Note that when the liquid crystal display element is used to act on light passing from one side of the element to the other side, both the two substrates have transparency. A transparent or opaque electrode may be disposed on the entire surface or a part of the substrate depending on the purpose. It should be noted that a spacer for maintaining a gap can be usually interposed between the two substrates in the same manner as a known liquid crystal display element.

<Interlayer insulation film>
The interlayer insulating film is formed using a positive radiation sensitive composition containing [A] polymer, [B] photoacid generator and [C] organic solvent, and constitutes the interlayer insulating film. The resin to be used has a crosslinked part of the polymer represented by the above formula (1). The liquid crystal display element has excellent heat resistance and light resistance by including an interlayer insulating film having a group represented by the above formula (1) and having a crosslinked portion of the polymer. As a result, the liquid crystal display element Can have a high voltage holding ratio.

In the above formula (1), R ⁰ is a group represented by any one of the above formulas (1-1) to (1-6).

  The cross-linked portion of the polymer represented by the above formula (1) is, for example, as shown in the following reaction formula, a polymer having a functional group such as a carboxyl group and a polymer having an epoxy group are thermally cross-linked. Or formed by thermal crosslinking between polymers having a carboxyl group and an epoxy group in one molecule. The functional group such as the carboxyl group corresponds to a group in which the protecting group represented by the above formula (2) is deprotected with an acid, for example.

  Moreover, this positive radiation sensitive composition may contain other arbitrary components. Hereinafter, each component of the positive radiation sensitive composition will be described in detail.

[[A] polymer]
[A] The polymer has the structural unit (1) and the epoxy group-containing structural unit in the same or different polymer molecules, and may have other structural units as necessary. [A] Since the functional group that reacts with the epoxy group is protected by the structure represented by the above formula (2), the polymer does not react in a normal state and is functional only after being deprotected by an acid. The group and the epoxy group will react. Therefore, this positive radiation-sensitive composition containing the [A] polymer is excellent in storage stability, and the liquid crystal display device has high productivity. In addition, the interlayer insulating film of the liquid crystal display element has excellent heat resistance and light resistance because it is hardened by a cross-linking reaction between the deprotected functional group and the epoxy group. As a result, the liquid crystal display element Can have a high voltage holding ratio.

The embodiment of the [A] polymer having the structural unit (1) and the epoxy group-containing structural unit is not particularly limited,
(I) When both the structural unit (1) and the epoxy group-containing structural unit are contained in the same polymer molecule, and one type of polymer molecule is present in [A] in the polymer;
(Ii) One polymer molecule has the structural unit (1), and a different polymer molecule has an epoxy group-containing structural unit, and the polymer [A] contains two kinds of polymer molecules. Is present;
(Iii) having both the structural unit (1) and the epoxy group-containing structural unit in one polymer molecule, and having the structural unit (1) in a different polymer molecule; When the polymer molecule has an epoxy group-containing structural unit, and there are three polymer molecules in [A] in the polymer;
(Iv) In addition to the polymer molecules specified in (i) to (iii), there may be mentioned a case where the polymer [A] further contains one or more polymer molecules.

(Structural unit (1))
In the structural unit (1), the group represented by the formula (2) is present as a group that dissociates in the presence of an acid to generate a polar group (hereinafter also referred to as “acid-dissociable group”). The acid-dissociable group is dissociated by the acid generated from the photoacid generator upon irradiation with radiation, and as a result, the [A] polymer that has been insoluble in alkali becomes alkali-soluble. The acid dissociable group has an acetal structure or a ketal structure that is relatively stable with respect to an alkali, and these are dissociated by the action of an acid.

In the above formula (2), the alkyl group represented by R ¹ and R ² is preferably a linear or branched alkyl group having 1 to 30 carbon atoms. The alkyl chain may have an oxygen atom, a sulfur atom, or a nitrogen atom. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n- Examples include linear alkyl groups such as octadecyl group, branched alkyl groups such as i-propyl group, i-butyl group, t-butyl group, neopentyl group, 2-hexyl group, and 3-hexyl group.

In the above formula (2), the cycloalkyl group represented by R ¹ and R ² is preferably a cycloalkyl group having 3 to 20 carbon atoms. The cycloalkyl group may be polycyclic and may have an oxygen atom in the ring. Examples of the cycloalkyl group include cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl, cyclooctyl, bornyl group, norbornyl group, adamantyl group and the like.

In the above formula (2), the aryl group represented by R ¹ and R ² is preferably an aryl group having 6 to 14 carbon atoms. The aryl group may be a single ring, a structure in which single rings are linked, or a condensed ring. Examples of the aryl group include a phenyl group and a naphthyl group.

Some or all of the hydrogen atoms of R ¹ and R ² may be substituted. Examples of the substituent include a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (as the cycloalkyl group, the description of the cycloalkyl group can be preferably applied), an aryl group ( As the aryl group, the description of the aryl group can be suitably applied), an alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, A pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, etc.), an acyl group (preferably an acyl group having 2 to 20 carbon atoms), for example, an acetyl group, a propionyl group, a butyryl group, i-butyryl Group), an acyloxy group (preferably an acyloxy group having 2 to 10 carbon atoms). Examples thereof include an acetoxy group, an ethylyloxy group, a butyryloxy group, a t-butyryloxy group, a t-amylyloxy group, and the like, and an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms. For example, a methoxycarbonyl group, Ethoxycarbonyl group, propoxycarbonyl group and the like), haloalkyl group (a group in which part or all of the hydrogen atoms of the above alkyl group or cycloalkyl group are substituted with halogen atoms. For example, perfluoromethyl group, A fluoroethyl group, a perfluoropropyl group, a fluorocyclopropyl group, a fluorocyclobutyl group, etc.). As for the cyclic structure in the aryl group, cycloalkyl group and the like, the above alkyl group may be mentioned as a further substituent.

In the above formula (2), the description of R ¹ and R ² can be applied to the alkyl group, cycloalkyl group and aryl group represented by R ³ . In the above formula (2), the aralkyl group represented by R ³ is preferably an aralkyl group having 7 to 20 carbon atoms. For example, benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group and the like can be mentioned. The group represented by ^{-M (R} _{3m) 3} of ^{R 3} in the above formula (1), for example trimethylsilanyl group, trimethylgermyl group and the like. A part or all of the hydrogen atoms of the aralkyl group represented by R ³ or the group represented by —M (R ^3m ) ₃ may be substituted with the above group substituent.

R ¹ and R ³ may be linked to form a cyclic ether. Examples of such cyclic ethers include 2-oxetanyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 2-dioxanyl group and the like. Some or all of the hydrogen atoms of the cyclic ether may be substituted with the above substituents.

  The structural unit (1) can have the acetal structure or the ketal structure by having a functional group that gives an acetal structure or a ketal structure by bonding to another carbon atom.

  Examples of the functional group that gives an acetal structure by bonding to the other carbon atom include 1-methoxyethoxy group, 1-ethoxyethoxy group, 1-n-propoxyethoxy group, 1-i-propoxyethoxy group, 1- n-butoxyethoxy group, 1-i-butoxyethoxy group, 1-sec-butoxyethoxy group, 1-t-butoxyethoxy group, 1-cyclopentyloxyethoxy group, 1-cyclohexyloxyethoxy group, 1-norbornyloxy Ethoxy group, 1-bornyloxyethoxy 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 , (Benzyl) (cyclohexyloxy) methoxy group, (benzyl) (phenoxy) methoxy group, (benzyl) (benzyloxy) methoxy group, 2-tetrahydrofuranyloxy group, 2-tetrahydropyranyloxy group, 1-trimethylsilanyl An oxyethoxy group, 1-trimethylgermyloxyethoxy group, etc. are mentioned.

  Among these, 1-ethoxyethoxy group, 1-cyclohexyloxyethoxy group, 2-tetrahydropyranyloxy group, 1-n-propoxyethoxy group, 1-n-butoxyethoxy group, 2-tetrahydropyranyloxy group are included. preferable.

  Examples of the functional group that gives a ketal structure by bonding to the other carbon atom include 1-methyl-1-methoxyethoxy group, 1-methyl-1-ethoxyethoxy group, 1-methyl-1-n-propoxy group. Ethoxy group, 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-bornyloxyethoxy group, 1-methyl-1-phenyloxyethoxy group, 1-methyl-1- (1-naphthyloxy) ester Xyl group, 1-methyl-1-benzyloxyethoxy 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 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- -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-methyl-tetrahydropyranyl) oxy group, 1-methoxy-cyclopentyloxy group, 1-methoxy-cyclohexyloxy group and the like.

  Of these, a 1-methyl-1-methoxyethoxy group and a 1-methyl-1-cyclohexyloxyethoxy group are preferable.

  Examples of the structural unit (1) having the acetal structure or ketal structure include structural units represented by the following formulas (2-1) to (2-3).

In the above formulas (2-1) and (2-3), R ⁴ is a hydrogen atom or a methyl group. R ¹ , R ² and R ³ are as defined in the above formula (2).

Examples of the monomer having radical polymerizability that gives the structural unit (1) represented by the above formulas (2-1) to (2-3) (hereinafter, also referred to as “acetal structure-containing monomer”) include: 1-alkoxyalkyl (meth) acrylate, 1- (cycloalkyloxy) alkyl (meth) acrylate, 1- (haloalkoxy) alkyl (meth) acrylate, 1- (aralkyloxy) alkyl (meth) acrylate, tetrahydropyranyl ( (Meth) acrylate-based acetal structure-containing monomers such as (meth) acrylate;
2,3-di (1- (trialkylsilanyloxy) alkoxy) carbonyl) -5-norbornene, 2,3-di (1- (trialkylgermyloxy) alkoxy) carbonyl) -5-norbornene, 2, 3-di (1-alkoxyalkoxycarbonyl) -5-norbornene, 2,3-di (1- (cycloalkyloxy) alkoxycarbonyl) -5-norbornene, 2,3-di (1- (aralkyloxy) alkoxycarbonyl ) Norbornene-based acetal structure-containing monomers such as -5-norbornene;
Examples thereof include styrene-based acetal structure-containing monomers such as 1-alkoxyalkoxystyrene, 1- (haloalkoxy) alkoxystyrene, 1- (aralkyloxy) alkoxystyrene, and tetrahydropyranyloxystyrene.

  As more specific acetal structure-containing monomers, for example, 1-ethoxyethyl methacrylate, 1-methoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 1-isobutoxyethyl methacrylate, 1-t-butoxyethyl methacrylate, 1 -(2-chloroethoxy) ethyl methacrylate, 1- (2-ethylhexyloxy) ethyl methacrylate, 1-n-propoxyethyl methacrylate, 1-cyclohexyloxyethyl methacrylate, 1- (2-cyclohexylethoxy) ethyl methacrylate, 1-benzyl Oxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, 1-ethoxyethyl acrylate, 1-methoxyethyl acrylate, 1-n-butoxyethyl acrylate, 1-iso 1-t-butoxyethyl acrylate, 1- (2-chloroethoxy) ethyl acrylate, 1- (2-ethylhexyloxy) ethyl acrylate, 1-n-propoxyethyl acrylate, 1-cyclohexyloxyethyl acrylate, 1 -(2-cyclohexylethoxy) ethyl acrylate, 1-benzyloxyethyl acrylate, 2-tetrahydropyranyl acrylate, 2,3-di (1- (trimethylsilanyloxy) ethoxy) carbonyl) -5-norbornene, 2,3 -Di (1- (trimethylgermyloxy) ethoxy) carbonyl) -5-norbornene, 2,3-di (1-methoxyethoxycarbonyl) -5-norbornene, 2,3-di (1- (cyclohexyloxy) ethoxy Carboni ) -5-norbornene, 2,3-di (1- (benzyloxy) ethoxycarbonyl) -5-norbornene, p or m-1-ethoxyethoxystyrene, p or m-1-methoxyethoxystyrene, p or m- 1-n-butoxyethoxystyrene, p or m-1-isobutoxyethoxystyrene, p or m-1- (1,1-dimethylethoxy) ethoxystyrene, p or m-1- (2-chloroethoxy) ethoxystyrene P or m-1- (2-ethylhexyloxy) ethoxystyrene, p or m-1-n-propoxyethoxystyrene, p or m-1-cyclohexyloxyethoxystyrene, p or m-1- (2-cyclohexylethoxy) ) Ethoxystyrene, p or m-1-benzyloxyethoxystyrene and the like. The said structural unit (1) can be used individually or in combination of 2 or more types.

  Of these acetal structure-containing monomers, 1-alkoxyalkyl (meth) acrylate, tetrahydropyranyl (meth) acrylate, 1-alkoxyalkoxystyrene, and tetrahydropyranyloxystyrene are preferable, and 1-alkoxyalkyl (meth) acrylate is preferable. Are more preferable, and 1-ethoxyethyl methacrylate, 1-n-butoxyethyl methacrylate, 2-tetrahydropyranyl methacrylate, and 1-benzyloxyethyl methacrylate are particularly preferable.

  As the acetal structure-containing monomer that gives the structural unit (1), a commercially available product may be used, or one synthesized by a known method may be used. For example, the acetal structure-containing monomer represented by the above formula (2-1) can be synthesized by reacting (meth) acrylic acid represented by the following reaction formula with vinyl ether in the presence of an acid catalyst.

In the above reaction formula, R ⁴ , R ¹ and R ³ have the same meanings as the above formulas (2) and (2-1), respectively. R ⁵ and R ⁶ have the same meaning as R ² in the above formula (2) as —CH (R ⁵ ) (R ⁶ ).

  [A] The content of the structural unit (1) in the polymer is not particularly limited as long as the [A] polymer is alkali-soluble by an acid and the desired heat resistance of the cured film is exhibited. When one polymer molecule contains both the structural unit (1) and the epoxy group-containing structural unit, the monomer charge ratio is 5% by mass to 70% with respect to all the structural units contained in the [A] polymer. % By mass is preferable, 10% by mass to 60% by mass or less is more preferable, and 20% by mass to 50% by mass is particularly preferable.

  On the other hand, when one polymer molecule has the structural unit (1) and another polymer molecule has an epoxy group-containing structural unit, the structural unit in the one polymer molecule having the structural unit (1) The content of (1) is preferably 40% by mass to 99% by mass and more preferably 50% by mass to 98% by mass with respect to the total structural units contained in the polymer molecule. 55 mass% to 95 mass% is particularly preferable.

(Epoxy group-containing structural unit)
[A] The polymer has an epoxy group-containing structural unit together with the structural unit (1). The epoxy group-containing structural unit is a structural unit derived from an epoxy group-containing monomer having radical polymerizability. Examples of the epoxy group include an oxanyl group (1,2-epoxy structure) and an oxetanyl group (1,3-epoxy structure). [A] When the polymer has a structural unit containing an oxiranyl group or an oxetanyl group in the molecule, the hardness of the cured film obtained from the composition can be improved and the heat resistance can be further increased.

Examples of the epoxy group-containing monomer that gives the epoxy group-containing structural unit include glycidyl acrylate, glycidyl methacrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, and acrylic acid-3. -Methyl-3,4-epoxybutyl, 3-ethyl-3,4-epoxybutyl methacrylate, acrylic acid-5,6-epoxyhexyl, methacrylic acid-5,6-epoxyhexyl, 5-methyl methacrylate -5,6-epoxyhexyl, methacrylic acid-5-ethyl-5,6-epoxyhexyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, 3,4-epoxycyclohexyl Methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxy Rohexylethyl methacrylate, 3,4-epoxycyclohexylpropyl methacrylate, 3,4-epoxycyclohexylbutyl methacrylate, 3,4-epoxycyclohexylhexyl methacrylate, 3,4-epoxycyclohexyl acrylate, 3 , 4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylethyl acrylate, 3,4-epoxycyclohexylpropyl acrylate, 3,4-epoxycyclohexylbutyl acrylate, 3,4-epoxycyclo Oxylanyl group-containing (meth) acrylic compounds such as xylhexyl acrylate;
o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl Vinyl benzyl glycidyl ethers such as benzyl glycidyl ether;
vinyl phenyl glycidyl ethers such as o-vinyl phenyl glycidyl ether, m-vinyl phenyl glycidyl ether, p-vinyl phenyl glycidyl ether;
3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-methyloxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -3-phenyloxetane, 3- (2-acryloyloxyethyl) oxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3-ethyloxetane, 3- (2-acryloyloxyethyl) -3 -Phenyloxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-methyloxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -3-phenyl Oxetane, -(2-methacryloyloxyethyl) oxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl) -3-ethyloxetane, 3- (2-methacryloyloxyethyl)- 3-phenyloxetane, 2- (acryloyloxymethyl) oxetane, 2- (acryloyloxymethyl) -2-methyloxetane, 2- (acryloyloxymethyl) -2-ethyloxetane, 2- (acryloyloxymethyl) -2- Phenyloxetane, 2- (2-acryloyloxyethyl) oxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyloxyethyl) -2-ethyloxetane, 2- (2-acryloyl) Oxyethyl) -2-fe Luoxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-methyloxetane, 2- (methacryloyloxymethyl) -2-ethyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (2-methacryloyloxyethyl) oxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) -2-ethyloxetane, 2- (2-methacryloyloxyethyl) Examples include oxetanyl group-containing (meth) acrylic compounds such as 2-phenyloxetane. The said epoxy group containing structural unit can be used individually or in combination of 2 or more types.

  Among the above epoxy group-containing monomers, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, 3- (methacryloyloxymethyl) -3-Methyloxetane and 3- (methacryloyloxymethyl) -3-ethyloxetane are preferable from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and developability of the composition.

  [A] The content of the epoxy group-containing structural unit in the polymer is not particularly limited as long as the desired heat resistance of the interlayer insulating film is exhibited, and the structural unit (1) and the epoxy group are contained in one polymer molecule. When the structural unit is included, the monomer charge ratio is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 55% by mass with respect to all the structural units contained in the [A] polymer. A mass% to 50 mass% is particularly preferred.

  On the other hand, when one polymer molecule has a structural unit (1) and another polymer molecule has an epoxy group-containing structural unit, it is included in one polymer molecule having an epoxy group-containing structural unit. As content of the epoxy group containing structural unit with respect to all the structural units, 20 mass%-80 mass% are preferable by monomer preparation ratio, 30 mass%-70 mass% are more preferable, 35 mass%-65 mass% are 35 mass%-65 mass%. Particularly preferred.

(Other structural units)
Examples of the radical polymerizable monomer that gives other structural units include a carboxyl group or a derivative thereof, a radical polymerizable monomer having a hydroxyl group, and the like.

Examples of the radical polymer monomer having a carboxyl group or a derivative thereof include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, and 2-acryloyloxyethyl hexahydro. Monocarboxylic acids such as phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid;
Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid;
The acid anhydride of the said dicarboxylic acid etc. are mentioned.

Examples of the radical polymerizable monomer having a hydroxyl group include acrylic acid-2-hydroxyethyl ester, acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, and acrylic acid-4-hydroxymethylcyclohexylmethyl. Hydroxyalkyl esters of acrylic acid such as esters;
Methacrylic acid-2-hydroxyethyl ester, methacrylic acid-3-hydroxypropyl ester, methacrylic acid-4-hydroxybutyl ester, methacrylic acid-5-hydroxypentyl ester, methacrylic acid-6-hydroxyhexyl ester, methacrylic acid-4- And methacrylic acid hydroxyalkyl esters such as hydroxymethyl-cyclohexylmethyl ester.

  Among these radical polymerizable monomers having a hydroxyl group, acrylic acid-2-hydroxyethyl ester, from the viewpoint of copolymerization reactivity with other radical polymerizable monomers and heat resistance of the resulting interlayer insulating film, Acrylic acid-3-hydroxypropyl ester, acrylic acid-4-hydroxybutyl ester, methacrylic acid-2-hydroxyethyl ester, methacrylic acid-4-hydroxybutyl ester, acrylic acid-4-hydroxymethyl-cyclohexylmethyl ester, methacrylic acid -4-Hydroxymethyl-cyclohexylmethyl ester is preferred.

Examples of other radical polymerizable monomers include alkyl acrylate esters such as methyl acrylate and i-propyl acrylate;
Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate;
Cyclohexyl acrylate, acrylate-2-methylcyclohexyl, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate, acrylate-2- (tricyclo [5.2.1.0 ^{2, 6} ] Acrylic alicyclic alkyl ester such as decan-8-yloxy) ethyl, isobornyl acrylate;
Cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacrylic acid-2- (tricyclo [5.2.1.0 ^{2, 6} ] decano-8-yloxy) ethyl, methacrylic acid alicyclic alkyl esters such as isobornyl methacrylate;
Aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate and aralkyl esters of acrylic acid;
Aryl esters of methacrylic acid such as phenyl methacrylate and benzyl methacrylate and aralkyl esters of methacrylic acid;
Dicarboxylic acid dialkyl esters such as diethyl maleate, diethyl fumarate, diethyl itaconate;
Unsaturated 5-membered ring methacrylates and unsaturated 6-membered ring methacrylates containing 1 atom of oxygen such as tetrahydrofurfuryl methacrylate, tetrahydrofuryl methacrylate, tetrahydropyran-2-methyl methacrylate;
4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-cyclohexyl- 2 oxygen atoms such as 1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-methacryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane Unsaturated heterocyclic 5-membered methacrylates containing:
4-acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxymethyl-2, 2-diethyl- 1,3-dioxolane, 4-acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4-acryloyloxymethyl-2-cyclopentyl-1,3-dioxolane, 4-acryloyloxymethyl-2- Cyclohexyl-1,3-dioxolane, 4-acryloyloxyethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-acryloyloxypropyl-2-methyl-2-ethyl-1,3-dioxolane, 4- Acryloyloxybutyl-2-methyl-2-ethyl-1,3-dioxola Unsaturated five-membered heterocyclic acrylic acid esters containing oxygen 2 atoms and the like;
Vinyl aromatic compounds such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, 4-isopropenylphenol;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -N-substituted maleimides such as maleimide propionate, N- (9-acridinyl) maleimide;
Conjugated diene compounds such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Other unsaturated compounds such as acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, vinyl acetate and the like can be mentioned.

Among these other radical polymerizable monomers, styrene, 4-isopropenylphenol, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, tetrahydrofurfuryl methacrylate, 1, 3-Butadiene, 4-acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, N-cyclohexylmaleimide, N-phenylmaleimide, and benzyl methacrylate are radical polymerizable monomers having the above reactive functional groups. From the viewpoint of copolymerization reactivity with the monomer and developability of the composition.

[A] The weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography) of the polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 × 10. ^{3 to} 5.0 × 10 ⁴ . [A] By making Mw of a polymer into the said specific range, the radiation sensitivity and alkali developability of the said composition can be improved.

[A] The number average molecular weight (Mn) in terms of polystyrene by GPC of the polymer is preferably 2.0 × 10 ^{3 to} 1.0 × 10 ⁵ , more preferably 5.0 × 10 ^{3 to} 5.0 × 10. ⁴ . By making Mn of a copolymer into the said specific range, the cure reactivity at the time of hardening of the coating film of the said composition can be improved.

  [A] The molecular weight distribution (Mw / Mn) of the polymer is preferably 3.0 or less, more preferably 2.6 or less. [A] By setting Mw / Mn of the polymer to 3.0 or less, the developability of the obtained interlayer insulating film can be improved. [A] The composition containing the polymer can easily form a desired pattern shape without causing development residue during development.

([A] Production method of polymer)
[A] The polymer can be produced, for example, by radical copolymerization of an acetal structure-containing monomer, an epoxy group-containing monomer, or another monomer that gives other structural units. In the case of producing the [A] polymer containing both the structural unit (1) and the epoxy group-containing structural unit in the same polymer molecule, a mixture containing at least an acetal structure-containing monomer and an epoxy group-containing monomer May be used for copolymerization. On the other hand, when the [A] polymer having the structural unit (1) in one polymer molecule and the epoxy group-containing structural unit in a different polymer molecule is produced, at least an acetal structure-containing monomer A polymer solution containing the structural unit (1) is obtained by radical polymerization of a polymerizable solution containing, and a polymer solution containing at least an epoxy group-containing monomer is radically polymerized to have an epoxy group-containing structural unit. What is necessary is just to obtain a polymer molecule | numerator and finally mix both to make [A] polymer.

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

  Examples of alcohols include methanol, ethanol, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol and the like.

  Examples of ethers include tetrahydrofuran.

  Examples of glycol ethers include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether.

  Examples of the ethylene glycol alkyl ether acetate include methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate.

  Examples of the diethylene glycol alkyl ether include diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol ethyl methyl ether.

  Examples of the propylene glycol monoalkyl ether include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and the like.

  Examples of the propylene glycol monoalkyl ether acetate include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate and the like.

  Examples of the propylene glycol monoalkyl ether propionate include propylene monoglycol methyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monopropyl ether propionate, propylene glycol monobutyl ether propionate and the like. .

  Examples of aromatic hydrocarbons include toluene and xylene.

  Examples of ketones include methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, and the like.

  Examples of other esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, hydroxy Methyl acetate, ethyl hydroxyacetate, butyl hydroxyacetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate Methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, propyl ethoxyacetate, butyl ethoxyacetate, Methyl ropoxyacetate, ethyl propoxyacetate, propylpropoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propylbutoxyacetate, butylbutoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropionate Propyl acid, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, 2-butoxypropionic acid Ethyl, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methyl Butyl xylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxy Examples include propyl propionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, and butyl 3-butoxypropionate.

  Of these solvents, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol monoalkyl ether acetate, and butyl methoxyacetate are preferred. Diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether acetate, propylene More preferred are glycol monomethyl ether and butyl methoxyacetate.

  As the polymerization initiator used in the polymerization reaction, those generally known as radical polymerization initiators can be used. Examples of the radical polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobis- (4-methoxy-). 2,4-dimethylvaleronitrile), azo compounds such as 2,2′-azobis (methyl 2-methylpropionate); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- (t -Organic peroxides such as -butylperoxy) cyclohexane and hydrogen peroxide.

  When a peroxide is used as the radical polymerization initiator, the peroxide may be used together with a reducing agent to form a redox initiator.

  [A] In the polymerization reaction for producing the polymer, a molecular weight modifier can be used to adjust the molecular weight. Examples of the molecular weight modifier include halogenated hydrocarbons such as chloroform and carbon tetrabromide; mercaptans such as n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, and thioglycolic acid; Xanthogens such as xanthogen sulfide and diisopropylxanthogen disulfide; terpinolene, α-methylstyrene dimer and the like.

<[B] Photoacid generator>
[B] The photoacid generator is a substance that generates an acid upon irradiation with radiation. Here, as the radiation, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used. By including the [B] photoacid generator and the [A] polymer having an acid dissociable group, the composition can exhibit positive radiation sensitive characteristics. [B] The photoacid generator is not particularly limited as long as it is a substance that generates an acid (for example, carboxylic acid, sulfonic acid, etc.) by irradiation with radiation. [B] The content of the photoacid generator in the composition may be the form of a photoacid generator (hereinafter also referred to as “[B] photoacid generator”) which is a compound as described later. It may be in the form of a photoacid generating group incorporated as part of a polymer or other polymer, or both forms.

  [B] Examples of the photoacid generator include oxime sulfonate compounds, onium salts, sulfonimide compounds, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, and the like. These can be used alone or in combination of two or more.

(Oxime sulfonate compound)
As said oxime sulfonate compound, the compound containing the oxime sulfonate group represented by following formula (3) is preferable.

In the above formula (3), R ⁵ is an optionally substituted linear, branched, or cyclic alkyl group, or an optionally substituted aryl group. As the alkyl group for R ^5, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable. The alkyl group of R ⁵ includes an alkoxy group having 1 to 10 carbon atoms or an alicyclic group (including a bridged alicyclic group such as a 7,7-dimethyl-2-oxonorbornyl group, preferably a bicycloalkyl group. Etc.). As the aryl group for R ^5, an aryl group having 6 to 11 carbon atoms is preferable, and a phenyl group or a naphthyl group is more preferable. The aryl group of R ⁵ may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group, or a halogen atom.

  The compound containing an oxime sulfonate group represented by the above formula (3) is particularly preferably an oxime sulfonate compound represented by the following formula (3-1).

In said formula (3-1), R < ⁵ > is synonymous with the said formula (3). R ⁶ is an alkyl group, an alkoxy group or a halogen atom. m is an integer of 0-3. However, when R ⁶ is plural, a plurality of R ⁶ may be the same or different. The alkyl group represented by R ⁶ is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

The alkoxy group represented by R ⁶ is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom represented by X is preferably a chlorine atom or a fluorine atom. m is preferably 0 or 1. In the above formula (3-1), a compound in which m is 1, R ⁶ is a methyl group, and the substitution position of R ⁶ is ortho is more preferable.

  Examples of the oxime sulfonate compound include compounds represented by the following formulas.

  The above compounds are respectively [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)- (2-methylphenyl) acetonitrile], [(camphorsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H-thiophene-2) Commercially available products are available as -ylidene)-(2-methylphenyl) acetonitrile] and [(5-octylsulfonyloxyimino)-(4-methoxyphenyl) acetonitrile].

(Onium salt)
Examples of the onium salt include diphenyliodonium salt, triphenylsulfonium salt, sulfonium salt, benzothiazonium salt, and tetrahydrothiophenium salt.

  Examples of the diphenyliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate, diphenyl Iodonium butyltris (2,6-difluorophenyl) borate, 4-methoxyphenylphenyliodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarce Bis (4-tert-butylphenyl) iodonium trifluoro Tansulfonate, bis (4-t-butylphenyl) iodonium trifluoroacetate, bis (4-t-butylphenyl) iodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium camphorsulfonic acid, etc. Can be mentioned.

  Examples of the triphenylsulfonium salt include triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphorsulfonic acid, triphenylsulfonium tetrafluoroborate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, and triphenyl. Examples include sulfonium butyl tris (2,6-difluorophenyl) borate.

  Examples of the sulfonium salt include alkylsulfonium salts, benzylsulfonium salts, dibenzylsulfonium salts, substituted benzylsulfonium salts and the like.

  Examples of the alkylsulfonium salt include 4-acetoxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium hexafluoroarsenate, dimethyl-4- (benzyloxycarbonyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (Benzoyloxy) phenylsulfonium hexafluoroantimonate, dimethyl-4- (benzoyloxy) phenylsulfonium hexafluoroarsenate, dimethyl-3-chloro-4-acetoxyphenylsulfonium hexafluoroantimonate and the like can be mentioned.

  Examples of the benzylsulfonium salt include benzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate, 4-acetoxyphenylbenzylmethylsulfonium hexafluoroantimonate, benzyl-4-methoxyphenyl. Methylsulfonium hexafluoroantimonate, benzyl-2-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, benzyl-3-chloro-4-hydroxyphenylmethylsulfonium hexafluoroarsenate, 4-methoxybenzyl-4-hydroxyphenyl Examples include methylsulfonium hexafluorophosphate.

  Examples of the dibenzylsulfonium salt include dibenzyl-4-hydroxyphenylsulfonium hexafluoroantimonate, dibenzyl-4-hydroxyphenylsulfonium hexafluorophosphate, 4-acetoxyphenyl dibenzylsulfonium hexafluoroantimonate, and dibenzyl-4-methoxyphenylsulfonium. Hexafluoroantimonate, dibenzyl-3-chloro-4-hydroxyphenylsulfonium hexafluoroarsenate, dibenzyl-3-methyl-4-hydroxy-5-t-butylphenylsulfonium hexafluoroantimonate, benzyl-4-methoxybenzyl- Examples include 4-hydroxyphenylsulfonium hexafluorophosphate.

  Examples of substituted benzylsulfonium salts include p-chlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, p-nitrobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, and p-chlorobenzyl-4-hydroxyphenylmethyl. Sulfonium hexafluorophosphate, p-nitrobenzyl-3-methyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, 3,5-dichlorobenzyl-4-hydroxyphenylmethylsulfonium hexafluoroantimonate, o-chlorobenzyl-3- Examples include chloro-4-hydroxyphenylmethylsulfonium hexafluoroantimonate.

  Examples of the benzothiazonium salt include 3-benzylbenzothiazonium hexafluoroantimonate, 3-benzylbenzothiazonium hexafluorophosphate, 3-benzylbenzothiazonium tetrafluoroborate, 3- (p-methoxy). Benzyl) benzothiazonium hexafluoroantimonate, 3-benzyl-2-methylthiobenzothiazonium hexafluoroantimonate, 3-benzyl-5-chlorobenzothiazonium hexafluoroantimonate, and the like.

  Examples of tetrahydrothiophenium salts include 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate and 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethane. Sulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (5-t-butoxycarbonyloxybicyclo) [2.2.1] Heptan-2-yl) -1,1, , 2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium-2- (6-t-butoxycarbonyloxybicyclo [2.2.1] heptan-2-yl ) -1,1,2,2-tetrafluoroethanesulfonate and the like.

(Sulfonimide compound)
Examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (camphorsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy). ) Succinimide, N- (4-fluorophenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (camphorsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N -(2-fluorophenylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (camphorsulfonyloxy) diphenyl monomer Imido, 4-methylphenylsulfonyloxy) diphenylmaleimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) diphenylmaleimide, N- (4-fluorophenylsulfonyloxy) Diphenylmaleimide, N- (phenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] Hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (nonafluorobutane Sulfonyloxy) bicyclo [2.2.1] Pto-5-ene-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-en-2,3-dicarboxylimide, N- (camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5 -Ene-2,3-dicarboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-methylphenyl) Sulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyl) Ruoxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept- 5-ene-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylimide, N- (4-fluoro Phenylsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo [2.2.1] heptane-5 , 6-oxy-2,3-dicarboxylimide, N- (camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-di Ruboxylimide, N- (4-methylphenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboxylimide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo [2.2.1] Heptane-5,6-oxy-2,3-dicarboxylimide, N- (4-fluorophenylsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2 , 3-dicarboxylimide, N- (trifluoromethylsulfonyloxy) naphthyl dicarboxylimide, N- (camphorsulfonyloxy) naphthyl dicarboxylimide, N- (4-methylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (Phenylsulfonyloxy) naphthyl dicarboxylimide, N- 2-trifluoromethylphenylsulfonyloxy) naphthyl dicarboxylimide, N- (4-fluorophenylsulfonyloxy) naphthyl dicarboxylimide, N- (pentafluoroethylsulfonyloxy) naphthyl dicarboxylimide, N- (heptafluoropropylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (nonafluorobutylsulfonyloxy) naphthyl dicarboxylimide, N- (ethylsulfonyloxy) naphthyl dicarboxylimide, N- (propylsulfonyloxy) naphthyl dicarboxylimide, N- (butylsulfonyl) Oxy) naphthyl dicarboxylimide, N- (pentylsulfonyloxy) naphthyl dicarboxylimide, N- (hexylsulfonyloxy) naphthyl dicarbo Xylimide, N- (heptylsulfonyloxy) naphthyl dicarboxylimide, N- (octylsulfonyloxy) naphthyl dicarboxylimide, N- (nonylsulfonyloxy) naphthyl dicarboxylimide, and the like.

(Halogen-containing compounds)
Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds.

(Diazomethane compound)
Examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-tolylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, Bis (p-chlorophenylsulfonyl) diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, cyclohexylsulfonyl (1,1-dimethylethylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, phenylsulfonyl (benzoyl) diazomethane, etc. Is mentioned.

(Sulfone compound)
Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, diaryldisulfone compounds, and the like.

(Sulfonate compound)
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.

(Carboxylic acid ester compound)
Examples of the carboxylic acid ester compound include carboxylic acid o-nitrobenzyl ester.

  Of these [B] photoacid generators, an oxime sulfonate compound is preferable from the viewpoint of radiation sensitivity and solubility in [C] an organic solvent, and a compound containing an oxime sulfonate group represented by the above formula (3). Is more preferable, and the oxime sulfonate compound represented by the above formula (3-1) is particularly preferable, and [(5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methyl) is available as a commercial product. Phenyl) acetonitrile], [(5-octylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile], [(5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene) )-(2-Methylphenyl) acetonitrile], [(camphorsulfonyloxy) Imino -5H- thiophen-2-ylidene) - (2-methylphenyl) acetonitrile], [(5-octyl sulfonyloxy imino) - (4-methoxyphenyl) acetonitrile] are most preferred.

  [B] The photoacid generator is also preferably an onium salt, more preferably a tetrahydrothiophenium salt and a benzylsulfonium salt, and 4,7-di-n-butoxy-1-naphthyltetrahydrothiophenium trifluoromethanesulfonate. Benzyl-4-hydroxyphenylmethylsulfonium hexafluorophosphate is particularly preferred.

  The content of [B] photoacid generator in the composition is preferably 0.1 parts by mass to 10 parts by mass, and more preferably 1 part by mass to 5 parts with respect to 100 parts by mass of the polymer [A]. Part by mass. [B] By setting the content of the photoacid generator within the above specific range, the radiation sensitivity of the composition can be optimized, and an interlayer insulating film having high surface hardness can be formed while maintaining transparency.

[[C] Organic solvent]
The composition was dissolved or dispersed by mixing [C] an organic solvent with [A] polymer, [B] photoacid generator, and optionally [D] surfactant, and other optional components. Prepared to a state. [C] As the organic solvent, a solvent that uniformly dissolves or disperses the above components and does not react with the components is preferably used.

  [C] Examples of the organic solvent include alcohols, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, diethylene glycol monoalkyl ether acetates, Examples include dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, lactic acid esters, aliphatic carboxylic acid esters, amides, and ketones. These can be used alone or in combination of two or more.

  [C] As the organic solvent, (C1) an organic solvent having a vapor pressure at 20 ° C. of 0.1 mmHg or more and less than 1 mmHg (hereinafter also referred to as “(C1) organic solvent”), and (C2) a vapor pressure at 20 ° C. Preferably contains an organic solvent (hereinafter also referred to as “(C2) organic solvent”) of 1 mmHg to 20 mmHg. By using the [C] organic solvent having a specific vapor pressure, for example, even when a discharge nozzle type coating method is employed, high-speed coating is possible while preventing coating unevenness. In addition, although a well-known method can be used for the measurement of vapor pressure, in this specification, it means the value measured by the transfection method (gas flow method).

(C1) Examples of the organic solvent include alcohols such as benzyl alcohol;
Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether;
Ethylene glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol diethyl ether and diethylene glycol ethyl methyl ether;
Diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate;
Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether and dipropylene glycol diethyl ether;
Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monopropyl ether acetate, dipropylene glycol monobutyl ether acetate;
Lactic acid esters such as n-propyl lactate, isopropyl lactate, n-butyl lactate, isobutyl lactate, n-amyl lactate, isoamyl lactate;
Ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-3-methylbutyrate, ethyl ethoxyacetate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetoacetate, ethyl acetoacetate, methyl pyruvate Aliphatic carboxylic acid esters such as ethyl pyruvate;
Amides such as N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide;
Examples thereof include ketones such as N-methylpyrrolidone and γ-butyrolactone. These can be used alone or in combination of two or more.

  (C2) Examples of the organic solvent include diethylene glycol dimethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl acetate, and acetic acid. Examples include propyl, n-butyl acetate, methyl propyl ketone, methyl isobutyl ketone, methyl 3-methoxypropionate, methyl lactate, and ethyl lactate. These can be used alone or in combination of two or more.

  When (C1) organic solvent and (C2) organic solvent are used in combination, diethylene glycol ethyl methyl ether / diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether / propylene glycol monomethyl ether acetate, diethylene glycol ethyl methyl ether / cyclohexanone, diethylene glycol diethyl Ether / diethylene glycol dimethyl ether, diethylene glycol diethyl ether / propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether / cyclohexanone, diethylene glycol diethyl ether / 3-methoxymethyl propionate, diethylene glycol diethyl ether / methyl isobutyl ketone, diethylene glycol The combination of ethyl ether / acetic acid n- butyl are preferred. In addition, (C1) organic solvent or (C2) organic solvent may be used as a mixture of two or more thereof. Examples of combinations include diethylene glycol diethyl ether / propylene glycol monomethyl ether acetate / cyclohexanone / 3-methyl methyl methoxypropionate. Etc.

  As content of (C2) organic solvent, 10 mass% or more and 50 mass% are preferable with respect to the total amount of (C1) organic solvent and (C2) organic solvent. By setting the mass ratio of the organic solvent having a low vapor pressure (C1) and the organic solvent having a high vapor pressure (C2) within the above specific range, the amount of the residual solvent in the coating film after pre-baking is optimized. As a result, the occurrence of coating unevenness (such as streak unevenness, pin mark unevenness, and mist unevenness) can be suppressed, and the film thickness uniformity can be further improved. Further, by optimizing the residual solvent amount, the acid generation amount and the acid dissociable group are highly balanced, and the radiation sensitivity tends to be good.

  The solid content concentration of the composition is 10% by mass or more and 30% by mass or less. More preferably, it is 20 mass% or more and 25 mass% or less. By setting the solid content concentration of the composition within the specific range, it is possible to effectively suppress the occurrence of coating unevenness.

  The viscosity at 25 ° C. of the composition is preferably 2.0 mPa · s or more and 10 mPa · s or less. By keeping the viscosity of the composition within the above specified range, it is possible to achieve a well-balanced viscosity that can be evenly distributed even if coating unevenness is maintained while maintaining film thickness uniformity, and realize high-speed coating properties. it can.

[[D] Surfactant]
The composition can further contain [D] a surfactant in order to further improve the film-forming property of the composition. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, and other surfactants. When the composition contains the [D] surfactant, the surface smoothness of the coating film can be improved, and as a result, the film thickness uniformity of the formed interlayer insulating film can be improved. Among these surfactants, silicone surfactants that are particularly excellent in film pressure uniformity are preferred.

  As the fluorosurfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable. Examples of the fluorosurfactant include 1,1,2,2-tetrafluoro n-octyl (1,1,2,2-tetrafluoro n-propyl) ether, 1,1,2,2-tetrafluoro n. -Octyl (n-hexyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoro n-pentyl) ether, octaethylene glycol di (1,1,2,2-tetrafluoron) -Butyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoro n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro n-butyl) ether Perfluoro n-dodecane sodium sulfonate, 1,1,2,2,3,3-hexafluoro n-decane, 1,1,2,2,3,3,9 9,10,10-decafluoro n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkyl Examples include betaine, fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, and carboxylic acid fluoroalkyl ester.

  Commercially available fluorosurfactants include, for example, BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, MegaFuck F172, MegaFuck F173, MegaFuck F183, MegaFuck F178, MegaFuck F191. , Megafuck F471, Megafuck F476 (above, manufactured by Dainippon Ink and Chemicals), Fluorard FC-170C, Fluorard FC-171, Fluorard FC-430, Fluorard FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112 , Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC-104, -Freon SC-105, Surflon SC-106 (above, manufactured by Asahi Glass), F-top EF301, F-top EF303, F-top EF352 (above, made by Shin-Akita Kasei), Aftergent FT-100, Aftergent FT-110, Aftergent FT-140A, Aftergent FT-150, Aftergent FT-250, Aftergent FT-251, Aftergent FT-300, Aftergent FT-310, Aftergent FT-400S, Aftergent FT-218, Aftergent FT- 251 (above, manufactured by Neos).

  Examples of the silicone surfactant include Torre Silicone DC3PA, Torre Silicone DC7PA, Torre Silicone SH11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH-190, Torree Silicone SH-193, Torrey Silicone SZ-6032, Torre Silicone SF-8428, Torre Silicone DC-57, Torre Silicone DC-190, SH 8400 FLUID (above, manufactured by Toray Dow Corning Silicone), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone), organosiloxane polymer KP3 41 (manufactured by Shin-Etsu Chemical Co., Ltd.).

  [D] Surfactant can be used individually or in combination of 2 or more types. The content of [D] surfactant in the composition is preferably 0.01 parts by mass or more and 2 parts by mass or less, more preferably 0.05 parts by mass with respect to 100 parts by mass of the [A] polymer. Part to 1 part by mass. [D] By making content of surfactant into the said specific range, the surface smoothness of a coating film can be improved more.

[Other optional ingredients]
The said composition can contain other arbitrary components, such as a close_contact | adherence adjuvant, a basic compound, and a quinonediazide compound, as needed in the range which does not impair the expected effect. Other optional components can be used alone or in combination of two or more.

(Adhesion aid)
In the composition, for example, an adhesion assistant can be contained in order to improve the adhesion between a silicone compound such as silicone, silicone oxide, and silicon nitride, or a metal such as gold, copper, and aluminum and an insulating film.

  As the adhesion assistant, a functional silane coupling agent is preferably used. Examples of the functional silane coupling agent include a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group (preferably an oxiranyl group), and a thiol group.

  Examples of the functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltri Examples include methoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like.

  Of these functional silane coupling agents, γ-glycidoxypropylalkyldialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane are preferred.

  The content of the adhesion assistant is preferably 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the [A] polymer. By making the usage-amount of adhesion | attachment adjuvant into the said specific range, the adhesiveness of the interlayer insulation film formed and a board | substrate is improved.

(Basic compound)
By containing the basic compound in the composition, the diffusion length of the acid generated from the [B] photoacid generator by exposure can be appropriately controlled, and the pattern developability can be improved. Examples of basic compounds include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, carboxylic acid quaternary ammonium salts, and the like.

  Examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, dicyclohexylamine, Examples include dicyclohexylmethylamine.

  Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, diphenylamine and the like.

  Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4 -Dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, pyrazole , Pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4,3,0] -5-nonene, 1,8-diazabicyclo [5,3,0] -7undecene Etc.

  Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.

  Examples of the carboxylic acid quaternary ammonium salt include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

  As content of the basic compound in the said composition, 0.001 mass part-1 mass part are preferable with respect to 100 mass parts of [A] polymers, and 0.005 mass part-0.2 mass part are more preferable. . When the content of the basic compound is within the specific range, pattern developability is improved.

(Quinonediazide compound)
A quinonediazide compound is a compound that generates a carboxylic acid upon irradiation with radiation. As the quinonediazide compound, a condensate of a phenolic compound or an alcoholic compound (hereinafter also referred to as “mother nucleus”) and 1,2-naphthoquinonediazidesulfonic acid halide can be used.

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

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

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

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

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

  Examples of (polyhydroxyphenyl) alkanes include bis (2,4-dihydroxyphenyl) methane, bis (p-hydroxyphenyl) methane, tris (p-hydroxyphenyl) methane, 1,1,1-tris (p-hydroxy). Phenyl) 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'-spirobiy Den -5,6,7,5 ', 6', 7'-hexanol, 2,2,4-trimethyl -7,2 ', 4'-trihydroxy flavan like.

  Examples of other mother nuclei include 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.

  Among 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 diazide sulfonic acid chloride is preferable. Examples of 1,2-naphthoquinonediazide sulfonic acid chloride include 1,2-naphthoquinonediazide-4-sulfonic acid chloride, 1,2-naphthoquinonediazide-5-sulfonic acid chloride, and the like. Of these, 1,2-naphthoquinonediazide-5-sulfonic acid chloride is preferred.

  As a condensate of a phenolic compound or an alcoholic compound and 1,2-naphthoquinone diazide sulfonic acid halide, 1,1,1-tri (p-hydroxyphenyl) ethane and 1,2-naphthoquinone diazide-5-sulfonic acid Condensate with chloride, 4,4 '-[1- [4- [1- [4-hydroxyphenyl] -1-methylethyl] phenyl] ethylidene] bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid chloride A condensate with is preferred.

  In the condensation reaction of the phenolic compound or alcoholic compound and 1,2-naphthoquinonediazide sulfonic acid halide, preferably 30 mol% to 85 mol%, based on the number of OH groups in the phenolic compound or alcoholic compound. Preferably, 1,2-naphthoquinonediazide sulfonic acid halide corresponding to 50 mol% to 70 mol% can be used. The condensation reaction can be carried out by a known method.

  Examples of the quinonediazide compound include 1,2-naphthoquinonediazidesulfonic acid amides in which the ester bond of the mother nucleus exemplified above is changed to an amide bond, such as 2,3,4-triaminobenzophenone-1,2-naphthoquinonediazide- 4-sulfonic acid amide and the like are also preferably used.

(Method for producing the composition)
The composition is obtained by mixing [C] organic solvent with [A] polymer, [B] photoacid generator, [D] surfactant as a suitable component, and other optional components as necessary. Prepared in a dissolved or dispersed state. For example, the composition can be prepared by mixing the components [A], [B] and [D] and other optional components in a predetermined ratio in the [C] organic solvent.

<Liquid crystal layer>
The liquid crystal layer provided in the liquid crystal display element is formed from a polymerizable liquid crystal composition. The polymerizable liquid crystal composition preferably has photopolymerizability or thermal polymerizability. Since the polymerizable liquid crystal composition has photopolymerizability or thermal polymerizability, a liquid crystal layer can be formed from the polymerizable liquid crystal composition by light irradiation or heating, and efficient production becomes possible. In addition, according to the liquid crystal display element, even when manufactured through such light irradiation or heating, deformation of the interlayer insulating film is suppressed, so that a high voltage holding ratio and excellent productivity can be exhibited. it can. Examples of the polymerizable liquid crystal composition include a thermosetting polymerizable liquid crystal composition and a photocurable polymerizable liquid crystal composition.

[Thermosetting polymerizable liquid crystal composition]
Examples of the thermosetting polymerizable liquid crystal composition include a composition containing a liquid crystal compound and a thermopolymerizable compound.

(Liquid crystal compound)
Examples of the liquid crystal compound include nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, and the like. As the liquid crystal compound, nematic liquid crystal is preferable. In addition, these liquid crystals may contain cholesteric liquid crystals, chiral nematic liquid crystals, chiral smectic liquid crystals, and chiral compounds in order to improve performance.

  Specific liquid crystal compounds include, for example, 4-substituted benzoic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenyl ester, 4- ( 4-substituted cyclohexanecarbonyloxy) benzoic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4′-substituted cyclohexyl ester, 4-substituted 4′-substituted biphenyl, 4-substituted phenyl 4′-substituted cyclohexane, 4-substituted 4 ″ -substituted terphenyl, 4-substituted biphenyl 4′-substituted cyclohexane, 2- (4-substituted phenyl) -5 -Substituted pyrimidine, compounds represented by the following formulas (a) to (d), etc.

  Among these liquid crystal compounds, compounds having a cyano group at least at one end of the molecule, such as the compounds represented by the above formulas (a) to (d), are preferable. These can be used alone or in combination of two or more. These liquid crystal compounds have characteristics of liquid crystal, that is, phase transition temperature between an isotropic liquid and liquid crystal, melting point, viscosity, refractive index anisotropy (Δn), dielectric anisotropy (Δε), and other components. Can be appropriately selected, blended and used in consideration of the solubility and the like.

  Moreover, what has a polymeric group as a liquid crystal compound is also preferable. When the liquid crystal compound has a polymerizable group, the liquid crystal compound itself can be provided with thermal polymerization or photopolymerization. Examples of the polymerizable group include a vinyl group, a (meth) acryl group, a (meth) acryloyl group, a (meth) acrylamide group, a styryl group, an epoxy group, and an isocyanate group.

  Examples of the liquid crystal compound having a polymerizable group include compounds represented by the following formula (4).

In the formula (4), ^{R 7} is a hydrogen atom or a methyl group. R ⁸ , R ¹⁰ and R ¹² are each independently any of the groups represented by the following formulae. n is 0 or 1. R ⁹ and R ¹¹ are each independently a single bond, —CH ₂ CH ₂ —, —CH ₂ O—, —OCH ₂ —, —COO—, —OCO—, —C≡C—, —CH═CH. _{-, - CF = CF -,} - (CH 2) 4 -, - CH 2 CH 2 CH 2 O -, - OCH 2 CH 2 CH 2 -, - CH 2 = CHCH 2 CH 2 -, or _-CH 2 CH ₂ CH = CH-. R ¹² is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkenyl group, or an alkenyloxy group.

  In said formula, m is an integer of 1-4.

Among the compounds represented by the above formula (4), R ⁸ , R ¹⁰ and R ¹² are each independently a group represented by the following formula, m is 1 or 2, and R ⁹ and R ¹¹ Are each independently a single bond or —C≡C—, and a compound in which R ¹³ is a halogen atom, a cyano group, an alkyl group having 1 to 20 carbon atoms or an alkoxy group is preferable.

  Examples of liquid crystal compounds having other polymerizable groups include compounds represented by the following formula (5).

In the above formula ^{(5), R 14} is a hydrogen atom or a methyl group. p is an integer of 2-12. R ¹⁵ is a single bond or —COO—. R ¹⁶ is a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group.

  Examples of the liquid crystal compound having a polymerizable group represented by the above formula (5) include compounds represented by the following formulas (5-1) to (5-3).

In the above formulas (5-1) to (5-3), R ¹⁷ , R ¹⁸ and R ¹⁹ are each independently a hydrogen atom or a methyl group. j, k, and q are each independently an integer of 2 to 12. R ²⁰ is an alkyl group having 1 to 6 carbon atoms or a phenyl group.

  The content of the liquid crystal compound in the thermosetting polymerizable liquid crystal composition is preferably 90% by mass or more, more preferably 96% by mass or more and 99.9% by mass or less, and particularly preferably 98% by mass or more and 99.5% by mass or less. preferable. By setting the content of the liquid crystal compound in the specific range, suitable liquid crystal response can be exhibited.

  As said thermopolymerizable compound, an epoxy compound is preferable. The epoxy compound is not particularly limited as long as it has one or more epoxy groups in the molecule and reacts and cures by heating, but an epoxy compound that is liquid at normal temperature is preferable from the viewpoint of coating properties.

  Examples of the epoxy compound include an aliphatic compound having an epoxy group, an alicyclic compound having an epoxy group, and an aromatic compound having an epoxy group.

Examples of the aliphatic compound having an epoxy group include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and polyethylene glycol diglycidyl ether. , Glycerin triglycidyl ether, polypropylene glycol diglycidyl ether; polyglycidyl of polyether polyol obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, etc. Ethers; diglycidyl esters of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols;
Glycidyl esters of higher fatty acids; epoxidized soybean oil; epoxy butyl stearate; octyl epoxy stearate; epoxidized linseed oil; epoxidized polybutadiene and the like.

  Examples of commercially available aliphatic compounds having an epoxy group include SR-NPG, SR-16H, SR-PG, SR-TPG (above, manufactured by Sakamoto Yakuhin Kogyo); PG-202, PG-207 (above, Toto Kasei). Manufactured); EX-610U, EX-1610-P (manufactured by Nagase ChemteX) and the like.

  Examples of the alicyclic compound having an epoxy group include 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4- Epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate, ε-caprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, trimethylcaprolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4'-D Xylcyclohexanecarboxylate, β-methyl-δ-valerolactone modified 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), di (3,4) of ethylene glycol 4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate), epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl and the like.

  Examples of commercially available alicyclic compounds having an epoxy group include Celoxide 2021, Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, Epolide GT-300, Epolide GT-301, Epolide GT-302, Epolide GT-400, Examples include Epolide 401, Epolide 403 (manufactured by Daicel Chemical Industries, Ltd.), and the like.

  Examples of the aromatic compound having an epoxy group include compounds having an aromatic ring structure in the main skeleton and having two or more epoxy groups. Examples of the aromatic ring structure of such a compound include a bisphenol A type structure, a bisphenol F type structure, a novolac type structure, a naphthalene skeleton, an anthracene skeleton structure, and a fluorene skeleton.

  Examples of commercially available aromatic compounds having an epoxy group include JER806, JER828, YL980 (above, manufactured by Japan Epoxy Resin); YD-127, YD-128, YDF-170, YDF-175S, YDPN-638, YDCN- 701 (manufactured by Toto Kasei); EPICLON 830, EPICLON 850, EPICLON 835, EPICLON HP-4032D (manufactured by DIC), and the like.

  In addition, an epoxy compound having a (meth) acryloyl group or a vinyl group can also be used. For example, glycidyl (meth) acrylate, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, (meth) acrylic acid-3,4-epoxybutyl, α-ethylacryl Acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, p-vinylbenzylglycidyl ether, 3-methyl-3- (meta ) Acryloyloxymethyl oxetane, 3-ethyl-3- (meth) acryloyloxymethyl oxetane, and the like.

  As the epoxy compound, an aromatic compound having an epoxy group is preferable.

  The content of the epoxy compound is preferably 0.1% by mass or more and 10% by mass or less, and more preferably 0.3% by mass or more and 3% by mass or less. By setting the content of the epoxy compound within the specific range, suitable liquid crystal response can be exhibited.

[Photocurable Polymerizable Liquid Crystal Composition]
Examples of the photocurable polymerizable liquid crystal composition include those containing a polymerizable liquid crystal compound and a photopolymerization initiator (hereinafter also referred to as “photocurable polymerizable liquid crystal composition A”), liquid crystal compounds, and photopolymerizable compounds. Examples thereof include those containing a compound and a photopolymerization initiator (hereinafter also referred to as “photocurable polymerizable liquid crystal composition B”). In addition, the presence or absence of the polymerizability of the liquid crystal compound in the photocurable polymerizable liquid crystal composition B may be any. In addition to the above, for example, a mixture of the photocurable polymerizable liquid crystal composition A and B may be used. The “light” in the photo-curing type includes not only visible light but also ultraviolet rays, far ultraviolet rays and the like.

  Examples of the liquid crystal compound having a polymerizable property in the photocurable polymerizable liquid crystal composition A and the liquid crystal compound in the photocurable polymerizable liquid crystal composition B include those exemplified in the above-mentioned thermosetting polymerizable liquid crystal composition. it can.

  The content of the liquid crystal compound (including a polymerizable liquid crystal compound) in the photocurable polymerizable liquid crystal composition is preferably 60% by mass or more, and preferably 70% by mass or more and 99% from the viewpoint of curability of the obtained liquid crystal layer. More preferable is 5% by mass or less.

  Examples of the photopolymerization initiator include 2-hydroxy-2-methyl-1-phenylpropan-1-one (Merck, Darocur 1173), 1-hydroxycyclohexyl phenyl ketone (Ciba Geigy, Irgacure 184), 1 -(4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck, Darocur 1116), 2,2-dimethoxy-1,2-diphenylethane-1-one (Ciba Geigy) Irgacure 651), 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 (Ciba Geigy, Irgacure 907), 2,4-diethylthioxanthone (Nippon Kayaku, Kayacure DETX) ) And ethyl p-dimethylaminobenzoate (manufactured by Nippon Kayaku, Kayacure-EPA) Mixture, isopropylthioxanthone (word pre Kin Sop made, Kantakyua ITX) include mixtures of the p- dimethylaminobenzoic acid ethyl.

  The content of the photopolymerization initiator is preferably 0.1% by mass or more and 10% by mass or less from the viewpoint of the curability of the liquid crystal layer.

  The photopolymerizable compound used in the photocurable polymerizable liquid crystal composition B has a vinyl group, a (meth) acryl group, a (meth) acryloyl group, a (meth) acrylamide group, a styryl group and the like as a polymerizable group.

Examples of the photopolymerizable compound include styrene, chlorostyrene, α-methylstyrene, divinylbenzene;
As substituents, methyl, ethyl, propyl, butyl, amyl, 2-ethylhexyl, octyl, nonyl, dodecyl, hexadecyl, octadecyl, cyclohexyl, benzyl, methoxyethyl, butoxy Acrylate having ethyl group, phenoxyethyl group, allyl group, methallyl group, glycidyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-chloro-2-hydroxypropyl group, dimethylaminoethyl group, diethylaminoethyl group, etc. , Methacrylate or fumarate;
Mono (meth) acrylate or poly (meta) such as ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, trimethylolpropane, glycerin and pentaerythritol ) Acrylate;
Vinyl acetate, vinyl butyrate, vinyl benzoate, acrylonitrile, cetyl vinyl ether, limonene, cyclohexene, diallyl phthalate, diallyl isophthalate, vinyl pyridine, acrylic acid, methacrylic acid, acrylamide, methacrylamide, N-hydroxymethylacrylamide or N-hydroxyethyl Methacrylamide and their alkyl ether compounds;
Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol;
Diol or tri (meth) acrylate of triol obtained by adding 3 mol or more of ethylene oxide or propylene oxide to 1 mol of trimethylolpropane;
Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of bisphenol A;
Reaction product of 1 mol of 2-hydroxyethyl (meth) acrylate and 1 mol of phenyl isocyanate or n-butyl isocyanate;
Poly (meth) acrylate of dipentaerythritol;
Examples include oligomers such as caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate.

  As content of a photopolymerizable compound, 3 mass% or more and 40 mass% or less are preferable, and 10 mass% or more and 30 mass% or less are more preferable from the sclerosing | hardenable point of the liquid crystal layer obtained.

  The photocurable polymerizable liquid crystal composition may contain, for example, a polymerization inhibitor as other components. Examples of the polymerization inhibitor include hydroquinone monomethyl ether (methoquinone), hydroquinone, p-benzoquinone, phenothiazone, mono-t-butylhydroquinone, catechol, pt-butylcatechol, benzoquinone, 2.5-di. -T-butylhydroquinone, anthraquinone, 2.6-di-t-butylhydroxytoluene and the like.

<Method for forming interlayer insulating film>
The method for forming an interlayer insulating film for a liquid crystal display element of the present invention comprises:
(1) The process of forming the coating film of the said composition on a board | substrate,
(2) A step of irradiating at least a part of the coating film formed in step (1),
(3) a step of developing the coating film irradiated with radiation in the step (2), and (4) a step of heating the coating film developed in the step (3).

  The interlayer insulating film is suitable as a method for forming an interlayer insulating film for a liquid crystal display element in which a liquid crystal layer is formed by heating or light irradiation. The interlayer insulation film of the liquid crystal display element of this invention is formed using the said positive radiation sensitive composition. The interlayer insulating film can be suitably used as an interlayer insulating film for a liquid crystal display element that forms a liquid crystal layer by heating or light irradiation as described above.

[Step (1)]
In the step (1), after coating the composition or the solution or dispersion on the substrate, the solvent is removed by heating (pre-baking) the coated surface, thereby forming a coating film.

  As a method for applying the composition solution or the dispersion, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, or the like can be employed. Among these coating methods, a spin coating method or a slit die coating method is preferable.

  The pre-baking conditions vary depending on the type of each component, the blending ratio, and the like, but preferably 60 to 120 ° C. for about 1 minute to 10 minutes. According to the composition, even when the prebake conditions are relatively low, such as 60 ° C. to 80 ° C., excellent pattern formability can be exhibited.

<Step (2)>
In the step (2), at least a part of the formed coating film is exposed. In this case, when a part of the coating film is exposed, it is usually exposed through a photomask having a predetermined pattern. As the radiation used for exposure, the radiation used for the photoacid generator is suitable. Among these radiations, radiation having a wavelength in the range of 190 nm to 450 nm is preferable, and radiation including ultraviolet light of 365 nm is particularly preferable.

The exposure dose is preferably 500 J / m ^{2 to} 6,000 J / m ² , more preferably 1,500 J as a value measured with a luminometer (OAI model 356, manufactured by OAI Optical Associates) for the intensity of radiation at a wavelength of 365 nm. / M ^{2 to} 1,800 J / m ² .

<Step (3)>
In the step (3), by developing the exposed coating film, unnecessary portions (radiation irradiated portions) are removed to form a predetermined pattern. As the developer used in the development step, an alkaline aqueous solution is preferable. Examples of the alkali include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; quaternary ammonium salts such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. .

  An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, or a surfactant can be added to the alkaline aqueous solution. The concentration of alkali in the aqueous alkali solution is preferably from 0.1% by mass to 5% by mass from the viewpoint of obtaining appropriate developability. Examples of the developing method include a liquid piling method, a dipping method, a rocking dipping method, and a shower method. The development time varies depending on the composition of the positive radiation sensitive composition, but is preferably about 10 seconds to 180 seconds. According to the composition, a stable pattern can be formed without being affected by this development time even if the development time is somewhat long or short. Subsequent to such development processing, for example, after washing with running water for 30 seconds to 90 seconds, a desired pattern can be formed by, for example, air drying with compressed air or compressed nitrogen.

<Step (4)>
In the step (4), by heating a patterned thin film using a heating device such as a hot plate or an oven, the curing reaction of the [A] polymer can be promoted to obtain a cured product. As heating temperature, it is 120 to 250 degreeC, for example. The heating time varies depending on the type of the heating device, but is, for example, 5 minutes to 30 minutes when the heating process is performed on a hot plate, and 30 minutes to 90 minutes when the heating process is performed in the oven. The step baking method etc. which perform a heating process 2 times or more can also be used. In this manner, a patterned thin film corresponding to the target interlayer insulating film or the like can be formed on the surface of the substrate.

  The thickness of the formed interlayer insulating film is preferably 0.1 μm to 8 μm, more preferably 0.1 μm to 6 μm, and particularly preferably 0.1 μm to 4 μm.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises two substrates arranged in this manner, an interlayer insulating film laminated on at least one inner surface side of the substrate, and a liquid crystal layer disposed between the substrates. This is a liquid crystal cell. A polarizing plate is usually provided on both sides of the liquid crystal cell, that is, outside the substrates. One of the two polarizing plates can be replaced with a reflecting plate. In addition, the liquid crystal display element may further include, for example, a micro color filter as another component.

  The liquid crystal display element can be used for various liquid crystal display devices such as a television receiver, a monitor device of a personal computer, a mobile phone, and a game machine.

<Method for manufacturing liquid crystal display element>
As a manufacturing method of a liquid crystal display element, the well-known manufacturing method of the liquid crystal display element using PSA technique can be used, for example. An example of the manufacturing method will be described with reference to FIG. A liquid crystal display element (liquid crystal cell) 10 in the middle of manufacturing in FIG. 1 includes two substrates 1a and 1b disposed mainly opposite to each other, an interlayer insulating film 2 stacked on the inner surface side of the substrate 1a, and substrates 1a and 1b. A liquid crystal layer 3 is provided between them.

  First, the interlayer insulating film 2 is formed on the surface of the substrate 1a by the method described above. Next, the transparent electrode film 4 is formed on the surface of the interlayer insulating film 2 and the substrate 1 b, and the liquid crystal alignment film 5 is further formed on the surface of each transparent electrode film 4. Two substrates 1a and 1b are arranged in parallel with the liquid crystal alignment film 5 side inward, and are bonded together with a sealing material 6 to form a cell. At this time, the injection hole 7 is provided in part without the sealing material 6 being laminated. After injecting the polymerizable liquid crystal composition into the cell from the injection hole 7 and sealing the injection hole 7 filled with the composition, the liquid crystal layer 3 is formed by heating or irradiation with light or the like to obtain a liquid crystal cell. (The state of the liquid crystal display element 10 in the middle of manufacture in FIG. 1). A liquid crystal display element is obtained by attaching polarizing plates to both surfaces of the liquid crystal cell.

Examples of the transparent conductive film 4 include an NESA film (registered trademark, manufactured by PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), and the like. . As a method for obtaining a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching, or using a mask having a desired pattern when forming the transparent conductive film Methods and the like.

  As a method for forming the liquid crystal alignment film 5, there is a method in which a composition for forming a liquid crystal alignment film is preferably applied by a printing method, a spinner method, or an inkjet method, and then a coating film is formed by heating each coated surface. Can be mentioned. As the composition for forming a liquid crystal alignment film, for example, a polyimide alignment agent or the like can be used. By subjecting the heated coating film to a rubbing treatment, the liquid crystal compound alignment ability is imparted to the coating film, and the liquid crystal alignment film 5 is formed.

  The polymerizable liquid crystal composition is injected by injecting a polymerizable liquid crystal composition between the substrates on which the liquid crystal alignment film 5 is formed as described above, and applying a voltage to the liquid crystal compound in a tilted state, thereby heating or irradiating light. The product will be cured. Here, when the rubbing treatment is performed on the coating film, the two substrates 1a and 1b are arranged to face each other so that the rubbing directions in each coating film are at a predetermined angle, for example, orthogonal or antiparallel. The

  The heating time when the polymerizable liquid crystal composition is a thermosetting type is preferably 10 minutes or longer and 60 minutes or shorter. Moreover, as heating temperature, 150 to 300 degreeC is preferable. When the heating time or temperature is outside the above specific range, the polymerization is not sufficiently performed, and the responsiveness of the obtained liquid crystal layer may be lowered. On the other hand, when the heating time or temperature exceeds the above upper limit, the interlayer insulating film or the like may be deformed.

In the case where the polymerizable liquid crystal composition is a photocurable type, ultraviolet light is preferred as the type of light. Further, the radiation amount of light is preferably 50 mJ / cm ² or more and 400 mJ / cm ² or less. When the amount of radiation is less than the lower limit, the polymerization is not sufficiently performed, and the responsiveness of the obtained liquid crystal layer may be lowered. On the other hand, when the irradiation dose exceeds the above upper limit, the interlayer insulating film or the like may be deformed.

  Thus, a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell after the liquid crystal layer 3 is formed.

  According to the liquid crystal display element that can be produced in this manner, the interlayer insulating film is formed from a positive radiation-sensitive composition containing a [A] polymer having a specific structural unit. Even if the liquid crystal layer is formed by irradiation with light or light, excellent heat resistance and light resistance can be provided. Accordingly, the liquid crystal display element has high production efficiency because of less deformation in the manufacturing process, and can exhibit a high voltage holding ratio.

  EXAMPLES Hereinafter, although this invention is explained in full detail based on an Example, this invention is not interpreted limitedly based on description of this Example.

Mw and Mn of the polymer were measured by GPC under the following conditions.
Apparatus: GPC-101 (made by Showa Denko)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 combined with mobile phase: tetrahydrofuran Column temperature: 40 ° C.
Flow rate: 1.0 mL / min Sample concentration: 1.0 mass%
Sample injection volume: 100 μL
Detector: Differential refractometer Standard material: Monodisperse polystyrene

<Preparation of polymerizable liquid crystal composition>
[Preparation Example 1]
Each liquid crystal compound (25% liquid crystal compound represented by the above formula (a), 30 mass% liquid crystal compound represented by formula (b), 30 mass% liquid crystal compound represented by formula (c), and formula (d ) To obtain a liquid crystal composition (i). 99 parts by mass of this liquid crystal composition (i) and 1 part by mass of trimethylolpropane triglycidyl ether as a thermopolymerizable compound were blended to obtain a thermosetting polymerizable liquid crystal composition (I).

[Preparation Example 2]
Each polymerizable liquid crystal compound represented by the following formula (47.5 mass% of a liquid crystal compound represented by the following formula (e), 47.5 mass% of a liquid crystal compound represented by the formula (f), and formula (g) A liquid crystal compound (ii) was obtained by blending a liquid crystal compound represented by the formula (5.0% by mass). 99 parts by mass of the polymerizable liquid crystal composition (ii) and 1 part by mass of 2,2-dimethoxy-1,2-diphenylethane-1-one (manufactured by Ciba-Geigy, Irgacure 651) as a photopolymerization initiator By blending, a photocurable polymerizable liquid crystal composition (II) was obtained.

[Preparation Example 3]
80 parts by mass of the above liquid crystal composition (i), 19 parts by mass of caprolactone-modified hydroxypivalate ester neopentyl glycol diacrylate (Nippon Kayaku, Kayrad HX620) as a photopolymerizable compound, and benzyl as a photopolymerization initiator 1 part by mass of dimethyl ketal (manufactured by Ciba Geigy, Irgacure 651) was blended to obtain a photocurable polymerizable liquid crystal composition (III).

<[A] Synthesis of polymer>
[Synthesis Example 1]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by mass of methacrylic acid, 40 parts by mass of 1-ethoxyethyl methacrylate, 5 parts by mass of styrene, 40 parts by mass of glycidyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, and 3 parts by mass of α-methylstyrene dimer were charged. After that, stirring was started gently. 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 polymer (A-1). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-1) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.1 mass%.

[Synthesis Example 2]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 5 parts by weight of methacrylic acid, 40 parts by weight of tetrahydro-2H-pyran-2-yl methacrylate, 5 parts by weight of styrene, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate and 3 parts by weight of α-methylstyrene dimer Was added, and the mixture was purged with nitrogen. 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 polymer (A-2). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-2) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.3 mass%.

[Synthesis Example 3]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 67 parts by mass of 1-n-butoxyethyl methacrylate, 23 parts by mass of benzyl methacrylate and 10 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-3). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-3) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 30.3% by mass.

[Synthesis Example 4]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 90 parts by mass of 1-benzyloxyethyl methacrylate, 6 parts by mass of 2-hydroxyethyl methacrylate, and 4 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-4). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-4) was 9,000. Moreover, the solid content concentration of the polymer solution obtained here was 31.2 mass%.

[Synthesis Example 5]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (methyl 2-methylpropionate) and 200 parts by mass of propylene glycol monomethyl ether acetate. Subsequently, 85 parts by mass of tetrahydro-2H-pyran-2-yl methacrylate, 7 parts by mass of 2-hydroxyethyl methacrylate, and 8 parts by mass of methacrylic acid were charged and replaced with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-5). The polymer (A-5) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 29.2 mass%.

[Synthesis Example 6]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, after 52 parts by mass of glycidyl methacrylate and 48 parts by mass of benzyl methacrylate were charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-6). The polymer (A-6) had a weight average molecular weight (Mw) in terms of polystyrene of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 7]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 45 parts by mass of 3,4-epoxycyclohexylmethyl methacrylate, 45 parts by mass of benzyl methacrylate, and 10 parts by mass of methacrylic acid were charged and purged with nitrogen, and then gently agitated. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-7). The polystyrene equivalent weight average molecular weight (Mw) of the polymer (A-7) was 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 33.2 mass%.

[Synthesis Example 8]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 35 parts by mass of 1-n-butoxyethyl methacrylate, 35 parts by mass of benzyl methacrylate, and 30 parts by mass of glycidyl methacrylate were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 80 ° C., and this temperature was maintained for 6 hours to obtain a polymer solution containing the polymer (A-8). The polymer (A-8) had a polystyrene equivalent weight average molecular weight (Mw) of 10,000. Moreover, the solid content concentration of the polymer solution obtained here was 32.3 mass%.

[Synthesis Example 9]
A flask equipped with a condenser and a stirrer was charged with 7 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile) and 200 parts by mass of diethylene glycol ethyl methyl ether. Subsequently, 16 parts by weight of methacrylic acid, 16 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of benzyl methacrylate, 40 parts by weight of glycidyl methacrylate, 10 parts by weight of styrene and After 3 parts by mass of α-methylstyrene dimer was charged and purged with nitrogen, stirring was started gently. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 4 hours to obtain a polymer solution containing the polymer (CA-1). The polymer (CA-1) had a polystyrene equivalent weight average molecular weight (Mw) of 9,000 and a molecular weight distribution (Mw / Mn) of 2.2. Moreover, the solid content concentration of the polymer solution obtained here was 33.4 mass%.

<Preparation of positive radiation sensitive composition>
[Example 1]
[5] (5) as a photoacid generator in the solution containing polymer (A-1) obtained in Synthesis Example 1 (amount corresponding to 100 parts by mass (solid content) of polymer (A-1)). -Propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl) acetonitrile (manufactured by Ciba Specialty Chemicals, IRGACURE PAG 103), 3 parts by mass, [C] diethylene glycol ethyl methyl ether as organic solvent , [D] 0.1 parts by mass of a silicone surfactant (manufactured by Toray Dow Corning, SH 8400 FLUID) as a surfactant is mixed, and filtered through a membrane filter having a pore size of 0.2 μm to obtain a positive feeling A radiation composition (S-1) was prepared.

[Examples 2 to 5 and Comparative Example 1]
The positive radiation sensitive compositions of Examples 2 to 5 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the [A] component having the type and blending amount shown in Table 1 was used. In addition, “-” in the column represents that the corresponding component was not used.

<Creation of liquid crystal cell>
[Example 6]
[Creation of transparent electrode film / interlayer insulating film / glass substrate]
A positive radiation sensitive composition (S-1) is applied by a spin coater on a 10 × 10 cm glass substrate on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface, and further at 90 ° C. for 10 minutes. By pre-baking, a coating film having a thickness of 2.0 μm was formed. Subsequently, the coating film was exposed using an exposure machine (manufactured by Canon, MPA-600FA). Next, an interlayer insulating film was formed on the glass substrate by post-baking at 230 ° C. for 30 minutes.

Next, a transparent electrode (ITO electrode) film was formed on the obtained interlayer insulating film by the following procedure. At 60 ° C. using an ITO target (ITO filling ratio of 95% or more, In ₂ O ₃ / SnO ₂ = 90/10 mass ratio) with a high-speed sputtering apparatus (manufactured by Nippon Vacuum Technology, SH-550-C12). ITO sputtering was performed. The atmosphere at this time was a pressure of 1.0 × 10 ⁻⁵ Pa, an Ar gas flow rate of 3.12 × 10 ⁻³ m ³ / Hr, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m ³ / Hr. The substrate after sputtering was heated in a clean oven at 240 ° C. for 60 minutes for annealing.

[Creation of transparent electrode film / glass substrate]
An ITO target (ITO filling rate of 95% or more, In ₂ O ₃ / SnO ₂ = 90) is formed on a 10 × 10 cm glass on which a SiO ₂ film for preventing elution of sodium ions is formed on the surface by the high-speed sputtering apparatus. / 10 mass ratio), ITO sputtering was performed at 60 ° C. The atmosphere at this time was a pressure of 1.0 × 10 ⁻⁵ Pa, an Ar gas flow rate of 3.12 × 10 ⁻³ m ³ / Hr, and an O ₂ gas flow rate of 1.2 × 10 ⁻⁵ m ³ / Hr. The substrate after sputtering was heated in a clean oven at 240 ° C. for 60 minutes for annealing.

[Formation of liquid crystal alignment film]
A polyimide alignment treatment agent (AL-1254, manufactured by JSR) was spin-coated on the transparent electrode surface of each transparent electrode film / interlayer insulating film / glass substrate and transparent electrode film / glass substrate prepared in the above procedure. This substrate was kept at 180 ° C. for 80 minutes to form a polyimide film on the substrate. This polyimide film was rubbed to produce an alignment-treated glass substrate.

[Create Cell]
Each of the glass substrates subjected to the alignment treatment was bonded to each other with a sealing material in which 0.8 mm glass beads were mixed so that the surfaces subjected to the alignment treatment were opposed to each other.

[Formation of liquid crystal layer]
The polymerizable liquid crystal composition (I) was poured into the cell and heated in a clean oven at 230 ° C. for 30 minutes to obtain a liquid crystal cell of Example 6.

[Examples 7 to 20 and Comparative Examples 2 to 4]
The liquid crystal cells of Examples 7 to 20 and Comparative Examples 2 to 4 were operated in the same manner as Example 6 except that positive radiation sensitive compositions and polymerizable liquid crystal compositions of the type shown in Table 2 were used. Obtained. When the polymerizable liquid crystal composition (II) or (III) is used as a polymerizable liquid crystal composition, an ultraviolet lamp is used at room temperature instead of heating at 230 ° C. for 30 minutes in a clean oven. A liquid crystal cell was obtained by irradiating ultraviolet rays with a light amount of 160 mJ / cm ² .

<Evaluation>
Each characteristic was evaluated about the positive type radiation sensitive composition of Examples 1-5 and Comparative Example 1, and the liquid crystal cell of Examples 6-20 and Comparative Examples 2-4. The evaluation results are shown in Tables 1 and 2.

[Storage stability]
The positive radiation sensitive resin composition was left in an oven at 40 ° C. for 1 week, and the viscosity before and after being placed in the oven was measured to determine the rate of change in viscosity. At this time, when the viscosity change rate is less than 5%, the storage stability is good, and when it is 5% or more, the storage stability is poor.

[Voltage holding ratio]
The liquid crystal cell was placed in a constant temperature layer at 60 ° C., and the voltage holding ratio was measured with a liquid crystal voltage holding ratio measuring system (manufactured by Toyo Technica, model HR-1A). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio (%) is a value of (liquid crystal cell potential difference after 16.7 milliseconds / voltage applied at 0 milliseconds) × 100 (%). If the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and there is a high possibility of affecting the reliability of the liquid crystal display panel. Furthermore, there is a high risk of causing display defects such as afterimages.

  From the results of Table 1, it was found that the positive radiation sensitive compositions of Examples 1 to 5 had higher storage stability than the composition of Comparative Example 1. Moreover, from the result of Table 2, the liquid crystal cell of Examples 6-20 is excellent in the voltage holding rate compared with the liquid crystal cell of Comparative Examples 2-4, and heat resistance and light resistance in the manufacturing process accompanied by a heating or light irradiation. It turned out that it is excellent in property.

  In the liquid crystal display element of the present invention, since the interlayer insulating film has excellent heat resistance and light resistance, it is possible to suppress deformation and the like in the manufacturing process, and as a result, to exhibit excellent voltage holding ability. it can. Moreover, since this positive radiation sensitive composition is excellent in storage stability, the liquid crystal display element has high productivity.

DESCRIPTION OF SYMBOLS 10 Liquid crystal display element in the middle of manufacture 1a, 1b board | substrate 2 interlayer insulation film 3 liquid crystal layer 4 transparent electrode film 5 liquid crystal aligning film 6 sealing material 7 injection hole

Claims (2)

Forming an interlayer insulating film on the surface side of at least one of the pair of substrates;
Forming a liquid crystal alignment film on the surface side of the interlayer insulating film and the surface side of the other substrate;
A step of filling a polymerizable liquid crystal composition between the substrates in a state where the surfaces on which the liquid crystal alignment film is formed are opposed to each other, and a step of forming a liquid crystal layer by heating or light irradiation of the polymerizable liquid crystal composition A method of manufacturing a liquid crystal display device comprising:
The interlayer insulating film is formed of a positive radiation sensitive composition,
This positive radiation sensitive composition is
[A] a polymer having a structural unit containing a group represented by the following formula (2) and an epoxy group-containing structural unit in the same or different polymer molecules;
[B] A method for producing a liquid crystal display element, comprising a photoacid generator, and [C] an organic solvent, and forming a crosslinked portion of a polymer represented by the following formula (1) by a crosslinking reaction.

(In Formula (1), R ⁰ is a group represented by any of the following Formulas (1-1) to (1-6).)

(In Formula (2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group, provided that one of the hydrogen atoms of the above-mentioned alkyl group, cycloalkyl group, or aryl group) Part or all may be substituted, and R ¹ and R ² are not both hydrogen atoms, R ³ is an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or —M (R ^3m ) is a group represented by _3. above M is, Si, a Ge or Sn .R ^3m is an alkyl group. However, some or all of the hydrogen atoms of these groups may be substituted R ¹ and R ³ may be linked to form a cyclic ether.) The method for producing a liquid crystal display element according to claim 1, wherein the positive radiation-sensitive composition further contains [D] a surfactant, and the [D] surfactant is a silicone-based surfactant .

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