JP2008024915A - Radiation-sensitive resin composition for use in spacer, spacer, and forming method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive resin composition suitable for forming a spacer which is capable of easily forming a patterned thin film having high sensitivity and high resolution and being excellent in various performances such as the pattern shape, compression strength, rubbing resistance and heat resistance, which is suppressed in the occurrence of a sublimate at the time of baking and is suppressed in the sticking on baking according to LCD, and which has a sufficient resistance to liquid chemicals such as an orientational film-removing liquid. <P>SOLUTION: The radiation-sensitive resin composition comprises a block copolymer comprising two or more block segments and having at least one block segment with polymerization units respectively derived from an epoxy group-containing ethylenically unsaturated compound, for example, glycidyl acrylate and from (meth)acryloyl alkyloxetane, a polymerizable unsaturated compound, and a radiation-sensitive polymerization initiator. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive resin composition, a spacer, and a method for forming the spacer.

Conventionally, liquid crystal display elements (LCDs) have used spacer particles such as glass beads and plastic beads having a predetermined particle size in order to keep the distance between two transparent substrates constant. Since the particles are randomly distributed on a transparent substrate such as a glass substrate, if spacer particles are present in the pixel formation region, the spacer particles may be reflected, or incident light may be scattered and the contrast of the liquid crystal display element There was a problem that decreased.
In order to solve these problems, a method of forming a spacer by photolithography has been adopted. In this method, a radiation-sensitive resin composition is applied onto a substrate, exposed to ultraviolet rays through a predetermined mask, and then developed to form dot-shaped or stripe-shaped spacers. Since the spacers can be formed only at predetermined locations, the above-described problems have been basically solved.

  By the way, radiation from a mercury lamp used as a light source in photolithography is usually around 436 nm (g line), around 404 nm (h line), around 365 nm (i line), around 335 nm, around 315 nm (j line), In order to show a strong spectrum around 303 nm, etc., the radiation-sensitive polymerization initiator that is a component of the radiation-sensitive resin composition is selected to have a maximum absorption wavelength in the wavelength region of these strong spectra. Usually, from the viewpoint of transparency, a radiation-sensitive polymerization initiator having a maximum absorption wavelength in the region of i-line or less is used (see Patent Document 1). However, in a conventionally known radiation-sensitive resin composition for forming a spacer, depending on the selection of the radiation-sensitive polymerization initiator, the cross-sectional shape of the spacer formed is inversely tapered (the side length of the film surface is the substrate). In some cases, the trapezoidal shape is longer than the length of the side edge), which causes the spacer to peel off during the subsequent rubbing treatment of the alignment film.

However, in conventional radiation-sensitive resin compositions, including those in Patent Document 1, there is a concern that sublimates generated during firing to form spacers may contaminate process lines and devices, and generated sublimates. There has been a demand for a radiation-sensitive resin composition with reduced selenium.
Furthermore, “image sticking” such as an afterimage in a liquid crystal display element presumed to be caused by impurities eluted from the in-cell permanent film formed from the radiation-sensitive resin composition is a problem, and the inside of the cell where “image sticking” does not occur. There has been a demand for a radiation-sensitive resin composition that forms a permanent film and enables production of a liquid crystal display panel with a high product yield.
On the other hand, if too much emphasis is placed on the high restoring force that restores the original cell gap after deformation due to compressive strength and external force, can external force be absorbed and the thin-layer transistor (TFT) and color filter (CF) be damaged? There was a problem that could be destroyed.

In addition, in order to shorten the filling process time for injecting liquid crystal in a vacuum after bonding the TFT plate and the CF plate, there is a new process for dropping the liquid crystal at a time and bonding the TFT plate and the CF plate. It has been developed. However, the conventional spacer has a problem that the amount of deformation is not sufficient, the margin for the liquid crystal dropping process is insufficient, and a defect occurs.
Furthermore, with the recent increase in the size of mother glass for liquid crystal display elements, there is an increasing tendency to recycle and use defective substrates generated in each process from the viewpoint of cost control. In particular, alignment film formation is performed after spacers are formed. When a defect occurs in a process, a case where an alignment film is peeled off by a chemical solution and an alignment film is formed again is becoming common. Therefore, the spacer is required to have sufficient resistance to the alignment film stripping solution.
JP 2001-261761 A Japanese Patent No. 3639859 (Japanese Patent Publication No. 2000-515181) Special Table 2002-2002 JP-T-2004-518773 Special table 2002-508409 gazette Japanese translation of PCT publication No. 2002-512653 Special table 2003-527458 gazette Japanese Patent No. 3634843 (Japanese Patent Publication No. 2003-536105) JP-T-2005-503452 MKGeorges, RPNVeregin, PMKazmaier, GKHamer, Macromolecules, 1993, Vol.26, p.2987 Matyjaszewski, K. Coca, S. Gaynor, G. wei, M. Woodworth, BE Macromolecules, 1997, Vol. 30, p. 7348 Hamasaki, S.Kamigaito, M.Sawamoto, M. Macromolecules, 2002, Vol.35, p.2934

  The present invention has been made based on the above situation. Therefore, the object of the present invention is to easily form a patterned thin film having high sensitivity, high resolution, and excellent performance such as pattern shape, compressive strength, rubbing resistance, heat resistance, etc. An object of the present invention is to provide a radiation-sensitive resin composition in which generation of sublimates is suppressed, image sticking in an LCD display is suppressed, and sufficient resistance to a chemical solution such as an alignment film peeling solution is provided.

  Another object of the present invention is to overcome the thickness deviation that occurs in the process, to reduce defects in the unfilled area due to the liquid crystal dripping amount, and to damage the thin layer transistor or color filter due to external force in the liquid crystal display device. It is an object of the present invention to provide a photosensitive resin composition that provides a spacer that can be prevented.

  Still another object of the present invention is to provide a spacer formed from the radiation-sensitive resin composition and a method for forming the spacer.

  Still other objects and advantages of the present invention will become apparent from the following description.

The above objects and advantages of the present invention are as follows.
(A) block copolymer (B) containing a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator, (A) the block copolymer has two or more block segments, of which at least One block segment is (a1) a polymerized unit derived from an epoxy group-containing ethylenically unsaturated compound and the following formulas (I) and (II):

[In Formula (I) and Formula (II), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 It is. And a polymerized unit derived from at least one monomer selected from the group consisting of compounds represented by each of the above-described compounds.

The above objects and advantages of the present invention are secondly,
It is preferably achieved by the radiation-sensitive resin composition in which at least one block segment of the (A) block copolymer contains a polymer unit derived from (a2) an alkali-soluble monomer.

Third, the above objects and advantages of the present invention are as follows:
(A) The block copolymer is preferably achieved by the radiation sensitive resin composition obtained by living radical polymerization.

The above objects and advantages of the present invention are, fourthly,
It is preferably achieved by the radiation-sensitive resin composition produced by polymerization using a thiocarbonylthio compound represented by the following formula (1), (2) or (3) as a molecular weight control agent. .

[In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. A monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OX, -SX, -N (X) ₂ , -OC (= O) X, -C (= O) OX, -C (═O) N (X) ₂ , —P (═O) (OX) ₂ , —P (═O) (X) ₂ , or a monovalent group having a polymer chain, wherein each X is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of carbon atoms and hetero atoms 1 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent compound having 3 to 20 atoms in total. Cyclic group and X may be each substituted, p is an integer of 1 or more, X ^1, when the p = 1, an alkyl group having 1 to 20 carbon atoms, monovalent C3-20 An alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, -OX,- SX, —N (X) ₂ or a monovalent group having a polymer chain, the definition of each X is the same as above, and when p ≧ 2, the p value derived from an alkane having 1 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a p-valent group derived from a heterocyclic compound having 3 to 20 total atoms of carbon atoms and hetero atoms, or a polymer A p-valent group having a chain, and the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 6 carbon atoms. 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 atoms in total, X, p-valent groups derived from alkanes having 1 to 20 carbon atoms, and aromatics having 6 to 20 carbon atoms A p-valent group derived from a group hydrocarbon and a p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted. ]

[In Formula (2), m is an integer greater than or equal to ² , Z2 is m-valent group derived from a C1-C20 alkane, m-valent group derived from a C6-C20 aromatic hydrocarbon. Group, a m-valent group having a polymer chain and a m-valent group derived from a heterocyclic compound having 3 to 20 total atoms of carbon atoms and hetero atoms, and the above-mentioned alkane having 1 to 20 carbon atoms The derived m-valent group, the m-valent group derived from the aromatic hydrocarbon having 6 to 20 carbon atoms, and the m-valent group derived from the heterocyclic compound having 3 to 20 atoms in total may be substituted. Well, X ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and different from carbon atoms. Yusuke monovalent heterocyclic group total atomic number from 3 to 20 with the atoms, -OX, -SX, a -N _{(X) 2} or a polymer chain Each X is independently of each other an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a carbon atom. A monovalent heterocyclic group having 3 to 18 atoms in total with the hetero atom is shown, the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, the number of carbon atoms The 6-20 monovalent aromatic hydrocarbon group, the monovalent heterocyclic group having 3 to 20 atoms in total, and X may each be substituted. ]

[In Formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic carbon atom having 6 to 20 carbon atoms. Hydrogen group, monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, —OR ¹ , —SR ¹ , —OC (═O) R ¹ , —N (R ¹ ) ( R ² ), —C (═O) OR ¹ , —C (═O) N (R ¹ ) (R ² ), —P (═O) (OR ¹ ) ₂ , —P (═O) (R ¹ ) ₂ or a monovalent group having a polymer chain, wherein R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or 1 having 6 to 18 carbon atoms. A monovalent heterocyclic group having a total of 3 to 18 atoms of a valent aromatic hydrocarbon group or a carbon atom and a hetero atom, and the alkyl group having 1 to 20 carbon atoms Monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent heterocyclic group Total atoms having 3 to 20 carbon atoms and the hetero atoms, be R ¹ and R ² are each optionally substituted Good. ]

Fifth, the object and advantage of the present invention are as follows. The ratio (Mw) of polystyrene-converted weight average molecular weight (Mw) and polystyrene-converted number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer (A). / Mn) is preferably achieved by the radiation sensitive resin composition having a value of 2.5 or less.
Sixth, the above objects and advantages of the present invention are achieved by a spacer formed from the above radiation sensitive resin composition.

Seventhly, the above objects and advantages of the present invention are achieved by a spacer forming method characterized by including at least the following steps (A) to (D).
(A) forming a film of the radiation sensitive resin composition on a substrate;
(B) a step of exposing radiation to at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development.

  Eighthly, the above objects and advantages of the present invention are achieved by a liquid crystal display device comprising the above spacer.

  The radiation sensitive resin composition of the present invention can easily form a patterned thin film having high sensitivity, high resolution, and excellent performance such as pattern shape, compressive strength, rubbing resistance, heat resistance, Generation of sublimates during firing can be suppressed, and image sticking such as afterimages on the LCD display can be suppressed. Moreover, it becomes possible to improve the tolerance with respect to chemical | medical solutions, such as alignment film peeling liquid. In addition, the amount of deformation of the spacer formed therefrom is sufficient, the TFT and CF are not damaged or destroyed by an external force, and a margin for the liquid crystal dropping process can be expected to be improved.

The following radiation-sensitive resin composition will be described in detail for each component in the radiation-sensitive resin composition of the present invention.

(A) Block copolymer The (A) block copolymer in the radiation-sensitive resin composition of the present invention is at least a block segment composed of polymerized units derived from polymerizable unsaturated compounds each having a different chemical structure. It shall mean a copolymer containing two or more. The block segment can be composed of a block obtained by polymerizing a single type of polymerizable unsaturated compound or a block obtained by polymerizing a plurality of types. The block segment may be a random copolymer block. (A) The block copolymer may contain two block segments each consisting of a random copolymer.
(A) The block copolymer has at least one of two segments of a first block segment produced by primary polymerization and a second block segment added to the first block segment by secondary polymerization. At least one monomer selected from the group consisting of (a1) a polymer unit derived from an epoxy group-containing ethylenically unsaturated compound and a compound represented by each of the above formulas (I) and (II) (hereinafter referred to as “compound”) (Al) (also referred to as “a1)”). In addition, it is preferable that at least one segment contains a polymer unit derived from (a2) an alkali-soluble monomer (hereinafter also referred to as “compound (a2)”). These (a1) and (a2) can exist in the same or different segments. Further, each block segment may have a polymer unit derived from an ethylenically unsaturated compound other than (a3), (a1), and (a2) (hereinafter also referred to as “compound (a3)”).
Hereinafter, (A) the unsaturated compound used for synthesizing the block polymer will be described.

  The compound (a1) is at least one selected from an epoxy group-containing ethylenically unsaturated compound and a monomer represented by the following formulas (I) to (II).

[In Formula (I) and Formula (II), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 It is. ]

Examples of the epoxy group-containing ethylenically unsaturated compound include glycidyl acrylate, 2-methylglycidyl acrylate, 3,4-epoxybutyl acrylate, 6,7-epoxyheptyl acrylate, 3,4-epoxycyclohexyl acrylate, and the like. An epoxy alkyl ester of acrylic acid;
Methacrylic acid such as glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate Acid epoxy alkyl ester;
α-alkylacrylic acid epoxy alkyl esters such as glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, α-ethyl acrylate 6,7-epoxyheptyl;
Examples thereof include glycidyl ethers such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

  Examples of the compound (a1) represented by the formula (I) include 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-methyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 3- (methacryloyloxymethyl) -2,2-difluorooxetane, 3- (methacryloyloxymethyl) -2,2,4-trifluorooxetane, 3- (methacryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- ( Methacryloyloxyethyl) oxetane, 3 (Methacryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxyethyl) -2-penta Fluoroethyloxetane, 3- (methacryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (methacryloyloxyethyl) oxetane, 3- (methacryloyloxyethyl) -2,2,4-trifluorooxetane, Methacrylic acid esters such as 3- (methacryloyloxyethyl) -2,2,4,4-tetrafluorooxetane;

3- (acryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) -3-ethyloxetane, 3- (acryloyloxymethyl) -2-methyloxetane, 3- (acryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxymethyl) -2-phenyloxetane, 3- (acryloyloxymethyl) -2,2-difluorooxetane, 3- (acryloyloxymethyl) ) -2,2,4-trifluorooxetane, 3- (acryloyloxymethyl) -2,2,4,4-tetrafluorooxetane, 3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -3 -Ethyloxetane, 2-ethyl-3 (Acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2-trifluoromethyloxetane, 3- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 3- (acryloyloxyethyl) -2-phenyloxetane, 2,2-difluoro-3- (acryloyloxyethyl) oxetane, 3- (acryloyloxyethyl) -2,2,4-trifluorooxetane, 3- (acryloyloxyethyl) -2,2,4,4-tetra Acrylic esters such as fluorooxetane can be mentioned.

  Examples of the compound (a1) represented by the formula (II) include 2- (methacryloyloxymethyl) oxetane, 2-methyl-2- (methacryloyloxymethyl) oxetane, 3-methyl-2- (methacryloyloxymethyl) oxetane, 4-methyl-2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -3-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (methacryloyloxymethyl) -2-pentafluoroethyl oxetane, 2- (methacryloyloxymethyl) -3-pentafluoroethyloxetane, 2- (methacryloyloxymethyl) -4-pentafluoro Tyloxetane, 2- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) -3-phenyloxetane, 2- (methacryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (Methacryloyloxymethyl) oxetane, 2,4-difluoro-2- (methacryloyloxymethyl) oxetane, 3,3-difluoro-2- (methacryloyloxymethyl) oxetane, 3,4-difluoro-2- (methacryloyloxymethyl) Oxetane, 4,4-difluoro-2- (methacryloyloxymethyl) oxetane,

2- (methacryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (methacryloyloxymethyl) -3,3,4, 4-tetrafluorooxetane, 2- (methacryloyloxyethyl) oxetane, 2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (methacryloyloxy) Ethyl) -2-methyloxetane, 2- (methacryloyloxyethyl) -4-methyloxetane, 2- (methacryloyloxyethyl) -2-trifluoromethyloxetane, 2- (methacryloyloxyethyl) -3-trifluoromethyloxetane , 2- (methacryloyloxyethyl -4-trifluoromethyl oxetane, 2- (methacryloyloxyethyl) -2-pentafluoroethyl oxetane, 2- (methacryloyloxyethyl) -3-pentafluoroethyl oxetane, 2- (methacryloyloxyethyl) -4-pentafluoro Ethyl oxetane, 2- (methacryloyloxyethyl) -2-phenyloxetane, 2- (methacryloyloxyethyl) -3-phenyloxetane, 2- (methacryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- (Methacryloyloxyethyl) oxetane, 2,4-difluoro-2- (methacryloyloxyethyl) oxetane, 3,3-difluoro-2- (methacryloyloxyethyl) oxetane, 3,4-difluoro-2- (methacryloyloxyethyl) ) Oxetane, 4,4-difluoro-2- (methacryloyloxyethyl) oxetane, 2- (methacryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (methacryloyloxyethyl) -3,4,4- Methacrylic acid esters such as trifluorooxetane and 2- (methacryloyloxyethyl) -3,3,4,4-tetrafluorooxetane;

2- (acryloyloxymethyl) oxetane, 2-methyl-2- (acryloyloxymethyl) oxetane, 3-methyl-2- (acryloyloxymethyl) oxetane, 4-methyl-2- (acryloyloxymethyl) oxetane, 2- (Acryloyloxymethyl) -2-trifluoromethyloxetane, 2- (acryloyloxymethyl) -3-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) 2-Pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -3-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -4-pentafluoroethyl oxetane, 2- (acryloyloxymethyl) -2-phenyloxet 2- (acryloyloxymethyl) -3-phenyloxetane, 2- (acryloyloxymethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxymethyl) oxetane, 2,4-difluoro-2 -(Acryloyloxymethyl) oxetane, 3,3-difluoro-2- (acryloyloxymethyl) oxetane, 3,4-difluoro-2- (acryloyloxymethyl) oxetane, 4,4-difluoro-2- (acryloyloxymethyl) ) Oxetane, 2- (acryloyloxymethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxymethyl) -3,3 , 4,4-Tetrafluorooxetane, 2- (acryloyloxy) Chill) oxetane,

2- (2- (2-methyloxetanyl)) ethyl methacrylate, 2- (2- (3-methyloxetanyl)) ethyl methacrylate, 2- (acryloyloxyethyl) -2-methyloxetane, 2- (acryloyloxyethyl) -4-methyloxetane, 2- (acryloyloxyethyl) -2-trifluoromethyloxetane, 2- (acryloyloxyethyl) -3-trifluoromethyloxetane, 2- (acryloyloxyethyl) -4-trifluoromethyloxetane 2- (acryloyloxyethyl) -2-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -3-pentafluoroethyloxetane, 2- (acryloyloxyethyl) -4-pentafluoroethyloxetane, 2- (acryloyl) Oxyethyl) 2-phenyloxetane, 2- (acryloyloxyethyl) -3-phenyloxetane, 2- (acryloyloxyethyl) -4-phenyloxetane, 2,3-difluoro-2- (acryloyloxyethyl) oxetane, 2,4- Difluoro-2- (acryloyloxyethyl) oxetane, 3,3-difluoro-2- (acryloyloxyethyl) oxetane, 3,4-difluoro-2- (acryloyloxyethyl) oxetane, 4,4-difluoro-2- ( (Acryloyloxyethyl) oxetane, 2- (acryloyloxyethyl) -3,3,4-trifluorooxetane, 2- (acryloyloxyethyl) -3,4,4-trifluorooxetane, 2- (acryloyloxyethyl)- Such as 3,3,4,4-tetrafluorooxetane Acrylic acid ester, and the like, respectively.
Among these, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, The photosensitive resin composition from which 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane and the like are obtained has a wide process margin and is preferably used from the viewpoint of enhancing the chemical resistance of the resulting spacer. These may be used alone or in combination.

  The alkali-soluble monomer of the compound (a2) is preferably an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride having radical polymerizability. Examples of the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride having radical polymerizability include monocarboxylic acid, dicarboxylic acid, dicarboxylic acid anhydride, and poly [carboxylic acid] mono [(meth) acryloyloxyalkyl]. Examples thereof include esters, mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, polycyclic compounds having a carboxyl group, and anhydrides thereof.

Specific examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid;
Examples of dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid and the like;
Examples of dicarboxylic acid anhydrides include, for example, acid anhydrides of the above compounds exemplified as the dicarboxylic acid;
Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
As a mono (meth) acrylate of a polymer having a carboxyl group and a hydroxyl group at each of both ends, for example, ω-carboxypolycaprolactone mono (meth) acrylate, etc .; As a polycyclic compound having a carboxyl group and its anhydride, for example, 5 -Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] ] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5 -Carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride Etc. can be mentioned.

Of these, monocarboxylic acid and dicarboxylic acid anhydrides are preferably used, and acrylic acid, methacrylic acid, and maleic anhydride are particularly preferably used from the viewpoints of copolymerization reactivity, solubility in alkaline aqueous solutions, and availability. . These may be used alone or in combination.
Compound (a2) may be regenerated by protecting the carboxyl group and then subjecting it to polymerization, followed by deprotection. Here, the protecting group for protecting the carboxyl group is not particularly limited, and a known protecting group for the carboxyl group can be used. For example, a trialkylsilyl group, 1-alkoxyalkyl group, cyclic 1-alkoxyalkyl group and the like can be mentioned. More specifically, for example, trimethylsilyl group, dimethylbutylsilyl group, 1-ethoxyethyl group, 1-propoxyethyl group, tetrahydrofuranyl group, tetrahydropyranyl group, triphenylmethyl group and the like can be mentioned.

Examples of the compound (a3) include acrylic acid alkyl esters such as methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, sec-butyl acrylate, and t-butyl acrylate;
Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate; cyclohexyl acrylate, 2-methylcyclohexyl acrylate , Tricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate (hereinafter “tricyclo [5.2.1.0 ^2,6 ] decan-8-yl” is referred to as “dicyclopentanyl”. ), Alicyclic esters of acrylic acid such as 2-dicyclopentanyloxyethyl acrylate, isobornyl acrylate, and tetrahydrofuryl acrylate; cyclohexyl methacrylate, 2-methylcyclohexyl Alicyclic esters of methacrylic acid such as tacrylate, dicyclopentanyl methacrylate, 2-dicyclopentanyloxyethyl methacrylate, isobornyl methacrylate, tetrahydrofuryl methacrylate;

Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; 2-hydroxyethyl acrylate, 2-hydroxy Acrylic acid hydroxyalkyl ester such as propyl acrylate; 2-hydroxyethyl methacrylate, methacrylic acid hydroxyalkyl ester such as 2-hydroxypropyl methacrylate; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene Aromatic vinyl compounds such as acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylic Amide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide Examples include benzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N- (9-acridinyl) maleimide.
Of these compounds (a3), 2-methylcyclohexyl acrylate, t-butyl methacrylate, dicyclopentanyl methacrylate, styrene, p-methoxystyrene, 1,3-butadiene and the like are preferable from the viewpoint of copolymerization reactivity.
The said compound (a3) can be used individually or in mixture of 2 or more types.

In the block copolymer (A) used in the present invention, as the first block segment, for example, a block segment composed of polymer units derived from all of the compounds (a1), (a2) and (a3), or a compound ( A block segment composed of polymerized units derived from two of a2) and (a3) is preferred.
When the first block segment is composed of polymerized units derived from all of the compounds (a1), (a2) and (a3), the content of the polymerized units derived from the compound (a1) in the block segment is the compound (a1 ), (A2) and (a3), preferably 5 to 70% by weight, more preferably 10 to 50% by weight based on the total of the polymerized units derived from (a3). In this case, when the content of the polymerized unit derived from the compound (a1) is less than 5% by weight, the compression strength, heat resistance and chemical resistance of the resulting spacer tend to be lowered, whereas it exceeds 70% by weight. And there exists a possibility that the storage stability of a radiation sensitive resin composition may fall.
The content of the polymerized units derived from the compound (a2) in the block segment is preferably 5 to 50% by weight based on the total of polymerized units derived from the compounds (a1), (a2) and (a3), More preferably, it is 10 to 40% by weight. In this case, if the content of the polymerized unit derived from the compound (a2) is less than 5% by weight, the compressive strength, heat resistance and chemical resistance of the resulting spacer tend to be lowered, whereas it exceeds 50% by weight. And there exists a possibility that the storage stability of a radiation sensitive resin composition may fall.
The content of the polymerized units derived from the compound (a3) in the block segment is preferably 10 to 85% by weight based on the total of polymerized units derived from the compounds (a1), (a2) and (a3), More preferably, it is 20 to 75% by weight. In this case, if the content of these polymerized units is less than 10% by weight, the storage stability of the radiation-sensitive resin composition may be lowered, whereas if it exceeds 85% by weight, the developability may be lowered. There is.

When the first block segment is composed of polymerized units derived from two of the compounds (a2) and (a3), the content of the polymerized units derived from the compound (a2) in the block segment is the compound (a2) and ( It is preferably 10 to 70% by weight, more preferably 15 to 60% by weight, based on the total of polymerized units derived from a3).
The content of the polymer units derived from the compound (a3) in the block segment is preferably 30 to 90% by weight, more preferably 40%, based on the total of polymer units derived from the compounds (a2) and (a3). ~ 85% by weight.

(A) The second block segment in the block copolymer is a block segment composed of a polymer unit derived from the compound (a1), a block segment composed of a polymer unit derived from the compound (a2), and a polymerization derived from the compound (a3). It can be a block segment composed of units or a block segment composed of polymerized units derived from two selected from the group of compounds (a1), (a2) and (a3). However, the polymerization units constituting the first block segment and the second block segment are not the same combination.
In the present invention, the second block segment is preferably a block segment consisting only of the compound (a1) or a block segment consisting only of the compound (a3). In this case, when the (A) block copolymer has the second block segment consisting only of the compound (a1) as a crosslinking component, it becomes possible to obtain a spacer having higher hardness and excellent chemical resistance, On the other hand, having the second block segment composed only of the compound (a3) not involved in cross-linking makes it possible to obtain a spacer having a lower hardness, excellent compatibility when forming the spacer, and a uniform surface state.
The block copolymer (A) can further control the hardness, chemical resistance, and shape of the spacer by having a third block segment as necessary. Examples of the third block segment include those similar to the second block segment, but the polymerization units constituting the second block segment and the third block segment are not the same combination. Moreover, it is preferable that a 3rd block segment is added to a 2nd block segment in the tertiary polymerization performed subsequent to the secondary polymerization which synthesize | combines a 2nd block segment.

As the (A) block copolymer of the present invention, for example,
A block copolymer comprising at least a first block segment comprising polymerized units derived from all of the compounds (a1), (a2) and (a3) and a second block segment comprising only the compound (a1),
A block copolymer comprising at least a first block segment comprising polymerized units derived from all of the compounds (a1), (a2) and (a3) and a second block segment comprising only the compound (a3),
A block copolymer comprising at least a first block segment composed of polymerized units derived from two of compounds (a2) and (a3) and a second block segment composed only of compound (a1);
A block comprising a first block segment comprising polymerized units derived from two compounds (a2) and (a3), a second block segment comprising only compound (a3), and a third block segment comprising only compound (a1). A copolymer or the like is preferred.

Such (A) block copolymer is, for example, (a1) an epoxy group-containing ethylenically unsaturated compound and a monomer represented by formulas (I) to (II),
(A2) Alkali-soluble monomers, such as unsaturated carboxylic acids and / or unsaturated carboxylic acid anhydrides having radical polymerizability, or protected products of these carboxylic acids, and ethylene other than compounds (a3) (a1) and (a2) The polymerizable mixture containing a polymerizable unsaturated compound is subjected to living radical polymerization (primary polymerization) in a solvent in the presence of a polymerization initiator to form a first block segment. Further, compounds (a1), (a2) and (a3 ) To add a second block segment by adding a polymerizable mixture containing at least one selected from (2) and continuing the polymerization (secondary polymerization). If necessary, the third block segment can be added by adding a polymerizable mixture and continuing the polymerization (tertiary polymerization).
The alkali-soluble part of the thus obtained (A) block copolymer is derived from the compound (a2).

(A) The weight ratio ((first block segment weight / (A) block copolymer weight) × 100) occupied by the first block segment in the block copolymer is preferably 30 to 95%, particularly preferably 50 ~ 90%. When this value is lower than 30%, the electrical properties of the obtained spacer may be deteriorated, and the pattern shape and developability may be deteriorated. On the other hand, if it is larger than 95%, there is a concern that volatile components increase during baking at the time of spacer formation, which is not preferable.
The (A) block copolymer used in the present invention has a polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) and a polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography. The ratio (Mw / Mn) is preferably 2.5 or less, more preferably 2.0 or less. If Mw / Mn exceeds 2.5, the pattern shape and developability of the resulting spacer may be inferior. Further, Mw is preferably 2 × 10 ³ to 1 × 10 ⁵ , more preferably 5 × 10 ^{3 to} 5 × 10 ⁴ . If the Mw is less than 2 × 10 ³ , the development margin may not be sufficient, and the remaining film ratio of the resulting film may decrease, or the pattern shape of the resulting spacer, heat resistance, etc. may be inferior. . On the other hand, if Mw exceeds 1 × 10 ⁵ , the sensitivity may decrease or the pattern shape may be inferior. Further, Mn is preferably 1.2 × 10 ³ to 1 × 10 ⁵ , and more preferably 2.9 × 10 ^{3 to} 5 × 10 ⁴ . The radiation-sensitive resin composition containing such a block copolymer (A) can easily form a predetermined pattern shape without causing development residue during development.

Further, the residual monomer amount measured by gel permeation chromatography of the (A) block copolymer used in the present invention is preferably less than 5.0% by weight, more preferably less than 3.0% by weight, particularly preferably. Less than 2.0% by weight.
A photosensitive resin composition having a weight average molecular weight Mw as described above, preferably further having the specific Mw / Mn, and using the (A) block copolymer having the residual monomer content described above. The generation of sublimates during exposure and baking of coating films obtained from products is low, the possibility of contamination of equipment used in LCD panel manufacturing is low, and “burn-in” of LCD panels is more effectively prevented. Can do.
The said (A) block copolymer can be used individually or in mixture of 2 or more types.
Moreover, in this invention, you may use together 1 type (s) or 2 or more types of another alkali-soluble resin with (A) block copolymer.

Next, (A) Living radical polymerization for producing a block copolymer will be described.
Forming the first block segment by living radical polymerization of the ethylenically unsaturated compound, preferably with other copolymerizable unsaturated compounds, in a solvent in the presence of a radical polymerization initiator system that generates a living radical Further, the (A) block copolymer can be produced by adding the ethylenically unsaturated compound once or a plurality of times as necessary.
In living radical polymerization, when using a compound having a functional group that may deactivate an active radical such as a carboxyl group as an ethylenically unsaturated compound, in order to prevent the growth terminal from being deactivated, The functional group in the ethylenically unsaturated compound can be protected and polymerized, for example, by esterification, and then deprotected, whereby (A) a block copolymer can be obtained.

  Various radical polymerization initiator systems for living radical polymerization of ethylenically unsaturated compounds have been proposed. For example, the TEMPO system proposed by Georges et al. (Non-Patent Document 1: MKGeorges, RPN Veregin, PMKazmaier, GKHamer) , Macromolecules, 1993, Vol. 26, p. 2987), a system composed of a combination of copper bromide and a bromine-containing ester compound proposed by Matyjaszewski et al. , G.wei, M. Woodworth, BE Macromolecules, 1997, Vol.30, p.7348), a system composed of a combination of carbon tetrachloride and ruthenium (II) complex proposed by Hamasaki et al. : Hamasaki, S. Kamigaito, M. Sawamoto, M. Macromolecules, 2002, Vol. 35, p. 2934) and Patent Document 2 (Japanese Patent No. 3639859 specification (JP 2000-515181 A)), A thiocarbonyl compound having a chain transfer constant greater than 0.1 and a radical initiator as disclosed in Permissive Document 3 (Japanese Patent Publication No. 2002-500261) and Patent Document 4 (Japanese Patent Publication No. 2004-518773) The system which consists of a combination of these can be mentioned.

As a suitable radical polymerization initiator system used for living radical polymerization, a system in which the active radical at the growth end is not deactivated is appropriately selected depending on the type of the polymerizable unsaturated compound used. In consideration of efficiency and metal-free system, a combination of a thiocarbonylthio compound that is a molecular weight control agent and a radical initiator is preferable.
Regarding the combination of the thiocarbonylthio compound and the radical initiator, in addition to Patent Document 2, Patent Document 3 and Patent Document 4, the following Patent Document 5 (JP 2002-508409 A) and Patent Document 6 (Special Table) 2002-512653 gazette), patent document 7 (Japanese translations of PCT publication 2003-527458 gazette), patent document 8 (patent 3634843 (Japanese translations of PCT publication No. 2003-536105 gazette)), and patent document 9 (Japanese translations of PCT publication No. 2005-503352 gazette). Are listed.
As described in Patent Document 3 to Patent Document 6, a random copolymer or block copolymer having a narrow molecular weight distribution is obtained by living radical polymerization of an unsaturated compound in the presence of a thiocarbonylthio compound and a radical initiator. Coalescence can be obtained. Moreover, since a functional group can be introduced into the obtained random copolymer and block copolymer, the copolymer is converted into an aqueous gel (see Patent Document 7), a photoresist (see Patent Document 8), a surface activity. It has been clarified that it can be used for applications such as an agent (see Patent Document 9).

Preferred examples of the thiocarbonylthio compound in the present invention include compounds represented by the above formula (1), the above formula (2), or the above formula (3).
In the above formula (1), examples of the alkyl group having 1 to 20 carbon atoms of Z ¹ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec- Butyl group, t-butyl group, n-pentyl group, 1,1-dimethylpropyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1-dimethyl-3,3-dimethyl A butyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-octadecyl group, n-eicosyl group, etc. can be mentioned.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms of Z ¹ include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 9-anthracenyl group, benzyl group, α -A methyl benzyl group, (alpha), (alpha)-dimethyl benzyl group, a phenethyl group etc. can be mentioned.

Examples of the monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms of Z ¹ include oxiranyl group, aziridinyl group, 2-furanyl group, 3-furanyl group, and 2-tetrahydrofuran. Nyl group, 3-tetrahydrofuranyl group, 1-pyrrole group, 2-pyrrole group, 3-pyrrole group, 1-pyrrolidinyl group, 2-pyrrolidinyl group, 3-pyrrolidinyl group, 1-pyrazole group, 2-pyrazole group, 3 -Pyrazole group, 2-tetrahydropyranyl group, 3-tetrahydropyranyl group, 4-tetrahydropyranyl group, 2-thianyl group, 3-thianyl group, 4-thianyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 2-piperidinyl group, 3-piperidinyl group, 4-piperidinyl group, 2-morpholinyl group, 3-morpholinyl group, etc. You can.
^Further, the _{Z 1 -OX, -SX, -N (} X) 2, -OC (= O) X, -C (= O) OX, -C (= O) N (X) 2, -P (= O) (OX) ₂ and —P (═O) (X) ₂ , an alkyl group having 1 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a carbon atom and a hetero atom. As the monovalent heterocyclic group having 3 to 18 atoms in total, for example, an alkyl group having 1 to 20 carbon atoms exemplified for Z ¹ , a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or carbon Among the monovalent heterocyclic groups having 3 to 20 total atoms of atoms and hetero atoms, there can be mentioned groups having 18 or less carbon atoms or total atoms.

Examples of the alkenyl group having 2 to 18 carbon atoms of X include, for example, a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like can be mentioned.
The above-mentioned alkyl group having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, and X Examples of the substituent include, for example, a hydroxyl group, a carboxyl group, a carboxylate group, a sulfonate group, a sulfonate group, an isocyanate group, a cyano group, a vinyl group, an epoxy group, a silyl group, a halogen atom, and Z ^1- OX, -SX, -N (X) ₂ , -OC (= O) X, -C (= O) OX, -C (= O) N (X) ₂ , -P (= O) (OX) ₂ Or -P (= O) (X) ₂ ;
The alkyl group having 1 to 18 carbon atoms, the alkenyl group having 2 to 18 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or the total number of atoms of carbon atoms and hetero atoms of 3 to 3 exemplified for X It can be appropriately selected from the same groups as the 18 monovalent heterocyclic groups, and one or more of these substituents can be present in the molecule. However, the total number of carbon atoms or the total number of atoms of the substituents in the molecule preferably does not exceed 20.

Examples of the monovalent group having a polymer chain of Z ¹ include α-olefins such as ethylene and propylene; aromatic vinyl compounds such as styrene and α-methylstyrene; vinyl fluoride, vinyl chloride, and vinylidene chloride. A vinyl halide, an unsaturated alcohol such as vinyl alcohol and allyl alcohol; an ester of an unsaturated alcohol such as vinyl acetate and allyl acetate; an unsaturated carboxylic acid such as (meth) acrylic acid and p-vinylbenzoic acid; Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, (meth) (Meth) acrylic acid esters such as n-hexyl acrylate and cyclohexyl (meth) acrylate; ) Acrylamide, (meth) acramide such as N, N-dimethyl (meth) acramide; Unsaturated nitrile such as (meth) acrylonitrile and vinylidene cyanide; One or more unsaturated compounds such as conjugated dienes such as butadiene and isoprene In addition to the monovalent group having an addition polymerization polymer chain to be formed, polyoxyethylene whose terminal may be etherified, polyether such as polyoxypropylene whose terminal may be etherified, and polyester And monovalent groups having polyaddition polymer chains such as polyamide and polyimide, polycondensation polymer chains, and the like. In the monovalent group having these polymer chains, even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (1), for example, —CH ₂ —COO—, —C (CH _{3) (CN) CH 2 CH} 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (1) via a connecting hands like.

In the formula (1), a plurality of Z ¹ may be the same as or different from each other.
In Formula (1), when p = 1, X ¹ is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, or a monovalent group having 6 to 20 carbon atoms. A monovalent heterocyclic group having a total of 3 to 20 carbon atoms and hetero atoms, a monovalent heterocyclic group, -OX, -SX, -N (X) ₂ or a polymer chain. Indicates a group.
The alkyl group having 1 to 20 carbon atoms, the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, the monovalent heterocyclic group having 3 to 20 atoms in total, -OX, -SX, -N (X As the monovalent group having ₂ or a polymer chain or a substituted derivative thereof, for example, the same groups as those exemplified for the corresponding groups of Z ¹ can be mentioned. In a monovalent group having a polymer chain of X ¹ (p = 1), even if the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, -C _{(CH 3)} (CN) may be through a linking hand, such _CH 2 CH 2 -COO- attached to the sulfur atom in the formula (1).
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopentyl group, a cyclohexyl group, a cyclopentenyl group, and a cyclohexenyl group.

Examples of the substituent for the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include, for example, an alkyl group having 1 to 20 carbon atoms in Z ^{1 and} a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms. , A monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom and a group similar to those exemplified for the substituent for X can be appropriately selected. There may be one or more or one or more types in the molecule. However, the total number of carbon atoms or the total number of atoms in the substituents in the molecule preferably does not exceed 20.
In addition, when p ≧ 2, X ¹ is a p-valent group derived from an alkane having 1 to 20 carbon atoms, a p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, or a carbon atom different from X ^1. A p-valent group or a p-valent group having a polymer chain derived from a heterocyclic compound having 3 to 20 atoms in total with the atom is shown.

Examples of the alkane having 1 to 20 carbon atoms include methane, ethane, propane, n-butane, i-butane, n-pentane, i-pentane, neopentane, n-hexane, n-heptane, n-octane, and n- Nonane, n-decane, n-dodecane, n-tetradecane, n-hexadecane, n-octadecane, n-eicosane and the like can be mentioned.
Examples of the aromatic hydrocarbon having 6 to 20 carbon atoms include benzene and 1,4-dimethylbenzene (for example, the carbon atom of each methyl group at the 1,4-position is bonded to the sulfur atom in the formula (1)). 1,2,4,5-tetramethylbenzene (for example, the carbon atom of each methyl group at the 1,2,4,5-position is bonded to the sulfur atom in formula (1)), 1, 2,3,4,5,6-hexamethylbenzene (for example, the carbon atom of each methyl group at the 1,2,3,4,5,6-position is bonded to the sulfur atom in formula (1)), 1,4-di-i-propylbenzene (for example, the 2-position carbon atom of each i-propyl group in the 1,4-position is bonded to the sulfur atom in formula (1)), naphthalene, anthracene group, etc. Can be mentioned.
Examples of the heterocyclic compound having 3 to 20 atoms in total include oxirane, aziridine, furan, tetrahydrofuran, pyrrole, pyrrolidine, pyrazole, tetrahydropyran, thiane, pyridine, piperidine, and morpholine.

P-valent group derived from the alkane having 1 to 20 carbon atoms, p-valent group derived from aromatic hydrocarbon having 6 to 20 carbon atoms and p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total. Examples of the substituent for the above group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a total number of 3 to 3 carbon atoms and hetero atoms. 20 monovalent heterocyclic groups and groups similar to those exemplified for the substituent for X can be selected as appropriate, and these substituents should be present in one or more or one or more kinds in the substituted derivative. Can do. However, the total number of carbon atoms or the total number of atoms of the substituents in the molecule preferably does not exceed 20.
Examples of the polymer chain giving a p-valent group of X ¹ include addition polymerization polymer chains, polyaddition polymer chains, and polycondensation systems exemplified for the monovalent group having the Z ¹ polymer chain. The thing similar to a polymer chain can be mentioned. In the p-valent group having the polymer chain of X ¹ , even when the polymer chain is directly bonded to the sulfur atom in the formula (1), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (1).
P in the formula (1) is preferably an integer of 1 to 6.

Next, in the formula (2), examples of the alkane having 1 to 20 carbon atoms that give an m-valent group of Z ² include compounds exemplified for the alkane having 1 to 20 carbon atoms that give the p-valent group of X ¹ above. The same thing can be mentioned.
In addition, examples of the aromatic hydrocarbon having 6 to 20 carbon atoms that give an m-valent group of Z ² include compounds exemplified for the aromatic hydrocarbon having 6 to 20 carbon atoms that give a p-valent group of X ¹ above, The same can be mentioned.
Further, examples of the heterocyclic compound having a total of 3 to 20 carbon atoms and a hetero atom including a m ² valent group of Z ² include, for example, a carbon atom and a hetero atom which provide a p valent group of X ¹ above. And the same compounds as those exemplified for the heterocyclic compound having 3 to 20 atoms in total.

Derived from an m-valent group derived from an alkane having 1 to 20 carbon atoms of Z ² , an m-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, and a heterocyclic compound having 3 to 20 atoms in total Examples of the substituent for the m-valent group include, for example, an alkyl group having 1 to 20 carbon atoms of Z ^1, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the total number of atoms of carbon atoms and hetero atoms. 3 to 20 monovalent heterocyclic groups and the same groups as those exemplified for the substituent for X can be appropriately selected, and one or more of these substituents are present in the molecule. be able to. However, the total number of carbon atoms or the total number of atoms of the substituents in the molecule preferably does not exceed 20.
Examples of the polymer chain that gives the Z ² m-valent group include addition polymerization polymer chains, polyaddition polymer chains and polycondensation exemplified for the monovalent group having the Z ¹ polymer chain. The thing similar to a system polymer chain can be mentioned. In the m-valent group having a polymer chain of Z ² , even when the polymer chain is directly bonded to the carbon atom of the thiocarbonyl group in the formula (2), for example, —CH ₂ —COO—, —C ( _{CH 3) (CN) CH 2} CH 2 -COO- may be bonded to the carbon atom of the thiocarbonyl group in the formula (2) via a connecting hands like.

In the formula (2), X ² alkyl group having 1 to 20 carbon atoms, monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, monovalent having 3 to 20 total atoms of carbon atoms and hetero atoms. As the monovalent group having a heterocyclic group, —OX, —SX, —N (X) ₂ and a polymer chain or a substituted derivative thereof, for example, the groups exemplified for the corresponding groups of Z ¹ above, The same can be mentioned. In the monovalent group having a polymer chain of X ² , even when the polymer chain is directly bonded to the sulfur atom in the formula (2), for example, —CH ₂ —COO—, —C (CH ₃ ) ( _CN) via a coupling hand, such as CH ₂ CH 2 -COO- may be bonded to the sulfur atom in the formula (2).
In addition, as the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms of X ² or a substituted derivative thereof, for example, the monovalent alicyclic group having 3 to 20 carbon atoms of the above X ¹ where p = 1). The thing similar to the group illustrated about the hydrocarbon group and its substituted derivative can be mentioned.
In the formula (2), a plurality of X ² may be the same or different from each other.
In the formula (2), if the ^{Z 2} and ^{-C (= S) -S-X} 2 is linked with aliphatic carbon atoms ^{Z 2,} -C aliphatic carbon atoms in ^{Z 2} (= S) When bonded to S—X ² and connected with an aromatic carbon atom, the aromatic carbon atom in Z ² is bonded to —C (═S) —S—X ^2, and further sulfur. In the case of being connected by an atom, a sulfur atom in —SX representing Z ² is bonded to —C (═S) —S—X ² .
M in the formula (2) is preferably an integer of 2 to 6.

In Formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic hydrocarbon having 6 to 20 carbon atoms. Group, monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, -OX ¹ , -SX ¹ , -OC (= O) X ¹ , -N (X ¹ ) (X ^{2), - C (= O} ) OX 1, -C (= O) N (X 1) (X 2), - P (= O) (OX 1) 2, -P (= O) (X 1) ₂ or a monovalent group having a polymer chain, wherein R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or a monovalent group having 6 to 18 carbon atoms. An aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, the alkyl group having 1 to 20 carbon atoms, Monovalent aromatic hydrocarbon radical of prime 6-20, monovalent heterocyclic group Total atoms having 3 to 20 carbon atoms and hetero atoms, X ¹ and X ² may be each substituted .

As Z ³ and Z ⁴ , those exemplified above as Z ¹ in the above formula (1) can be exemplified.
Z ³ and Z ⁴ are each an alkyl group having 1 to 20 carbon atoms, and particularly from the viewpoint of reactivity with the polymerizable unsaturated compound, in particular, the thiocarbonyl group (C═S) in formula (1) A group in which a carbon atom and a hetero atom such as a nitrogen atom or an oxygen atom in Z ³ and Z ⁴ are covalently bonded, more specifically, the total number of atoms of the carbon atom and the hetero atom is 3 to 20 Are preferably a monovalent heterocyclic group, -OX ¹ , -N (X ¹ ) (X ² ), and the like, particularly a methyl group, an ethyl group, a 1-pyrrole group, a 1-pyrazole group, a methoxy group, an ethoxy group, A dimethylamino group, a diethylamino group, etc. are preferable.

  Specific examples of particularly preferred thiocarbonylthio compounds in the present invention include compounds represented by the following formulas (4) to (29).

These thiocarbonylthio compounds can be used alone or in admixture of two or more.
Next, a preferred polymerization method for producing the (A) block copolymer will be described. (A) The block copolymer is, for example, (a1) at least one selected from an epoxy group-containing ethylenically unsaturated compound and a monomer represented by formulas (I) to (II), (a2) radical polymerizability A polymerizable mixture containing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride, or a protected product of the carboxylic acid, and an ethylenically unsaturated compound other than the compounds (a3), (a1), and (a2) In the solvent, living radical polymerization was carried out in the presence of at least one selected from a polymerization initiator and thiocarbonylthio compounds (1) to (29) to synthesize a first block segment, followed by compound ( a polymerization mixture containing at least one selected from a1), (a2) and (a3) is further added to continue the polymerization, and the second block series It can be manufactured by forming a cement. Moreover, if necessary, a polymerizable mixture can be further added to continue the polymerization, and the third block segment can be added.

When the polymerization takes the form of living radical polymerization, when a compound having a functional group that may deactivate an active radical such as a carboxyl group is used as the polymerizable unsaturated compound, in order to prevent the growth terminal from being deactivated. If necessary, the functional group in the unsaturated compound is protected and polymerized by, for example, esterification, followed by deprotection, whereby a copolymer (A) having a narrower molecular weight distribution can be obtained.
The radical polymerization initiator is appropriately selected according to the type of the polymerizable unsaturated compound used, and those generally known as radical polymerization initiators can be used, for example, 2,2 ′ -Azo compounds such as azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide , Lauroyl peroxide, 1,1′-bis (t-butylperoxy) cyclohexane, t-butylperoxypivalate and other organic peroxides; hydrogen peroxide; a redox initiator comprising these peroxides and a reducing agent And so on.
Among these radical polymerization initiators, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) are particularly preferable from the viewpoint that side reactions due to oxygen and the like are unlikely to occur. Azo compounds such as are preferred. The radical polymerization initiator can be used alone or in admixture of two or more kinds. In the polymerization, another molecular weight control agent, for example, α-methylstyrene dimer, t-dodecyl mercaptan, etc. The above may be used in combination with the thiocarbonylthio compounds (1) to (3).

The solvent used for the polymerization is not particularly limited, and examples thereof include diethylene glycol, propylene glycol monomethyl ether, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol, and 3-methoxybutanol. Alcohols;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, (Poly) alkylene glycol monoalkyl ether acetates such as dipropylene glycol monoethyl ether acetate and cyclohexanol acetate;
(Poly) alkylene glycol diethers such as diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ethyl ether, dipropylene glycol diethyl ether;
Other ethers such as tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
Ketoalcohols such as diacetone alcohol (ie 4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropion Ethyl acetate, ethyl ethoxy acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate , Methyl acetoacetate, ethyl acetoacetate, 2-oxobutanoic acid Other esters such as Le;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

  Among these solvents, active radicals are not deactivated during living radical polymerization, and from the viewpoint of solubility and coating properties of each component when used as a radiation sensitive resin composition, propylene glycol monomethyl ether, ethylene glycol monomethyl Ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, cyclohexanone, 2 -Heptanone, 3-heptanone, 3-methoxyp Ethyl pionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate N-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like are preferable.

The said solvent can be used individually or in mixture of 2 or more types.
In the said polymerization, the usage-amount of a radical polymerization initiator becomes like this. Preferably it is 0.1-50 weight part with respect to 100 weight part of all the unsaturated compounds, More preferably, it is 0.1-20 weight part.
The amount of the thiocarbonylthio compounds (1) to (3) used is preferably 0.1 to 50 parts by weight, more preferably 0.2 to 16 parts by weight, with respect to 100 parts by weight of the total unsaturated compounds. Especially preferably, it is 0.4-8 weight part. When the amount of the thiocarbonylthio compounds (1) to (3) used is less than 0.1 parts by weight, the regulation effect on the molecular weight and the molecular weight distribution tends to be reduced. May be generated automatically.

The amount of the other molecular weight control agent used is preferably 80 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the total molecular weight control agent. When the usage-amount of another molecular weight control agent exceeds 200 weight part, there exists a possibility that the desired effect of this invention may be impaired.
Moreover, the amount of the solvent used is preferably 50 to 1,000 parts by weight, more preferably 100 to 500 parts by weight with respect to 100 parts by weight of the total unsaturated compounds.
The polymerization temperature is preferably 0 to 150 ° C., more preferably 50 to 120 ° C., and the polymerization time is preferably 10 minutes to 20 hours, more preferably 30 minutes to 6 hours per block segment.

(B) Polymerizable unsaturated compound (B) The polymerizable unsaturated compound (hereinafter also referred to as “component (B)”) in the radiation-sensitive resin composition of the present invention is a bifunctional or higher functional acrylate and methacrylate ( Hereinafter, “(meth) acrylate”) is preferable.
Examples of the bifunctional (meth) acrylate include ethylene glycol acrylate, ethylene glycol methacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate, 1,9- Nonanediol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, polypropylene glycol diacrylate, polypropylene glycol dimethacrylate, bisphenoxyethanol full orange acrylate, bisphenoxyethanol full orange methacrylate and the like can be mentioned.

  Examples of commercially available bifunctional (meth) acrylates include Aronix M-210, M-240, M-6200 (manufactured by Toagosei Co., Ltd.), KAYARAD HDDA, KAYARAD HX-220, HX- 620, R-526, R-167, R-604, R-684, R-551, R-712, UX-2201, UX-2301, UX-3204, UX-3301, UX- 4101, UX-6101, UX-7101, UX-8101, UX-0937, MU-2100, MU-4001 (manufactured by Nippon Kayaku Co., Ltd.), Art Resin UN-9000PEP, UN-9200A, UN -7600, UN-333, UN-1003, UN-1255, UN-6060PTM, UN-6060P (Negami) Kogyo Co., Ltd.), SH-500B Biscoat 260, 312 and 335HP (Osaka Organic Chemical Co., Ltd.).

  Examples of the tri- or higher functional (meth) acrylate include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol penta. Acrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, tri (2-acryloyloxyethyl) phosphate, tri (2-methacryloyloxyethyl) phosphate, linear alkylene groups and A compound having an alicyclic structure and having two or more isocyanate groups; Having one or more hydroxyl groups, and 3, and the like four or five acryloyloxy groups and / or methacryloyloxy compound a urethane acrylate compound obtained by reacting with a group.

Examples of commercially available trifunctional or higher functional (meth) acrylates include Aronix M-309, -400, -402, -405, -450, -1310, -1600, -1960, and- 7100, -8030, -8060, -8100, -8530, -8560, -8560, -9050, Aronix TO-1450 (manufactured by Toagosei Co., Ltd.), KAYARAD TMPTA, DPHA, DPCA- 20, DPCA-30, DPCA-60, DPCA-120, MAX-3510 (above, manufactured by Nippon Kayaku Co., Ltd.), Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.) and urethane acrylate compounds such as New Frontier R-1150 (Daiichi Kogyo Seiyaku) Co., Ltd.)), KAYARAD DPHA-40H, manufactured by UX-5000 (manufactured by Nippon Kayaku (Ltd.)), UN-9000H (Negami Chemical Industry Co., Ltd.), and the like.
In this invention, a polymerizable unsaturated compound can be used individually or in mixture of 2 or more types.
The proportion of the (B) polymerizable unsaturated compound used in the radiation-sensitive resin composition of the present invention is preferably 40 to 250 parts by weight, more preferably 60 parts per 100 parts by weight of the (A) block copolymer. -180 parts by weight.

(C) Radiation-sensitive polymerization initiator (C) Radiation-sensitive polymerization initiator (hereinafter also referred to as “component (C)”) is sensitive to radiation and (B) polymerizes a polymerizable unsaturated compound. A component that produces an active species that can be initiated.
Such (C) radiation sensitive polymerization initiators include O-acyloxime compounds, acetophenone compounds, biimidazole compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples include xanthone compounds, phosphine compounds, triazine compounds, and radiation-sensitive cationic polymerization initiators.

  As the O-acyloxime compound, 9. H. An O-acyloxime polymerization initiator having a carbazole structure is preferred. For example, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H.-Carbazol-3-yl] -1- (O-acetyloxime).

Of these O-acyloxime compounds, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H.-Carbazol-3-yl] -1- (O-acetyloxime) is preferred.
The O-acyloxime compounds can be used alone or in admixture of two or more. In the present invention, the use of an O-acyloxime compound makes it possible to obtain a spacer having sufficient sensitivity and adhesion even at a low exposure amount.
Examples of the acetophenone compounds include α-hydroxy ketone compounds, α-amino ketone compounds, and other acetophenone compounds.

  Examples of the α-hydroxyketone compound include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropane-1- ON, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, and the like. Examples of the α-aminoketone compound include 2-methyl-1 -(4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2- (4-methylbenzoyl)- And 2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one. Examples of other acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and the like.

Among these acetophenone compounds, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one or 2- (4-methylbenzoyl) -2- (dimethylamino) -1- ( 4-morpholinophenyl) -butan-1-one is preferred.
In the present invention, it is possible to further improve sensitivity, spacer shape and compressive strength by using an acetophenone compound.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-chlorophenyl) ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-bromophenyl) -4 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dibromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 Examples include '-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, and the like.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are preferable, and 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ is particularly preferable. -Biimidazole is preferred.

In the present invention, sensitivity, resolution and adhesion can be further improved by using a biimidazole compound.
When a biimidazole compound is used, an aliphatic or aromatic compound having a dialkylamino group (hereinafter referred to as “amino sensitizer”) may be added to sensitize it. it can.
Examples of amino sensitizers include N-methyldiethanolamine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, ethyl p-dimethylaminobenzoate, and p-dimethylaminobenzoate. An acid i-amyl etc. can be mentioned.
Of these amino sensitizers, 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amino sensitizers can be used alone or in admixture of two or more.
Furthermore, when a biimidazole compound and an amino sensitizer are used in combination, a thiol compound can be added as a hydrogen donor compound. The biimidazole compound is sensitized and cleaved by the amino sensitizer to generate an imidazole radical, but as it is, high polymerization initiating ability is not expressed, and the resulting spacer has an unfavorable shape such as a reverse taper shape. In many cases. However, by adding a thiol compound to a system in which a biimidazole compound and an amino sensitizer coexist, hydrogen radicals are donated from the thiol compound to the imidazole radical, so that the imidazole radical is neutral imidazole. And a component having a sulfur radical having a high polymerization initiating ability is generated, whereby the spacer can be made into a more preferable forward tapered shape.

Examples of such thiol compounds include aromatic compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-methoxybenzimidazole. Compound; aliphatic monothiol such as 3-mercaptopropionic acid, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate; 3,6-dioxa-1,8-octanedithiol, penta Bifunctional or higher aliphatic thiols such as erythritol tetra (mercaptoacetate) and pentaerythritol tetra (3-mercaptopropionate) can be mentioned.
Of these thiol compounds, 2-mercaptobenzothiazole is particularly preferable.
Further, when the biimidazole compound and the amino sensitizer are used in combination, the addition amount of the amino sensitizer is preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the biimidazole compound. Preferably it is 1-20 weight part. If the addition amount of the amino sensitizer is less than 0.1 parts by weight, the effect of improving the sensitivity, resolution and adhesion tends to decrease. On the other hand, if it exceeds 50 parts by weight, the shape of the resulting spacer tends to be impaired. There is.
In addition, when a biimidazole compound and an amino sensitizer are used in combination, the addition amount of the thiol compound is preferably 0.1 to 50 parts by weight, more preferably 100 parts by weight of the biimidazole compound. 1 to 20 parts by weight. If the addition amount of the thiol compound is less than 0.1 parts by weight, the effect of improving the spacer shape tends to be reduced or the film tends to be reduced. There is a tendency to be damaged.

Furthermore, examples of the radiation-sensitive cationic polymerization initiator include onium salts and metallocene compounds. Examples of onium salts include phenyldiazonium tetrafluoroborate, phenyldiazonium hexafluorophosphonate, phenyldiazonium hexafluoroarsenate, and phenyldiazonium trifluoride. L-methanesulfonate, phenyldiazonium trifluoroacetate, phenyldiazonium-p-toluenesulfonate, 4-methoxyphenyldiazonium tetrafluoroborate, 4-methoxyphenyldiazonium hexafluorophosphonate, 4-methoxyphenyldiazonium hexafluoroarsenate, 4-methoxy Phenyldiazonium trifluoromethanesulfonate, 4-methoxyphenyl Azonium trifluoroacetate, 4-methoxyphenyldiazonium-p-toluenesulfonate, 4-ter-butylphenyldiazonium tetrafluoroborate, 4-ter-butylphenyldiazonium hexafluorophosphonate, 4-ter-butylphenyldiazonium hexafluoroarce Diazonium salts such as 4-ter-butylphenyldiazonium trifluoromethanesulfonate, 4-ter-butylphenyldiazonium trifluoroacetate, 4-ter-butylphenyldiazonium-p-toluenesulfonate;
Triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenylsulfonium-p-toluenesulfonate, 4-methoxy Phenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4 -Methoxy Phenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4-phenylthiophenyldiphenyltrifluoromethanesulfone Sulfonium salts such as narate, 4-phenylthiophenyldiphenyltrifluoroacetate, 4-phenylthiophenyldiphenyl-p-toluenesulfonate;
Examples thereof include iodonium salts such as bis (p-tolyl) iodonium tetrakis (pentafluorophenyl) borate and (p-tolyl) (p-isopropylphenyl) iodonium tetrakis (pentafluorophenyl) borate.

Examples of the metallocene compound include (1-6-η-cumene) (η-cyclopentadienyl) iron (1+) hexafluorophosphate (1-).
Commercially available products of these radiation-sensitive cationic polymerization initiators include, for example, Adeka Ultra Set PP-33 (manufactured by ADEKA) which is a diazonium salt, OPTOMER SP-150 which is a sulfonium salt, and -170 (manufactured by ADEKA). And Irgacure 261 (manufactured by Ciba Specialty Chemicals) which are metallocene compounds.

Said radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types.
In the radiation-sensitive resin composition of the present invention, the use ratio of (C) the radiation-sensitive polymerization initiator is (A)
Preferably it is 1-50 weight part with respect to 100 weight part of block copolymers, More preferably, it is 3-40 weight part.

Optional additives In the radiation-sensitive resin composition of the present invention, optional additives other than those described above, for example, adhesion assistants, surfactants, storage stabilizers, heat resistance, as long as they do not impair the effects of the present invention. A property improver etc. can be mix | blended.
The adhesion assistant is a component used for improving the adhesion between the formed spacer and the substrate.
As such an adhesion assistant, a functional silane coupling agent having a reactive functional group such as a carboxyl group, a methacryloyl group, a vinyl group, an isocyanate group, or an epoxy group is preferable. Examples thereof include trimethoxysilylbenzoic acid, γ -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy Examples include silane.
These adhesion assistants can be used alone or in admixture of two or more.

The compounding amount of the adhesion assistant is preferably 20 parts by weight or less, more preferably 15 parts by weight or less with respect to 100 parts by weight of the polymer (A). When the blending amount of the adhesion assistant exceeds 20 parts by weight, there is a tendency that development residue is likely to occur.
The said surfactant is a component used in order to improve applicability | paintability.
As such a surfactant, for example, a fluorine-based surfactant, a silicone-based surfactant and the like are preferable.

  The fluorine-based surfactant is preferably a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain, and examples thereof 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-tetrafluoro-n-butyl) ether, hexapropylene glycol di (1,1,2, 2,3,3-hexafluoro-n-pentyl) ether, octapropylene glycol di (1,1,2,2-tetrafluoro-n- Til) ether, sodium perfluoro-n-dodecanesulfonate, 1,1,2,2,3,3-hexafluoro-n-decane, 1,1,2,2,8,8,9,9,10,10 -Decafluoro-n-dodecane, sodium fluoroalkylbenzenesulfonate, sodium fluoroalkylphosphate, sodium fluoroalkylcarboxylate, diglycerin tetrakis (fluoroalkylpolyoxyethylene ether), fluoroalkylammonium iodide, fluoroalkylbetaine, other Fluoroalkyl polyoxyethylene ether, perfluoroalkyl polyoxyethanol, perfluoroalkyl alkoxylate, carboxylic acid fluoroalkyl ester and the like can be mentioned.

  Examples of commercially available fluorosurfactants include BM-1000, BM-1100 (above, manufactured by BM CHEMIE), MegaFuck F142D, F172, F173, F183, F178, F191, F191, F471, F476 (above, Dainippon Ink & Chemicals, Inc.), Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M), Surflon S-112,- 113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, manufactured by Asahi Glass Co., Ltd.) ), F-top EF301, 303, 352 (above, Shin-Akita Kasei Co., Ltd.), FT-100, -110, -140A, -1 0, the -250, the -251, the -300, the -310, the same -400S, Ftergent FTX-218, the -251 (or more, (Ltd.) NEOS), and the like.

  Examples of the silicone surfactant include Toray Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, SF- 8428, DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( As mentioned above, what is marketed by brand names, such as GE Toshiba Silicone Co., Ltd. and organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.), can be mentioned.

Moreover, as surfactants other than the above, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether; polyoxyethylene-n-octylphenyl ether, polyoxyethylene-n -Polyoxyethylene aryl ethers such as nonylphenyl ether; nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and (meth) acrylic acid copolymer polyflow No. . 57, no. 95 (above, manufactured by Kyoeisha Chemical Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is preferably 1.0 part by weight or less, and more preferably 0.5 part by weight or less with respect to 100 parts by weight of the (A) block copolymer. In this case, when the compounding amount of the surfactant exceeds 1.0 part by weight, film unevenness tends to occur.

Examples of the storage stabilizer include sulfur, quinones, hydroquinones, polyoxy compounds, amines, nitronitroso compounds, and more specifically, 4-methoxyphenol, N-nitroso-N-phenylhydroxyl. An amine aluminum etc. can be mentioned.
These storage stabilizers can be used alone or in admixture of two or more.
The amount of the storage stabilizer is preferably 3.0 parts by weight or less, more preferably 0.5 parts by weight or less with respect to 100 parts by weight of the (A) block copolymer. When the amount of the storage stabilizer exceeds 3.0 parts by weight, the sensitivity may be lowered and the pattern shape may be deteriorated.
Examples of the heat resistance improver include N- (alkoxymethyl) glycoluril compounds, N- (alkoxymethyl) melamine compounds, and compounds having two or more epoxy groups.
Examples thereof include N- (alkoxymethyl) glycoluril compounds and N- (alkoxymethyl) melamine compounds.

Examples of the N- (alkoxymethyl) glycoluril compound include N, N, N ′, N′-tetra (methoxymethyl) glycoluril, N, N, N ′, N′-tetra (ethoxymethyl) glycoluril, N, N, N ′, N′-tetra (n-propoxymethyl) glycoluril, N, N, N ′, N′-tetra (i-propoxymethyl) glycoluril, N, N, N ′, N′— Examples thereof include tetra (n-butoxymethyl) glycoluril, N, N, N ′, N′-tetra (t-butoxymethyl) glycoluril and the like.
Of these N- (alkoxymethyl) glycoluril compounds, N, N, N ′, N′-tetra (methoxymethyl) glycoluril is preferred.
Examples of the N- (alkoxymethyl) melamine compound include N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine, N, N, N ′, N ′, N ″, N "-Hexa (ethoxymethyl) melamine, N, N, N ', N', N", N "-hexa (n-propoxymethyl) melamine, N, N, N ', N', N", N "- Hexa (i-propoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ -hexa (n-butoxymethyl) melamine, N, N, N ′, N ′, N ″, N ″ — Examples include hexa (t-butoxymethyl) melamine.
Of these N- (alkoxymethyl) melamine compounds, N, N, N ′, N ′, N ″, N ″ -hexa (methoxymethyl) melamine is preferred, and examples of commercially available products thereof include Nicalac N-2702, MW-30M (manufactured by Sanwa Chemical Co., Ltd.).

Examples of the compound having two or more epoxy groups include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and dipropylene glycol diglycidyl ether. , Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, hydrogenated bisphenol A diglycidyl ether Bisphenol A diglycidyl ether, etc. Kill.
Examples of commercially available compounds having two or more epoxy groups include Epolite 40E, 100E, 200E, 70P, 200P, 400P, 1500NP, 80MF, 100MF, 1600, 3002, and the like. 4000 (above Kyoeisha Chemical Co., Ltd.), Epicoat 152, Epikote 154 (above Japan Epoxy Resin Co., Ltd.) and the like. These can be used individually or in mixture of 2 or more types.

Preparation of Radiation Sensitive Resin Composition The radiation sensitive resin composition of the present invention comprises the above (A) block copolymer, (B) component, (C) component and other components optionally added as described above. Is prepared by mixing uniformly. The radiation-sensitive resin composition of the present invention is preferably used in a solution state after being dissolved in an appropriate solvent. For example, a (A) block copolymer, (B) component, (C) component and other components optionally added are mixed at a predetermined ratio to prepare a radiation sensitive resin composition in a solution state. can do.
As the solvent used for the preparation of the radiation sensitive resin composition of the present invention, (A) block copolymer, (B) component, (C) component and other components optionally blended are uniform. Those which are dissolved in and do not react with each component are used.
As such a solvent, the thing similar to what was illustrated as a solvent which can be used in order to manufacture the above-mentioned (A) block copolymer can be mentioned.

  Among these solvents, for example, diethylene glycol, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether from the viewpoints of solubility of each component, reactivity with each component, and ease of film formation. , Propylene glycol monomethyl ether, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, cyclohexanol acetate, benzyl alcohol, 2-phenylethyl alcohol, 3-phenyl-1-propanol or 3-methoxybutanol Can be particularly preferably used. These solvents can be used alone or in combination of two or more.

Furthermore, in order to improve the in-plane uniformity of the film thickness together with the above solvent, a high boiling point solvent can be used in combination. Examples of the high-boiling solvent that can be used in combination include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, and benzylethyl ether. , Dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl Examples include cellosolve acetate. Of these, N-methylpyrrolidone, γ-butyrolactone, and N, N-dimethylacetamide are preferable.
When a high boiling point solvent is used in combination as the solvent for the radiation sensitive resin composition of the present invention, the amount used is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably, based on the total amount of solvent. It can be 30 wt% or less. When the amount of the high-boiling solvent used exceeds this amount, the coating film thickness uniformity, sensitivity, and residual film rate may be reduced.

When the radiation-sensitive resin composition of the present invention is prepared in a solution state, components other than the solvent in the solution, that is, (A) block copolymer, (B) component and (C) component and optionally added. The ratio of the total amount of the other components can be arbitrarily set according to the purpose of use and the value of the desired film thickness, for example, 5 to 50% by weight, preferably 10 to 40% by weight, more preferably 15 to 35% by weight.
The composition solution thus prepared can be used after being filtered using a Millipore filter having a pore diameter of about 0.5 μm.

Method of forming spacers Next, a method of forming a spacer of the present invention will be described with reference to radiation-sensitive resin composition of the present invention.
The spacer forming method of the present invention is characterized in that the following steps are performed in the order described below.
(1) A step of forming a film of the radiation sensitive resin composition on a substrate,
(2) a step of exposing radiation to at least a part of the coating;
(3) a step of developing the film after exposure, and (4) a step of heating the film after development.
Hereinafter, each of these steps will be described sequentially.

(1) Step of forming a film of the radiation sensitive resin composition of the present invention on a substrate A transparent conductive film is formed on one surface of a transparent substrate, and the radiation sensitive resin composition of the present invention is formed on the transparent conductive film. After coating the composition solution, the coating surface is heated (prebaked) to form a coating.
Examples of the transparent substrate used for forming the spacer include a glass substrate and a resin substrate. More specifically, glass substrates such as soda lime glass and non-alkali glass; polyethylene terephthalate, polybutylene terephthalate, poly Examples thereof include a resin substrate made of a synthetic resin such as ether sulfone, polycarbonate, and polyimide.
As a transparent conductive film provided on one surface of the transparent substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) And so on.
The method for applying the composition solution is not particularly limited, and for example, 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 an ink jet coating method is adopted. In particular, spin coating and slit die coating are preferred.
Moreover, although the conditions of prebaking differ also with the kind of each component, a mixture ratio, etc., Preferably it is about 1 to 15 minutes at 70-120 degreeC.
In addition, the film thickness after the pre-baking of the film is not particularly limited, but is preferably about 0.5 to 10 μm, more preferably about 1.0 to 7.0 μm.

(2) Step of irradiating at least a part of the coating film Next, at least a part of the formed coating film is exposed to radiation. In this case, when exposing a part of the film, the exposure is performed through a photomask having a predetermined pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light and the like can be used. Radiation having a wavelength in the range of 350 to 450 nm is preferable, and radiation including ultraviolet light having a wavelength of 365 nm is particularly preferable.
The exposure dose is preferably 100 to 10,000 J / m ² , more preferably 1, as a value measured by an illuminometer (OAI model 356, manufactured by OAI Optical Associates Inc.) at a wavelength of 365 nm of the radiation to be exposed. it is a 500~3,000J / ^{m 2.}

(3) Development Step Next, the exposed film is developed to remove unnecessary portions and form a predetermined pattern.
Examples of the developer used for development include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and ammonia; aliphatic primary amines such as ethylamine and n-propylamine; Aliphatic secondary amines such as diethylamine and di-n-propylamine; Aliphatic tertiary amines such as trimethylamine, methyldiethylamine, dimethylethylamine and triethylamine; pyrrole, piperidine, N-methylpiperidine, N-methylpyrrolidine, 1,8 -Alicyclic tertiary amines such as diazabicyclo [5.4.0] -7-undecene and 1,5-diazabicyclo [4.3.0] -5-nonene; aromatics such as pyridine, collidine, lutidine, quinoline Tertiary amine; dimethylethanolamine, methyldi Ethanolamine, alkanolamines such as triethanolamine; tetramethylammonium hydroxide, the aqueous solution of an alkaline compound such as quaternary ammonium salts such as tetraethyl ammonium hydroxide may be used.
Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant may be added to the aqueous solution of the alkaline compound.
The developing method may be any of a liquid piling method, a dipping method, a shower method, and the like, and the developing time is preferably about 10 to 180 seconds at room temperature.
After development, for example, after washing with running water for 30 to 90 seconds, a desired pattern is formed by, for example, air drying with compressed air or compressed nitrogen.

(4) Heating step Next, the obtained pattern (coating film) is heated at a predetermined temperature, for example, 100 to 250 ° C., for a predetermined time, for example, 5 to 30 minutes on the hot plate, by a heating device such as a hot plate or an oven. A desired spacer can be obtained by heating (post-baking) for 30 to 180 minutes in an oven.
As described above, it is possible to obtain a spacer excellent in various properties such as compressive strength, rubbing resistance during liquid crystal alignment, and adhesion to a transparent substrate.

Liquid crystal display element The liquid crystal display element of this invention can be produced, for example with the following method (a) or (b).
(A) First, a pair (two) of transparent substrates having a transparent conductive film (electrode) on one side is prepared, and the radiation-sensitive resin composition of the present invention is used on the transparent conductive film of one of the substrates. A spacer is formed according to the method described above. Subsequently, an alignment film having a liquid crystal alignment brain is formed on the transparent conductive film and spacers of these substrates. These substrates are arranged to face each other with a certain gap (cell gap) so that the liquid crystal alignment direction of each alignment film is orthogonal or antiparallel, with the surface on which the alignment film is formed on the inside. A liquid crystal is filled in the cell gap defined by the surface of the substrate (alignment film) and the spacer, and the filling hole is sealed to form a liquid crystal cell. Then, the liquid crystal display element of the present invention is bonded to both outer surfaces of the liquid crystal cell so that the polarizing direction is aligned or orthogonal to the liquid crystal alignment direction of the alignment film formed on one surface of the substrate. Can be obtained.
(B) First, a pair of transparent substrates on which a transparent conductive film, a spacer and an alignment film are formed are prepared in the same manner as in the first method. After that, along the edge of one substrate, an ultraviolet curable sealant is applied using a dispenser, and then the liquid crystal is dropped in the form of fine droplets using a liquid crystal dispenser, and the two substrates are bonded together under vacuum. . Then, both substrates are sealed by irradiating the above-mentioned sealant part with ultraviolet rays using a high-pressure mercury lamp. Finally, the liquid crystal display element of the present invention can be obtained by attaching polarizing plates to both outer surfaces of the liquid crystal cell.

Examples of the liquid crystal used in each of the above methods include nematic liquid crystal and smectic liquid crystal. Among them, nematic liquid crystal is preferable, for example, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane. Type liquid crystal, cubane type liquid crystal, etc. are used. Further, for these liquid crystals, for example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate, and chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck). Etc. can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used.
Further, the polarizing plate used outside the liquid crystal cell is composed of a polarizing plate or an H film itself in which a polarizing film called an H film that absorbs iodine while sandwiching and stretching polyvinyl alcohol is sandwiched between cellulose acetate protective films. A polarizing plate etc. can be mentioned.

The present invention will be described more specifically with reference to synthesis examples and examples. However, the present invention is not limited to the following examples.
In the following synthesis examples, the molecular weight (Mw and Mn) of the copolymer was measured by gel permeation chromatography (GPC) under the following apparatus and conditions.
Apparatus: GPC-101 (made by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 are combined Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid

Synthesis examples 1 to 13 and comparative synthesis examples 1 to 3 of the block copolymer (A)
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester (compound represented by the above formula (29)) and 200 parts by weight of diethylene glycol methyl ethyl ether, and subsequently. 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, 20 parts by weight of glycidyl methacrylate, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 20 parts by weight of benzyl methacrylate After purging with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added and polymerization was carried out while maintaining this temperature for 5 hours. [S] A living copolymer solution was obtained. This polymer is referred to as [S-1] polymer. About the obtained [S-1] polymer, it was 6,800 when Mw was measured by GPC, and it was Mw / Mn = 1.7.
100 parts by weight of this [S-1] polymer, 40 parts by weight of benzyl methacrylate, and 40 parts by weight of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer as before, and after substituting with nitrogen, gently stirred. However, after raising the temperature of the solution to 70 ° C., 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and this temperature was maintained for 4 hours for polymerization. A (A) block copolymer solution having a solid content concentration of 36.4% was obtained. This is referred to as [A-1] polymer. About the obtained [A-1] polymer, when Mw was measured by GPC, it was 7,520 and it was Mw / Mn = 1.7.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide (a compound represented by the above formula (25)) and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts of methacrylic acid. Parts by weight, 5 parts by weight of styrene, 20 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane, 30 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, methacryl After charging 20 parts by weight of benzyl acid and replacing with nitrogen, 5 parts of 1,3-butadiene was further charged, and the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and polymerization was carried out while maintaining this temperature for 5 hours, whereby a solid content concentration of 32.1% [S] A living copolymer solution was obtained. This polymer is referred to as [S-2] polymer.
100 parts by weight of this [S-2] polymer, 40 parts by weight of benzyl methacrylate and 40 parts by weight of diethylene glycol methyl ethyl ether were charged into a flask equipped with a condenser and a stirrer in the same manner as described above, and after substituting with nitrogen, gently stirred. However, after raising the temperature of the solution to 80 ° C., 1 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and this temperature was maintained for 4 hours to perform polymerization. A (A) block copolymer solution having a solid content concentration of 36.5% was obtained. This is referred to as [A-2] polymer. With respect to the obtained [A-2] polymer, Mw was measured by GPC to be 7,240 and Mw / Mn = 1.9.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of acrylic acid and 10 parts by weight of styrene. Parts, 40 parts by weight of methyl methacrylate and 30 parts by weight of tetrahydrofurfuryl methacrylate were substituted with nitrogen, and then the temperature of the solution was raised to 70 ° C. while gently stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and this temperature was maintained for 3 hours. After polymerization, 30 parts by weight of 2-methylglycidyl methacrylate was added. By adding and holding for 3 hours, a block copolymer solution (A) having a solid content concentration of 35.6% was obtained. This is referred to as [A-3] polymer. With respect to the obtained [A-3] polymer, Mw was measured by GPC, which was 6,600 and Mw / Mn = 1.8.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl and 30 parts by weight of benzyl acrylate and purging with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. Raised. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 20 parts by weight of n-butyl methacrylate was added. After maintaining the time, 20 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane was further added and maintained for 2 hours to obtain a (A) block copolymer solution having a solid content concentration of 35.3%. This is designated as [A-4] polymer. About the obtained [A-4] polymer, when Mw was measured by GPC, it was 5,700 and was Mw / Mn = 1.6.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of methacrylic acid, 18 parts by weight of styrene, 3- (Acryloyloxymethyl) -3-ethyloxetane 10 parts by weight, cyclohexyl methacrylate 20 parts by weight, tetrahydrofurfuryl methacrylate 10 parts by weight, cyclohexylmaleimide 22 parts by weight were charged with nitrogen, and further 1,3-butadiene was added. 5 parts by weight were charged and the temperature of the solution was raised to 70 ° C. while gently stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and after maintaining at this temperature for 2 hours, 10 parts by weight of 3,4-epoxycyclohexyl methacrylate was added. The mixture was further maintained for 3 hours to obtain a block copolymer solution (A) having a solid content concentration of 32.5%. This is designated as [A-7] polymer. About the obtained [A-7] polymer, when Mw was measured by GPC, it was 6,100 and was Mw / Mn = 2.1.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol dimethyl ether, followed by 25 parts by weight of 2-methacryloyloxyethyl hexahydrophthalic acid and 5 parts of styrene. 1 part by weight, 30 parts by weight of 2-ethylhexyl methacrylate, 10 parts by weight of 2-methylglycidyl methacrylate and 35 parts by weight of benzyl acrylate were substituted with nitrogen, and 5 parts by weight of 1,3-butadiene was further added. The temperature of the solution was raised to 70 ° C. while stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 3,4-epoxycyclohexyl methacrylate 10 weights A (A) block copolymer solution having a solid content concentration of 32.0% was obtained by adding 3 parts thereof and maintaining the mixture for 3 hours. This is designated as [A-8] polymer. About the obtained [A-8] polymer, when Mw was measured by GPC, it was 6,220 and was Mw / Mn = 2.2.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 6 parts by weight of bis-3,5-dimethylpyrazol-1-ylthiocarbonyl disulfide (compound represented by the above formula (26)) and 200 parts by weight of diethylene glycol methyl ethyl ether. Then, 10 parts by weight of methacrylic acid, 5 parts by weight of styrene, 35 parts by weight of 2-ethylhexyl methacrylate, 15 parts by weight of 2-methylglycidyl methacrylate, 15 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane After charging and purging with nitrogen, the temperature of the solution was raised to 70 ° C. while gently stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 3,4-epoxycyclohexyl methacrylate 10 weights Then, 10 parts by weight of 3- (acryloyloxymethyl) -3-ethyloxetane was added, and the mixture was further maintained for 3 hours to obtain a (A) block copolymer solution having a solid content concentration of 32.8%. This is designated as [A-9] polymer. About the obtained [A-9] polymer, it was 6,700 and Mw / Mn = 2.1 when Mw was measured by GPC.

Synthesis example 8
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of dipropylene glycol dimethyl ether, followed by 10 parts by weight of methacrylic acid, 5 parts by weight of acrylic acid and styrene. 5 parts by weight, 20 parts by weight of tetrahydrofurfuryl methacrylate, 20 parts by weight of benzyl methacrylate, 40 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane were substituted with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 18 parts by weight of styrene and 22 parts by weight of cyclohexylmaleimide were added. Further, by holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 36.7% was obtained. This is designated as [A-10] polymer. With respect to the obtained [A-10] polymer, Mw was measured by GPC. As a result, it was 7,200 and Mw / Mn = 1.7.

Synthesis Example 9
A flask equipped with a condenser and a stirrer was charged with 4 parts by weight of cyano (dimethyl) methyl ester of pyrazole-1-dithiocarboxylic acid and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 18 parts by weight of methacrylic acid and 5 parts of styrene. After adding parts by weight, 20 parts by weight of isobornyl acrylate, 27 parts by weight of butyl acrylate, and 30 parts by weight of benzyl acrylate, the atmosphere was replaced with nitrogen, and the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 15 parts by weight of 2-methylglycidyl methacrylate and tetrahydromethacrylate methacrylate were added. By adding 15 parts by weight of furfuryl and holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 35.0% was obtained. This is designated as [A-11] polymer. With respect to the obtained [A-11] polymer, Mw was measured by GPC. As a result, it was 7,100 and Mw / Mn = 2.0.

Synthesis Example 10
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 25 parts by weight of 2-acryloyloxyethylphthalic acid and styrene. 5 parts by weight, 20 parts by weight of n-stearyl acrylate, 20 parts by weight of 3- (acryloyloxymethyl) -3-ethyloxetane and 30 parts by weight of benzyl acrylate were substituted with nitrogen, and then gently stirred. The temperature of the solution was raised to 80 ° C. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, the temperature was maintained for 2 hours, and after polymerization, 10 parts by weight of n-lauryl methacrylate was added. After polymerization for 2 hours, 10 parts by weight of glycidyl methacrylate was added, and the mixture was further maintained for 3 hours to obtain a (A) block copolymer solution having a solid content concentration of 33.8%. This is designated as [A-12] polymer. About the obtained [A-12] polymer, when Mw was measured by GPC, it was 7,000 and Mw / Mn = 1.8.

Synthesis Example 11
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid, 5 parts by weight of styrene, After charging 20 parts by weight of cyclohexyl acid, 20 parts by weight of tetrahydrofurfuryl methacrylate, and 30 parts by weight of benzyl methacrylate and replacing with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 3- (methacryloyloxymethyl) -3-ethyloxetane 10 (A) Block copolymer solution having a solid content concentration of 33.6% by adding 10 parts by weight of 2-methylglycidyl methacrylate and holding for 3 hours after polymerization. Got. This is designated as [A-13] polymer. About the obtained [A-13] polymer, when Mw was measured by GPC, it was 6,800 and was Mw / Mn = 1.9.

Synthesis Example 12
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 30 parts by weight of n-butyl and 40 parts by weight of benzyl acrylate and replacing with nitrogen, the temperature of the solution was raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 30 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate was added. By adding and maintaining for 3 hours, a (A) block copolymer solution having a solid content concentration of 34.5% was obtained. This is referred to as [A-5] polymer. With respect to the obtained [A-5] polymer, Mw was measured by GPC, which was 6,600 and Mw / Mn = 1.7.

Synthesis Example 13
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of methacrylic acid, 18 parts by weight of styrene, 3- After charging 10 parts by weight of (acryloyloxymethyl) -3-ethyloxetane, 20 parts by weight of tetrahydrofurfuryl methacrylate, 10 parts by weight of 2-hydroxyethyl methacrylate, and 22 parts by weight of cyclohexylmaleimide, and replacing with nitrogen, 3-Butadiene (5 parts by weight) was charged, and the temperature of the solution was raised to 70 ° C. while gently stirring. When the temperature reached 70 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 10 parts by weight of 3,4-epoxycyclohexylmethyl methacrylate was added. By adding and maintaining for 3 hours, a (A) block copolymer solution having a solid content concentration of 32.8% was obtained. This is designated as [A-6] polymer. About the obtained [A-6] polymer, when Mw was measured by GPC, it was 6,400 and was Mw / Mn = 2.2.

Comparative Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 4 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid and 5 parts by weight of styrene. After charging 25 parts of tricyclo [5.2.1.0 ^2,6 ] decan-8-yl methacrylate, 25 parts of glycidyl methacrylate and 20 parts of tetrahydrofurfuryl methacrylate, and substituting with nitrogen, 1,3- A copolymer solution having a solid content concentration of 28.2% was prepared by charging 5 parts of butadiene and raising the temperature of the solution to 70 ° C. while gently stirring, and maintaining the temperature for 5 hours for polymerization. Got. This is referred to as [a-1] polymer.
With respect to the obtained [a-1] polymer, Mw was measured by GPC to be 9,800.

Comparative Synthesis Example 2
A flask equipped with a condenser and a stirrer was charged with 4 parts of 2,2′-azobis (isobutyronitrile) and 250 parts of diethylene glycol methyl ethyl ether, followed by 20 parts by weight of methacrylic acid, 5 parts by weight of styrene, and methacrylic acid. After charging 35 parts of n-butyl, 10 parts by weight of 3- (methacryloyloxymethyl) -3-ethyloxetane and 25 parts of benzyl methacrylate, and substituting with nitrogen, 5 parts of 1,3-butadiene was further added and stirred gently. However, the temperature of the solution was raised to 80 ° C., and this temperature was maintained for 5 hours for polymerization to obtain an [a] copolymer solution having a solid content concentration of 28.5%. This is referred to as [a-2] polymer.
It was 8,800 when Mw was measured by GPC about the obtained [a-2] polymer.

Comparative Synthesis Example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of bispyrazol-1-ylthiocarbonyl disulfide and 200 parts by weight of diethylene glycol methyl ethyl ether, followed by 15 parts by weight of acrylic acid, 10 parts by weight of styrene, and methacrylic acid. After charging 40 parts by weight of methyl and 30 parts by weight of tetrahydrofurfuryl methacrylate and replacing with nitrogen, the temperature of the solution is raised to 80 ° C. while gently stirring. When the temperature reached 80 ° C., 2 parts by weight of 2,2′-azobis (isobutyronitrile) was added, and this temperature was maintained for 2 hours. After polymerization, 30 parts by weight of n-butyl methacrylate was added. By holding for 3 hours, a (A) block copolymer solution having a solid content concentration of 35.5% was obtained. This is referred to as [a-3] polymer. About the obtained [a-3] polymer, when Mw was measured by GPC, it was 6,300 and was Mw / Mn = 1.7.

Examples 1-15 and Comparative Examples 1-5
(I) Preparation of Radiation Sensitive Resin Composition Above Synthetic Examples Polymers (A), (B) and (C), and 5 parts by weight of γ-glycidoxypropyltrimethoxysilane as an adhesion assistant, as a surfactant Propylene glycol monomethyl was mixed with 0.5 parts by weight of FTX-218 (trade name, manufactured by Neos Co., Ltd.) and 0.5 parts by weight of 4-methoxyphenol as a storage stabilizer so that the solid content concentration was 30% by weight. After dissolving in ether acetate, the solution was filtered through a Millipore filter having a pore size of 0.5 μm to prepare a composition solution. The amount of each component is shown in Table 1.

(A) component described in the above synthesis example (B) component B-1: dipentaerythritol hexaacrylate (C) component C-1: 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate (trade name “CGI-242”, manufactured by Ciba Specialty Chemicals)
C-2: 2- (4-methylbenzoyl) -2- (dimethylamino) -1- (4-morpholinophenyl) -butan-1-one (trade name “Irgacure 379”, Ciba Specialty Chemicals) Made)
Optional additive D-1: Novolac type epoxy resin (trade name “Epicoat 152”, manufactured by Japan Epoxy Resins Co., Ltd.)
Evaluation The composition prepared as described above was evaluated as follows. The evaluation results are shown in Table 2.

(II) Formation of Spacer The composition solution was applied onto a non-alkali glass substrate using a spinner and then pre-baked on an 80 ° C. hot plate for 3 minutes to form a film having a thickness of 4.0 μm.
Next, the obtained film was exposed to ultraviolet rays having an intensity of 365 W / m ² at 365 nm for 10 seconds through a photomask having a 15 μm square remaining pattern. Thereafter, development was performed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by washing with pure water for 1 minute. Then, the spacer of the predetermined pattern was formed by post-baking for 20 minutes at 230 degreeC in oven.
(III) Evaluation of developability When the development time is shortened to 40 seconds during development in (II), the pattern is formed as good (◯), and the residue is evaluated as bad (×). did. The evaluation results are shown in Table 2.
(IV) Evaluation of resolution When the pattern was formed in the above (II), the case where the remaining pattern was resolved was evaluated as good (◯), and the case where the pattern was not resolved was evaluated as defective (x). The evaluation results are shown in Table 2.
(V) Evaluation of spacer shape The cross-sectional shape of the pattern obtained in the above (II) was observed with a scanning electron microscope and evaluated according to which of A and B shown in FIG. At this time, if the spacer shape is round type as in A, the upper part of the spacer is easily deformed, and it has a sufficient amount of deformation when the TFT plate and the CF plate are bonded together, and the margin for the liquid crystal dropping process is improved. To do. On the other hand, if the pattern shape is close to a trapezoid as in B, the spacer is hardly deformed and the margin of the liquid crystal dropping process is insufficient. The evaluation results are shown in Table 2.

(VI) Evaluation of compression displacement amount With respect to the pattern obtained in (II) above, a load of 50 mN was applied with a flat indenter having a diameter of 50 μm using a micro compression tester (DUH-201, manufactured by Shimadzu Corporation). The amount of deformation was measured at a measurement temperature of 23 ° C. When this value is 0.5 or more, it can be said that the amount of compressive displacement is good. The evaluation results are shown in Table 2.
(VII) Evaluation of heat resistance About the pattern obtained in the above (II), after leaving it in an oven at 230 ° C. for 20 minutes, if the change in the height of the spacer is 4% or less, good (◯), 4% If it exceeded, it evaluated as a defect (x). The evaluation results are shown in Table 2.
(VIII) Evaluation of chemical resistance The pattern obtained in the above (II) was immersed for 15 minutes in the alignment film stripping solution Chemiclean TS-204 (manufactured by Sanyo Chemical Industries) heated to 60 ° C, and washed with water. After further drying in an oven at 120 ° C. for 15 minutes, the spacer was evaluated as good (◯) if the change in height was 4% or less, and evaluated as bad (×) if it exceeded 4%. The evaluation results are shown in Table 2.
(IX) Evaluation of Sublimation Quantity The radiation-sensitive resin composition prepared in Table 1 was applied on a substrate so as to have a predetermined film thickness, thereby forming a film. Head space gas chromatography / mass spectrometry (head space sampler: Nippon Analytical Industry Co., Ltd., model name “JHS-100A”, gas chromatography / mass spectrometer: “JEOL JMS-AX505W type mass spectrometer” ). The purge conditions were 100 ° C./10 min, and the generated peak area was determined. Octane is used as the standard substance (octane specific gravity: 0.701, octane injection amount: 0.02 μl), and the amount of volatile components derived from the photopolymerization initiator in terms of octane is calculated from the following formula based on the peak area. did. When the amount of the volatile component was 2 μg or less, the amount of sublimation was small (◯). The evaluation results are shown in Table 2.
(X) Evaluation of rubbing resistance After applying AL3046 (trade name, manufactured by JSR Co., Ltd.) as a liquid crystal aligning agent to a substrate on which the pattern obtained in (II) is formed, using a printing machine for applying a liquid crystal alignment film. And dried at 180 ° C. for 1 hour to form a coating film of an orientation agent having a dry film thickness of 0.05 μm. Thereafter, a rubbing machine having a roll around which a polyamide cloth was wound was applied to this coating film, and the rubbing treatment was performed at a roll rotation speed of 500 rpm and a stage moving speed of 1 cm / sec. At this time, the presence or absence of pattern shaving or peeling was evaluated. The evaluation results are shown in Table 2.

The (XI) Voltage holding ratio evaluation <br/> prepared liquid composition, SiO ₂ film is formed to prevent the elution of sodium on the surface ions, further ITO - depositing (indium tin oxide alloy) electrode in a predetermined shape After spin coating on the soda glass substrate, pre-baking was performed in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 2.0 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 200 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. And the coating film was cured to form a permanent cured film.
Next, the substrate on which this pixel is formed and the substrate on which ITO electrodes are simply deposited in a predetermined shape are bonded together with a sealant mixed with 0.8 mm glass beads, and then Merck liquid crystal MLC6608 (trade name) is injected. Thus, a liquid crystal cell was produced.
Next, the liquid crystal cell was placed in a constant temperature layer of 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured with a liquid crystal voltage holding ratio measuring system “VHR-1A type” (trade name) manufactured by Toyo Corporation. The applied voltage at this time is a square wave of 5.5 V, and the measurement frequency is 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). If the voltage holding ratio of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot hold the applied voltage at a predetermined level for a time of 16.7 milliseconds, and the liquid crystal cannot be sufficiently aligned. There is a high risk of “burn-in”.

It is a schematic diagram which illustrates the cross-sectional shape of a spacer.

Claims (8)

(A) block copolymer (B) containing a polymerizable unsaturated compound and (C) a radiation-sensitive polymerization initiator, (A) the block copolymer has two or more block segments, of which at least One block segment is (a1) a polymerized unit derived from an epoxy group-containing ethylenically unsaturated compound and the following formulas (I) and (II):

[In Formula (I) and Formula (II), R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 6 It is. ]
A radiation-sensitive resin composition comprising polymerized units derived from at least one monomer selected from the group consisting of compounds represented by: The radiation-sensitive resin composition according to claim 1, wherein at least one block segment of (A) the block copolymer contains a polymer unit derived from (a2) an alkali-soluble monomer. (A) The radiation sensitive resin composition according to any one of claims 1 to 2, wherein the block copolymer is obtained by living radical polymerization. (A) The block copolymer is produced through polymerization using a thiocarbonylthio compound represented by each of the following formulas (1), (2) or (3) as a molecular weight control agent. The radiation sensitive resin composition in any one of -3.

[In Formula (1), Z ¹ is different from a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, or a carbon atom. A monovalent heterocyclic group having 3 to 20 atoms in total with the term atom, -OX, -SX, -N (X) ₂ , -OC (= O) X, -C (= O) OX, -C (═O) N (X) ₂ , —P (═O) (OX) ₂ , —P (═O) (X) ₂ , or a monovalent group having a polymer chain, wherein each X is mutually Independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms, or a total of 3 to 18 atoms of carbon atoms and hetero atoms 1 represents a monovalent heterocyclic group, the above alkyl group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and a monovalent compound having 3 to 20 atoms in total. Cyclic group and X may be each substituted, p is an integer of 1 or more, X ^1, when the p = 1, an alkyl group having 1 to 20 carbon atoms, monovalent C3-20 An alicyclic hydrocarbon group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a monovalent heterocyclic group having 3 to 20 total atoms of carbon atoms and hetero atoms, -OX,- SX, —N (X) ₂ or a monovalent group having a polymer chain, the definition of each X is the same as above, and when p ≧ 2, the p value derived from an alkane having 1 to 20 carbon atoms A p-valent group derived from an aromatic hydrocarbon having 6 to 20 carbon atoms, a p-valent group derived from a heterocyclic compound having 3 to 20 total atoms of carbon atoms and hetero atoms, or a polymer A p-valent group having a chain, and the above alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, and 6 to 6 carbon atoms. 20 monovalent aromatic hydrocarbon groups, monovalent heterocyclic groups having 3 to 20 atoms in total, X, p-valent groups derived from alkanes having 1 to 20 carbon atoms, and aromatics having 6 to 20 carbon atoms A p-valent group derived from a group hydrocarbon and a p-valent group derived from a heterocyclic compound having 3 to 20 atoms in total may be substituted. ]

[In Formula (2), m is an integer greater than or equal to ² , Z2 is m-valent group derived from a C1-C20 alkane, m-valent group derived from a C6-C20 aromatic hydrocarbon. Group, a m-valent group having a polymer chain and a m-valent group derived from a heterocyclic compound having 3 to 20 total atoms of carbon atoms and hetero atoms, and the above-mentioned alkane having 1 to 20 carbon atoms The derived m-valent group, the m-valent group derived from the aromatic hydrocarbon having 6 to 20 carbon atoms, and the m-valent group derived from the heterocyclic compound having 3 to 20 atoms in total may be substituted. Well, X ² is an alkyl group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and different from carbon atoms. Yusuke monovalent heterocyclic group total atomic number from 3 to 20 with the atoms, -OX, -SX, a -N _{(X) 2} or a polymer chain Each X is independently of each other an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 18 carbon atoms or a carbon atom. A monovalent heterocyclic group having 3 to 18 atoms in total with the hetero atom is shown, the alkyl group having 1 to 20 carbon atoms, the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, the number of carbon atoms The 6-20 monovalent aromatic hydrocarbon group, the monovalent heterocyclic group having 3 to 20 atoms in total, and X may each be substituted. )

[In the formula (3), Z ³ and Z ⁴ are each independently a hydrogen atom, a chlorine atom, a carboxyl group, a cyano group, an alkyl group having 1 to 20 carbon atoms, or a monovalent aromatic carbon atom having 6 to 20 carbon atoms. Hydrogen group, monovalent heterocyclic group having 3 to 20 total atoms of carbon atom and hetero atom, —OR ¹ , —SR ¹ , —OC (═O) R ¹ , —N (R ¹ ) ( ^{R 2), - C (=} O) OR 1, -C (= O) N (R 1) (R 2), - P (= O) (OR 1) 2, -P (= O) (R 1 ) ₂ or a monovalent group having a polymer chain, wherein R ¹ and R ² are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, or 1 having 6 to 18 carbon atoms. A valent aromatic hydrocarbon group or a monovalent heterocyclic group having 3 to 18 total atoms of carbon atoms and hetero atoms, wherein the alkyl group having 1 to 20 carbon atoms, carbon Monovalent aromatic hydrocarbon group having 6 to 20, a monovalent heterocyclic group Total atoms having 3 to 20 carbon atoms and the hetero atom, R ¹ and R ² may be each substituted . ) The ratio (Mw / Mn) of polystyrene-converted weight average molecular weight (Mw) and polystyrene-converted number average molecular weight (Mn) measured by gel permeation chromatography of the block copolymer (A) is 2.5 or less. The radiation sensitive resin composition in any one of -4. The spacer formed from the radiation sensitive resin composition in any one of Claims 1-5. A method for forming a spacer, comprising at least the following steps (a) to (d).
(A) forming a film of the radiation sensitive resin composition according to any one of claims 1 to 5 on a substrate;
(B) a step of exposing radiation to at least a part of the coating;
(C) a step of developing the film after exposure, and (d) a step of heating the film after development. A liquid crystal display device comprising the spacer according to claim 6.

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