Fluorine-containing compound, living polymerization initiator, fluorine-containing polymer, method for producing fluorine-containing polymer, and resist composition

Abstract

An object of the present invention is to provide a fluorine-containing compound that can be easily obtained and is suitable for use as an initiator for living radical polymerization, and a fluorine-containing polymer that does not generate foreign substances, has excellent liquid repellency such as water repellency, and is suitable for use as a leveling agent in a resist composition, and to provide a fluorine-containing compound represented by the following general formula (1) or general formula (2) (wherein, PFPE is a poly(perfluoroalkylene ether) chain. Each X1 is a monovalent organic group having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom. Each of R1 and R2 is an alkylene group having 1 to 4 carbon atoms. R3 is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms).

Description

Technical Field

[0001] The present invention relates to a fluorine-containing compound that can be easily obtained and is suitable for use as an initiator for living radical polymerization. In addition, the present invention also relates to a fluorine-containing polymer that does not generate foreign substances, has excellent liquid repellency such as water repellency, and is suitable for use as a leveling agent in a resist composition. Background Art

[0002] In a wide range of fields such as the manufacture of semiconductor integrated circuits such as LSIs, the display surface of flat panel displays (FPDs), the manufacture of circuit boards, and the manufacture of color filters, lithography techniques (lithography techniques) have been used for forming fine elements or performing fine processing. In the lithography technique, for example, the following steps are performed: a resist film formed of a resist composition is formed on a substrate, the resist film is selectively exposed through a mask having a predetermined pattern formed thereon by radiation such as light or electron beams, and a developing process is performed, whereby a resist pattern having a predetermined shape is formed on the resist film.

[0003] In recent years, in the field of semiconductor integrated circuits, with the progress of high integration and high speed, miniaturization of pattern rules has been required. Among them, in the lithography technique, far ultraviolet lithography and vacuum ultraviolet lithography are promising as new generation fine processing techniques. Among them, lithography using an ArF excimer laser as a light source is an indispensable technique for ultra-fine processing of 0.13 μm or less.

[0004] For the aforementioned ArF lithography, it has been partially used since the production of devices at the 130 nm node, and has become the main lithography technique since the 90 nm node devices. As the next lithography technique for the 45 nm node, initially 157 nm lithography using an F2 laser was promising, but development was delayed due to various problems. Therefore, ArF immersion lithography that can design the numerical aperture (NA) of the projection lens to 1.0 or more and can achieve high resolution by inserting a liquid (aqueous liquid) having a refractive index higher than that of air such as water, ethylene glycol, or glycerin between the projection lens and the resist coating film applied to the wafer has attracted attention.

[0005] In ArF immersion lithography, as described above, a liquid is inserted between the projection lens and the resist coating film applied to the wafer. In this state, the liquid follows the projection lens and moves on the wafer for exposure to form a resist pattern. For the resist coating film used here, in addition to the leveling property required for the resist coating film, water repellency is required in order for the liquid to follow the projection lens.

[0006] In the field of lithography technology, in order to obtain a resist coating film having leveling property and water repellency, for example, a resist composition containing a fluorine atom-containing resin having a poly(perfluoroalkylene ether) chain and a group that decomposes by the action of an acid to generate an alkali-soluble group as a surfactant has been disclosed. Specifically, a resist composition containing a fluorine atom-containing resin is disclosed, and the fluorine atom-containing resin is obtained by subjecting a polymerizable monomer having (meth)acryloyl groups at both ends of a poly(perfluoroalkylene ether) chain and a polymerizable monomer having a group such as a tert-butyl group or a 2-alkyladamantyl group that decomposes by the action of an acid to generate an alkali-soluble group to radical polymerization using a polymerization initiator such as benzoyl peroxide or an azo compound (for example, refer to Patent Document 1).

[0007] Regarding the fluorine atom-containing resin disclosed in Patent Document 1, the above two polymerizable monomers are polymerized randomly during radical polymerization. Therefore, the obtained fluorine atom-containing resin is a mixture of resins having various molecular weights and fluorine atom contents. In this mixture, the resin having a high fluorine atom content has poor compatibility with the alkali-soluble resin and the solvent, which are the main film-forming components in the resist composition, and there is a problem that particulate and filamentous foreign substances considered to be caused by the resin having a high fluorine atom content are mixed into the resist coating film obtained using the resist composition disclosed in Patent Document 1.

[0008] When polymerizing polymerizable monomers, living radical polymerization is known as a method for obtaining a resin composed of more uniform components by controlling the molecular weight, fluorine atom content, etc. In this living radical polymerization, in order to make the fluorine atom content in one molecule uniform, it is known to use a fluorine atom-containing initiator as the initiator for living radical polymerization. As such an initiator, for example, a compound having a carbon-iodine bond at both ends or a single end of a perfluoropolyether structure is known (for example, refer to Patent Document 2). Specifically, this compound is obtained by reacting a carboxylic acid having a perfluoropolyether structure with potassium hydroxide to form a potassium salt of the carboxylic acid and then reacting the potassium salt with iodine at a high temperature of 200 °C. As described above, the initiator for living radical polymerization disclosed in Patent Document 2 requires a reaction at a high temperature, etc., and is very difficult to obtain.

[0009] Prior Art Documents

[0010] Patent Documents

[0011] Patent Document 1: Japanese Patent Application Laid-Open No. 2014-181322

[0012] Patent Document 2: Japanese Patent Application Laid-Open No. 2010-144080 Summary of the Invention

[0013] Problems to be Solved by the Invention

[0014] The problem to be solved by the present invention is to provide a fluorine-containing compound that can be easily obtained and is suitable for use as an initiator for living radical polymerization. Another object of the present invention is to provide a fluorine-containing polymer that can provide a coating film having excellent liquid repellency such as water repellency and leveling property without the generation of foreign matters and is suitable for use in various resist compositions used in the manufacture of LSI, color filters, etc., and a method for producing the fluorine-containing polymer.

[0015] Solutions for Solving the Problems

[0016] The present inventors have conducted intensive studies repeatedly to solve the above problems, and as a result, have found that a compound having a poly(perfluoroalkylene ether) chain and an ester bond and containing a monovalent organic group having a secondary carbon atom or a tertiary carbon atom at the terminal and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom can be easily obtained by performing a usual esterification reaction as described below; the compound is suitable for use as an initiator for living radical polymerization; a fluorine-containing polymer can be obtained by using the compound as an initiator for living radical polymerization; and a coating film of various resist compositions obtained by using the fluorine-containing polymer has no generation of foreign matters and can provide a coating film having excellent liquid repellency such as water repellency and good leveling property, thereby completing the present invention.

[0017] That is, the present invention provides a fluorine-containing compound represented by the following general formula (1) or general formula (2):

[0018]

[0019] (In the formula, PFPE is a poly(perfluoroalkylene ether) chain. Each X1 is a monovalent organic group having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom. Each of R1 and R2 is an alkylene group having 1 to 4 carbon atoms. R3 is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.).

[0020] In addition, the present invention provides a living radical polymerization initiator represented by the aforementioned general formula (1) or (2).

[0021] In addition, the present invention provides a fluorine-containing polymer having a structure derived from the aforementioned fluorine-containing compound and a polymer structure of a radically polymerizable unsaturated monomer (A).

[0022] In addition, the present invention provides a method for producing a fluorine-containing polymer, characterized by subjecting a radically polymerizable unsaturated monomer (A) to living radical polymerization using the aforementioned fluorine-containing compound as an initiator.

[0023] Furthermore, the present invention provides a resist composition containing the aforementioned fluorine-containing polymer.

[0024] Effects of the Invention

[0025] According to the present invention, a fluorine-containing compound that can be preferably used as an initiator for living radical polymerization can be easily obtained. In addition, by using a resist composition containing a fluorine-containing polymer as described below, a coating film excellent in liquid repellency such as water repellency and also excellent in leveling property can be obtained without generation of foreign matters. The fluorine-containing polymer is characterized by having a polymer structure of a structure derived from the fluorine-containing compound of the present invention and a radically polymerizable unsaturated monomer (A), specifically, obtained by using the fluorine-containing compound of the present invention as an initiator and subjecting the radically polymerizable unsaturated monomer (A) to living radical polymerization. The resist composition of the present invention not only has the above effects, but also has excellent developability with an alkaline solution, and thus can be suitably used as a composition used in the above-mentioned ArF immersion lithography and KrF excimer laser lithography, ArF excimer laser lithography, etc. for forming semiconductor integrated circuits such as LSIs. In addition, the resist composition of the present invention can also be suitably used as a composition (black resist composition) for forming a black matrix (BM) used in the manufacture of a color filter, and a composition (color resist composition) for forming each color pixel of red (R), green (G), and blue (B). Furthermore, the fluorine-containing polymer of the present invention can be suitably used not only as a resist composition used in lithography technology, but also as a leveling agent in various applications such as hard coat materials for display screens of liquid crystal displays, plasma displays, organic EL displays (PDP), etc., gravure printing inks; inkjet inks; coatings or hard coat materials for mobile phone casings; hard coat materials for mobile phone screens; hard coat materials for optical recording media such as CDs, DVDs, and Blu-ray discs; hard coat materials for transfer films for insert molds (IMD, IMF); printing inks or coatings for various building materials such as decorative panels; coating materials for window glasses of houses; coatings for woodworking such as furniture; coating materials for artificial and synthetic leathers; coatings or coating materials for various plastic molded products such as casings of home appliances; coatings or coating materials for FRP bathtubs, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 IR spectrum of the fluorine-containing compound (1) obtained in Example 1.

[0027] Figure 2 For the fluorine-containing compound (1) obtained in Example 1 13 C-NMR spectrum.

[0028] Figure 3 IR spectrum of the fluorine-containing polymer (1) obtained in Example 3.

[0029] Figure 4 19F-NMR spectrum of the fluoropolymer (1) obtained in Example 3 13 C-NMR spectrum

[0030] Figure 5 GPC chart of the fluoropolymer (1) obtained in Example 3 Detailed implementation mode

[0031] The fluorine-containing compound of the present invention is characterized by being represented by the general formula (1) or general formula (2),

[0032]

[0033] (In the formula, PFPE is a poly(perfluoroalkylene ether) chain. Each X1 is a monovalent organic group having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom. Each of R1 and R2 is an alkylene group having 1 to 4 carbon atoms. R3 is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms).

[0034] As the aforementioned monovalent organic group having a secondary carbon atom and having a bromine atom directly bonded to the secondary carbon atom, for example, 1-bromoethyl, 1-bromopropyl, 1-bromobutyl, 1-bromo-2-methylpropyl, etc. can be cited.

[0035] As the aforementioned monovalent organic group having a secondary carbon atom and having a chlorine atom directly bonded to the secondary carbon atom, for example, 1-chloroethyl, 1-chloropropyl, 1-chlorobutyl, 1-chloro-2-methylpropyl, etc. can be cited.

[0036] As the aforementioned monovalent organic group having a tertiary carbon atom and having a bromine atom directly bonded to the tertiary carbon atom, for example, 1-bromo-1-methylethyl, 1-bromo-1-methylpropyl, 1-bromo-1-methylbutyl, 1-bromo-1,2-dimethylpropyl, etc. can be cited.

[0037] As the aforementioned monovalent organic group having a tertiary carbon atom and having a chlorine atom directly bonded to the tertiary carbon atom, for example, 1-chloro-1-methylethyl, 1-chloro-1-methylpropyl, 1-chloro-1-methylbutyl, 1-chloro-1,2-dimethylpropyl, etc. can be cited.

[0038] Among the aforementioned X1, from the aspect of becoming a polymerization initiator that is likely to cause living radical polymerization (with good initiation efficiency), each is preferably a monovalent organic group having a tertiary carbon atom and having a chlorine atom directly bonded to the tertiary carbon atom or a monovalent organic group having a bromine atom directly bonded to the tertiary carbon atom, more preferably 1-bromo-1-methylethyl, 1-chloro-1-methylethyl, and further preferably 1-bromo-1-methylethyl. It should be noted that the X1 in the general formula (1) can be the same or different.

[0039] R1 and R2 in the aforementioned general formula (1) or general formula (2) are alkylene groups having 1 to 4 carbon atoms. Among them, from the aspect that they can be easily obtained as raw materials when manufacturing the fluorine-containing compound of the present invention, and a fluorine-containing polymer with excellent leveling property can be obtained when using the fluorine-containing compound of the present invention as a living radical polymerization initiator, R1 and R2 are each preferably a methylene group or an ethylene group.

[0040] R3 in the aforementioned general formula (2) is a fluorine atom or an alkyl group having 1 to 4 carbon atoms. Among them, from the aspect that it can be easily obtained as a raw material when manufacturing the fluorine-containing compound of the present invention, and a fluorine-containing polymer with excellent leveling property can be obtained when using the fluorine-containing compound of the present invention as a living radical polymerization initiator, R3 is preferably a fluorine atom.

[0041] Specific examples of the PFPE [poly(perfluoroalkylene ether)] chain in general formula (1) or general formula (2) include PFPE chains having a structure in which divalent fluorocarbon groups having 1 to 3 carbon atoms and oxygen atoms are alternately linked. The divalent fluorocarbon groups having 1 to 3 carbon atoms can be one kind or a mixture of multiple kinds. Specifically, groups represented by the following structural formula 1 can be cited.

[0042]

[0043] (In the above structural formula 1, X is the following structural formulas a to e. All X in structural formula 1 can be of the same structure, or multiple structures can exist randomly or in a block form. In addition, n is a number of 1 or more representing a repeating unit.)

[0044]

[0045] Among these, especially from the aspects of easy acquisition and synthesis, obtaining a coating film with excellent liquid repellency such as water repellency and few foreign substances, and obtaining a fluorine-containing polymer suitable for use in a resist composition, coexistence of the perfluoromethylene structure represented by the aforementioned structural formula a and the perfluoroethylene structure represented by the aforementioned structural formula b is particularly preferred. Here, for the molar ratio (structure a / structure b) of the perfluoromethylene structure represented by the aforementioned structural formula a and the perfluoroethylene structure represented by the aforementioned structural formula b, in order to obtain a coating film with excellent antifouling property in addition to the above effects, a ratio of 1 / 4 to 4 / 1 is preferred. In addition, the value of n in the aforementioned structural formula 1 is preferably in the range of 3 to 60, more preferably 6 to 40.

[0046] In addition, for the aforementioned poly(perfluoroalkylene ether) chain, from the viewpoints of obtaining a coating film having excellent liquid repellency such as water repellency and few foreign substances, and obtaining a fluoropolymer suitable for use in a resist composition, the total number of fluorine atoms contained in one poly(perfluoroalkylene ether) chain is preferably in the range of 18 to 250, and particularly preferably in the range of 25 to 90.

[0047] Hereinafter, specific examples of the fluoride of the present invention are shown.

[0048]

[0049] In the above formulas (1-1) to (1-9), n is on average 1 to 30, and p is on average 1 to 30. In addition, in the compounds represented by the above formulas (1-1) to (1-9), (CF2CF2O) having a repeating number n and (CF2O) having a repeating number p in [] may exist randomly or in a block form. When (CF2CF2O) or (CF2O) exists randomly in [], the total number of repeating units of (CF2CF2O) is the aforementioned n, and the total number of repeating units of (CF2O) is the aforementioned p.

[0050]

[0051]

[0052] In the formulas (2-1) to (2-10), n and p are each on average 1 to 50. In addition, in the compounds represented by the above formulas (2-1) to (2-10), (CF2CF2O) having a repeating number n and (CF2O) having a repeating number p in [] may exist randomly or in a block form. When (CF2CF2O) or (CF2O) exists randomly in [], the total number of repeating units of (CF2CF2O) is the aforementioned n, and the total number of repeating units of (CF2O) is the aforementioned p.

[0053] Among the fluorine-containing compounds of the present invention, from the viewpoints of excellent leveling properties and good compatibility with the solvent in the resist composition described below and the resin as the main film-forming component, the fluorine-containing compound represented by the general formula (1) is preferred, and the fluorine-containing compound represented by the above formula (1-1) is more preferred. In addition, among the compounds represented by the general formula (2), the compound represented by the formula (2-1) is preferred.

[0054] The fluorine-containing compound represented by the general formula (1) or (2) of the present invention can be obtained, for example, by reacting an alcohol compound (α) represented by the following general formula (α-1) or (α-2) with a compound (β) such as the following (β-1) to (β-4) (esterification reaction).

[0055]

[0056] (In the formula, PFPE is a poly(perfluoroalkylene ether) chain. Each of R1 and R2 is an alkylene group having 1 to 4 carbon atoms. R3 is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms.).

[0057] 1) An acyl halide (β-1) having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom.

[0058] 2) An acid anhydride (β-2) having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom.

[0059] 3) An acid alkyl ester (β-3) having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom.

[0060] 4) A carboxylic acid compound (β-4) having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom.

[0061] As the compound represented by the aforementioned general formula (α-1), for example, the following compounds can be exemplified.

[0062]

[0063] (In the formula, the average value of n is 1 to 30, and the average value of p is 1 to 30)

[0064] As the compound represented by the aforementioned general formula (α-2), for example, the following compounds can be exemplified.

[0065]

[0066] As the aforementioned acyl halide (β-1), for example, 2-bromoisobutyryl bromide, 2-chloroisobutyryl bromide, 2-bromo-2-methylbutyryl bromide, 2-chloro-2-methylbutyryl bromide, 2-bromoisobutyryl chloride, 2-chloroisobutyryl chloride, 2-bromo-2-methylbutyryl chloride, 2-chloro-2-methylbutyryl chloride, etc. can be cited.

[0067] As the aforementioned acid anhydride (β-2), for example, 2-bromoisobutyric anhydride, 2-chloroisobutyric anhydride, 2-bromo-2-methylbutyric anhydride, 2-chloro-2-methylbutyric anhydride, etc. can be cited.

[0068] As the aforementioned acid alkyl ester (β-3), for example, ethyl 2-bromoisobutyrate, ethyl 2-chloroisobutyrate, ethyl 2-bromo-2-methylbutyrate, ethyl 2-chloro-2-methylbutyrate, methyl 2-bromoisobutyrate, methyl 2-chloroisobutyrate, methyl 2-bromo-2-methylbutyrate, methyl 2-chloro-2-methylbutyrate, etc. can be cited.

[0069] Examples of the aforementioned carboxylic acid compound (β-4) include 2-bromoisobutyric acid, 2-chloroisobutyric acid, 2-bromo-2-methylbutyric acid, 2-chloro-2-methylbutyric acid, etc.

[0070] When reacting the aforementioned alcohol compound (α) with an acyl halide (β-1), acid anhydride (β-2), alkyl ester of an acid (β-3), or carboxylic acid compound (β-4), they can be charged into the reaction system all at once for reaction, or after charging the alcohol compound (α), the aforementioned (β-1) to (β-4) can be charged in batches for reaction.

[0071] When reacting the alcohol compound (α) with the compound (β), an organic solvent other than the aforementioned alcohol compound (α) can be mixed in the reaction system as a reaction medium. Examples of the aforementioned organic solvent preferably include ketones, esters, amides, sulfoxides, ethers, and hydrocarbons. Specifically, examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, xylene, isopropyl ether, benzene, heptane, etc. The amount of the organic solvent is usually 50 to 1000 parts by mass relative to a total of 100 parts by mass of the alcohol compound (α) and the compound (β) as raw materials.

[0072] When using an acyl halide (β-1) or acid anhydride (β-2) as the compound (β), acids such as hydrogen halide and carboxylic acid are generated by the reaction with the alcohol compound (α). To neutralize these acids, it is preferable to pre-add a basic compound such as triethylamine as a neutralizing agent in the reaction system. Here, for the amount of the basic compound, an amount usually added in excess of the estimated amount of the acid generated based on the charged amounts of the aforementioned alcohol compound (α) and (β-1), acid anhydride (β-2) is added. Specifically, for example, 1.1 to 3 equivalents are added relative to 1 equivalent of the acid.

[0073] After adding a basic compound to the reaction system to react the alcohol compound (α) with an acyl halide (β-1) or acid anhydride (β-2), an acid can be added to the reaction system. By adding the acid, a salt (inorganic salt) of the basic compound remaining in the reaction system and the acid is generated, and in the subsequent washing step, the basic compound can be removed more easily compared to the case where it exists in the system in the form of a basic compound. Examples of the aforementioned acid include hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, acetic acid, etc. The addition amount of the acid is usually 10 to 500 parts by mass relative to a total of 100 parts by mass of the raw materials [alcohol compound (α), acyl halide (β-1), acid anhydride (β-2), etc.] and the solvent that can be added to the reaction system described later.

[0074] When using acyl halides (β-1) or acid anhydrides (β-2) as compound (β), after reacting with alcohol compound (α), a step (washing step) of adding water to the reaction system, mixing, and then discharging the water out of the reaction system can be carried out. Through this washing step, the inorganic salts present in the solvent can be moved into the water and discharged out of the reaction system together with the water. The number of times of the washing step can be 1 time or can be carried out in multiple stages. The addition amount of water is usually 10 to 500 parts by mass relative to the total 100 parts by mass of the above-mentioned raw materials and solvent.

[0075] Furthermore, after the above-mentioned washing step, a step (washing step) of adding a weak basic compound such as sodium bicarbonate to the reaction system, mixing, and then discharging the water out of the reaction system can be carried out. Through this step, the acid that has not been completely removed in the above-mentioned washing step can be neutralized. The number of times of adding and discharging the weak basic compound can be 1 time or can be carried out multiple times. The addition amount of the weak basic compound is usually 10 to 500 parts by mass relative to the total 100 parts by mass of the above-mentioned raw materials and solvent.

[0076] Regarding the reaction ratio of the aforementioned alcohol compound (α) and compound (β), a reaction ratio of 1 to 5 moles of the acid group in compound (β) relative to 1 mole of the hydroxyl group in alcohol compound (α) is preferred from the aspects of good reaction efficiency and easy purification treatment such as the above-mentioned washing step, and more preferably 1 to 3 moles.

[0077] The reaction temperature of alcohol compound (α) and acyl halide (β-1) is usually -40 to 60 °C. The reaction time is usually 1 to 8 hours.

[0078] The reaction temperature of alcohol compound (α) and acid anhydride (β-2) is usually 0 to 80 °C. The reaction time is usually 1 to 10 hours.

[0079] The reaction temperature of alcohol compound (α) and acid alkyl ester (β-3) is usually 60 to 120 °C. The reaction time is usually 6 to 24 hours.

[0080] The reaction temperature of alcohol compound (α) and carboxylic acid compound (β-4) is usually 80 to 150 °C. The reaction time is usually 10 to 30 hours.

[0081] As described above, the fluorine-containing compound of the present invention has a group represented by X1 (a monovalent organic group having a secondary carbon atom or a tertiary carbon atom and having a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom). Thus, if there is a bromine atom or a chlorine atom directly bonded to the secondary carbon atom or the tertiary carbon atom, it is easy to generate the free radical binding equilibrium of the halogen to the metal catalyst, and it is easy to carry out living polymerization. Therefore, it can be preferably used as an initiator for living radical polymerization (living radical polymerization initiator).

[0082] In living radical polymerization, dormant species in which the living polymerization terminus is protected by an atom or atomic group reversibly generate radicals and react with monomers, whereby a growth reaction proceeds. Even when the first monomer is consumed, the growth terminus does not lose its activity but reacts with the successively added second monomer, enabling the production of block polymers. Examples of such living radical polymerization include atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer radical polymerization (RAFT), nitroxide-mediated radical polymerization (NMP), tellurium-mediated radical polymerization (TERP), and the like. The fluorine-containing compound of the present invention is easily polymerizable (has good initiation efficiency), and thus can be preferably used in ATRP. Specifically, ATRP using the fluorine-containing compound of the present invention can be carried out by using the fluorine-containing compound as an initiator and a metal complex formed from a transition metal compound and a ligand as a catalyst.

[0083] The transition metal compound used in the aforementioned ATRP is represented by M n+ X n As M of the transition metal n+ may be selected from the group consisting of Cu + 、Cu 2+ 、Fe 2+ 、Fe 3+ 、Ru 2+ 、Ru 3+ 、Cr 2+ 、Cr 3+ 、Mo 0 、Mo + 、Mo 2+ 、Mo 3+ 、W 2+ 、W 3+ 、Rh 3+ 、Rh 4+ 、Co + 、Co 2+ 、Re 2+ 、Re 3+ 、Ni 0 、Ni + 、Mn 3+ 、Mn 4+ 、V 2+ 、V 3+ 、Zn + 、Zn 2+ 、Au + 、Au 2+ 、Ag + and Ag 2+ and the group consisting of Ag 1 / 2 、(SO4) 1 / 3 、(PO4)1 / 2 , (H2PO4), trifluoromethanesulfonate, hexafluorophosphate, methanesulfonate, arylsulfonate (preferably benzenesulfonate or toluenesulfonate), SeR 1 , CN and R 2 COO. Here, R 1 represents aryl, a linear or branched alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and R 2 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms (preferably methyl) that can be substituted with halogen 1 to 5 times (appropriately substituted with fluorine or chlorine 1 to 3 times). Further, n represents the formal charge on the metal and is an integer from 0 to 7.

[0084] The above transition metal complex is not particularly limited. As preferred transition metal complexes, transition metal complexes of Groups 7, 8, 9, 10, and 11 can be cited. As more preferred transition metal complexes, complexes of copper(0), copper(I), ruthenium(II), iron(II), or nickel(II) can be cited.

[0085] As the compound having a ligand capable of coordinating with the above transition metal, compounds having a ligand containing one or more nitrogen atoms, oxygen atoms, phosphorus atoms, or sulfur atoms capable of coordinating with the transition metal via a σ bond, compounds having a ligand containing two or more carbon atoms capable of coordinating with the transition metal via a π bond, and compounds having a ligand capable of coordinating with the transition metal via a μ bond or η bond can be cited.

[0086] As specific examples of the compound having the above ligand, for example, when the central metal is copper, complexes with ligands such as 2,2'-bipyridine and its derivatives, 1,10-phenanthroline and its derivatives, polyamines such as tetramethylethylenediamine, pentamethyldiethylenetriamine, and hexamethyltris(2-aminoethyl)amine can be cited. In addition, as ruthenium(II) complexes, dichlorotris(triphenylphosphine)ruthenium, dichlorotris(tributylphosphine)ruthenium, dichloro(cyclooctadiene)ruthenium, dichlorobenzene ruthenium, dichloro(p-cymene)ruthenium, dichloro(norbornadiene)ruthenium, cis-dichlorobis(2,2'-bipyridine)ruthenium, dichlorotris(1,10-phenanthroline)ruthenium, carbonylchlorohydridotris(triphenylphosphine)ruthenium, etc. can be cited. Further, as iron(II) complexes, bis(triphenylphosphine) complexes, triazanonane complexes, etc. can be cited.

[0087] The fluorine-containing polymer of the present invention is characterized by having a structure derived from the fluorine-containing compound of the present invention and a polymer structure of the radically polymerizable unsaturated monomer (A). Here, the "structure derived from the fluorine-containing compound" means a structure in which a bromine atom or a chlorine atom has been removed from X1 in the aforementioned general formula (1) or general formula (2).

[0088] The fluorine-containing polymer of the present invention can be exemplified, for example, by a polymer obtained by subjecting a radical polymerizable unsaturated monomer (A) to living radical polymerization using the fluorine-containing compound of the present invention as an initiator for living radical polymerization. More specifically, for example, a polymer obtained by subjecting a radical polymerizable unsaturated monomer (A) to living radical polymerization in the presence of the fluorine-containing compound of the present invention, the aforementioned transition metal compound, a compound having a ligand capable of coordinating with the aforementioned transition metal, and a solvent described later can be mentioned.

[0089] Examples of the solvent that can be used during living radical polymerization include ester solvents such as ethyl acetate, butyl acetate, and propylene glycol monomethyl ether acetate; ether solvents such as diisopropyl ether, dimethoxyethane, and diethylene glycol dimethyl ether; halogen solvents such as dichloromethane and dichloroethane; aromatic solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohol solvents such as methanol, ethanol, and isopropanol; aprotic polar solvents such as dimethylformamide and dimethyl sulfoxide. In addition, these solvents can be used alone or in combination of two or more.

[0090] In addition, the fluorine-containing polymer of the present invention is represented by the following general formula (I) or general formula (II), for example.

[0091]

[0092] In the above formula, PFPE is a poly(perfluoroalkylene ether) chain. R1 and R2 are each an alkylene group having 1 to 4 carbon atoms. R3 is a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. R4 is a monovalent organic group. R5, R6, and R7 are each a hydrogen atom or a methyl group. X is each a halogen atom or an alkyl group having 1 to 10 carbon atoms. The total average of n1 and n2 is 1 to 800. The average of n3 is 1 to 800.

[0093] When X1 in the fluorine-containing compound used in the production of the polymer represented by the general formula (I) or general formula (II) is a group having a tertiary carbon atom and a bromine atom or a chlorine atom directly bonded to the carbon atom, from the viewpoint of improving the efficiency of living radical polymerization of the radical polymerizable unsaturated monomer (A) and resulting in a polymer having a narrow molecular weight distribution and being uniform, it is preferable that R5, R6, and R7 are methyl groups.

[0094] The total of the aforementioned n1 and n2 and n3 are each preferably an average of 3 to 500, more preferably 5 to 300. Examples of the monovalent organic group represented by R4 include an alkyl group, a cycloalkyl group, an aromatic group, an oxyalkylene group, a siloxane group, and the like.

[0095] In addition, as the monovalent organic group represented by R4, a group that decomposes by the action of an acid to generate a base-soluble group (acid-decomposable group) can also be exemplified. As the acid-decomposable group, for example, the acid-decomposable groups described later can be exemplified.

[0096] As the radically polymerizable unsaturated monomer (A) used to obtain the fluoropolymer of the present invention, for example, (meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid n-butyl ester, (meth)acrylic acid isobutyl ester, (meth)acrylic acid n-pentyl ester, (meth)acrylic acid n-hexyl ester, (meth)acrylic acid n-heptyl ester, (meth)acrylic acid n-octyl ester, (meth)acrylic acid 2-ethylhexyl ester, (meth)acrylic acid nonyl ester, (meth)acrylic acid decyl ester, (meth)acrylic acid dodecyl ester, (meth)acrylic acid cyclohexyl ester, (meth)acrylic acid isobornyl ester, etc. (meth)acrylic acid esters;

[0097] Aromatic vinyls such as styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene; maleimides such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide, etc.

[0098] In addition, as the radically polymerizable unsaturated monomer (A), a radically polymerizable unsaturated monomer (A1) having a polyoxyalkylene can also be exemplified. Among the fluoropolymers of the present invention, a fluoropolymer containing a structure derived from the aforementioned radically polymerizable unsaturated monomer (A1) becomes a composition capable of obtaining a coating film with excellent leveling properties, and can be particularly preferably used for a color resist composition.

[0099] As the aforementioned radically polymerizable unsaturated monomer (A1), those having an oxyalkylene group with 2 to 4 carbon atoms as a repeating unit can be preferably used. Specifically, for example, polypropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polytetramethylene glycol (meth)acrylate, poly(ethylene glycol·propylene glycol) mono(meth)acrylate, polyethylene glycol·polypropylene glycol mono(meth)acrylate, poly(ethylene glycol·tetramethylene glycol) mono(meth)acrylate, polyethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·tetramethylene glycol) mono(meth)acrylate, polypropylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(propylene glycol·butylene glycol) mono(meth)acrylate, polypropylene glycol·polybutylene glycol mono(meth)acrylate, poly(ethylene glycol·butylene glycol) mono(meth)acrylate, polyethylene glycol·polybutylene glycol mono(meth)acrylate, poly(tetraethylene glycol·butylene glycol) mono(meth)acrylate, poly(tetraethylene glycol·polybutylene glycol) mono(meth)acrylate, polybutylene glycol mono(meth)acrylate, poly(ethylene glycol·trimethylene glycol) mono(meth)acrylate, polyethylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(propylene glycol·trimethylene glycol) mono(meth)acrylate, polypropylene glycol·polytrimethylene glycol mono(meth)acrylate, poly(trimethylene glycol·tetramethylene glycol) mono(meth)acrylate, polytrimethylene glycol·polytetramethylene glycol mono(meth)acrylate, poly(butylene glycol·trimethylene glycol) mono(meth)acrylate, polybutylene glycol·polytrimethylene glycol mono(meth)acrylate, etc. can be mentioned.

[0100] Among them, from the aspect of obtaining a coating film with less foreign matter and excellent leveling property, the polyoxyalkylene is preferably polyoxypropylene or polyoxybutylene. A radically polymerizable unsaturated monomer having polyoxypropylene and polyoxybutylene is more preferred.

[0101] In the present invention, "poly(ethylene glycol·propylene glycol)" means a random copolymer of ethylene glycol and propylene glycol, and "polyethylene glycol·polypropylene glycol" means a block copolymer of ethylene glycol and propylene glycol.

[0102] As the aforementioned substance having an oxyalkylene group with 2 to 4 carbon atoms as a repeating unit, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, poly(ethylene glycol·propylene glycol), polyethylene glycol·polypropylene glycol, poly(propylene glycol·butylene glycol, polypropylene glycol·polybutylene glycol), poly(propylene glycol·trimethylene glycol) polypropylene glycol·polytrimethylene glycol are preferably used, and polypropylene glycol, polybutylene glycol, poly(ethylene glycol·propylene glycol), polyethylene glycol·polypropylene glycol, poly(propylene glycol·butylene glycol, polypropylene glycol·polybutylene glycol) are more preferred.

[0103] In addition, as the radically polymerizable unsaturated monomer (A), a radically polymerizable unsaturated monomer (A2) having a group that decomposes by the action of an acid to generate an alkali-soluble group can also be exemplified. Among the fluoropolymers of the present invention, a fluoropolymer containing a structure derived from the aforementioned radically polymerizable unsaturated monomer (A2) forms a composition that can form a coating film with less generation of foreign matter, excellent liquid repellency such as water repellency, and good developability based on an alkali developer, and can be particularly preferably used in a resist composition used in the manufacture of semiconductor integrated circuits such as LSIs.

[0104] As the group (acid-decomposable group) that decomposes by the action of an acid to generate an alkali-soluble group in the aforementioned radically polymerizable unsaturated monomer (A2), for example, groups in which a hydrogen atom of an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group, or a thiol group is protected by a group that dissociates by the action of an acid can be cited.

[0105] Here, as a group in which a hydrogen atom of an alkali-soluble group is protected by a group that dissociates by the action of an acid, for example, a group in which a hydrogen atom of an alkali-soluble group is protected by a tert-butyl group, a 2-alkyl-2-adamantyl group, or a 1-alkoxyethyl group can be preferably exemplified. In addition, the aforementioned acid-decomposable group is preferably a group that decomposes by the action of an acid to generate a carboxylic acid.

[0106] As the aforementioned 2-alkyl-2-adamantyl group, for example, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group, 2-propyl-2-adamantyl group, 2-isopropyl-2-adamantyl group, 2-butyl-2-adamantyl group, 2-pentyl-2-adamantyl group, 2-hexyl-2-adamantyl group, etc. can be cited.

[0107] As the aforementioned 1-alkoxyethyl group, for example, 1-methoxyethyl group, 1-ethoxyethyl group, 1-propoxyethyl group, 1-isopropoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-pentoxyethyl group, 1-hexoxyethyl group, 1-cyclohexoxyethyl group, etc. can be cited.

[0108] As specific examples of the aforementioned radically polymerizable unsaturated monomer (A2), for example, (meth)acrylic acid tert-butyl esters such as tert-butyl acrylate and tert-butyl methacrylate; (meth)acrylic acid adamantyl esters such as 2-methyl-2-adamantyl acrylate, 2-methyl-2-adamantyl methacrylate, 2-ethyl-2-adamantyl acrylate, and 2-ethyl-2-adamantyl methacrylate; (meth)acrylic acid alkoxy esters such as (meth)acrylic acid 1-butoxyethyl ester and (meth)acrylic acid 1-cyclohexyloxy ester, etc. can be preferably exemplified.

[0109] It should be noted that in the present invention, "(meth)acrylate" refers to one or both of methacrylate and acrylate, "(meth)acryloyl" refers to one or both of methacryloyl and acryloyl, and "(meth)acrylic acid" refers to one or both of methacrylic acid and acrylic acid.

[0110] The method for producing a fluoropolymer of the present invention is characterized in that the fluorine-containing compound of the present invention is used as an initiator to carry out living radical polymerization of a radically polymerizable unsaturated monomer (A). The temperature for carrying out the living radical polymerization of the radically polymerizable unsaturated monomer (A) is usually 20 to 80 °C. The reaction time is usually 3 to 24 hours.

[0111] When a radically polymerizable unsaturated monomer (A2) is used as an essential component and monomers other than the radically polymerizable unsaturated monomer (A2) are used in combination as the radically polymerizable unsaturated monomer (A), the amount thereof is preferably 10 to 400 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the radically polymerizable unsaturated monomer (A2).

[0112] As described above, the fluoropolymer of the present invention is obtained by living radical polymerization, and sometimes the metal derived from the transition metal compound used during living radical polymerization remains in the fluoropolymer. Therefore, when the fluoropolymer of the present invention is used in semiconductor applications such as a photoresist composition where the remaining metal causes problems, it is preferable to remove the remaining metal from the fluoropolymer using activated alumina or the like after the polymerization reaction.

[0113] The fluoropolymer of the present invention can be preferably contained in a resist composition, for example. From the aspect of good solubility in the above resist composition, the number average molecular weight (Mn) of the fluoropolymer of the present invention is preferably in the range of 500 to 200,000, more preferably in the range of 600 to 100,000. In addition, the weight average molecular weight (Mw) is preferably in the range of 700 to 400,000, more preferably in the range of 1,000 to 200,000. The number average molecular weight (Mn) and the weight average molecular weight (Mw) can be determined by the above-described GPC measurement.

[0114] Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values converted to polystyrene based on the measurement by gel permeation chromatography (hereinafter, simply referred to as "GPC"). It should be noted that the measurement conditions of GPC are as follows.

[0115] [GPC Measurement Conditions]

[0116] Measurement device: "HLC-8220GPC" manufactured by Tosoh Corporation

[0117] Column: Guard column “HHR-H” (6.0 mm I.D. × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMPW-HHR-N” (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + “TSK-GEL GMPW-HHR-N” (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + “TSK-GEL GMPW-HHR-N” (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + “TSK-GEL GMPW-HHR-N” (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation

[0118] Detector: ELSD (“ELSD2000” manufactured by Alltech Japan Co., Ltd.)

[0119] Data processing: “GPC-8020 model II data analysis version 4.30” manufactured by Tosoh Corporation

[0120] Measurement conditions: Column temperature 40 °C

[0121] Developing solvent: Tetrahydrofuran (THF)

[0122] Flow rate: 1.0 ml / min

[0123] Sample: Substance obtained by filtering a tetrahydrofuran solution with a resin solid content of 1.0 mass% through a microporous filter (5 μl).

[0124] Standard sample: The following monodisperse polystyrene with a known molecular weight was used according to the measurement manual of the aforementioned “GPC-8020 model II data analysis version 4.30”.

[0125] (Monodisperse polystyrene)

[0126] “A-500” manufactured by Tosoh Corporation

[0127] “A-1000” manufactured by Tosoh Corporation

[0128] “A-2500” manufactured by Tosoh Corporation

[0129] “A-5000” manufactured by Tosoh Corporation

[0130] “F-1” manufactured by Tosoh Corporation

[0131] “F-2” manufactured by Tosoh Corporation

[0132] “F-4” manufactured by Tosoh Corporation

[0133] “F-10” manufactured by Tosoh Corporation

[0134] “F-20” manufactured by Tosoh Corporation

[0135] "F-40" manufactured by Tosoh Corporation

[0136] "F-80" manufactured by Tosoh Corporation

[0137] "F-128" manufactured by Tosoh Corporation

[0138] "F-288" manufactured by Tosoh Corporation

[0139] "F-550" manufactured by Tosoh Corporation

[0140] The resist composition of the present invention is characterized by containing the fluorine-containing polymer of the present invention [hereinafter, sometimes simply referred to as fluorine-containing polymer (B)]. As the resist composition of the present invention, for example, the following substances can be exemplified.

[0141] A resist composition [hereinafter, sometimes simply referred to as resist composition (1).], which contains a fluorine-containing polymer (B), an alkali-soluble resin (C), a polymerizable compound (D) other than the alkali-soluble resin (C), and a colorant (E). This resist composition (1) can be suitably used, for example, as a composition for forming each pixel of a color filter (color resist composition), and a composition for forming a black matrix provided between each pixel (black matrix resist composition).

[0142] A resist composition [hereinafter, sometimes simply referred to as resist composition (2).], which contains a fluorine-containing polymer (B), a resin (F) whose solubility in an alkaline solution increases by the action of an acid, and an acid-generating component (G) that generates an acid upon exposure. This resist composition (2) can be suitably used, for example, as a positive resist composition for forming semiconductor integrated circuits such as LSIs.

[0143] A resist composition [hereinafter, sometimes simply referred to as resist composition (3).], which contains a fluorine-containing polymer (B), a resin (H) whose solubility in an organic solvent decreases by the action of an acid, and an acid-generating component (G) that generates an acid upon exposure. This resist composition (3) can be suitably used, for example, as a negative resist composition for forming semiconductor integrated circuits such as LSIs.

[0144] Hereinafter, the resist composition (1) will be described in detail. The aforementioned alkali-soluble resin (C) is a resin having alkali solubility. Here, alkali solubility means the property of being soluble in an aqueous solution of an alkali compound (developer). Specifically, for example, the following properties can be exemplified: a resin film with a film thickness of 1 μm is formed on a substrate using a resin solution with a resin concentration of 20% by mass (solvent: propylene glycol monomethyl ether acetate), and when immersed in a 0.05% by mass aqueous KOH solution for 1 minute, the property that a film thickness of 0.01 μm or more dissolves.

[0145] The above-mentioned alkali-soluble resin (C) is not particularly limited as long as it is soluble in an alkali developing solution, and a resin having at least one acid group or its salt selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid group is preferred.

[0146] Examples of the above-mentioned alkali-soluble resin (C) include an alkali-soluble resin having no photocurability (an alkali-soluble resin not containing a photocurable group), an alkali-soluble resin having photocurability (an alkali-soluble resin containing a photocurable group), and the like.

[0147] Examples of the above-mentioned alkali-soluble resin not containing a photocurable group include the following resins and the like.

[0148] · An alkali-soluble resin (C1) obtained by polymerizing a (meth)acrylic polymerizable monomer having an acidic group as an essential component

[0149] · An alkali-soluble resin (C2) obtained by reacting a polymer having no acidic group obtained by polymerizing a (meth)acrylic polymerizable monomer having a reactive group as an essential component with a compound having a reactive group reactive with the reactive group and an acid group

[0150] Examples of the above-mentioned alkali-soluble resin containing a photocurable group include the following resins and the like.

[0151] · An alkali-soluble resin (C3) obtained by adding at least a part of the epoxy groups of a copolymer of an epoxy group-containing (meth)acrylate and other polymerizable monomers to an unsaturated monocarboxylic acid, and then adding at least a part of the hydroxyl groups generated by the addition reaction of the unsaturated monocarboxylic acid to an acid anhydride of a polycarboxylic acid

[0152] · An epoxy (meth)acrylate resin (C4) having a carboxyl group and a polymerizable unsaturated group

[0153] · A Cardo-type resin (C5) having a carboxyl group and a polymerizable unsaturated group

[0154] Hereinafter, the above (C1) to (C5) will be described in detail.

[0155] Examples of the above-mentioned alkali-soluble resin (C1) include an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component, an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a sulfonic acid group as an essential component, and the like. Among them, an alkali-soluble resin obtained by polymerizing a (meth)acrylic polymerizable monomer having a carboxyl group as an essential component is preferred.

[0156] Examples of the above-mentioned (meth)acrylic polymerizable monomer having a carboxyl group include polymerizable monomers such as (meth)acrylic acid, maleic acid, crotonic acid, itaconic acid, fumaric acid, cinnamic acid, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxyethyl adipate, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl succinate, 2-(meth)acryloyloxypropyl adipate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxybutyl succinate, 2-(meth)acryloyloxybutyl adipate, 2-(meth)acryloyloxybutyl maleate, 2-(meth)acryloyloxybutyl hydrogen phthalate, 2-(meth)acryloyloxybutyl phthalate;

[0157] Polymerizable monomers obtained by adding lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone to acrylic acid; polymerizable monomers obtained by adding succinic acid, maleic acid, phthalic acid, or their acid anhydrides to (meth)acrylic acid hydroxyalkyl esters, etc. These (meth)acrylic polymerizable monomers having a carboxyl group can be used alone or in combination of two or more. Among the above-mentioned (meth)acrylic polymerizable monomers having a carboxyl group, (meth)acrylic acid and 2-(meth)acryloyloxyethyl succinate are preferred.

[0158] Examples of the above-mentioned (meth)acrylic polymerizable monomer having a sulfonic acid group include 2-sulfoethyl (meth)acrylate, 2-sulfopropyl (meth)acrylate, 2-hydroxy-3-(meth)acryloyloxypropanesulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid or their salts, etc.

[0159] When preparing the alkali-soluble resin (C1), other polymerizable monomers can be used in combination within the range not damaging the effects of the present invention. Examples of other monomers include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxymethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate;

[0160] 2-Hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate and other hydroxyalkyl (meth)acrylates, (meth)acrylic esters having a hydroxyl group such as glycerol mono(meth)acrylate;

[0161] Aromatic vinyl compounds such as styrene and its derivatives; vinyl compounds such as N-vinylpyrrolidone; N-substituted maleimides such as N-cyclohexylmaleimide, N-phenylmaleimide, N-benzylmaleimide;

[0162] Macromonomers such as poly(methyl)acrylate methyl macromonomer, polystyrene macromonomer, poly(2-hydroxyethyl (meth)acrylate) macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer, polycaprolactone macromonomer. These other polymerizable monomers may be used alone or in combination of two or more.

[0163] Among the above other polymerizable monomers, styrene, (meth)acrylic acid methyl ester, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide are preferred in terms of good transparency and not easily damaging heat resistance.

[0164] The amount of these other polymerizable monomers is preferably 95% by mass or less, more preferably 85% by mass or less in all polymerizable monomer components.

[0165] Specific examples of the alkali-soluble resin (C1) include, for example, copolymers of (meth)acrylic acid with polymerizable monomers without a hydroxyl group such as (meth)acrylic acid methyl ester, benzyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, cyclohexyl (meth)acrylate, cyclohexylmaleimide, and polymerizable monomers with a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate;

[0166] Copolymers of (meth)acrylic acid with (meth)acrylic esters such as (meth)acrylic acid methyl ester, benzyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl methacrylate;

[0167] Copolymers of (meth)acrylic acid and styrene; copolymers of (meth)acrylic acid, styrene and α-methylstyrene; copolymers of (meth)acrylic acid and cyclohexyl maleimide, etc. Among the alkali-soluble resins (A1), from the aspect of obtaining a color resist composition with excellent pigment dispersibility, an alkali-soluble resin of benzyl (meth)acrylate is preferably used.

[0168] The acid value of the aforementioned alkali-soluble resin (C1) is preferably in the range of 30 to 500, more preferably in the range of 40 to 350, and still more preferably in the range of 50 to 300. In addition, the polystyrene-reduced weight-average molecular weight (Mw) of the aforementioned alkali-soluble resin (C1) measured by GPC is preferably in the range of 2000 to 80000, more preferably in the range of 3000 to 50000, and still more preferably in the range of 4000 to 30000.

[0169] It should be noted that in the alkali-soluble resin (C1), an alkali-soluble resin (C1-1) obtained by adding an epoxy group-containing unsaturated compound to the carboxyl group of a carboxyl group-containing alkali-soluble resin obtained by polymerizing a (meth)acrylic acid-based polymerizable monomer having a carboxyl group as an essential component can also be used as an alkali-soluble resin containing a photocurable group.

[0170] Examples of the aforementioned epoxy group-containing unsaturated compound include glycidyl (meth)acrylate, allyl glycidyl ether, glycidyl-α-ethyl acrylate, crotonyl glycidyl ether, (iso)crotonic acid glycidyl ether, N-(3,5-dimethyl-4-glycidyl)benzyl acrylamide, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. In addition, from the aspect of achieving improved heat resistance and improved dispersibility when using a pigment as the colorant (B), an epoxy group-containing unsaturated compound having an alicyclic epoxy group is preferred.

[0171] Examples of the alicyclic epoxy group of the aforementioned epoxy group-containing unsaturated compound having an alicyclic epoxy group include 2,3-epoxycyclopentyl, 3,4-epoxycyclohexyl, 7,8-epoxy〔tricyclo[5.2.1.0]dec-2-yl〕, etc. In addition, as the ethylenic unsaturated group, (meth)acryloyl is preferred. The epoxy group-containing unsaturated compound having an alicyclic epoxy group can be used alone or in combination of two or more.

[0172] When adding the epoxy group-containing unsaturated compound to the carboxyl group of the aforementioned carboxyl group-containing alkali-soluble resin, a well-known method can be used. For example, by reacting the carboxyl group-containing alkali-soluble resin and the epoxy group-containing unsaturated compound in the presence of a tertiary amine such as triethylamine and benzylmethylamine; a quaternary ammonium salt such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and benzyltriethylammonium chloride; a catalyst such as pyridine and triphenylphosphine, in an organic solvent at a reaction temperature of 50 to 150 °C for several hours to several tens of hours, the carboxyl group of the resin can be added to the epoxy group-containing unsaturated compound.

[0173] The acid value of the aforementioned alkali-soluble resin (C1-1) is preferably in the range of 10 to 200, more preferably in the range of 20 to 150, and further preferably in the range of 30 to 150. In addition, the weight-average molecular weight in terms of polystyrene measured by GPC of the alkali-soluble resin (C1-1) is preferably in the range of 2000 to 100,000, more preferably in the range of 4000 to 50,000, and further preferably in the range of 5000 to 30,000.

[0174] In addition, among the aforementioned alkali-soluble resins (C1), an alkali-soluble resin (C1-2) obtained by using an ether dimer and a (meth)acrylate having an alicyclic structure such as adamantyl as a polymerizable monomer is preferably used.

[0175] Examples of the aforementioned ether dimers include dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(isobutyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-amyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(stearyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(lauryl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(1-methoxyethyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(1-ethoxyethyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, dibenzyl 2,2'-[oxybis(methylene)]bis-2-acrylate, diphenyl 2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl 2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-butylcyclohexyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(dicyclopentadienyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(tricyclodecyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, di(isobornyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, didiadamantyl 2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-methyl-2-adamantyl) 2,2'-[oxybis(methylene)]bis-2-acrylate, and the like. Among these, dimethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl 2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl 2,2'-[oxybis(methylene)]bis-2-acrylate, and dibenzyl 2,2'-[oxybis(methylene)]bis-2-acrylate are preferred. These ether dimers may be used alone or in combination of two or more.

[0176] When an ether dimer is used as a raw material of the alkali-soluble resin (C1-2), from the viewpoint of suppressing gelation to obtain an alkali-soluble resin having a low molecular weight and forming a color resist composition excellent in transparency and heat resistance, the proportion of the ether dimer in the polymerizable monomers is preferably in the range of 2 to 60% by mass, more preferably in the range of 5 to 55% by mass, and further preferably in the range of 5 to 50% by weight, based on the total mass of all the polymerizable monomers.

[0177] On the other hand, when a (meth)acrylate having an alicyclic structure such as adamantyl is used as a raw material of the alkali-soluble resin (C1-2), from the viewpoint of improving the pigment dispersibility when a pigment is used in the colorant (B) and obtaining a color resist composition having good printing plate stain adaptability, the use proportion of the (meth)acrylate is preferably in the range of 0.5 to 60% by mass, more preferably in the range of 1 to 55% by mass, and further preferably in the range of 5 to 50% by weight, based on the total mass of all the polymerizable monomers.

[0178] As a method for producing the alkali-soluble resin (C1) used in the present invention, there is no particular limitation, and various conventionally known methods can be adopted, and solution polymerization is particularly preferred. It should be noted that the polymerization temperature and the polymerization concentration (polymerization concentration = [total weight of polymerizable monomers / (total weight of polymerizable monomers + weight of solvent)] × 100) vary depending on the type and ratio of the polymerizable monomers used and the molecular weight of the target alkali-soluble resin. Regarding the polymerization temperature, a range of 40 to 150°C is preferred, and a range of 60 to 130°C is more preferred. In addition, regarding the polymerization concentration, a range of 5 to 50% is preferred, and a range of 10 to 40% is more preferred.

[0179] The solvent used in the solution polymerization method can be a solvent used in a usual radical polymerization reaction. Specifically, for example, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether can be mentioned; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and 3-methoxybutyl acetate; alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, ethylene glycol monomethyl ether, and propylene glycol monomethyl ether; aromatic hydrocarbons such as toluene, xylene, and ethylbenzene; chloroform; dimethyl sulfoxide, etc. These solvents can be used alone or in combination of two or more.

[0180] When polymerizing the aforementioned polymerizable monomers, a polymerization initiator can be used as needed. Examples of the polymerization initiator include organic peroxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-tert-butyl peroxide, lauroyl peroxide, benzoyl peroxide, tert-butyl isopropyl carbonate peroxide, tert-amyl 2-ethylhexanoate peroxide, and tert-butyl 2-ethylhexanoate peroxide; and azo compounds such as 2,2'-azobis(isobutyronitrile), 1,1'-azobis(cyclohexanecarbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and dimethyl 2,2'-azobis(2-methylpropionate). These polymerization initiators can be used alone or in combination of two or more. The amount of these polymerization initiators can be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target alkali-soluble resin (C1), etc., and there is no particular limitation. From the aspect of obtaining an alkali-soluble resin with a weight-average molecular weight of several thousand to several tens of thousands without gelation, it is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass, relative to all polymerizable monomer components.

[0181] In addition, to adjust the molecular weight, a chain transfer agent can be added. Examples of the chain transfer agent include mercaptan-based chain transfer agents such as n-dodecyl mercaptan, mercaptoacetic acid, and methyl mercaptoacetate; and α-methylstyrene dimer, etc. Preferably, n-dodecyl mercaptan and mercaptoacetic acid, which have a high chain transfer effect, can reduce the polymerizable monomers remaining in the reaction system and are easy to obtain. The amount used in the case of using a chain transfer agent can be appropriately set according to the combination of monomers used, reaction conditions, the molecular weight of the target monomer, etc., and there is no particular limitation. From the aspect of obtaining an alkali-soluble resin with a weight-average molecular weight of several thousand to several tens of thousands without gelation, it is preferably in the range of 0.1 to 15% by mass, more preferably in the range of 0.5 to 10% by mass, relative to all monomers.

[0182] The alkali-soluble resin (C2) used in the present invention is obtained by reacting a polymer having no acidic group, which is obtained by polymerizing a (meth)acrylic acid-based polymerizable monomer having a reactive group as an essential component, with a compound having a group reactive with the reactive group and an acid group. Examples of the alkali-soluble resin (C2) include the following alkali-soluble resins.

[0183] · An alkali-soluble resin obtained by adding an acid anhydride such as succinic anhydride, tetrahydrophthalic anhydride, or maleic anhydride to a polymer obtained by using a polymerizable monomer having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate as an essential component.

[0184] · A base-soluble resin obtained by polymerizing a polymerizable monomer having an epoxy group such as glycidyl (meth)acrylate as an essential component and then adding a compound having an amino group and an acid group such as N-methylaminobenzoic acid and N-methylaminophenol.

[0185] · A base-soluble resin obtained by polymerizing a polymerizable monomer having an isocyanate group such as 2-isocyanatoethyl (meth)acrylate as an essential component and then adding a compound having a hydroxyl group and an acid group such as 2-hydroxybutyric acid.

[0186] Regarding the weight-average molecular weight of the aforementioned base-soluble resin (C2), from the viewpoint of forming a good coating film and obtaining a coating film with excellent heat resistance, the weight-average molecular weight in terms of polystyrene measured by GPC is preferably in the range of 1,000 to 200,000, more preferably in the range of 2,000 to 50,000, and further preferably in the range of 2,000 to 30,000. In addition, if necessary, the polymerizable monomers used in the preparation of the aforementioned base-soluble resin (C1) can be used in combination to obtain the base-soluble resin (C2).

[0187] The base-soluble resin (C3) used in the present invention is a copolymer of an epoxy group-containing (meth)acrylate and other polymerizable monomers, and at least a part of the epoxy groups possessed by the copolymer is added with an unsaturated monocarboxylic acid, and then at least a part of the hydroxyl groups generated by the addition reaction of the unsaturated monocarboxylic acid is added with an acid anhydride of a polycarboxylic acid.

[0188] Examples of the aforementioned epoxy group-containing (meth)acrylate include glycidyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, (3,4-epoxycyclohexyl)methyl (meth)acrylate, 4-hydroxybutyl glycidyl ether (meth)acrylate, etc. Among them, glycidyl (meth)acrylate is preferred. These epoxy group-containing (meth)acrylates can be used alone or in combination of two or more.

[0189] In addition, for other polymerizable monomers other than the epoxy group-containing (meth)acrylate as the raw material of the aforementioned base-soluble resin (C3), if monomers having an alicyclic structure such as a norbornene skeleton and a dicyclopentadiene skeleton are used, the heat resistance and mechanical strength of the cured product of the color resist composition of the present invention can be improved, so they are preferred.

[0190] In addition, polymerizable monomers without an alicyclic structure can also be used as other polymerizable monomers other than the epoxy group-containing (meth)acrylate. Examples of such polymerizable monomers include vinyl aromatics such as styrene and α-, o-, m-, p-alkyl, nitro, cyano, amide, and ester derivatives of styrene;

[0191] Dienes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, etc.;

[0192] (Meth)acrylate esters such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, anthryl (meth)acrylate, anthrylnonyl (meth)acrylate, piperonyl (meth)acrylate, salicyl (meth)acrylate, furyl (meth)acrylate, furfuryl (meth)acrylate, tetrahydrofuryl (meth)acrylate, pyranyl (meth)acrylate, benzyl (meth)acrylate, phenethyl (meth)acrylate, tolyl (meth)acrylate, 1,1,1-trifluoroethyl (meth)acrylate, perfluoroethyl (meth)acrylate, perfluoron-propyl (meth)acrylate, perfluoroisopropyl (meth)acrylate, triphenylmethyl (meth)acrylate, cumyl (meth)acrylate, 3-(N,N-dimethylamino)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.;

[0193] (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-diisopropyl(meth)acrylamide, anthrylamide (meth)acrylate, etc.; Vinyl compounds such as (meth)acrylanilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, etc.;

[0194] Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itaconate, etc.; Monomaleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N-(4-hydroxyphenyl)maleimide, etc.; N-(meth)acryloylphthalimide, etc.

[0195] Among the above-mentioned other polymerizable monomers, from the viewpoint of improving the heat resistance and mechanical strength of the cured product when the colored curable composition of the present invention is used as a resist composition, it is preferable to use at least one selected from styrene, benzyl (meth)acrylate, and maleimide monomers. Regarding the use ratio of styrene, benzyl (meth)acrylate, and maleimide monomers, based on the total amount of other polymerizable monomers, it is preferably 1 to 70 mol%, more preferably 3 to 50 mol%.

[0196] It should be noted that the copolymerization reaction of the aforementioned epoxy group-containing (meth)acrylate and the aforementioned other polymerizable monomers can use a known polymerization method such as solution polymerization using a radical polymerization initiator. The solvent used is not particularly limited as long as it is non-reactive to radical polymerization, and commonly used organic solvents can be used.

[0197] As the copolymer of the aforementioned epoxy group-containing (meth)acrylate and the aforementioned other polymerizable monomers, it preferably contains 5 to 90 mol% of repeating units derived from the epoxy group-containing (meth)acrylate and 10 to 95 mol% of repeating units derived from other radical polymerizable monomers, more preferably contains 20 to 80 mol% of the former and 80 to 20 mol% of the latter, and further preferably contains 30 to 70 mol% of the former and 70 to 30 mol% of the latter.

[0198] The aforementioned alkali-soluble resin (C3) is obtained, for example, by reacting the epoxy group portion of the copolymer of the aforementioned epoxy group-containing (meth)acrylate and other polymerizable monomers with an unsaturated monocarboxylic acid (polymerizable component) and an acid anhydride of a polycarboxylic acid (alkali-soluble component).

[0199] Examples of the aforementioned unsaturated monocarboxylic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and (meth)acrylic acid substituted at the α-position with a halogenated alkyl group, an alkoxy group, a halogen atom, a nitro group, or a cyano group. Among these, (meth)acrylic acid is preferable. These unsaturated monocarboxylic acids can be used alone or in combination of two or more. By using this unsaturated monocarboxylic acid, polymerizability can be imparted to the aforementioned alkali-soluble resin (C3).

[0200] The aforementioned unsaturated monocarboxylic acid is usually preferably added to 10 to 100 mol% of the epoxy groups possessed by the aforementioned copolymer, more preferably added to 30 to 100 mol% of the epoxy groups, and further preferably added to 50 to 100 mol% of the epoxy groups.

[0201] Examples of the acid anhydrides of the aforementioned polycarboxylic acids include acid anhydrides of dicarboxylic acids such as maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and chlorendic anhydride; and anhydrides of carboxylic acids having three or more carboxyl groups such as trimellitic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and biphenyltetracarboxylic dianhydride. Among these, tetrahydrophthalic anhydride and succinic anhydride are preferred. These acid anhydrides of polycarboxylic acids may be used alone or in combination of two or more. By using the acid anhydride of the polycarboxylic acid, the aforementioned alkali-soluble resin (C3) can be imparted with alkali solubility.

[0202] The acid anhydride of the aforementioned polycarboxylic acid is usually preferably added in an amount of 10 to 100 mol%, more preferably 20 to 90 mol%, and still more preferably 30 to 80 mol% of the hydroxyl groups formed by adding an unsaturated monocarboxylic acid to the epoxy group of the aforementioned copolymer.

[0203] The weight-average molecular weight (Mw) in terms of polystyrene of the aforementioned alkali-soluble resin (C3) measured by gel permeation chromatography (GPC) is preferably in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. In addition, the dispersity (Mw / Mn) of the aforementioned alkali-soluble resin (C3) is preferably in the range of 2.0 to 5.0.

[0204] The aforementioned epoxy (meth)acrylate resin (C4) is obtained, for example, by adding an epoxy resin to an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group in the ester moiety, and then reacting a polyacid anhydride.

[0205] As the aforementioned epoxy resin, for example, bisphenol A type epoxy resin (as commercially available products, "EPIKOTE 828", "EPIKOTE 1001", "EPIKOTE 1002", "EPIKOTE 1004", etc. manufactured by Japan Epoxy Resins Co., Ltd.), epoxy resin obtained by the reaction of the alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (as commercially available products, "NER-1302" (epoxy equivalent 323, softening point 76°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol F type resin (as commercially available products, "EPIKOTE 807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Japan Epoxy Resins Co., Ltd.), epoxy resin obtained by the reaction of the alcoholic hydroxyl group of bisphenol F type epoxy resin with epichlorohydrin (as commercially available products, "NER-7406" (epoxy equivalent 350, softening point 66°C) manufactured by Nippon Kayaku Co., Ltd.), bisphenol S type epoxy resin, biphenyl glycidyl ether (as commercially available products, "YX-4000" manufactured by Japan Epoxy Resins Co., Ltd.), phenol novolac type epoxy resin (as commercially available products, "EPPN-201" manufactured by Nippon Kayaku Co., Ltd., "EP-152", "EP-154" manufactured by Japan Epoxy Resins Co., Ltd., "DEN-438" manufactured by The Dow Chemical Company), cresol novolac type epoxy resin (as commercially available products, "EOCN-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), triglycidyl isocyanurate (as commercially available products, "TEPIC" manufactured by Nissan Chemical Industries, Ltd.), triphenylmethane type epoxy resin (as commercially available products, "EPPN-501", "EPN-502", "EPPN-503" manufactured by Nippon Kayaku Co., Ltd.), fluorene epoxy resin (as commercially available products, Cardo epoxy resin "ESF-300" manufactured by Nippon Steel Chemical Co., Ltd.), alicyclic epoxy resin ("CELLOXIDE 2021P", "CELLOXIDE EHPE" manufactured by Daicel Chemical Industries, Ltd.), dicyclopentadiene type epoxy resin obtained by glycidylating the phenolic resin obtained by the reaction of dicyclopentadiene and phenol (for example, "XD-1000" manufactured by Nippon Kayaku Co., Ltd., "EXA-7200" manufactured by DIC Corporation, "NC-3000", "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resin having a fluorene skeleton (refer to Japanese Patent Laid-Open No. 4-355450), etc. These epoxy resins can be used alone or in combination of two or more kinds.

[0206] As other examples of the epoxy resin, copolymer-type epoxy resins can be cited. As the copolymer-type epoxy resin, for example, copolymers obtained by copolymerizing monomers having an epoxy group such as glycidyl (meth)acrylate, (meth)acryloylmethylcyclohexene oxide, vinylcyclohexene oxide, etc. with polymerizable monomers not having an epoxy group such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth)acrylate, (meth)acrylic acid, styrene, phenoxyethyl (meth)acrylate, benzyl (meth)acrylate, α-methylstyrene, glycerol mono(meth)acrylate, (meth)acrylate having a polyoxyalkylene chain, etc. can be cited.

[0207] As the aforementioned (meth)acrylate having a polyoxyalkylene chain, for example, polyethylene glycol mono(meth)acrylate such as diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, etc.; alkoxy polyethylene glycol (meth)acrylate such as methoxydiethylene glycol mono(meth)acrylate, methoxytriethylene glycol mono(meth)acrylate, methoxytetraethylene glycol mono(meth)acrylate, etc. can be cited.

[0208] The molecular weight of the aforementioned copolymer-type epoxy resin is preferably in the range of 1000 to 200000. In addition, the amount of the monomer having an epoxy group used as a raw material of the copolymer-type epoxy resin is preferably in the range of 10 to 70% by mass, more preferably in the range of 20 to 50% by mass, relative to the monomer not having an epoxy group.

[0209] As commercially available products of the aforementioned copolymer-type epoxy resin, for example, "CP-15", "CP-30", "CP-50", "CP-20SA", "CP-510SA", "CP-50S", "CP-50M", "CP-20MA", etc. manufactured by NOF Corporation can be cited.

[0210] Regarding the molecular weight of the aforementioned epoxy resin, from the aspect of good film formation and prevention of gelation during the addition reaction of α,β-unsaturated monocarboxylic acid, as the polystyrene-converted weight-average molecular weight measured by GPC, it is preferably in the range of 200 to 200000, more preferably in the range of 300 to 100000.

[0211] Examples of α,β-unsaturated monocarboxylic acids include itaconic acid, crotonic acid, cinnamic acid, acrylic acid, and methacrylic acid. Acrylic acid and methacrylic acid are preferred, and acrylic acid is more preferred due to its good reactivity. Examples of α,β-unsaturated monocarboxylic acid esters having a carboxyl group in the ester portion include 2-succinyloxyethyl acrylate, 2-maleyloxyethyl acrylate, 2-phthaloyloxyethyl acrylate, 2-hexahydrophthaloyloxyethyl acrylate, 2-succinyloxyethyl methacrylate, 2-maleyloxyethyl methacrylate, 2-phthaloyloxyethyl methacrylate, 2-hexahydrophthaloyloxyethyl methacrylate, and 2-succinyloxyethyl crotonic acid. Examples include 2-maleyloxyethyl acrylate and 2-phthaloyloxyethyl acrylate, and 2-maleyloxyethyl acrylate is more preferred. These α,β-unsaturated monocarboxylic acids and α,β-unsaturated monocarboxylic acid esters may be used alone or in combination of two or more.

[0212] The addition reaction of the α,β-unsaturated monocarboxylic acid or its ester with the epoxy resin can be carried out by a known method, for example, a method of reacting at a temperature of 50 to 150° C. in the presence of an esterification catalyst. As the esterification catalyst, tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, benzyldiethylamine, etc.; quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, dodecyltrimethylammonium chloride, etc. can be used.

[0213] The amount of the α,β-unsaturated monocarboxylic acid or its ester used is preferably in the range of 0.5 to 1.2 equivalents, more preferably in the range of 0.7 to 1.1 equivalents, relative to 1 equivalent of epoxy groups of the epoxy resin as a raw material.

[0214] As the polyanhydride further added to the epoxy resin to which α,β-unsaturated carboxylic acid or its ester is added, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, biphenyltetracarboxylic anhydride, etc. can be listed. Among these, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, trimellitic anhydride, biphenyltetracarboxylic anhydride, etc. are preferred, and tetrahydrophthalic anhydride and biphenyltetracarboxylic anhydride are more preferred. These polyanhydrides can be used alone or in combination of two or more.

[0215] Regarding the addition reaction of polyanhydrides, known methods can be used, and the reaction can be continuously carried out under the same conditions as the addition reaction with α,β-unsaturated carboxylic acids or their esters. Regarding the amount of polyanhydride used, from the aspect of enabling good alkali developability and film formation, an amount such that the acid value of the resulting epoxy(meth)acrylate resin falls within the range of 10 to 150 is preferred, and an amount within the range of 20 to 140 is more preferred.

[0216] In addition, as the epoxy(meth)acrylate resin having a carboxyl group, examples include the naphthalene-containing resin described in Japanese Patent Laid-Open No. 6-49174; the fluorene-containing resins described in Japanese Patent Laid-Open Nos. 2003-89716, 2003-165830, 2005-325331, and 2001-354735; the resins described in Japanese Patent Laid-Open Nos. 2005-126674, 2005-55814, 2004-295084, etc. In addition, as commercially available products, examples include "ACA-200M" manufactured by Daicel Chemical Industries, Ltd.

[0217] The aforementioned Cardo resin type resin (C5) has a carboxyl group and a polymerizable unsaturated group. Generally, Cardo type resins are high molecular materials having various properties such as high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, and high gas permeability, and are used as binder resins when forming each pixel and black matrix of a color filter, and can be preferably used as a binder resin when forming a black matrix in particular.

[0218] The aforementioned Cardo type resin refers to a general term for resins having a structure in which a cyclic group is directly bonded to the polymer main chain, and it has been found that by having a bulky substituent in the main chain, (1) restricted rotation of the polymer main chain, (2) conformational restriction of the main chain and side chains, (3) hindrance to intermolecular packing, (4) increase in aromaticity due to the introduction of aromatic substituents in the side chains, etc. are exhibited. Furthermore, as physical property characteristics, not only high heat resistance, solvent solubility, high transparency, high refractive index, low birefringence, etc. are exhibited, but also higher gas permeability is exhibited.

[0219] As the aforementioned Cardo type resin (C5), for example, the resin represented by the following general formula (C5-1) is preferably exemplified.

[0220]

[0221] In the formula, X is a group represented by the following chemical formula (C5-2), Y is a residue obtained by removing the carboxylic anhydride group (-CO-O-CO-) from a dicarboxylic anhydride, and Z is a residue obtained by removing two carboxylic anhydride groups from a tetracarboxylic dianhydride. n is an integer of 0 to 20.)

[0222]

[0223] Specific examples of the dicarboxylic anhydride (dicarboxylic anhydride before removing the carboxylic anhydride group) used for derivatizing the aforementioned Y include, for example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylene tetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, glutaric anhydride, and the like.

[0224] In addition, specific examples of the tetracarboxylic dianhydride (tetracarboxylic dianhydride before removing two carboxylic anhydride groups) used for derivatizing the aforementioned Z include, for example, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, biphenyl ether tetracarboxylic dianhydride, and other tetracarboxylic dianhydrides.

[0225] The polystyrene-reduced weight average molecular weight (Mw) of the aforementioned Cardo resin measured by gel permeation chromatography (GPC) is preferably 1000 to 1000000, more preferably 3000 to 50000, and most preferably 5000 to 15000.

[0226] The alkali-soluble resin (C) may be used alone one of the above alkali-soluble resins (C1) to (C5), or two or more thereof may be used in combination. In addition, the alkali-soluble resin (C) is preferably used in combination with a pigment dispersant described later, so that a high-concentration color pixel having excellent adhesion to the substrate can be formed without leaving undissolved substances in the non-pixel portion on the substrate. Specifically, it is preferable to use a part of the alkali-soluble resin (C) together with the pigment dispersant described later in the dispersion treatment step. In this case, the alkali-soluble resin (C) is preferably used in the range of 5 to 200% by mass, more preferably in the range of 10 to 100% by mass, based on the colorant (E) described later.

[0227] In addition, as the alkali-soluble resin (C) used in the present invention, an alkali-soluble resin other than the above-mentioned alkali-soluble resins (C1) to (C5) can be used. Examples of such resins include alkali-soluble resins obtained by using a polymerizable monomer having a phenolic hydroxyl group as an acidic group as an essential component, alkali-soluble resins obtained by using a polymerizable monomer having a sulfonic acid group as an acidic group as an essential component, and the like. Here, examples of the polymerizable monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, and the like. In addition, compounds in which one or more hydrogen atoms other than the phenolic hydroxyl group and vinyl group bonded to the aromatic ring are substituted with an alkyl group, an alkoxy group, a halogen atom, a nitro group, a cyano group, an amide group, etc. can also be cited. Examples of the polymerizable monomer having a sulfonic acid group as an acidic group include vinylsulfonic acid, styrenesulfonic acid, (meth)allylsulfonic acid, 2-hydroxy-3-(meth)allyloxypropanesulfonic acid, 2-sulfoethyl (meth)acrylate, or salts thereof.

[0228] In the resist composition (1) of the present invention, the content ratio of the alkali-soluble resin (C) in the composition is preferably in the range of 0.1 to 80% by mass, more preferably in the range of 1 to 60% by mass, in all solid components, from the viewpoint of good appearance of the coating film and good adhesion to the substrate.

[0229] In addition, as the content ratio of the fluoropolymer (B) in the resist composition (1), 0.01 to 10 parts by mass relative to 100 parts by mass of the alkali-soluble resin (C) is preferable from the viewpoint of being able to exhibit the surface activity of the fluoropolymer (B) without hindering the performance of the resist resin, and more preferably 0.05 to 5 parts by mass.

[0230] Examples of the polymerizable compound (D) used in the present invention include a polymerizable compound (D1) having one or more ethylenically unsaturated bonds.

[0231] Examples of the polymerizable compound (D1) having one ethylenically unsaturated bond include polymerizable monomers used in the preparation of the alkali-soluble resin (C). Among them, (meth)acrylates are preferred.

[0232] As the polymerizable compound (D2) having two ethylenically unsaturated bonds, for example, 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate, etc. can be cited.

[0233] As the polymerizable compound (D3) having three ethylenically unsaturated bonds, for example, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, product of pentaerythritol tri(meth)acrylate and acid anhydride, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, product of caprolactone-modified pentaerythritol tri(meth)acrylate and acid anhydride, product of caprolactone-modified dipentaerythritol penta(meth)acrylate and acid anhydride, etc. can be cited.

[0234] As the polymerizable compound (D4) having four ethylenically unsaturated bonds, for example, pentaerythritol tetra(meth)acrylate, tripentaerythritol tetra(meth)acrylate, caprolactone-modified tripentaerythritol tetra(meth)acrylate, etc. can be cited.

[0235] As the polymerizable compound (D5) having 5 or more ethylenically unsaturated bonds, for example, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tripentaerythritol octa(meth)acrylate, product of dipentaerythritol penta(meth)acrylate and acid anhydride, product of tripentaerythritol hepta(meth)acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol penta(meth)acrylate, caprolactone-modified tripentaerythritol hexa(meth)acrylate, caprolactone-modified tripentaerythritol hepta(meth)acrylate, caprolactone-modified tripentaerythritol octa(meth)acrylate, product of caprolactone-modified tripentaerythritol hepta(meth)acrylate and acid anhydride, etc. can be cited.

[0236] In addition, as the polymerizable compound (D) used in the present invention, a photocurable resin can also be exemplified.

[0237] Examples of the aforementioned photocurable resin include urethane (meth)acrylate resin, unsaturated polyester resin, epoxy (meth)acrylate resin, resin containing a maleimide group, and Cardo-type resin.

[0238] Examples of the aforementioned urethane (meth)acrylate resin include resins having a urethane bond and a (meth)acryloyl group obtained by reacting an aliphatic polyisocyanate compound or an aromatic polyisocyanate compound with a hydroxy group-containing (meth)acrylate compound.

[0239] Examples of the aforementioned aliphatic polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, decamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, dodecamethylene diisocyanate, 2-methylpentamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated toluene diisocyanate, hydrogenated benzene diisocyanate, hydrogenated tetramethylbenzene diisocyanate, cyclohexyl diisocyanate, etc. In addition, examples of the aromatic polyisocyanate compound include toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzene diisocyanate, 1,5-naphthalene diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, etc.

[0240] Examples of the aforementioned aromatic polyisocyanate compound include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, naphthalene diisocyanate, etc.

[0241] As the aforementioned hydroxy group-containing (meth)acrylate compound, for example, monomethacrylates or dimethacrylates of dihydric alcohols such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 1,5-pentanediol monomethacrylate, 1,6-hexanediol monomethacrylate, neopentyl glycol monomethacrylate, hydroxypivalic acid neopentyl glycol monomethacrylate; monomethacrylates or dimethacrylates of trihydric alcohols such as trimethylolpropane dimethacrylate, ethoxylated trimethylolpropane (meth)acrylate, propoxylated trimethylolpropane dimethacrylate, glycerol dimethacrylate, bis(2-(meth)acryloyloxyethyl)hydroxyethyl isocyanurate, or hydroxy group-containing monomethacrylates and dimethacrylates obtained by modifying a part of their alcoholic hydroxyl groups with ε-caprolactone; compounds having a monofunctional hydroxyl group and a trifunctional or higher (meth)acryloyl group such as pentaerythritol tri(meth)acrylate, di(trimethylolpropane) tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, or polyfunctional (meth)acrylates containing hydroxyl groups obtained by further modifying the compound with ε-caprolactone; (meth)acrylate compounds having an oxyalkylene chain such as dipropylene glycol monomethacrylate, diethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polyethylene glycol monomethacrylate; (meth)acrylate compounds having a block-structured oxyalkylene chain such as polyethylene glycol-polypropylene glycol monomethacrylate, polyoxybutylene-polyoxypropylene monomethacrylate; (meth)acrylate compounds having a random-structured oxyalkylene chain such as poly(ethylene glycol-tetramethylene glycol) monomethacrylate, poly(propylene glycol-tetramethylene glycol) monomethacrylate, etc.

[0242] The reaction between the above-mentioned aliphatic polyisocyanate compound or aromatic polyisocyanate compound and the hydroxy group-containing (meth)acrylate compound can be carried out, for example, according to a conventional method in the presence of a urethanization catalyst. Specific examples of the urethanization catalyst that can be used here include amines such as pyridine, pyrrole, triethylamine, diethylamine, dibutylamine; phosphines such as triphenylphosphine, triethylphosphine; organotin compounds such as dibutyltin dilaurate, octyltin trilaurate, octyltin diacetate, dibutyltin diacetate, tin octoate; and organometallic compounds such as zinc octoate.

[0243] Among these urethane (meth)acrylate resins, resins obtained by reacting an aliphatic polyisocyanate compound with a hydroxyl group-containing (meth)acrylate compound are particularly preferred because they have excellent transparency of a cured film, good sensitivity to active energy rays, and excellent curability.

[0244] Examples of the unsaturated polyester resin include curable resins obtained by polycondensation of an α,β-unsaturated dibasic acid or an anhydride thereof, a dibasic acid other than the dibasic acid or anhydride thereof, and a glycol. Examples of the α,β-unsaturated dibasic acid or anhydride thereof include maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, chloromaleic acid, and esters thereof.

[0245] Examples of dibasic acids and anhydrides thereof other than the aforementioned α,β-unsaturated dibasic acids or their anhydrides include aromatic saturated dibasic acids, aliphatic dibasic acids, alicyclic saturated dibasic acids, and their anhydrides. Examples of aromatic saturated dibasic acids and their anhydrides include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, halogenated phthalic anhydride, and their esters. Examples of aliphatic dibasic acids and alicyclic saturated dibasic acids and their anhydrides include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and their esters. Examples of the glycols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methylpropane-1,3-diol, neopentyl glycol, triethylene glycol, tetraethylene glycol, 1,5-pentanediol, 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, ethylene carbonate, 2,2-di-(4-hydroxypropoxydiphenyl)propane, and oxides such as ethylene oxide and propylene oxide can also be used in the same manner.

[0246] Examples of the epoxy (meth)acrylate resin include epoxy (meth)acrylate resins obtained by reacting (meth)acrylic acid with epoxy groups of epoxy resins such as bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, and cresol novolac epoxy resin.

[0247] As the aforementioned resin containing a maleimide group, for example, a bifunctional maleimide carbamate compound obtained by carbamoylation of N-hydroxyethyl maleimide and isophorone diisocyanate, a bifunctional maleimide ester compound obtained by esterification of maleimide acetic acid and polytetramethylene glycol, a tetrafunctional maleimide ester compound obtained by esterification of maleimide hexanoic acid and a tetraethylene oxide adduct of pentaerythritol, a polyfunctional maleimide ester compound obtained by esterification of maleimide acetic acid and a polyol compound, etc. can be cited. These active energy ray-curable resins can be used alone or in combination of two or more.

[0248] The aforementioned Cardo resin is generally a general term for resins having a structure in which a cyclic group is directly bonded to a polymer chain. For example, resins having the following structure can be cited.

[0249]

[0250] (In the formula, R represents a hydrogen atom or an alkyl group. R' represents a hydrogen atom or a methyl group. n is an integer of 0 to 20.)

[0251] Among the polymerizable compounds (D) used in the present invention, from the aspect of excellent hardness of the cured film, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol tetra(meth)acrylate and other polyfunctional (meth)acrylates having 3 or more functional groups are particularly preferred. These polymerizable compounds (D) can be used alone or in combination of two or more.

[0252] The total content of the polymerizable compound (D) is preferably 10 to 50% by mass, more preferably 15 to 50% by mass, based on the solid content of the colored curable resin composition. When the total content of the polymerizable compound (D) is within the above range, the sensitivity, strength, smoothness and reliability of the cured film tend to be improved.

[0253] Among the polymerizable compounds (D), the content of the polymerizable compound (D5) is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, particularly preferably 5 to 35% by mass, based on the solid content of the colored curable resin composition. When the content of the polymerizable compound (D5) is within the above range, the sensitivity, strength, smoothness and reliability become good.

[0254] In addition, among the polymerizable compounds (D), the content of the polymerizable compound (D5) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, relative to the total amount of the polymerizable compounds (D1), (D2), (D3), (D4), and (D5). When the content of the polymerizable compound (D5) is within the above range, the sensitivity, the strength of the cured film, the smoothness, and the reliability tend to be good.

[0255] The colorant (E) used in the present invention only needs to be able to color, and for example, pigments (e1) and dyes (e2) can be exemplified.

[0256] As the aforementioned pigment (e1), either an organic pigment or an inorganic pigment can be used. As the aforementioned organic pigment, for example, pigments of various hues such as red pigments, green pigments, blue pigments, yellow pigments, purple pigments, orange pigments, brown pigments, and black pigments can be used. In addition, as the chemical structure of the organic pigment, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perylene-based, etc. can be cited. It should be noted that "C.I." below refers to the Colour Index.

[0257] As the aforementioned red pigments, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc. Among these, C.I. Pigment Red 48:1, 122, 168, 177, 202, 206, 207, 209, 224, 242 or 254 are preferred, and C.I. Pigment Red 177, 209, 224 or 254 are more preferred.

[0258] As the aforementioned green pigments, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, etc. Among these, C.I. Pigment Green 7, 36, 58 or 59 are preferred.

[0259] As the aforementioned blue pigments, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. can be cited. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. Pigment Blue 15:6 is more preferred.

[0260] As the aforementioned yellow pigments, for example, C.I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc. can be cited. Among these, C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 is preferred, and C.I. Pigment Yellow 83, 129, 138, 139, 150, 180 or 185 is more preferred.

[0261] As the aforementioned purple pigment, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. can be cited. Among these, C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

[0262] As the aforementioned orange pigment, for example, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79, etc. can be cited. Among these, C.I. Pigment Orange 38 or 71 is preferred.

[0263] Since each pixel of the three primary colors of the color filter used in the liquid crystal display device and the organic EL display device is red (R), green (G), and blue (B), the aforementioned red pigment, green pigment, and blue pigment can be used as the main components, and organic pigments of colors such as yellow, purple, and orange can be used for hue adjustment for the purpose of improving color reproducibility.

[0264] For the aforementioned black pigment, the coloring curable resin composition of the present invention can be used as a colorant when used for forming a black matrix (BM). As the black pigment, for example, carbon black, lamp black, acetylene black, bone black, thermal cracking carbon black, channel carbon black, furnace black, graphite, iron black, titanium black, etc. can be cited. In addition, it can be a combination of two or more organic pigments that become black by color mixing. Among these, from the viewpoints of light shielding rate and image characteristics, carbon black and titanium black are preferred.

[0265] As commercially available products of the aforementioned carbon black, for example, MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, #5, #10, #20, #25, #30, #32, #33, #40, #44, #45, #47, #50, #52, #55, #650, #750, #850, #950, #960, #970, #980, #990, #1000, #2200, #2300, #2350, #2400, #2600, #3050, #3150, #3250, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31B manufactured by Mitsubishi Chemical Corporation, Printex3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, PrintexV, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, ColorBlackFW1, ColorBlackFW2, ColorBlackFW2V, ColorBlackFW18, ColorBlackFW18, ColorBlackFW200, ColorBlackS160, ColorBlackS170 manufactured by Evonik Degussa Japan Co., Ltd., Cabot Japan K.K.Monarch 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL 99, REGAL 99R, REGAL 415, REGAL 415R, REGAL 250, REGAL 250R, REGAL 330, REGAL 400R, REGAL 55R0, REGAL 660R, BLACK PEARLS 480, PEARLS 130, VULCAN XC72R, ELFTEX-8, etc. can be listed, and RAVEN 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 30, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850, RAVEN 890H, RAVEN 1000, RAVEN 1020, RAVEN 1040, RAVEN 1060U, RAVEN 1080U, RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000, etc. manufactured by Columbian Carbon Co., Ltd. can also be listed.

[0266] Among the above carbon blacks, as the carbon black required for the black matrix with a color filter having high optical density and high surface resistivity, carbon black coated with resin is preferably used. It should be noted that the carbon black coated with resin can be obtained, for example, by treating known carbon black by the methods described in Japanese Patent Laid-Open No. 9-26571, Japanese Patent Laid-Open No. 9-71733, Japanese Patent Laid-Open No. 9-95625, Japanese Patent Laid-Open No. 9-238863, or Japanese Patent Laid-Open No. 11-60989.

[0267] In addition, as the method for producing the aforementioned titanium black, examples thereof include: the method of heating a mixture of titanium dioxide and metallic titanium in a reducing atmosphere for reduction as described in Japanese Patent Laid-Open No. Sho 49-5432; the method of reducing ultrafine titanium dioxide obtained by high-temperature hydrolysis of titanium tetrachloride in a reducing atmosphere containing hydrogen as described in Japanese Patent Laid-Open No. Sho 57-205322; the method of performing high-temperature reduction of titanium dioxide or titanium hydroxide in the presence of ammonia as described in Japanese Patent Laid-Open Nos. Sho 60-65069 and Sho 61-201610; the method of causing a vanadium compound to adhere to titanium dioxide or titanium hydroxide and performing high-temperature reduction in the presence of ammonia as described in Japanese Patent Laid-Open No. Sho 61-201610. As commercially available products of titanium black, for example, titanium black 10S, 12S, 13R, 13M, 13M-C, etc. manufactured by Mitsubishi Materials Corporation can be cited.

[0268] In addition, pigments obtained by mixing two or more organic pigments and becoming black by color mixing can also be used as black pigments. As a combination of mixing two or more organic pigments and becoming black by color mixing, for example, a black pigment obtained by mixing pigments of three colors, red, green, and blue, can be cited. As colorants that can be mixed and used for preparing black pigments, examples thereof include Victoria Pure Blue (C.I. 42595), Auramine O (C.I. 41000), Cathilon Brilliant Flavine, Basic 13, Rhodamine 6GCP (C.I. 45160), Rhodamine B (C.I. 45170), Safranin OK 70:100 (C.I. 50240), Ponceau X (C.I. 42080), No. 120 / Lionol Yellow (C.I. 21090), Lionol Yellow GRO (C.I. 21090), SYMULER Fast Yellow 8GF (C.I. 21105), Benzidine Yellow 4T-564D (C.I. 21095), SYMULER Fast red 4015 (C.I. 12355), LIONOGEN Red 7B4401 (C.I. 15850), FASTOGEN Blue TGR-L (C.I. 74160), Lionol Blue SM (C.I. 26150), Lionol Blue ES (C.I. Pigment Blue 15:6), LIONOGEN Red GD (C.I. Pigment Red 168), Lionol Green 2YS (C.I. Pigment Green 36), etc.

[0269] As other colorants that can be used in combination for preparing black pigments, for example, C.I. Pigment Yellow 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. Pigment Orange 36, 43, 51, 55, 59, 61, C.I. Pigment Red 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Pigment Blue 15, 15:1, 15:4, 22, 60, 64, C.I. Pigment Green 7, C.I. Pigment Brown 23, 25, 26, etc. can be cited.

[0270] In addition, as the aforementioned inorganic pigments, for example, barium sulfate, lead sulfate, titanium oxide, chrome yellow, bengala, chromium oxide, etc. can be cited.

[0271] In order to improve the brightness of color liquid crystal display devices and organic EL display devices, the average particle diameter of the aforementioned organic pigments is preferably 1 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. It is preferable to perform a dispersion treatment on the organic pigment to obtain such an average particle diameter and then use it. In addition, the average primary particle diameter of the aforementioned organic pigments is preferably 100 nm or less, more preferably 50 nm or less, further preferably 40 nm or less, and particularly preferably in the range of 10 to 30 nm. It should be noted that the average particle diameter of the organic pigment is measured using a dynamic light scattering type particle size distribution meter, and it can be measured using, for example, the Nanotrac particle size distribution measuring devices "UPA-EX150", "UPA-EX250", etc. manufactured by Nikkiso Co., Ltd.

[0272] It should be noted that when carbon black is used among black pigments, the average primary particle diameter is preferably in the range of 0.01 to 0.08 μm, and more preferably in the range of 0.02 to 0.05 μm from the aspect of good developability. In addition, the dibutyl phthalate (hereinafter, simply referred to as "DBP".) absorption amount of the carbon black used is preferably in the range of 40 to 100 cm 3 / 100 g, and more preferably in the range of 50 to 80 cm 3 / 100 g from the aspect of good dispersibility and developability. Furthermore, the specific surface area of the carbon black used obtained by the BET method is preferably in the range of 50 to 120 m 2 / g, and more preferably in the range of 60 to 95 m 2 / g from the aspect of good dispersion stability.

[0273] In addition, the particle shape of carbon black is different from that of organic pigments, etc., and it exists in a state of a structure formed by welding so-called primary particles. In addition, fine pores may be formed on the particle surface by post-treatment. Therefore, in order to represent the particle shape of carbon black, in addition to the average particle diameter of the primary particles obtained by the same method as the aforementioned organic pigments, it is usually also preferable to measure the DBP absorption amount (JIS K6221) and the specific surface area obtained by the BET method (JIS K6217) as indicators of the structure and the amount of pores.

[0274] The aforementioned organic pigments can be subjected to surface treatments such as rosin treatment, surface treatment using pigment derivatives into which acidic groups or basic groups are introduced, graft treatment of the pigment surface with a polymer compound, etc., micronization treatment based on the sulfuric acid micronization method, etc., or cleaning treatment using an organic solvent, water, etc. for removing impurities, removal treatment of ionic impurities based on the ion exchange method, etc., as needed.

[0275] In addition, the aforementioned organic pigments preferably have a uniform particle diameter. An organic pigment with a uniform particle diameter can be obtained, for example, by containing a pigment dispersant and performing a dispersion treatment.

[0276] Examples of the aforementioned pigment dispersants include surfactants such as cationic, anionic, nonionic, amphoteric, polyester-based, polyamine-based, and acrylic types. These pigment dispersants can be used alone or in combination of two or more.

[0277] When using the aforementioned pigment dispersant, regarding its dosage, it is preferably 1 part by mass or less relative to 1 part by mass of the pigment (e1), and more preferably 0.05 part by mass or more and 0.5 part by mass or less. When the dosage of the pigment dispersant is within this range, there is a tendency to obtain a pigment dispersion liquid with a uniform dispersion state, so it is preferable.

[0278] Examples of the dye (e2) used in the present invention include salts represented by the following (e-2-1), xanthene dyes, etc.

[0279]

[0280] Examples of the aforementioned xanthene dyes include C.I. Acid Red 51, 52, 87, 92, 289, 388, C.I. Acid Violet 9, 30, C.I. Basic Red 8, C.I. Mordant Red 27, rose bengal B, sulfonyl rhodamine G, rhodamine 6G, xanthene dyes described in Japanese Patent Laid-Open No. 2010-032999, Japanese Patent Laid-Open No. 2011-138094, etc.

[0281] Among the above-mentioned xanthene dyes, a dye mainly composed of the compound represented by the following formula (e-2-2) is preferred.

[0282]

[0283] In formula (e-2-2), R 1 ~R 4 are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms (wherein a part or all of the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by a halogen atom. Hereinafter, it is referred to as R 8 ), or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms [wherein the hydrogen atoms contained in the aromatic hydrocarbon group may be substituted by a halogen atom, -R 8 , -OH, -OR 8 , -SO3-, -SO3H, -SO3 - M + 〔wherein M + is + N(R 11 )4 (R 11 are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms), Na + or K + 〕, -CO2H, -CO2R 8 , -SO3R 8 or -SO2NR 9 R 10 (R 9 and R 10 each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atoms contained in the saturated hydrocarbon group may be substituted by -OH or a halogen atom, and -CH2- contained in the saturated aliphatic hydrocarbon group may be substituted by -O-, -CO-, -NH- or -NR 8 -, and R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom). ],

[0284] R 5 is -OH, -SO3-, -SO3H, -SO3 - M + , -CO2H, -CO2 - M + , -CO2R 8 , -SO3R 8 or -SO2NR 9 R 10 , and m represents an integer of 0 to 5 (wherein when m is an integer of 2 or more, a plurality of R 5They may be the same or different.)

[0285] R 6 and R 7 each independently represents an alkyl group having 1 to 6 carbon atoms.

[0286] As R in the aforementioned formula (e-2-2) 1 ~R 4 The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, examples thereof include phenyl, toluyl, xylyl, mesityl, propylphenyl, butylphenyl and the like.

[0287] For the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in the aforementioned formula (e-2-2), it preferably has at least one selected from the group consisting of -SO3-, -SO3H, -SO3 - M + and -SO2NR 9 R 10 as a substituent, more preferably having at least one selected from the group consisting of -SO3 - M + and -SO2NR 9 R 10 As -SO3 - M + in this case, -SO3 -+ N(R 11 )4 is preferred. When R 1 ~R 4 are these groups, it can be expected that the colored curable resin composition can obtain a cured film with less foreign matter generation and excellent heat resistance.

[0288] As the aforementioned R 8 ~R 11 The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, examples thereof include alkyl groups having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, dodecyl, hexadecyl, icosyl; cycloalkyl groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and the like.

[0289] As R in the aforementioned formula (e-2-2) 6 and R 7 The alkyl group having 1 to 6 carbon atoms, examples thereof include groups having 1 to 6 carbon atoms among the alkyl groups listed above.

[0290] As the aforementioned R 11The aralkyl group having 7 to 10 carbon atoms, such as benzyl, phenylethyl, phenylbutyl, etc. can be cited.

[0291] The aforementioned M + is, for example, + N(R 11 )4, Na + or K + , preferably + N(R 11 )4. As the aforementioned + N(R 11 )4, for example, at least 2 of the 4 Rs 11 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total number of carbon atoms of the 4 Rs 11 is preferably 20 to 80, more preferably 20 to 60. When using a compound in which R 11 is these groups, it is easy to obtain a cured film with few foreign matters from the colored curable resin composition of the present invention.

[0292] In addition, among the aforementioned xanthene dyes, the compound represented by the following formula (e-2-3) is more preferably used.

[0293]

[0294] In the formula (e-2-3), R 21 to R 24 are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms [hereinafter referred to as R 26 , or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms [wherein, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -SO3-, -SO3 - M a+ [M a+ is + N(R 27 )4 (R 27 are each independently a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or benzyl), Na + or K + , -SO3H, -SO3R 26 or -SO2NHR 26 substituted.],

[0295] X is a halogen atom, a1 is an integer of 0 or 1,

[0296] R 25 is -SO3-, -SO3 - M a+ , -SO3H or SO2NHR 26 , m1 is an integer of 0 to 5 (wherein, when m1 is an integer of 2 or more, a plurality of Rs 25may be the same or different).

[0297] As R in the aforementioned formula (e-2-3) 21 ~R 24 a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, for example, groups similar to those listed as the aromatic hydrocarbon group in R 1 ~R 4 can be cited. Among them, preferably, R 21 and R 23 are hydrogen atoms, and R 22 and R 24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are optionally replaced by -SO 3 -, -SO 3- M + -, -SO3H, -SO3R 26 or -SO2NHR 26 substituted. More preferably, R 21 and R 23 are hydrogen atoms, and R 22 and R 24 are a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atoms contained in the aromatic hydrocarbon group are optionally replaced by -SO3 - M + or -SO2NHR 26 substituted. When using a compound in which R 21 ~R 24 is these groups, a cured film excellent in heat resistance can be easily obtained from the colored curable resin composition of the present invention.

[0298] As the aforementioned R 26 and R 27 a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, for example, groups similar to those listed as the saturated hydrocarbon group in the aforementioned R 8 ~R 11 can be cited and the like.

[0299] Preferably, -R 21 ~R 24 in the aforementioned R 26 are each independently a hydrogen atom, a methyl group or an ethyl group.

[0300] As the aforementioned R 26 preferably a branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, and still more preferably 2-ethylhexyl. When using a compound in which R 26 is these groups, a cured film with fewer foreign matters can be easily obtained from the colored curable resin composition of the present invention.

[0301] The aforementioned Ma+ is + N(R 27 )4, Na + or K + , preferably + N(R 27 )4. As the aforementioned + N(R 27 )4, preferably at least 2 of the 4 Rs 27 are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. In addition, the total number of carbon atoms of the 4 Rs 27 is preferably 20 to 80, more preferably 20 to 60. When using a compound in which R 27 is these groups, a cured film with few foreign matters can be easily obtained from the coloring curable resin composition of the present invention.

[0302] As the preferably usable xanthene dyes in the present invention, for example, dyes mainly composed of the compounds represented by the formulas (e-2-4) to (e-2-21) can be cited. It should be noted that in the following formulas, Ra represents 2-ethylhexyl.

[0303]

[0304]

[0305] Among the compounds as the main components of the xanthene dyes, the sulfonamide of C.I. Acid Red 289 or the quaternary ammonium salt of C.I. Acid Red 289 is preferred. As such compounds, for example, the compounds represented by the formulas (e-2-4) to (e-2-11), (e-2-16) and (e-2-17) can be cited.

[0306] The compound represented by the aforementioned formula (e-2-1) can be produced, for example, by chlorinating a pigment or pigment intermediate having -SO3H by a conventional method and reacting the resulting pigment or pigment intermediate having -SO2Cl with an amine represented by R 8 -NH2. In addition, it can also be produced by chlorinating a pigment produced by the method described in the upper right column to the lower left column on page 3 of Japanese Patent Laid-Open No. 3-78702 in the same manner as above and then reacting it with an amine.

[0307] The dyes (e2) used in the present invention may also be other dyes such as triarylmethane dyes, coumarin dyes, trimethine dyes, anthraquinone dyes, etc., other than the salts and xanthene dyes represented by the aforementioned formula (e-2-1). Examples of the aforementioned other dyes include oil-soluble dyes, acid dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, etc. Specifically, for example, compounds classified as dyes in the Color Index (published by The Society of Dyers and Colourists), various dyes described in the Dyeing Note (Color Dyeing Society), etc.

[0308] Examples of the aforementioned other dyes include C.I. Solvent Yellow 4 (hereinafter, the description of C.I. Solvent Yellow will be omitted, and only the number will be described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99; C.I. Solvent Red 45, 49, 125, 130; C.I. Solvent Orange 2, 7, 11, 15, 26, 56; etc. C.I. solvent dyes,

[0309] C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

[0310] C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;

[0311] C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

[0312] C.I. Acid Violet 6B, 7, 9, 17, 19; etc. C.I. Acid Dyes,

[0313] C.I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;

[0314] C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

[0315] C.I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; etc. C.I. Direct Dyes,

[0316] C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0317] C.I. Solvent Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;

[0318] C.I. Solvent Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0319] C.I. Solvent Violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; etc. C.I. solvent dyes, etc.

[0320] In the present invention, as the colorant (E), by using the pigment (e1), a cured film having excellent light resistance, weather resistance and fastness can be finally obtained. In addition, by using the pigment (e1) and the dye (e2) in combination, a cured film having excellent light resistance, weather resistance and fastness and being easy to optimize the transmission spectrum can be easily obtained.

[0321] When the pigment (e1) and the dye (e2) are used in combination as the colorant (E), the content ratio of the dye (e2) is preferably 5 to 60% by mass based on the total of the fluoropolymer (B), the alkali-soluble resin (C), the photocurable compound (D) and the colorant (E). From the viewpoint of sufficient color density when the cured film obtained using the resist composition of the present invention is used as a color filter and being able to form a pattern having sufficient mechanical strength, it is more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass.

[0322] In addition, when the pigment (e1) and the dye (e2) are used in combination as the colorant (E), the content ratio of the pigment (e1) is preferably 3 to 70% by mass, more preferably 3 to 50% by mass, and further preferably 50 to 97% by mass based on the total of the foregoing (B), (C), (D) and (E).

[0323] The content ratio of the pigment (e1) to the dye (e2) is preferably 1:99 to 99:1, preferably 99:1 to 40:60, and more preferably 95:5 to 60:40 in terms of mass ratio [(e1):(e2)]. By containing the pigment (e1) and the dye (e2) in such a ratio, a cured film of the colored curable resin composition is easy to obtain a cured film with an easily optimized transmission spectrum. Furthermore, a cured film having good heat resistance and chemical resistance can be formed.

[0324] The resist composition (1) of the present invention usually contains a photopolymerization initiator. As the photopolymerization initiator, there is no particular limitation as long as it is a compound that generates active radicals, acids, etc. by the action of light and initiates the polymerization of the polymerizable compound (D), and various polymerization initiators can be used.

[0325] As the aforementioned photopolymerization initiator, for example, imidazole compounds, alkyl phenyl ketone compounds, triazine compounds, acylphosphine oxide compounds, and oxime compounds are preferably used. In addition, the photo cationic polymerization initiator described in JP-A-2008-181087 (for example, a polymerization initiator composed of an onium cation and an anion derived from a Lewis acid) can be used. Among them, oxime compounds are preferred in terms of sensitivity.

[0326] As the aforementioned imidazole compounds, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylimidazole (for example, refer to JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxyphenyl)imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)imidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)imidazole (for example, refer to JP-B-48-38403, JP-A-62-174204, etc.), imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups (for example, refer to JP-A-7-10913, etc.), etc. Preferred examples include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylimidazole, and 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenylimidazole.

[0327] As the aforementioned alkyl phenyl ketone compounds, examples include diethoxyacetophenone, 2-methyl-2-morpholin-1-(4-methylsulfonylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-((4-methylbenzyl)methyl)butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzil dimethyl ketal, 2-hydroxy-2-methyl-1-(4-(2-hydroxyethoxy)phenyl)propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, etc. Preferred examples include 2-methyl-2-morpholin-1-(4-methylsulfonylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, etc. Commercially available products such as Irgacure 369, 907 (manufactured by BASF Japan Co., Ltd.) can be used.

[0328] As the aforementioned triazine compounds, examples include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(2-(5-methylfuran-2-yl)ethylidene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(2-(furan-2-yl)ethylidene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(2-(4-diethylamino-2-methylphenyl)ethylidene)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(2-(3,4-dimethoxyphenyl)ethylidene)-1,3,5-triazine, etc.

[0329] As the aforementioned acylphosphine oxide initiator, examples include 2,4,6-trimethylbenzoyl diphenylphosphine oxide, etc. Commercially available products such as Irgacure 819 (manufactured by Ciba Japan Co., Ltd.) can be used.

[0330] As the aforementioned oxime compounds, for example, N-benzoyloxy-1-(4-phenylsulfonylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfonylphenyl)octane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, etc. can be mentioned. Commercially available products such as Irgacure OXE-01, OXE-02 (the above are manufactured by BASF Japan Co., Ltd.), N-1919 (manufactured by ADEKA Corporation) can be used.

[0331] In addition, as the polymerization initiator having a group capable of causing chain transfer, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2002-544205 can be used. As the aforementioned polymerization initiator having a group capable of causing chain transfer, for example, the following compounds, etc. can be mentioned.

[0332]

[0333] Furthermore, as the polymerization initiator, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc.; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, etc.; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, metallocene compounds, etc. can be mentioned. They are preferably used in combination with the polymerization initiator aids (especially amines) described later.

[0334] The resist composition (1) of the present invention may further contain a polymerization initiator aid. The polymerization initiator aid is a compound or a sensitizer that is used in combination with a photopolymerization initiator to promote the polymerization of a polymerizable compound that is polymerized by the polymerization initiator.

[0335] As polymerization initiation aids, for example, amine compounds, thiazoline compounds, alkoxy anthracene compounds, thioxanthone compounds, carboxylic acid compounds, etc. can be cited. As the aforementioned amine compounds, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. can be cited. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

[0336] As the aforementioned thiazoline compounds, for example, the following compounds, etc. can be cited.

[0337]

[0338] As the aforementioned alkoxy anthracene compounds, for example, 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. can be cited.

[0339] As the aforementioned thioxanthone compounds, for example, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc. can be cited.

[0340] As the aforementioned carboxylic acid compounds, for example, phenylsulfonylacetic acid, methylphenylsulfonylacetic acid, ethylphenylsulfonylacetic acid, methylethylphenylsulfonylacetic acid, dimethylphenylsulfonylacetic acid, methoxyphenylsulfonylacetic acid, dimethoxyphenylsulfonylacetic acid, chlorophenylsulfonylacetic acid, dichlorophenylsulfonylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc. can be cited.

[0341] The content of the photopolymerization initiator is preferably 0.1 to 40 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the total amount of the alkali-soluble resin (C) and the polymerizable compound (D). When the total amount of the photopolymerization initiator is within this range, there is a tendency to form a pattern with high sensitivity, and the chemical resistance, mechanical strength, and surface smoothness of the pattern become good.

[0342] When a polymerization initiation aid is used in the present invention, its amount is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 40 parts by mass, based on 100 parts by mass of the total amount of the alkali-soluble resin (C) and the polymerizable compound (D). Further, based on 1 mole of the photopolymerization initiator (E), it is preferably 0.01 to 10 moles, more preferably 0.01 to 5 moles. When the amount of the polymerization initiation aid is within this range, there is a tendency to be able to form a pattern with higher sensitivity and improve the productivity of the pattern.

[0343] In addition, the resist composition (1) of the present invention may further contain a polyfunctional thiol compound. The polyfunctional thiol compound is a compound having two or more sulfonyl groups in the molecule. Among them, when a compound having two or more sulfonyl groups adjacent to an aliphatic hydrocarbon group is used, a pattern can be formed with high sensitivity, and thus it is preferred.

[0344] The resist composition (1) of the present invention usually contains a solvent. The solvent is not particularly limited, and solvents commonly used in the art can be used. For example, it can be selected from ester solvents (solvents containing -COO-), ether solvents other than ester solvents (solvents containing -O-), ether ester solvents (solvents containing -COO- and -O-), ketone solvents other than ester solvents (solvents containing -CO-), alcohol solvents, aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. These solvents can be used alone or in combination of two or more.

[0345] Examples of the aforementioned ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, γ-butyrolactone, etc.

[0346] Examples of the aforementioned ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methylanisole, etc.

[0347] As the aforementioned ether ester solvents, examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.

[0348] As the aforementioned ketone solvents, examples include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone, and the like.

[0349] As the aforementioned alcohol solvents, examples include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerol, and the like.

[0350] As the aforementioned aromatic hydrocarbon solvents, examples include benzene, toluene, xylene, mesitylene, and the like.

[0351] As the aforementioned amide solvents, examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

[0352] Among the above solvents, from the aspects of coatability and drying property, an organic solvent having a boiling point of 120 °C or higher and 180 °C or lower at 1 atm is preferred. Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like are preferred.

[0353] The content of the solvent is preferably 60 to 95% by mass, more preferably 70 to 90% by mass, relative to the coloring curable resin composition. In other words, the solid content of the coloring curable resin composition is preferably 5 to 40% by mass, more preferably 10 to 30% by mass. When the content of the solvent is within the aforementioned range, the flatness during coating tends to be good.

[0354] The resist composition (1) of the present invention may contain various additives such as a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anti-aggregation agent, an organic amine compound, a curing agent, etc. as needed.

[0355] As the aforementioned filler, examples include fine particles such as glass and alumina.

[0356] As the aforementioned adhesion promoter, examples thereof include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc.

[0357] As the aforementioned antioxidant, examples thereof include 4,4'-thio-bis(6-tert-butyl-3-methylphenol), triethylene glycol-bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythrityl-tetra[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thio-bis(3-methyl-6-tert-butylphenol), 4,4'-butylidene-bis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(4-hydroxybenzyl)benzene, and tetra[methylene-3-(3,5'-di-tert-butyl-4'-hydroxyphenylpropionate)]methane, etc.

[0358] As the aforementioned ultraviolet absorber, examples thereof include benzotriazole-based such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole; benzophenone-based such as 2-hydroxy-4-octyloxybenzophenone; benzoate-based such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; triazine-based such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol, etc.

[0359] As the aforementioned anti-aggregation agent, examples thereof include sodium polyacrylate, etc.

[0360] By adding an organic amine compound, a pixel that does not produce residues on the substrate in the unexposed area during development and has excellent adhesion to the substrate can be obtained. Examples of the aforementioned organic amine compound include monoalkylamine compounds such as n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;

[0361] monocycloalkylamine compounds such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine; dialkylamine compounds such as methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, di-n-pentylamine, di-n-hexylamine;

[0362] monoalkylmonocycloalkylamine compounds such as methylcyclohexylamine, ethylcyclohexylamine; dicycloalkylamine compounds such as dicyclohexylamine; trialkylamine compounds such as dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;

[0363] dialkylmonocycloalkylamine compounds such as dimethylcyclohexylamine, diethylcyclohexylamine; monoalkyldicycloalkylamine compounds such as methyl dicyclohexylamine, ethyl dicyclohexylamine, tricyclohexylamine; monoalkanolamine compounds such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol; monocycloalkanolamine compounds such as 4-amino-1-cyclohexanol; dialkanolamine compounds such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;

[0364] dicycloalkanolamine compounds such as bis(4-cyclohexanol)amine; trialkanolamine compounds such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine; tricycloalkanolamine compounds such as tris(4-cyclohexanol)amine; aminopolyhydric alcohol compounds such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;

[0365] 4 - amino - 1,2 - cyclohexanediol, 4 - amino - 1,3 - cyclohexanediol and other aminocycloalkanediols; 1 - aminocyclopentanone methanol, 4 - aminocyclopentanone methanol and other aminocycloalkanone methanols containing amino groups; 1 - aminocyclohexanone methanol, 4 - aminocyclohexanone methanol, 4 - dimethylaminocyclopentane methanol, 4 - diethylaminocyclopentane methanol, 4 - dimethylaminocyclohexane methanol, 4 - diethylaminocyclohexane methanol and other aminocycloalkane methanols containing amino groups; β - alanine, 2 - aminobutyric acid, 3 - aminobutyric acid, 4 - aminobutyric acid, 2 - amino - isobutyric acid, 3 - amino - isobutyric acid, 2 - aminovaleric acid, 5 - aminovaleric acid, 6 - aminohexanoic acid, 1 - aminocyclopropanecarboxylic acid, 1 - aminocyclohexanecarboxylic acid, 4 - aminocyclohexanecarboxylic acid and other aminocarboxylic acids;

[0366] Aniline, o - toluidine, m - toluidine, p - toluidine, p - ethylaniline, p - n - propylaniline, p - isopropylaniline, p - n - butylaniline, p - tert - butylaniline, 1 - naphthylamine, 2 - naphthylamine, N,N - dimethylaniline, N,N - diethylaniline, p - methyl - N,N - dimethylaniline and other aromatic amines; o - aminobenzyl alcohol, m - aminobenzyl alcohol, p - aminobenzyl alcohol, p - dimethylaminobenzyl alcohol, p - diethylaminobenzyl alcohol and other aminobenzyl alcohols; o - aminophenol, m - aminophenol, p - aminophenol, p - dimethylaminophenol, p - diethylaminophenol and other aminophenols; m - aminobenzoic acid, p - aminobenzoic acid, p - dimethylaminobenzoic acid, p - diethylaminobenzoic acid and other aminobenzoic acids, etc.

[0367] As the aforementioned curing agent, for example, when a resin having a carboxyl group is used as the alkali - soluble resin (C), compounds that can cross - link the alkali - soluble resin (C) by reacting with the carboxyl group by heating can be cited. In addition, compounds that can be polymerized alone to cure the coating film of the colored curable composition of the present invention and can form a cured film can also be cited. As the aforementioned compounds, for example, epoxy compounds, oxetane compounds, etc. can be cited.

[0368] As the aforementioned epoxy compound, for example, bisphenol A - type epoxy resins, hydrogenated bisphenol A - type epoxy resins, bisphenol F - type epoxy resins, hydrogenated bisphenol F - type epoxy resins, novolac - type epoxy resins, other aromatic - type epoxy resins, alicyclic - type epoxy resins, heterocyclic - type epoxy resins, glycidyl ester - type resins, glycidyl amine - type resins, epoxy oils and other epoxy resins, brominated derivatives of these epoxy resins, aliphatic, alicyclic or aromatic epoxy compounds other than epoxy resins and their brominated derivatives, epoxides of (co)polymers of butadiene, epoxides of (co)polymers of isoprene, (co)polymers of glycidyl (meth)acrylate, triglycidyl isocyanurate, etc.

[0369] As the aforementioned oxetane compounds, for example, carbonate dioxetane, benzene dimethylene dioxetane, adipate dioxetane, terephthalate dioxetane, cyclohexanedicarboxylate dioxetane, etc. can be cited.

[0370] When the resist composition (1) of the present invention contains an epoxy compound, an oxetane compound, etc. as a curing agent, a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound can be contained. As such a compound, for example, polycarboxylic acids, polycarboxylic anhydrides, acid generators, etc. can be cited.

[0371] As the aforementioned polycarboxylic acids, for example, aromatic polycarboxylic acids such as phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid; aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;

[0372] alicyclic polycarboxylic acids such as hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc.

[0373] As the aforementioned polycarboxylic anhydrides, for example, aromatic polycarboxylic anhydrides such as phthalic anhydride, pyromellitic dianhydride, trimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride; aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarboxylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride; alicyclic polycarboxylic anhydrides such as hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, nadic anhydride (Himicanhydride), norbornenedicarboxylic anhydride (carbic anhydride); carboxylic anhydrides containing an ester group such as ethylene glycol bis(trimellitate), glycerol tris(trimellitate), etc.

[0374] As the aforementioned carboxylic anhydrides, commercially available carboxylic anhydrides as epoxy resin curing agents can be used. As the aforementioned epoxy resin curing agents, for example, trade names such as Adeka Hardener EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH, MH-700 (all manufactured by Shin Nippon Rika Co., Ltd.) can be cited.

[0375] The above-mentioned curing agent can be used alone or in combination of two or more kinds.

[0376] In addition, the resist composition (1) of the present invention may contain an organic acid having a molecular weight of 1000 or less. Examples of the above-mentioned organic acid include those disclosed in Japanese Patent Laid-Open No. 5-343631. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid, methacrylic acid can be cited, and preferably malonic acid, oxalic acid, fumaric acid, phthalic acid can be cited.

[0377] Hereinafter, the resist composition (2) will be described in detail. Examples of the resin (F) whose solubility in an alkaline solution increases by the action of an acid include the following resins: resins obtained by dissociating and substituting the hydrogen atom of one or more oxygen-containing functional groups such as a carboxyl group, an alcohol hydroxyl group, and a phenolic hydroxyl group in a resin having one or more acid-dissociable groups capable of dissociating in the presence of an acid, which are themselves alkali-insoluble or alkali-difficultly soluble and become alkali-easily soluble when the acid-dissociable group dissociates (resins containing acid-dissociable groups).

[0378] Examples of the preferred resin containing an acid-dissociable group include a resin having a repeating unit represented by the following general formula (3) (hereinafter referred to as "repeating unit (3)"), a resin having a repeating unit represented by the following general formula (4) (hereinafter referred to as "repeating unit (4)"), a resin having a repeating unit containing a lactone structure, and the like.

[0379]

[0380] 〔In general formula (3) and general formula (4), R 4 represents a hydrogen atom, a hydroxyl group, a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 1 to 3 carbon atoms. Each Z represents a linear alkyl group having 1 to 10 carbon atoms or a derivative thereof, a branched alkyl group having 1 to 10 carbon atoms or a derivative thereof, a non-bridged monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, a bridged monovalent alicyclic hydrocarbon group having 4 to 20 carbon atoms or a derivative thereof, or any two Zs are bonded to each other and together with the carbon atoms to which they are bonded form a non-bridged divalent alicyclic hydrocarbon group having 2 to 20 carbon atoms or a derivative thereof, or a bridged divalent alicyclic hydrocarbon group having 2 to 20 carbon atoms or a derivative thereof, and the remaining Z is a linear alkyl group having 1 to 4 carbon atoms or a derivative thereof, or a branched alkyl group having 1 to 4 carbon atoms or a derivative thereof.〕

[0381] In the above general formula (3) and general formula (4), as R 4A linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 1 to 3 carbon atoms, examples of which include methyl, ethyl, n-propyl, and isopropyl.

[0382] As R in the aforementioned general formula (3) 4 , preferably a hydrogen atom or a methyl group.

[0383] In the aforementioned general formula (3) and general formula (4), as Z, a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms, examples of which include methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, etc.

[0384] Among these alkyl groups, methyl, ethyl, n-propyl, 2-methylpropyl, etc. are preferred.

[0385] In addition, as derivatives of the aforementioned alkyl group, groups having one or more or one or more of the following substituents can be cited, and the substituents are: for example, a hydroxyl group; a carboxyl group; an oxo group (i.e., =O group); a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc., a hydroxyalkyl group having 1 to 6 carbon atoms; a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, tert-butoxy group, etc., an alkoxy group having 1 to 6 carbon atoms; a cyano group; a cyanomethyl group, 2-cyanoethyl group, 3-cyanopropyl group, 4-cyanobutyl group, etc., a cyanoalkyl group having 2 to 6 carbon atoms, etc.

[0386] Among these substituents, hydroxyalkyl groups, alkoxy groups, etc. are preferred, and hydroxymethyl group, 1-hydroxyethyl group, methoxy group, ethoxy group, etc. are particularly preferred.

[0387] In addition, as a monovalent alicyclic hydrocarbon group having 2 to 20 carbon atoms or a bridged or unbridged divalent alicyclic hydrocarbon group having 2 to 20 carbon atoms formed by any two Zs bonding to each other and the carbon atoms to which they are bonded together, for example, groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc. can be cited; groups derived from bridged hydrocarbons such as adamantane, bicyclo[2.2.1]heptane, tetracyclo[6.2.1.13,6.02,7]dodecane, tricyclo[5.2.1.02,6]decane, etc.

[0388] Among these monovalent alicyclic hydrocarbon groups and divalent alicyclic hydrocarbon groups, groups derived from cyclopentane, cyclohexane, adamantane, and bicyclo[2.2.1]heptane are preferred.

[0389] In addition, as derivatives of the aforementioned monovalent or divalent alicyclic hydrocarbon group, groups having one or more or one or more substituents such as a hydroxyl group; a carboxyl group; an oxy group; a hydroxymethyl group, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl and other hydroxyalkyl groups having 1 to 4 carbon atoms; methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy and other alkoxy groups having 1 to 4 carbon atoms; a cyano group; a cyanomethyl group, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl and other cyanoalkyl groups having 2 to 5 carbon atoms can be cited.

[0390] Among these substituents, a hydroxyl group, a carboxyl group, a hydroxymethyl group, a cyano group, a cyanomethyl group and the like are preferable.

[0391] As a preferable structure corresponding to -C(Z)3 in the aforementioned general formula (3), for example, a tert-butyl group, 2-methyl-2-butyl, 2-ethyl-2-butyl, 3-ethyl-3-butyl, groups represented by the following formulas (3-1) to (3-8) and the like can be cited.

[0392]

[0393] 〔In the aforementioned formulas (3-1) to (3-8), each R 5 individually represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms, and a and b are each an integer of 0 to 2.〕

[0394] In the aforementioned formulas (3-1) to (3-8), R 5 are each preferably a methyl group or an ethyl group. a and b are each preferably 0 or 1.

[0395] As the aforementioned repeating unit (3), for example, repeating units represented by the following general formulas (3-1) to general formula (3-8) and the like can be cited.

[0396]

[0397] 〔In the aforementioned R 4 each represents a hydrogen atom, a hydroxyl group, a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 1 to 3 carbon atoms. Each R 5 represents a linear alkyl group having 1 to 4 carbon atoms or a branched alkyl group having 1 to 4 carbon atoms.〕

[0398] In the repeating units represented by the aforementioned general formulas (3-1) to general formula (3-8), as R 4 , a hydrogen atom and a methyl group are particularly preferable. In addition, as R 5 , a methyl group and an ethyl group are particularly preferable.

[0399] As the aforementioned repeating unit (4), for example, repeating units represented by the following general formula (4-1) to general formula (4-8) etc. can be cited.

[0400]

[0401] [The aforementioned R 6 each represents a hydrogen atom, a hydroxyl group, a linear alkyl group having 1 to 3 carbon atoms or a branched alkyl group having 1 to 3 carbon atoms. ]

[0402] As the aforementioned repeating unit having a lactone structure, for example, repeating units represented by the following general formula (5-1) to (5-4) etc. can be cited.

[0403]

[0404] [The aforementioned R 6 each represents a hydrogen atom or a methyl group. Y 1 represents a methylene group, a methylmethylene group, a dimethylmethylene group, an oxygen atom or a sulfur atom. R 7 each represents a linear alkyl group having 1 to 5 carbon atoms, a branched alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 5 carbon atoms or a branched alkoxy group having 1 to 5 carbon atoms. j and k are each an integer of 0 to 4, and Y 2 represents a single bond or a methylene group. ]

[0405] As the aforementioned linear alkyl group having 1 to 5 carbon atoms or branched alkyl group having 1 to 5 carbon atoms of R 7 , for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl, n-pentyl etc. can be cited.

[0406] In addition, as the linear alkyl group having 1 to 5 carbon atoms or branched alkoxy group having 1 to 5 carbon atoms of R 7 , for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butoxy, n-pentyloxy etc. can be cited.

[0407] The aforementioned resin having an acid dissociable group may have a repeating unit other than the aforementioned repeating unit (3), repeating unit (4) or repeating unit having a lactone structure (hereinafter, referred to as "other repeating unit").

[0408] As monomers to be imparted to other repeating units, for example, bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-n-butylbicyclo[2.2.1]hept-2-ene, 5-n-hexylbicyclo[2.2.1]hept-2-ene, 5-n-octylbicyclo[2.2.1]hept-2-ene, 5-n-decylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-(3-hydroxypropyl)bicyclo[2.2.1]hept-2-ene,

[0409] 5-[(fluoro)(hydroxy)methyl]bicyclo[2.2.1]hept-2-ene, 5-[(difluoro)(hydroxy)methyl]bicyclo[2.2.1]hept-2-ene, 5-(1,2-difluoro-2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-(1,1,2,2-tetrafluoro-2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-(2-trifluoromethyl-2-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-[2,2-bis(trifluoromethyl)-2-hydroxyethyl]bicyclo[2.2.1]hept-2-ene,

[0410] Bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, bicyclo[2.2.1]hept-2-ene-5-acetic acid, bicyclo[2.2.1]hept-2-ene-5-propionic acid,

[0411] 5-cyanobicyclo[2.2.1]hept-2-ene, 5-cyanomethylbicyclo[2.2.1]hept-2-ene, 5-(2-cyanoethyl)bicyclo[2.2.1]hept-2-ene, 5-(3-cyanopropyl)bicyclo[2.2.1]hept-2-ene,

[0412] tert-Butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 2-methyl-2-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0413] 2-Ethyl-2-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 3-ethyl-3-butyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0414] 1-Methylcyclopentyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-ethylcyclopentyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-methylcyclohexyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-ethylcyclohexyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0415] 1-Methyl-1-cyclopentylethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-Methyl-1-(2-hydroxycyclopentyl)ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-Methyl-1-(3-hydroxycyclopentyl)ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-Methyl-1-cyclohexylethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-Methyl-1-(3-hydroxycyclohexyl)ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1-Methyl-1-(4-hydroxycyclohexyl)ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0416] 1,1-Dicyclopentylethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, 1,1-Dicyclohexylethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0417] Methyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, Ethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, n-Propyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, Cyclopentyl bicyclo[2.2.1]hept-2-ene-5-carboxylate, Cyclohexyl bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0418] 〔(Tetrahydrofuran-2-yl)methyl〕 bicyclo[2.2.1]hept-2-ene-5-carboxylate, (1,1-Dimethyl-2-oxopropyl) bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0419] (5-Oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (9-Methoxycarbonyl-5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (7-Oxo-6-oxabicyclo[3.2.1]octan-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (2-Methoxycarbonyl-7-oxo-6-oxabicyclo[3.2.1]octan-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (2-Oxotetrahydropyran-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (4-Methyl-2-oxotetrahydropyran-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (4-Ethyl-2-oxotetrahydropyran-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate, (4-n-Propyl-2-oxotetrahydropyran-4-yl) bicyclo[2.2.1]hept-2-ene-5-carboxylate,

[0420] (5-Oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, (2,2-dimethyl-5-oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, (4,4-dimethyl-5-oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid,

[0421] (2-Oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, (4,4-dimethyl-2-oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, (5,5-dimethyl-2-oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid,

[0422] (2-Oxotetrahydrofuran-3-yl) esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, [(5-oxotetrahydrofuran-2-yl)methyl] esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, [(3,3-dimethyl-5-oxotetrahydrofuran-2-yl)methyl] esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid, [(4,4-dimethyl-5-oxotetrahydrofuran-2-yl)methyl] esters of bicyclo[2.2.1]hept-2-ene-5-carboxylic acid and other bicyclo[2.2.1]hept-2-enes or their derivatives;

[0423] Tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-methyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-ethyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-n-butyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-n-hexyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-n-octyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-n-decyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene,

[0424] 9-Hydroxytetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-hydroxymethyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(2-hydroxyethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(3-hydroxypropyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene,

[0425] 9-[(fluoro)(hydroxy)methyl]tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-[(difluoro)(hydroxy)methyl]tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(1,2-difluoro-2-hydroxyethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(1,1,2,2-tetrafluoro-2-hydroxyethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(2-trifluoromethyl-2-hydroxyethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-[2,2-bis(trifluoromethyl)-2-hydroxyethyl]tetracyclo[6.2.1.13,6.02,7]dodec-4-ene,

[0426] tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-acetic acid, tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-propanoic acid,

[0427] 9-cyanotetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-cyanomethyltetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(2-cyanoethyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene, 9-(3-cyanopropyl)tetracyclo[6.2.1.13,6.02,7]dodec-4-ene,

[0428] tert-butyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 2-methyl-2-butyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 2-ethyl-2-butyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 3-ethyl-3-butyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate,

[0429] 1-methylcyclopentyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-ethylcyclopentyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-methylcyclohexyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-ethylcyclohexyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate,

[0430] 1-Methyl-1-cyclopentylethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-Methyl-1-(2-hydroxycyclopentyl)ethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-Methyl-1-(3-hydroxycyclopentyl)ethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-Methyl-1-cyclohexylethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-Methyl-1-(3-hydroxycyclohexyl)ethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1-Methyl-1-(4-hydroxycyclohexyl)ethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate

[0431] 1,1-Dicyclopentylethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, 1,1-Dicyclohexylethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, Methyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, Ethyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, n-Propyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, Cyclopentyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, Cyclohexyl tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate

[0432] [(Tetrahydrofuran-2-yl)methyl] tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (1,1-Dimethyl-2-oxopropyl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate

[0433] (5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (9-methoxycarbonyl-5-oxo-4-oxatricyclo[4.2.1.03,7]nonan-2-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (7-oxo-6-oxabicyclo[3.2.1]octan-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (2-methoxycarbonyl-7-oxo-6-oxabicyclo[3.2.1]octan-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (2-oxotetrahydropyran-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (4-methyl-2-oxotetrahydropyran-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (4-ethyl-2-oxotetrahydropyran-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate, (4-n-propyl-2-oxotetrahydropyran-4-yl) tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylate

[0434] (5-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (2,2-dimethyl-5-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (4,4-dimethyl-5-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (2-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (4,4-dimethyl-2-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (5,5-dimethyl-2-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, (2-oxotetrahydrofuran-3-yl) esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, [(5-oxotetrahydrofuran-2-yl)methyl] esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, [(3,3-dimethyl-5-oxotetrahydrofuran-2-yl)methyl] esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid, [(4,4-dimethyl-5-oxotetrahydrofuran-2-yl)methyl] esters of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene-9-carboxylic acid and the like of tetracyclo[6.2.1.13,6.02,7]dodec-4-ene or its derivatives;

[0435] (hydroxymethyl) (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, (fluoro)(hydroxy)methyl (meth)acrylate, (difluoro)(hydroxy)methyl (meth)acrylate, 1,2-difluoro-2-hydroxyethyl (meth)acrylate, 1,1,2,2-tetrafluoro-2-hydroxyethyl (meth)acrylate, 2-(trifluoromethyl)-2-hydroxyethyl (meth)acrylate, 2,2-bis(trifluoromethyl)-2-hydroxyethyl (meth)acrylate,

[0436] (3-hydroxyadamantan-1-yl) (meth)acrylate, (5-hydroxybicyclo[2.2.1]heptan-2-yl) (meth)acrylate, (6-hydroxybicyclo[2.2.1]heptan-2-yl) (meth)acrylate, (9-hydroxytetracyclo[6.2.1.13,6.02,7]dodec-4-yl) (meth)acrylate, (10-hydroxytetracyclo[6.2.1.13,6.02,7]dodec-4-yl) (meth)acrylate,

[0437] (Meth)acrylic acid, carboxymethyl (meth)acrylate, 2-carboxyethyl (meth)acrylate, 3-carboxypropyl (meth)acrylate, 3-carboxyadamantan-1-yl (meth)acrylate, 5-carboxybicyclo[2.2.1]heptan-2-yl (meth)acrylate, 6-carboxybicyclo[2.2.1]heptan-2-yl (meth)acrylate, 9-carboxytetracyclo[6.2.1.13,6.02,7]dodecan-4-yl (meth)acrylate, 10-carboxytetracyclo[6.2.1.13,6.02,7]dodecan-4-yl (meth)acrylate, cyanomethyl (meth)acrylate, 2-cyanoethyl (meth)acrylate, 3-cyanopropyl (meth)acrylate, 3-cyanoadamantan-1-yl (meth)acrylate, 5-cyanobicyclo[2.2.1]heptan-2-yl (meth)acrylate, 6-cyanobicyclo[2.2.1]heptan-2-yl (meth)acrylate, 9-cyanotetracyclo[6.2.1.13,6.02,7]dodecan-4-yl (meth)acrylate, 10-cyanotetracyclo[6.2.1.13,6.02,7]dodecan-4-yl (meth)acrylate,

[0438] (Meth)acrylic acid methyl ester, (meth)acrylic acid ethyl ester, (meth)acrylic acid n-propyl ester, (meth)acrylic acid cyclopentyl ester, (meth)acrylic acid cyclohexyl ester, adamantan-1-yl (meth)acrylate, bicyclo[2.2.1]heptan-2-yl (meth)acrylate, 7,7-dimethylbicyclo[2.2.1]heptan-1-yl (meth)acrylate, tetracyclo[6.2.1.13,6.02,7]dodecan-4-yl (meth)acrylate, tricyclo[5.2.1.02,6]dec-8-yl (meth)acrylate, (tetrahydrofuran-2-yl)methyl (meth)acrylate, 1,1-dimethyl-2-oxopropyl (meth)acrylate, etc. (meth)acrylic acid or its derivatives;

[0439] Vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.; unsaturated nitrile compounds such as (meth)acrylonitrile, α-chloroacrylonitrile, crotononitrile, maleonitrile, fumaronitrile, mesacononitrile, citracononitrile, itacononitrile, etc.; unsaturated amide compounds or unsaturated imide compounds such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, crotonamide, maleamide, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, fumaramide, mesaconamide, citraconamide, itaconamide, etc.; other nitrogen-containing vinyl compounds such as N-vinyl-ε-caprolactam, N-vinylpyrrolidone, vinylpyridine, vinylimidazole, etc.; monofunctional monomers such as unsaturated carboxylic acids (anhydrides) such as crotonic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid, etc.

[0440] Polyfunctional monomers such as methylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2,5-dimethyl-2,5-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,4-bis(2-hydroxypropyl)benzene di(meth)acrylate, 1,3-bis(2-hydroxypropyl)benzene di(meth)acrylate, 1,2-adamantanediol di(meth)acrylate, 1,3-adamantanediol di(meth)acrylate, 1,4-adamantanediol di(meth)acrylate, tricyclodecyl dimethylol di(meth)acrylate, etc.

[0441] The polystyrene-reduced weight average molecular weight (hereinafter referred to as "Mw") of the resin containing an acid dissociable group obtained by gel permeation chromatography (GPC) is generally 1,000 to 300,000, preferably 2,000 to 200,000, and more preferably 3,000 to 100,000. When it is in this range, a resin containing an acid dissociable group that can be expected to satisfy both the heat resistance as a resist and the solubility of the exposed portion in the developer can be obtained. In addition, the ratio (Mw / Mn) of the Mw of the resin containing an acid dissociable group to the polystyrene-reduced number average molecular weight (hereinafter referred to as "Mn") obtained by gel permeation chromatography (GPC) is generally 1 to 5, preferably 1 to 3.

[0442] Resins such as the aforementioned resin containing an acid dissociable group, whose solubility in an alkaline solution increases by the action of an acid, can be used alone or in combination of two or more.

[0443] The resin containing an acid-dissociable group described above can be produced, for example, by polymerizing a mixture of monomers corresponding to each repeating unit in a suitable solvent in the presence of a radical polymerization initiator such as hydrogen peroxide, dialkyl peroxides, diacyl peroxides, azo compounds, etc., and if necessary, in the presence of a chain transfer agent. Examples of the solvent used in the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cycloalkanes such as cyclohexane, cycloheptane, cyclooctane, decalin, and norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, chlorofluoroethanes, hexamethylene dibromide, and chlorobenzene; saturated carboxylic acid esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate; alkyl lactones such as γ-butyrolactone; ethers such as tetrahydrofuran, dimethoxyethanes, and diethoxyethanes; alkyl ketones such as 2-butanone, 2-heptanone, and methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone; and alcohols such as 2-propanol and propylene glycol monomethyl ether. These solvents can be used alone or in combination of two or more. In addition, the reaction temperature in the polymerization is usually 40 to 120°C, preferably 50 to 100°C, and the reaction time is usually 1 to 48 hours, preferably 1 to 24 hours.

[0444] Of course, the resin containing an acid-dissociable group preferably has as few impurities such as halogens and metals as possible. Regarding the residual monomers and oligomer components, it is also preferably below a specified value. For example, the value measured by high performance liquid chromatography (HPLC) is 0.1 wt% or less. Thus, it is possible to provide a radiation-sensitive resin composition that can not only further improve the sensitivity, resolution, process stability, pattern shape, etc. as a resist, but also has little variation in the amount of foreign matter in the composition solution used in the formation of the resist pattern and little change over time in sensitivity, etc., and exhibits stable resist performance. As a purification method for the resin containing an acid-dissociable group, for example, the following methods can be cited. First, as a method for removing impurities such as metals, a method of adsorbing metals in the resin solution using a zeta potential filter; a method of removing metals in the form of chelates by washing the resin solution with an acidic aqueous solution such as oxalic acid or sulfonic acid, etc. In addition, as a method for reducing the residual monomers and oligomer components to below a specified value, the following can be cited: liquid-liquid extraction such as water washing, selecting or combining appropriate solvents to remove the residual monomers and oligomer components, ultrafiltration such as selecting or combining appropriate solvents to extract and remove only low molecular weight components below a specific molecular weight, reprecipitation such as dropping the resin solution into a poor solvent to solidify the resin and remove the residual monomers, and a method of washing the filtered resin with a poor solvent, etc. These solid-phase purification methods, and these methods can also be combined. The solvent used in the liquid-phase purification method and the poor solvent used in the solid-phase purification method are appropriately selected according to the resin to be purified.

[0445] The acid generator component (G) that generates acid by exposure used in the present invention is not particularly limited, and substances that have been proposed as acid generators for chemically amplified resists so far can be used. As such acid generators, for example, onium salt-based acid generators such as iodonium salts and sulfonium salts, oxime sulfonate-based acid generators, diazomethane-based acid generators such as bis(alkyl or arylsulfonyl) diazomethanes and poly(bisulfonyl) diazomethanes, nitrobenzyl sulfonate-based acid generators, iminosulfonate-based acid generators, disulfone-based acid generators, etc. can be cited.

[0446] As the content ratio of the fluoropolymer (B) in the resist composition (2), when it is 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin (F) whose solubility in an alkaline solution increases by the action of acid, the surface activity of the fluoropolymer (B) can be exhibited without hindering the performance of the resist resin, and thus it is preferably 0.05 to 5 parts by mass.

[0447] When the resist composition (2) is used as, for example, a positive resist composition for LSI, resins for improving the performance of the resist film, surfactants for improving coatability, dissolution inhibitors, plasticizers, stabilizers, colorants, antihalation agents, dyes, etc. can be appropriately added and contained as needed.

[0448] Hereinafter, the resist composition (3) will be described in detail. As the resin (H) whose solubility in an organic solvent decreases by the action of acid, for example, resins having a group that decomposes by the action of acid to generate a polar group on the main chain or side chain of the resin, or both the main chain and side chain can be exemplified.

[0449] As the aforementioned polar group, as long as it is a group that is hardly soluble or insoluble in a developer containing an organic solvent, it is not particularly limited, and phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene, tris(alkylsulfonyl)methylene, etc. (groups that dissociate in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide used as a developer for resists in the past) and alcoholic hydroxyl groups can be cited.

[0450] The aforementioned alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group and excluding a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). As the hydroxyl group, aliphatic alcohols in which the α-position is substituted with an electron-withdrawing group such as a fluorine atom (for example, fluorinated alcohol groups (such as hexafluoroisopropanol groups)) are excluded. As the alcoholic hydroxyl group, a hydroxyl group having a pKa of 12 or more and 20 or less is preferred.

[0451] Examples of preferred polar groups include a carboxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

[0452] As the group that decomposes by the action of an acid to generate a polar group, a preferred group is a group in which a hydrogen atom of these groups is replaced by a group that is eliminated by an acid. Examples of the group eliminated by an acid include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ), etc.

[0453] Each of the aforementioned (R 36 ) to (R 39 ) independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. (R 36 ) and (R 37 ) may be bonded to each other to form a ring.

[0454] Each of the aforementioned (R 01 ), (R 02 ) independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

[0455] The alkyl groups of the aforementioned (R 36 ) to (R 39 ), (R 01 ) and (R 02 ) preferably have 1 to 8 carbon atoms. Specifically, examples include a methyl group, an ethyl group, a propyl group, a n-butyl group, a sec-butyl group, a hexyl group, an octyl group, etc.

[0456] The cycloalkyl groups of the aforementioned (R 36 ) to (R 39 ), (R 01 ) and (R 02 ) may be monocyclic or polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferred, and examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferred, and examples include an adamantyl group, a norbornyl group, an isobornyl group, a camphenyl group, a dicyclopentyl group, an α-pinene group, a tricyclodecyl group, a tetracyclododecyl group, an androstan-17-yl group, etc. It should be noted that at least one carbon atom in the cycloalkyl group may be replaced by a heteroatom such as an oxygen atom.

[0457] Each of the aforementioned (R 36 ) to (R 39 ), (R01 ) and (R 02 ) The aryl group is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl group, naphthyl group, anthryl group, etc.

[0458] The aforementioned (R 36 ) to (R 39 ), (R 01 ) and (R 02 ) The aralkyl group is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl group, phenethyl group, naphthylmethyl group, etc.

[0459] The aforementioned (R 36 ) to (R 39 ), (R 01 ) and (R 02 ) The alkenyl group is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl group, allyl group, butenyl group, cyclohexenyl group, etc.

[0460] As the ring formed by bonding the aforementioned (R 36 ) and (R 37 ), a cycloalkyl group (monocyclic or polycyclic) is preferred. As the cycloalkyl group, a monocyclic cycloalkyl group such as cyclopentyl group, cyclohexyl group, etc., and a polycyclic cycloalkyl group such as norbornyl group, tetracyclodecyl group, tetracyclododecyl group, adamantyl group, etc. are preferred. A monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred, and a monocyclic cycloalkyl group having 5 carbon atoms is particularly preferred.

[0461] As the group that decomposes by the action of an acid to generate a polar group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group, etc. are preferred. A tertiary alkyl ester group is further preferred.

[0462] The resin (H) preferably contains a repeating unit having a group that decomposes by the action of an acid to generate a polar group.

[0463] As the repeating unit of the group that decomposes by the action of an acid to generate a polar group contained in the resin (H), a repeating unit represented by the following general formula (III) is preferred.

[0464]

[0465] In the above general formula (III), R0 represents a hydrogen atom, a straight-chain alkyl group or a branched-chain alkyl group. R1 to R3 each independently represent a straight-chain alkyl group, a branched-chain alkyl group, a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. For R1 to R3, two of R1 to R3 may bond to form a monocyclic or polycyclic cycloalkyl group.

[0466] As the straight-chain alkyl group or branched-chain alkyl group for R0, it may have substituents, preferably a straight-chain alkyl group or branched-chain alkyl group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. As the substituent, examples thereof include a hydroxyl group, a halogen atom (for example, a fluorine atom), etc.

[0467] As R0, a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group is preferred.

[0468] As the alkyl group for R1 to R3, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, etc., which are alkyl groups having 1 to 4 carbon atoms, are preferred.

[0469] As the cycloalkyl group for R1 to R3, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group is preferred.

[0470] As the cycloalkyl group formed by bonding two of R1 to R3, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, or an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 or 6 carbon atoms is more preferred.

[0471] As one of the preferred embodiments, there is a case where R1 is a methyl group or an ethyl group, and R2 and R3 are bonded to form the above-mentioned cycloalkyl group.

[0472] The above-mentioned respective groups may have substituents, and as the substituents, for example, a hydroxyl group, a halogen atom (for example, a fluorine atom), an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a carboxyl group, an alkoxycarbonyl group having 2 to 6 carbon atoms, etc. can be cited.

[0473] As a particularly preferred embodiment of the repeating unit represented by the aforementioned general formula (III), R1, R2 and R3 are each independently a straight-chain alkyl group or a branched-chain alkyl group. In this embodiment, as the straight-chain alkyl group or branched-chain alkyl group for R1, R2 and R3, an alkyl group having 1 to 4 carbon atoms is preferred, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group.

[0474] As R1, a methyl group, an ethyl group, an n-propyl group, an n-butyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred. As R2, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group are preferred, a methyl group and an ethyl group are more preferred, and a methyl group is particularly preferred. As R3, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group are preferred, a methyl group, an ethyl group, an isopropyl group, an isobutyl group are more preferred, and a methyl group, an ethyl group, an isopropyl group are particularly preferred.

[0475] Preferred specific examples of the repeating unit having a group that decomposes by the action of an acid to generate a polar group are shown below. In the specific examples, R x represents a hydrogen atom, CH3, CF3, or CH2OH. R xa , R xb each represents an alkyl group having 1 to 4 carbon atoms. Z represents a substituent, and when there are a plurality of Zs, the plurality of Zs may be the same as or different from each other. p represents 0 or a positive integer. Specific examples and preferred examples of Z are the same as those of the substituents that each group such as R1 to R3 can have.

[0476]

[0477]

[0478] In the case of the resin (H), when having a repeating unit represented by the above general formula (III) as a repeating unit having a group that decomposes by the action of an acid to generate a polar group, the repeating unit having a group that decomposes by the action of an acid to generate a polar group is preferably composed of at least one of the repeating units represented by the above general formula (III).

[0479] In addition, the repeating unit having a group that decomposes by the action of an acid to generate a polar group is also preferably a repeating unit represented by the following general formula (IV) that decomposes by an acid to generate a carboxyl group. Thereby, it is possible to obtain a pattern forming method that is more excellent in roughness performance such as line width roughness, uniformity of local pattern size, and exposure latitude, and can further suppress the film thickness reduction of the pattern portion formed by development, so-called film reduction.

[0480]

[0481] (In the formula, Xa represents a hydrogen atom, an alkyl group, a cyano group, or a halogen atom. Ry1 to Ry3 each independently represent an alkyl group or a cycloalkyl group. Two of Ry1 to Ry3 may be linked to form a ring. Z represents an (n + 1)-valent linking group containing a polycyclic hydrocarbon structure optionally having a hetero atom as a ring member. L1 and L2 each independently represent a single bond or a divalent linking group. n represents an integer of 1 to 3. When n is 2 or 3, the plurality of L2s, the plurality of Ry1s, the plurality of Ry2s, and the plurality of Ry3s may be the same as or different from each other.)

[0482] The alkyl group of Xa may have a substituent, and examples of the substituent include a hydroxyl group, a halogen atom (preferably a fluorine atom), etc. The alkyl group of Xa is preferably an alkyl group having 1 to 4 carbon atoms, and examples include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a trifluoromethyl group, etc. Among them, a methyl group is preferred. Xa is preferably a hydrogen atom or a methyl group.

[0483] The alkyl groups of Ry1 to Ry3 can be linear or branched, and alkyl groups having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl are preferred.

[0484] As the cycloalkyl groups of Ry1 to Ry3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferred; polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred.

[0485] As the ring formed by bonding two of Ry1 to Ry3, monocyclic hydrocarbon rings such as cyclopentane ring and cyclohexane ring are preferred; polycyclic hydrocarbon rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring are preferred. A monocyclic hydrocarbon ring having 5 to 6 carbon atoms is particularly preferred.

[0486] Each of Ry1 to Ry3 is independently preferably an alkyl group, more preferably a linear or branched alkyl group having 1 to 4 carbon atoms. In addition, the total number of carbon atoms of the linear or branched alkyl groups of Ry1 to Ry3 is preferably 5 or less.

[0487] Ry1 to Ry3 may further have substituents. Examples of the substituents include alkyl groups having 1 to 4 carbon atoms, cycloalkyl groups having 3 to 8 carbon atoms, halogen atoms, alkoxy groups having 1 to 4 carbon atoms, carboxyl groups, alkoxycarbonyl groups having 2 to 6 carbon atoms, etc., and preferably those having 8 or less carbon atoms. Among them, from the viewpoint of further improving the comparison of the dissolution rate in a developer containing an organic solvent before and after acid decomposition, a substituent having no heteroatoms such as oxygen atoms, nitrogen atoms, and sulfur atoms is more preferred, a group containing only hydrogen atoms and carbon atoms is further preferred, and a linear alkyl group, a branched alkyl group, and a cycloalkyl group are particularly preferred.

[0488] As the linking group having a polycyclic hydrocarbon structure for Z, it includes a fused hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group, and examples thereof include a group formed by removing (n + 1) arbitrary hydrogen atoms from the fused hydrocarbon ring and a group formed by removing (n + 1) arbitrary hydrogen atoms from the crosslinked cyclic hydrocarbon ring.

[0489] Examples of the cycloalkyl group as a cycloalkane ring group include a dicyclohexyl group, a perhydro naphthalene group, etc. Examples of the crosslinked cycloalkane ring group include bicyclic cycloalkane ring groups such as a pinane group, a camphane group, a norpinane group, a norbornane group, a bicyclooctane group (bicyclo[2.2.2]octane group, bicyclo[3.2.1]octane group, etc.); tricyclic cycloalkane ring groups such as a tricyclo[5.2.1.0(3,8)]decanyl group, an adamantane group, a tricyclo[5.2.1.02,6]decane group, a tricyclo[4.3.1.12,5]undecane group; tetracyclic cycloalkane ring groups such as a tetracyclo[4.4.0.12,5.17,10]dodecane group, a perhydro-1,4-methano-5,8-methano naphthalene group, etc. In addition, the crosslinked cycloalkane ring group also includes a fused cycloalkane ring group, for example, a fused ring group formed by condensing multiple 5- to 8-membered cycloalkane rings such as a perhydro naphthalene (decahydronaphthalene) group, a perhydro anthracene group, a perhydro phenanthrene group, a perhydro acenaphthene group, a perhydro fluorene group, a perhydro indene group, a perhydro phenanthrene group, etc.

[0490] Examples of the preferred crosslinked cycloalkane ring group include a norbornane group, an adamantane group, a bicyclooctane group, a tricyclo[5,2,1,02,6]decane group, etc. Examples of the more preferred crosslinked cycloalkane ring group include a norbornane group, an adamantane group.

[0491] The linking group having a polycyclic hydrocarbon structure represented by Z may have a substituent. Examples of the substituent that Z may have include an alkyl group, a hydroxyl group, a cyano group, a keto group (=O), an acyloxy group, -COR, -COOR, -CON(R)2, -SO2R, -SO3R, -SO2N(R)2 and other substituents. Here, R represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group.

[0492] The alkyl group, alkylcarbonyl group, acyloxy group, -COR, -COOR, -CON(R)2, -SO2R, -SO3R, -SO2N(R)2 as the substituent that Z may have may further have a substituent. Examples of such a substituent include a halogen atom (preferably a fluorine atom).

[0493] In the linking group having a polycyclic hydrocarbon structure represented by Z, the carbon atoms constituting the polycycle (carbons contributing to ring formation) may be carbonyl carbons. In addition, as described above, the polycycle may have heteroatoms such as an oxygen atom and a sulfur atom as ring members.

[0494] Examples of the linking group represented by L1 and L2 include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 3 to 10 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, a linking group formed by combining multiple of them, etc., and a linking group having a total of 12 or less carbon atoms is preferred.

[0495] L1 is preferably a single bond, alkylene, -COO-, -OCO-, -CONH-, -NHCO-, -alkylene-COO-, -alkylene-OCO-, -alkylene-CONH-, -alkylene-NHCO-, -CO-, -O-, -SO2-, -alkylene-O-, more preferably a single bond, alkylene, -alkylene-COO-, -alkylene-O-.

[0496] L2 is preferably a single bond, alkylene, -COO-, -OCO-, -CONH-, -NHCO-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, -NHCO-alkylene-, -CO-, -O-, -SO2-, -O-alkylene-, -O-cycloalkylene-, more preferably a single bond, alkylene, -COO-alkylene-, -O-alkylene-, -O-cycloalkylene-.

[0497] In the above-described method of description, the atomic bond "-" at the left end is, in L1, connected to the ester bond on the main chain side and, in L2, connected to Z, and the atomic bond "-" at the right end is, in L1, bonded to Z and, in L2, bonded to the ester bond connected to the group represented by (Ry1)(Ry2)(Ry3)C-.

[0498] It should be noted that L1 and L2 can be bonded to the same atom constituting the polycycle in Z.

[0499] n is preferably 1 or 2, more preferably 1.

[0500] Specific examples of the repeating unit represented by the general formula (IV) are given below. In the following specific examples, Xa represents a hydrogen atom, an alkyl group, a cyano group or a halogen atom.

[0501]

[0502]

[0503] In addition, the resin (H) may have a repeating unit having a structure in which a group that decomposes by the action of an acid to generate an alcohol hydroxyl group (hereinafter, also referred to as an OH protection structure) is contained in the side chain as a repeating unit having a group that decomposes by the action of an acid to generate a polar group. Here, "alcohol hydroxyl group" means that the hydroxyl group as the object is not a phenolic hydroxyl group, that is, it means that it is not directly connected to a benzene ring.

[0504] As the OH protection structure, the structures represented by the following general formulas (V-1) to (V-4) are preferred.

[0505]

[0506] (In the formula, each R3 independently represents a hydrogen atom or a monovalent organic group. R3s may be bonded to each other to form a ring. Each R4 independently represents a monovalent organic group. R4s may be bonded to each other to form a ring. R3 and R4 may be bonded to each other to form a ring. Each R5 independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. At least two R5s may be bonded to each other to form a ring. Among them, when one or two of the three aforementioned R5s are hydrogen atoms, at least one of the remaining aforementioned R5s represents an aryl group, an alkenyl group, or an alkynyl group.)

[0507] In addition, as the OH protecting structure, the structures represented by the following general formulas (V-5) to (V-9) can also be listed as preferred embodiments.

[0508]

[0509] In the formula, R4 has the same meaning as in the general formulas (V-1) to (V-3). Each R6 independently represents a hydrogen atom or a monovalent organic group. R6s may be bonded to each other to form a ring.

[0510] The group that decomposes by the action of an acid to generate an alcohol hydroxyl group is more preferably selected from the general formulas (V-1) to (V-3), further preferably represented by the general formula (V-1) or (V-3), and particularly preferably represented by the general formula (V-1).

[0511] As described above, R3 represents a hydrogen atom or a monovalent organic group. R3 is preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, and more preferably a hydrogen atom or an alkyl group.

[0512] The alkyl group of R3 may be linear or branched. The number of carbon atoms of the alkyl group of R3 is preferably 1 to 10, more preferably 1 to 3. Examples of the alkyl group of R3 include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a n-butyl group.

[0513] The cycloalkyl group of R3 may be monocyclic or polycyclic. The number of carbon atoms of the cycloalkyl group of R3 is preferably 3 to 10, more preferably 4 to 8. Examples of the cycloalkyl group of R3 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group.

[0514] R4 represents a monovalent organic group. R4 is preferably an alkyl group or a cycloalkyl group, and more preferably an alkyl group. These alkyl groups and cycloalkyl groups may have substituents.

[0515] The alkyl group of R4 preferably has no substituent, or has one or more aryl groups or one or more silyl groups as substituents. The number of carbon atoms of the unsubstituted alkyl group is preferably 1 to 20. The number of carbon atoms of the alkyl moiety in the alkyl group substituted with one or more aryl groups is preferably 1 to 25. The number of carbon atoms of the alkyl moiety in the alkyl group substituted with one or more silyl groups is preferably 1 to 30. In addition, when the cycloalkyl group of R4 has no substituent, the number of its carbon atoms is preferably 3 to 20.

[0516] R5 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, or an alkynyl group. Among them, in (V-4), when one or two of the three R5s are hydrogen atoms, at least one of the remaining R5s represents an aryl group, an alkenyl group, or an alkynyl group. R5 is preferably a hydrogen atom or an alkyl group. The alkyl group may or may not have a substituent. When the alkyl group has no substituent, the number of its carbon atoms is preferably 1 to 6, more preferably 1 to 3.

[0517] As described above, R6 represents a hydrogen atom or a monovalent organic group. R6 is preferably a hydrogen atom, an alkyl group, or a cycloalkyl group, more preferably a hydrogen atom or an alkyl group, and further preferably a hydrogen atom or an unsubstituted alkyl group. R6 is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and further preferably a hydrogen atom or an unsubstituted alkyl group having 1 to 10 carbon atoms.

[0518] It should be noted that as the alkyl group and cycloalkyl group of R4, R5, and R6, for example, the same examples as those described for R3 can be cited.

[0519] Specific examples of the repeating unit having an OH protecting structure in the side chain include, for example, the specific examples shown below, the units of the monomers exemplified in paragraph

[0025] of US2012 / 0064456A, etc. It should be noted that in the following specific examples, Xa1 represents a hydrogen atom, CH3, CF3, or CH2OH.

[0520]

[0521] The repeating unit of the resin (H) having a group that decomposes by the action of an acid to generate a polar group may be one kind, or two or more kinds may be used in combination.

[0522] In the present invention, preferably, the resin (H) has, relative to all the repeating units in the resin, 50 mol% or more of the repeating units having a group that decomposes by the action of an acid to generate a polar group and the molecular weight of the detached product generated by the decomposition of the group (in the case where a plurality of detached products are generated, the weighted average of the molecular weights based on the mole fraction (hereinafter, also referred to as the molar average)) is 140 or less (in the case where a plurality are contained, the total thereof). Thus, in the case of forming a negative-type image, in order to leave the exposed portion as a pattern, by reducing the molecular weight of the detached product, a decrease in the film thickness of the pattern portion can be prevented.

[0523] The above-mentioned "detached product generated by the decomposition of a group that decomposes by the action of an acid to generate a polar group" refers to a substance that decomposes and detaches by the action of an acid and corresponds to the group that decomposes and detaches by the action of an acid. For example, in the case of the repeating unit (α) described later (the leftmost repeating unit in the examples described later), it refers to the olefin (H2C=C(CH3)2) generated by the decomposition of the tert-butyl moiety.

[0524] In the present invention, from the viewpoint of preventing a decrease in the film thickness of the pattern portion, the molecular weight of the detached product generated by the decomposition of a group that decomposes by the action of an acid to generate a polar group (in the case where a plurality of detached products are generated, the molar average) is more preferably 100 or less.

[0525] In addition, regarding the lower limit of the molecular weight of the detached product generated by the decomposition of a group that decomposes by the action of an acid to generate a polar group (in the case where a plurality of detached products are generated, the average thereof), there is no particular limitation, and from the viewpoint of the acid-decomposable group exerting its function, it is preferably 45 or more, more preferably 55 or more.

[0526] In the present invention, from the viewpoint of more reliably maintaining the film thickness of the pattern portion as the exposed portion, relative to all the repeating units in the resin, preferably 60 mol% or more of the repeating units having a group that decomposes by the action of an acid to generate a polar group and the molecular weight of the detached product generated by the decomposition of the group is 140 or less (in the case where a plurality are contained, the total thereof), more preferably 65 mol% or more, and further preferably 70 mol% or more. In addition, as the upper limit, there is no particular limitation, and it is preferably 90 mol% or less, more preferably 85 mol% or less.

[0527] Hereinafter, specific examples of a repeating unit having a group that decomposes by the action of an acid to generate a polar group and generates a leaving substance having a molecular weight of 140 or less by the decomposition are shown. In the following specific examples, Xa1 represents a hydrogen atom, CH3, CF3, or CH2OH.

[0528]

[0529] Regarding the total content ratio of the repeating units having a group that decomposes by the action of an acid to generate a polar group, relative to all the repeating units in the resin (H), it is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 45 mol% or more, particularly preferably 50 mol% or more, and most preferably 60 mol% or more.

[0530] In addition, regarding the total content ratio of the repeating units having a group that decomposes by the action of an acid to generate a polar group, relative to all the repeating units in the resin (H), it is preferably 100 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less.

[0531] Preferably, the resin (H) contains a repeating unit having a group that decomposes by the action of an acid to generate a polar group, and the repeating unit is composed of at least one of the repeating units represented by the above general formula (III), and the content ratio of the repeating unit represented by the general formula (III) relative to all the repeating units in the resin (H) is 60 mol% to 100 mol%.

[0532] The resin (H) may further contain a repeating unit having a lactone structure. As the lactone structure, any lactone structure can be used as long as it has a lactone structure. A 5- to 7-membered ring lactone structure is preferred, and other ring structures are preferably fused in a form of forming a bicyclic structure or a spiro ring structure in the 5- to 7-membered ring lactone structure. More preferably, it contains a repeating unit having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-17). In addition, the lactone structure can be directly bonded to the main chain. As preferred lactone structures, they are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14), (LC1-17), and the particularly preferred lactone structure is (LC1-4). By using such a specific lactone structure, LWR and development defects become good.

[0533]

[0534] The lactone structure portion may or may not have a substituent (Rb2).

[0535] As preferred substituents (Rb2), examples include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, an acid-decomposable group, etc. More preferably, an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, the multiple substituents (Rb2) present may be the same or different. In addition, the multiple substituents (Rb2) present may bond to each other to form a ring.

[0536] The repeating unit having a lactone group usually has optical isomers, and any optical isomer can be used. In addition, one kind of optical isomer can be used alone, or multiple optical isomers can be used in combination. When mainly using one kind of optical isomer, its optical purity (ee) is preferably 90% by mass or more, more preferably 95% by mass or more.

[0537] As the repeating unit having a lactone structure, the repeating unit represented by the following general formula (VI) is preferred.

[0538]

[0539] The aforementioned Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent (preferably an alkyl group having 1 to 4 carbon atoms). Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb0 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, and particularly preferably a hydrogen atom and a methyl group.

[0540] Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic cycloalkyl structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group formed by combining them. Ab is preferably a single bond, a divalent linking group represented by -Ab1-CO2-.

[0541] Ab1 is a straight-chain or branched alkylene group, a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, a norbornylene group.

[0542] V represents a group having a lactone structure. Specifically, for example, it represents a group having a structure shown in any of the above general formulas (LC1-1) to (LC1-17).

[0543] When the resin (H) contains repeating units having a lactone structure, the content of the repeating units having a lactone structure is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 65 mol%, still more preferably in the range of 5 to 60 mol%, particularly preferably in the range of 3 to 50 mol%, and most preferably in the range of 10 to 50 mol% with respect to all the repeating units of the resin (H).

[0544] The repeating units having a lactone structure may be one kind or two or more kinds may be used in combination.

[0545] The following shows specific examples of the repeating units having a lactone structure. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0546]

[0547] The resin (H) preferably contains repeating units having a hydroxyl group or a cyano group. Thereby, the substrate adhesion and the developer affinity are improved. The repeating units having a hydroxyl group or a cyano group are preferably repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group.

[0548] In addition, the repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group are preferably different from the repeating units represented by the above general formula (VI).

[0549] As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, adamantyl, diamantyl, and norbornyl are preferred. As the preferred alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, partial structures represented by the following general formulas (VIIa) to (VIId) are preferred.

[0550]

[0551] In the general formulas (VIIa) to (VIIc), R 2c ~R 4c each independently represents a hydrogen atom, a hydroxyl group, or a cyano group. Among them, at least one of R 2c ~R 4c represents a hydroxyl group or a cyano group. Preferably, one or two of R 2c ~R 4c are hydroxyl groups and the rest are hydrogen atoms. In the general formula (VIIa), it is further preferred that two of R 2c ~R 4c are hydroxyl groups and the rest are hydrogen atoms.

[0552] As the repeating units having the partial structures represented by the general formulas (VIIa) to (VIId), repeating units represented by the following general formulas (AIIa) to (AIId) can be cited.

[0553]

[0554] In general formulas (AIIa) to (AIId), R 1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R 2c to R 4c are synonymous with R 2c to R 4c in general formulas (VIIa) to (VIIc).

[0555] Resin (H) may or may not contain repeating units having a hydroxyl group or a cyano group. When resin (H) contains repeating units having a hydroxyl group or a cyano group, the content of the repeating units having a hydroxyl group or a cyano group is preferably 1 to 40 mol%, more preferably 3 to 30 mol%, and further preferably 5 to 25 mol% relative to all the repeating units in resin (H).

[0556] Specific examples of the repeating units having a hydroxyl group or a cyano group are listed below.

[0557]

[0558] Resin (H) may contain repeating units having an acid group. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bis-sulfonylimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α-position (e.g., a hexafluoroisopropanol group). More preferably, it contains repeating units having a carboxyl group. By containing repeating units having an acid group, the resolution in contact hole applications is increased. As the repeating units having an acid group, any of the repeating units in which an acid group is directly bonded to the main chain of the resin, such as the repeating units obtained from acrylic acid and methacrylic acid, or the repeating units in which an acid group is bonded to the main chain of the resin via a linking group, or further those formed by using a polymerization initiator or a chain transfer agent having an acid group during polymerization and introducing it to the end of the polymer chain are preferred. The linking group may have a monocyclic or polycyclic hydrocarbon structure. Particularly preferred are the repeating units obtained from acrylic acid and methacrylic acid.

[0559] Resin (H) may or may not contain repeating units having an acid group. When it contains them, the content ratio of the repeating units having an acid group is preferably 15 mol% or less, more preferably 10 mol% or less, relative to all the repeating units in resin (H). When resin (H) contains repeating units having an acid group, the content of the repeating units having an acid group in resin (A) is usually 1 mol% or more. Specific examples of the repeating units having an acid group are shown below. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0560]

[0561] The resin (H) may further contain a repeating unit having an alicyclic hydrocarbon structure that does not contain a polar group (e.g., the aforementioned acid group, hydroxyl group, cyano group) and does not exhibit a group that decomposes by the action of an acid to generate a polar group. Thereby, when performing liquid immersion exposure, the elution of low molecular components from the resist film into the liquid immersion liquid is reduced, and the solubility of the resin can be appropriately adjusted during development using a developer containing an organic solvent. As such a repeating unit, a repeating unit represented by the general formula (VIII) can be cited.

[0562]

[0563] In the general formula (VIII), R5 represents a hydrocarbon group having at least one cyclic structure and no polar group. Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. Ra2 represents a hydrogen atom, an alkyl group, or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0564] The cyclic structure of R5 includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. As the monocyclic hydrocarbon group, for example, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, etc., which are cycloalkyl groups having 3 to 12 carbon atoms, and cyclohexenyl, etc., which are cycloalkenyl groups having 3 to 12 carbon atoms can be cited. As the preferred monocyclic hydrocarbon group, it is a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably cyclopentyl or cyclohexyl.

[0565] The polycyclic hydrocarbon group includes a ring assembly hydrocarbon group and a crosslinked cyclic hydrocarbon group. As an example of the ring assembly hydrocarbon group, it includes dicyclohexyl, perhydro-naphthyl, etc. As the crosslinked cyclic hydrocarbon ring, for example, bicyclic hydrocarbon rings such as pinane, camphane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.), and tricyclic hydrocarbon rings such as tricyclo[5.2.1.0(3,8)]decane, adamantane, tricyclo[5.2.1.02,6]decane, tricyclo[4.3.1.12,5]undecane ring, and tetracyclic hydrocarbon rings such as tetracyclo[4.4.0.12,5.17,10]dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, etc. In addition, the crosslinked cyclic hydrocarbon ring also includes a fused ring hydrocarbon ring, for example, a fused ring formed by condensing a plurality of 5 to 8-membered cycloalkane rings such as perhydro-naphthalene (decahydronaphthalene), perhydro-anthracene, perhydro-phenanthrene, perhydro-acenaphthene, perhydro-fluorene, perhydro-indene, perhydro-phenanthrene ring.

[0566] As the preferred crosslinked cyclic hydrocarbon ring, norbornyl, adamantyl, bicyclooctyl, tricyclo[5,2,1,02,6]decyl, etc. can be cited. As the more preferred crosslinked cyclic hydrocarbon ring, norbornyl and adamantyl can be cited.

[0567] These alicyclic hydrocarbon groups may have substituents. Preferred substituents include halogen atoms, alkyl groups, hydroxyl groups in which the hydrogen atom is substituted, amino groups in which the hydrogen atom is substituted, etc. Preferred halogen atoms include bromine, chlorine, and fluorine atoms. Preferred alkyl groups include methyl, ethyl, butyl, and tert-butyl groups. The above alkyl groups may further have substituents. Substituents that the alkyl groups may further have include halogen atoms, alkyl groups, hydroxyl groups in which the hydrogen atom is substituted, and amino groups in which the hydrogen atom is substituted.

[0568] As substituents of the above hydrogen atom, for example, alkyl groups, cycloalkyl groups, aralkyl groups, substituted methyl groups, substituted ethyl groups, alkoxycarbonyl groups, and aralkoxycarbonyl groups can be cited. Preferred alkyl groups include alkyl groups having 1 to 4 carbon atoms. Preferred substituted methyl groups include methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, and 2-methoxyethoxymethyl. Preferred substituted ethyl groups include 1-ethoxyethyl and 1-methyl-1-methoxyethyl. Preferred acyl groups include aliphatic acyl groups having 1 to 6 carbon atoms such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl. As alkoxycarbonyl groups, alkoxycarbonyl groups having 1 to 4 carbon atoms can be cited.

[0569] Resin (H) may optionally contain: repeating units having an alicyclic hydrocarbon structure that does not contain polar groups and does not exhibit acid decomposability. When contained, the content rate of the repeating units is preferably 1 to 40 mol%, more preferably 1 to 20 mol%, relative to all the repeating units in resin (H).

[0570] Specific examples of repeating units having an alicyclic hydrocarbon structure that does not contain polar groups and does not exhibit acid decomposability are given below. In the formula, Ra represents H, CH3, CH2OH, or CF3.

[0571]

[0572] In addition to the above repeating structural units, resin (H) may have various repeating structural units for the purpose of adjusting dry etching resistance, adaptability to standard developing solutions, substrate adhesion, resist profile, and further resolution, heat resistance, sensitivity, etc., which are generally required characteristics of resists.

[0573] As such repeating structural units, repeating structural units corresponding to the following monomers can be cited.

[0574] Thereby, fine adjustment of the performance required for the resin used in the composition of the present invention, particularly (1) solubility in coating solvents, (2) film-forming properties (glass transition temperature), (3) alkali developability, (4) film reduction (hydrophilicity / hydrophobicity, selection of alkali-soluble groups), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance, etc., can be achieved.

[0575] Examples of the monomer described above include compounds having one addition-polymerizable unsaturated bond, such as those selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

[0576] In addition, any addition-polymerizable unsaturated compound that can copolymerize with the monomers corresponding to the various repeating structural units described above can be copolymerized.

[0577] In the resin (H), the molar ratio of the content of each repeating structural unit is appropriately set to adjust the dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, and further the resolution, heat resistance, sensitivity, etc., which are the performance generally required for a resist.

[0578] The form of the resin (H) can be any of a random type, a block type, a comb type, and a star type. The resin (A) can be synthesized, for example, by radical, cationic, or anionic polymerization of unsaturated monomers corresponding to each structure. Alternatively, a target resin can be obtained by polymerizing unsaturated monomers corresponding to precursors of each structure and then performing a polymer reaction.

[0579] When the resist composition (3) is used as a composition for ArF exposure, from the viewpoint of transparency to ArF light, the resin (A) used in the composition of the present invention preferably does not substantially have an aromatic ring (specifically, in the resin, the ratio of repeating units having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally 0 mol%, that is, preferably does not have an aromatic group), and the resin (H) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

[0580] The mass content rate of the CH3 partial structure in the side chain portion of the resin (H) is preferably 1.0% or more and less, more preferably 2.0% or more and less, and further preferably 3.0% or more and less.

[0581] As the resin (H), it is preferable that all the repeating units are composed of (meth)acrylate-based repeating units. In this case, a resin in which all the repeating units are methacrylate-based repeating units, a resin in which all the repeating units are acrylate-based repeating units, and a resin obtained based on both methacrylate-based repeating units and acrylate-based repeating units can all be used, and the acrylate-based repeating units are preferably 50 mol% or less of all the repeating units. In addition, a copolymer containing 20 to 50 mol% of (meth)acrylate-based repeating units having a group that decomposes by the action of an acid to generate a polar group, 20 to 50 mol% of (meth)acrylate-based repeating units having a lactone group, 5 to 30 mol% of (meth)acrylate-based repeating units having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and 0 to 20 mol% of other (meth)acrylate-based repeating units is also preferable.

[0582] When irradiating the resist composition (3) with a KrF excimer laser, electron beam, X-ray, high-energy light having a wavelength of 50 nm or less (EUV, etc.), the resin (H) preferably further has a hydroxystyrene-based repeating unit. More preferably, it preferably has a hydroxystyrene-based repeating unit, a hydroxystyrene-based repeating unit protected by an acid-decomposable group, and an acid-decomposable repeating unit such as a tert-alkyl (meth)acrylate.

[0583] As the repeating unit of the hydroxystyrene-based having a preferable acid-decomposable group, for example, repeating units based on tert-butoxycarbonyloxystyrene, 1-alkoxyethoxystyrene, tert-alkyl (meth)acrylate, etc. can be cited, and repeating units based on 2-alkyl-2-adamantyl (meth)acrylate and dialkyl(1-adamantyl)methyl (meth)acrylate are more preferable.

[0584] The resin (H) can be synthesized by a conventional method (for example, radical polymerization). For example, as a general synthesis method, a one-shot polymerization method in which monomer species and an initiator are dissolved in a solvent and polymerized by heating can be cited; a dropwise polymerization method in which a solution of monomer species and an initiator is dropwise added to a heated solvent over 1 to 10 hours, etc., and the dropwise polymerization method is preferred. As the reaction solvent, for example, ethers such as tetrahydrofuran, 1,4-dioxane, diisopropyl ether, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ester solvents such as ethyl acetate, amide solvents such as dimethylformamide, dimethylacetamide, and further solvents such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone that dissolve the composition of the present invention can be cited. More preferably, the same solvent as that used in the resist composition (3) is preferably used for polymerization. Thereby, generation of fine particles during storage can be suppressed.

[0585] The polymerization reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon. A commercially available radical initiator (azo initiator, peroxide, etc.) is used as the polymerization initiator to initiate the polymerization. As the radical initiator, an azo initiator is preferred, and an azo initiator having an ester group, a cyano group, or a carboxyl group is more preferred. Examples of preferred initiators include azobisisobutyronitrile, azobis(dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), etc. The initiator is added additionally or batchwise according to requirements. After the reaction is completed, it is put into a solvent and the desired polymer is recovered by methods such as powder or solid component recovery. The reaction concentration is 5 to 50% by mass, preferably 10 to 30% by mass. The reaction temperature is usually 10°C to 150°C, preferably 30°C to 120°C, and more preferably 60 to 100°C.

[0586] After the reaction is completed, it is cooled to room temperature and purified. Purification can be carried out by conventional methods such as liquid-liquid extraction methods for removing residual monomers and oligomer components by washing with water and combining appropriate solvents, ultrafiltration for extracting and removing only components below a specific molecular weight in the solution state, reprecipitation methods for removing residual monomers by dropping the resin solution into a poor solvent to solidify the resin in the poor solvent, and purification methods in the solid state such as washing the filtered resin slurry with a poor solvent. For example, the resin is precipitated in solid form by bringing the above resin into contact with a poorly soluble or insoluble solvent (poor solvent) in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

[0587] As the solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation of the polymer solution, any solvent that is a poor solvent for the polymer can be used, and it can be appropriately selected from hydrocarbons, halogenated hydrocarbons, nitro compounds, ethers, ketones, esters, carbonates, alcohols, carboxylic acids, water, mixed solvents containing these solvents, etc. according to the type of polymer. Among these, as the precipitation or reprecipitation solvent, a solvent containing at least an alcohol (especially methanol, etc.) or water is preferred.

[0588] The amount of the precipitation or reprecipitation solvent can be appropriately selected considering efficiency, yield, etc., and is usually 100 to 10000 parts by mass, preferably 200 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass relative to 100 parts by mass of the polymer solution.

[0589] As the temperature for precipitation or reprecipitation, it can be appropriately selected considering efficiency and operability, and is usually about 0 to 50°C, preferably around room temperature (e.g., about 20 to 35°C). The precipitation or reprecipitation operation can be carried out using a conventional mixing container such as a stirring tank by known methods such as batchwise or continuous methods.

[0590] Precipitated or reprecipitated polymers are usually subjected to conventional solid-liquid separation such as filtration and centrifugation, and then dried for use. Filtration is carried out using a solvent-resistant filter medium, preferably under pressure. Drying is carried out at normal pressure or reduced pressure (preferably reduced pressure), at a temperature of about 30 to 100 °C, preferably about 30 to 50 °C.

[0591] It should be noted that the resin can be temporarily precipitated, separated, and then redissolved in a solvent to bring the resin into contact with a poorly soluble or insoluble solvent. That is, it can be a method including the following steps: after the above radical polymerization reaction is completed, bringing the polymer into contact with a poorly soluble or insoluble solvent to precipitate the resin (step a); separating the resin from the solution (step b); redissolving it in a solvent to prepare a resin solution A (step c); then, for this resin solution A, bringing the resin into contact with a poorly soluble or insoluble solvent in a volume less than 10 times the volume of the resin solution A (preferably 5 times or less the volume), so that the resin solid precipitates (step d); separating the precipitated resin (step e).

[0592] In addition, after the preparation of the composition, in order to inhibit resin aggregation, etc., for example, as described in Japanese Patent Laid-Open No. 2009-037108, the synthesized resin is dissolved in a solvent to form a solution, and a step of heating the solution at about 30 °C to 90 °C for about 30 minutes to 4 hours is applied. The weight average molecular weight of the resin (H) is preferably 1000 to 200000, more preferably 2000 to 100000, still more preferably 3000 to 70000, and particularly preferably 5000 to 50000. By setting the weight average molecular weight to 1000 to 200000, deterioration of heat resistance and dry etching resistance can be prevented, and deterioration of developability or an increase in viscosity resulting in deterioration of film formability can be prevented.

[0593] The dispersity (molecular weight distribution) of the resin (H) is usually in the range of 1.0 to 3.0. Resins in the range of preferably 1.0 to 2.6, more preferably 1.1 to 2.5, still more preferably 1.2 to 2.4, particularly preferably 1.3 to 2.2, and most preferably 1.4 to 2.0 are used. When the molecular weight distribution satisfies the above range, the resolution and resist shape are excellent, and the side walls of the resist pattern are smooth and the roughness is excellent.

[0594] Regarding the blending ratio of the resin (H) in the resist composition (3) in the whole composition, it is preferably 30 to 99% by mass, more preferably 60 to 95% by mass in all solid components. In addition, the resin (H) of the present invention can be used alone or in combination of multiple kinds.

[0595] As the mixing ratio of the resin (H) and the fluoropolymer (B) in the resist composition (3), with respect to 100 parts by mass of the resin (H), the fluoropolymer (B) is preferably 0.01 to 10 parts by mass.

[0596] The resist composition (3) may contain a solvent as needed. Examples of the solvent include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds that may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, alkyl pyruvates, and other organic solvents. Specific examples of these solvents can be found in the solvents described in U.S. Patent Application Publication No. 2008 / 0187860, paragraphs

[0441] to

[0455] .

[0597] In addition, in the resist composition (3), as the organic solvent, a mixed solvent obtained by mixing a solvent containing a hydroxyl group in its structure and a solvent not containing a hydroxyl group can be used. As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the aforementioned exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ethers, alkyl lactates, etc. are preferred, and propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol), ethyl lactate are more preferred. In addition, as the solvent not containing a hydroxyl group, alkylene glycol monoalkyl ether acetates, alkyl alkoxypropionates, monoketone compounds that may contain a ring, cyclic lactones, alkyl acetates, etc. are preferred. Among these, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate are particularly preferred, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone are most preferred.

[0598] The mixing ratio (by mass) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is preferably 1 / 99 to 99 / 1, 10 / 90 to 90 / 10, and more preferably 20 / 80 to 60 / 40. A mixed solvent containing 50% by mass or more of the solvent not containing a hydroxyl group is particularly preferred in terms of coating uniformity.

[0599] The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[0600] As a method of forming a pattern (cured film) such as a color filter using the aforementioned resist composition (1), examples include: coating the resist composition (1) of the present invention on a substrate or another resin layer (for example, another colored curable resin composition layer previously formed on the substrate, etc.), removing volatile components such as solvents to form a colored layer, performing lithography by exposing the colored layer through a photomask, developing, and forming a pattern; coating a colored curable resin composition on a substrate or another resin layer using an inkjet device, removing volatile components such as solvents to form a colored layer, and curing it by exposure to form a pattern, etc.

[0601] When forming a resist pattern using the resist composition (2) and resist composition (3) of the present invention, it is suitable for application not only on a substrate of about 6 inches commonly used but also on a large-diameter substrate of 8 inches or more. As the aforementioned substrate, it is usually a silicon substrate. Of course, it can have a film such as a metal film, silicon oxide, silicon nitride, or silicon oxynitride on the silicon. In addition, the substrate material is not limited to silicon and can be any of the substrate materials used in the manufacture of conventional ICs such as LSIs. Further, if the coating of the resist composition (2) of the present invention, the baking method, exposure method, developer, and development method of the obtained coating film are known methods or conditions used when forming a resist pattern using a positive photoresist in the past, they can be any methods or conditions. Furthermore, the exposure light source used in the exposure can be any of ultraviolet rays, far ultraviolet rays, X-rays, electron rays, etc.

[0602] Examples

[0603] Specific examples are given below to explain the present invention in more detail. In the examples, "parts" and "%" are based on mass unless otherwise specified. It should be noted that the measurement conditions for the IR spectrum, 13 C-NMR spectrum, and GPC of the obtained fluorine-containing compound are as follows.

[0604] [IR spectrum measurement conditions]

[0605] Apparatus: "FTIR-8400S" manufactured by Shimadzu Corporation

[0606] Measurement method: KBr method

[0607] 13 C-NMR spectrum measurement conditions]

[0608] Apparatus: "JNM-AL400" manufactured by JEOL Ltd.

[0609] Solvent: chloroform-d6

[0610] [GPC measurement conditions]

[0611] ​Measuring device: "HLC-8220GPC" manufactured by Tosoh Corporation,

[0612] Column: Guard column "HHR-H" (6.0 mm I.D. × 4 cm) manufactured by Tosoh Corporation + "TSK-GEL GMPWXL-N" (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + "TSK-GEL GMPWXL-N" (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + "TSK-GEL GMPWXL-N" (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation + "TSK-GEL GMPWXL-N" (7.8 mm I.D. × 30 cm) manufactured by Tosoh Corporation

[0613] Detector: ELSD ("ELSD2000" manufactured by Alltech Japan Co., Ltd.)

[0614] Data processing: "GPC-8020 model II data analysis version 4.30" manufactured by Tosoh Corporation

[0615] Measurement conditions: Column temperature 40°C

[0616] Developing solvent: Tetrahydrofuran (THF)

[0617] Flow rate: 1.0 ml / min

[0618] Sample: Substance obtained by filtering a tetrahydrofuran solution with a resin solid content of 1.0 mass% through a microporous filter (5 μl).

[0619] Standard sample: According to the measurement manual of the aforementioned "GPC-8020 model II data analysis version 4.30", the following monodisperse polystyrene with a known molecular weight is used.

[0620] (Monodisperse polystyrene)

[0621] "A-500" manufactured by Tosoh Corporation

[0622] "A-1000" manufactured by Tosoh Corporation

[0623] "A-2500" manufactured by Tosoh Corporation

[0624] "A-5000" manufactured by Tosoh Corporation

[0625] "F-1" manufactured by Tosoh Corporation

[0626] "F-2" manufactured by Tosoh Corporation

[0627] "F-4" manufactured by Tosoh Corporation

[0628] "F-10" manufactured by Tosoh Corporation

[0629] "F-20" manufactured by Tosoh Corporation

[0630] "F-40" manufactured by Tosoh Corporation

[0631] "F-80" manufactured by Tosoh Corporation

[0632] "F-128" manufactured by Tosoh Corporation

[0633] "F-288" manufactured by Tosoh Corporation

[0634] "F-550" manufactured by Tosoh Corporation

[0635] Example 1 (Synthesis of Fluorine-Containing Compound)

[0636] In a glass flask equipped with a stirring device, a thermometer, a condenser tube, and a dropping device, 200 g of a perfluoropolyether compound (X-1) having hydroxyl groups at both ends represented by the following structural formula (X-1), 110 g of diisopropyl ether as a solvent, and 29.1 g of triethylamine as a neutralizing agent were introduced. Stirring was started under a nitrogen stream, and 58.1 g of 2-bromoisobutyryl bromide was added dropwise over 30 minutes while maintaining the temperature inside the flask at 5°C or lower. After the addition was completed, the mixture was stirred at room temperature for 2 hours, then heated to 40°C and stirred for 3 hours to carry out the reaction. The disappearance of 2-bromoisobutyryl bromide was confirmed by gas chromatography measurement.

[0637]

[0638] (In the formula, the average of a is 5, the average of b is 8, and the average number of fluorine atoms is 46. In addition, the number average molecular weight obtained by GPC is 1500.)

[0639] Next, cleaning was carried out by the following method: After adding 275 g of diisopropyl ether as a solvent, 250 g of a 1 N hydrochloric acid aqueous solution was mixed and stirred, then allowed to stand, and the aqueous layer was separated and removed. Cleaning was carried out in the same manner using 250 g of a saturated sodium bicarbonate aqueous solution, and then cleaning was carried out in the same manner using 250 g of a saturated sodium chloride aqueous solution. Next, 20 g of magnesium sulfate as a dehydrating agent was added, allowed to stand for 1 day to complete dehydration, then the dehydrating agent was filtered off to obtain a filtrate. The solvent of this filtrate was distilled off under reduced pressure to obtain 180 g of the fluorine-containing compound (1) of the present invention. As a result of analysis by 13 13C-NMR, it was confirmed that the fluorine-containing compound (1) showed the following structure. The IR spectrum of the fluorine-containing compound (1) is shown in Figure 1 , and the 13 13C-NMR spectrum is shown in Figure 2 .

[0640]

[0641] (In the formula, the average of a is 5, the average of b is 8, and the number average of fluorine atoms is 46.)

[0642] Example 2 (same as above)

[0643] In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 200 g of a perfluoropolyether compound (X-2) having a hydroxyl group at one end represented by the following structural formula (X-2), 250 g of diisopropyl ether as a solvent, and 24 g of triethylamine as a neutralizing agent were charged. Stirring was started under a nitrogen stream, and while maintaining the inside of the flask at 5°C or lower, 38 g of 2-bromo-2-methylpropionyl bromide was added dropwise over 30 minutes. After the addition was completed, the mixture was stirred at room temperature for 2 hours, then heated to 40°C and stirred for 5 hours to carry out the reaction. The disappearance of 2-bromo-2-methylpropionyl bromide was confirmed by gas chromatography measurement.

[0644]

[0645] (In the formula, the average of n is 12, and the number average of fluorine atoms is 77.)

[0646] Next, cleaning was carried out by the following method: After adding 275 g of diisopropyl ether as a solvent, 250 g of a 1N hydrochloric acid aqueous solution was mixed and stirred, allowed to stand, and the aqueous layer was separated and removed. After washing in the same manner with 250 g of a saturated sodium hydrogen carbonate aqueous solution, washing was carried out in the same manner with 250 g of a saturated sodium chloride aqueous solution. Then, 20 g of magnesium sulfate as a dehydrating agent was added, allowed to stand for 1 day to completely dehydrate, and then the dehydrating agent was filtered off to obtain a filtrate. The solvent of the filtrate was distilled off under reduced pressure to obtain 180 g of the fluorine-containing compound (2) of the present invention.

[0647]

[0648] (In the formula, the average of n is 12, and the number average of fluorine atoms is 77.)

[0649] Example 3 (Synthesis of fluoropolymer)

[0650] In a flask subjected to nitrogen substitution, 81.5 g of methyl ethyl ketone as a solvent and 40.9 g of tert-butyl methacrylate were charged, and the temperature was raised to 50°C while stirring under a nitrogen stream. Next, 1.7 g of 2,2'-bipyridine and 0.7 g of copper(I) chloride were added, and while maintaining the inside of the flask at 50°C, the mixture was stirred for 30 minutes. Then, 3.3 g of the fluorine-containing compound (1) synthesized in Example 1 was added, and the reaction was carried out at 50°C for 21 hours under a nitrogen stream to obtain a product.

[0651] Next, 30 g of activated alumina was added to the obtained product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain the fluoropolymer (1) of the present invention. As a result of measuring the molecular weight of the fluoropolymer (1) by GPC, the weight-average molecular weight (Mw) was 8,400 and the number-average molecular weight (Mn) was 5,100. In addition, the fluorine atom content was 13% by mass. The IR spectra of the fluoropolymer (1) are respectively shown in Figure 3 , and 13 the C-NMR spectra are shown in Figure 4 , and the GPC diagrams are shown in Figure 5 . It should be noted that the fluoropolymer (1) is such that in the polymer represented by the above general formula (I), X is a bromine atom, R5 and R6 are methyl groups, R1 and R2 are methylene groups. The total average of n1 and n2 is 45.

[0652] A coating film of a solution containing the obtained fluoropolymer (1) was prepared, the presence or absence of foreign substances (leveling property) in the coating film was confirmed, and the liquid repellency and developability were evaluated. The evaluation methods are shown below. In addition, the results of each evaluation are shown in Table 1.

[0653] <Evaluation of the presence or absence of foreign substances in the coating film (evaluation of leveling property)>

[0654] · Preparation of solution

[0655] A solution (positive resist composition) was prepared by mixing 5 parts of a propylene glycol monomethyl ether acetate (PGMEA) solution containing 20% of the fluoropolymer (1), 10 parts of an acid generator (tritolylsulfonium trifluoromethanesulfonate), 1 part of a quencher (triethylamine), and 1000 parts of an ArF resist resin solution (a solution obtained by dissolving a copolymer of 2-methyl-2-adamantyl methacrylate / γ-butyrolactone methacrylate / 3-hydroxy-1-adamantyl methacrylate at a concentration of 10% in PGMEA).

[0656] · Preparation of coating film

[0657] 3 mL of this solution was dropped onto the central part of a 6-inch silicon wafer, spin-coated at a rotational speed of 3000 rpm for 30 seconds, and then heated and dried at 110 °C for 1 minute to prepare a coating film.

[0658] · Evaluation method of coating film

[0659] The obtained coating film was visually observed and evaluated according to the following criteria.

[0660] ○: No foreign substances were confirmed in a 3 cm square coating film.

[0661] △: 1 to 10 foreign substances were confirmed in a 3 cm square coating film.

[0662] ×: More than 10 foreign substances were confirmed in a 3 cm square coating film.

[0663] <Evaluation of liquid repellency>

[0664] For the surface of the coating film obtained in the aforementioned <Evaluation of the presence or absence of foreign substances in the coating film>, the contact angle of water was measured using a contact angle measuring device ("MODEL CA-W150" manufactured by Kyowa Interface Science Co., Ltd.).

[0665] <Evaluation of developability>

[0666] ·Developing method

[0667] For the coating film phase obtained in the aforementioned <Evaluation of the presence or absence of foreign substances in the coating film>, without using a mask pattern, an ArF excimer lamp (center wavelength 193 nm, irradiation dose 30 mJ / cm2) was irradiated. After irradiation, a heat treatment (PEB treatment) was performed at 110 °C for 60 seconds, and then a development treatment was performed in a 2.38% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds. Then, it was rinsed with pure water for 30 seconds and dried by air spraying. After measuring the film thickness before and after development, the residual film rate was calculated, and the developability was evaluated therefrom. The lower the residual film rate, the more excellent the developability of the coating film.

[0668] ·Evaluation method of developability

[0669] ◎: Residual film rate is 0% (no residual film).

[0670] ○: Residual film rate exceeds 0% and is 10% or less.

[0671] △: Residual film rate exceeds 10% and is 50% or less.

[0672] ×: Residual film rate exceeds 50%.

[0673] Example 4 (the same as above)

[0674] In a flask in which nitrogen substitution was carried out, 81.5 g of methyl ethyl ketone as a solvent and 40.9 g of 2-methyl-2-adamantyl methacrylate were charged, and the temperature was raised to 50 °C while stirring under a nitrogen stream. Then, 1.7 g of 2,2'-bipyridine and 0.7 g of copper chloride were added, and the inside of the flask was maintained at 50 °C while stirring for 30 minutes. Then, 3.3 g of the fluorine-containing compound (1) synthesized in Example 1 was added, and the reaction was carried out at 50 °C for 30 hours under a nitrogen stream to obtain a product.

[0675] Next, 30 g of activated alumina was added to the obtained product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain the fluorine-containing polymer (2) of the present invention. As a result of measuring the molecular weight of the fluorine-containing polymer (2) by GPC, the weight-average molecular weight (Mw) was 7100 and the number-average molecular weight (Mn) was 4600. In addition, the fluorine atom content was 15% by mass. It should be noted that the fluorine-containing polymer (2) is a polymer represented by the aforementioned general formula (I), where X is a bromine atom, R5 and R6 are methyl groups, R1 and R2 are methylene groups. The total average of n1 and n2 is 21.

[0676] Using the fluorine-containing polymer (2), except for this, the same operations as in Example 3 were carried out to prepare a coating film of a solution containing the fluorine-containing polymer (2), the presence or absence of foreign substances in the coating film was confirmed, and the liquid repellency and developability were evaluated. The results of each evaluation are shown in Table 1.

[0677] Example 5 (same as above)

[0678] In a flask in which nitrogen substitution was carried out, 81.5 g of methyl ethyl ketone as a solvent and 40.9 g of 1-isobutoxyethyl methacrylate were charged, and the temperature was raised to 50 °C while stirring under a nitrogen stream. Next, 1.7 g of 2,2'-bipyridine and 0.7 g of copper chloride were added, and the mixture was stirred for 30 minutes while maintaining the temperature inside the flask at 50 °C. Then, 3.3 g of the fluorine-containing compound (1) synthesized in Example 1 was added, and the reaction was carried out at 50 °C for 24 hours under a nitrogen stream to obtain a product.

[0679] Next, 30 g of activated alumina was added to the obtained product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain the fluorine-containing polymer (3) of the present invention. As a result of measuring the molecular weight of the fluorine-containing polymer (3) by GPC, the weight-average molecular weight (Mw) was 7900 and the number-average molecular weight (Mn) was 4900. In addition, the fluorine atom content was 14% by mass. It should be noted that the fluorine-containing polymer (3) is a polymer represented by the aforementioned general formula (I), where X is a bromine atom, R5 and R6 are methyl groups, R1 and R2 are methylene groups. The total average of n1 and n2 is 42.

[0680] Using the fluorine-containing polymer (3), except for this, the same operations as in Example 3 were carried out to prepare a coating film of a solution containing the fluorine-containing polymer (3), the presence or absence of foreign substances in the coating film was confirmed, and the liquid repellency and developability were evaluated. The results of each evaluation are shown in Table 1.

[0681] Example 6 (same as above)

[0682] In a nitrogen-substituted flask, 81.5 g of methyl ethyl ketone as a solvent and 40.9 g of tert-butyl methacrylate were charged, and the temperature was raised to 50 °C while stirring under a nitrogen stream. Next, 1.7 g of 2,2'-bipyridine and 0.7 g of copper(I) chloride were added, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 50 °C. Then, 3.3 g of the fluorine-containing compound (2) synthesized in Example 2 was added, and the reaction was carried out at 50 °C for 21 hours under a nitrogen stream to obtain a product.

[0683] Next, 30 g of activated alumina was added to the obtained product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain the fluorine-containing polymer (4) of the present invention. As a result of measuring the molecular weight of the fluorine-containing polymer (4) by GPC, the weight-average molecular weight (Mw) was 8400 and the number-average molecular weight (Mn) was 5100. In addition, the fluorine atom content was 13% by mass. It should be noted that the fluorine-containing polymer (1) is a polymer represented by the general formula (II) in which X is a bromine atom, R5 and R6 are methyl groups, R1 and R2 are methylene groups, and n3 is on average 48.

[0684] Using the fluorine-containing polymer (4), in the same manner as in Example 3 except for this, a coating film of a solution containing the fluorine-containing polymer (4) was produced, the presence or absence of foreign substances in the coating film was confirmed, and the liquid repellency and developability were evaluated. The results of each evaluation are shown in Table 1.

[0685] Example 7 (same as above)

[0686] In a nitrogen-substituted flask, 81.5 g of methyl ethyl ketone as a solvent and 40.9 g of poly(propylenoxy)methyl acrylate (the repeating number of propylenoxy is 5) were charged, and the temperature was raised to 60 °C while stirring under a nitrogen stream. Next, 1.7 g of 2,2'-bipyridine and 0.7 g of copper(I) chloride were added, and the mixture was stirred for 30 minutes while maintaining the temperature in the flask at 60 °C. Then, 3.3 g of the fluorine-containing compound (1) synthesized in Example 1 was added, and the reaction was carried out at 60 °C for 30 hours under a nitrogen stream to obtain a product.

[0687] Next, 30 g of activated alumina was added to the obtained product and stirred. After filtering the activated alumina, the solvent was removed by distillation under reduced pressure to obtain the fluorine-containing polymer (5) of the present invention. As a result of measuring the molecular weight of the fluorine-containing polymer (5) by GPC, the weight-average molecular weight (Mw) was 7800 and the number-average molecular weight (Mn) was 5200. In addition, the fluorine atom content was 11% by mass. It should be noted that the fluorine-containing polymer (5) is a polymer represented by the general formula (I) in which X is a bromine atom, R5 and R6 are methyl groups, R1 and R2 are methylene groups, and the total average of n1 and n2 is 15.

[0688] Using a fluoropolymer (5), except for this, the operation was carried out in the same manner as in Example 3 to produce a coating film of a solution containing a fluoropolymer (2), and the presence or absence of foreign substances (leveling property) in the coating film was confirmed, and the liquid repellency was evaluated. The evaluation of the presence or absence of foreign substances (leveling property) in the coating film was carried out according to the following method, and the evaluation of the liquid repellency was carried out in the same manner as in Example 3. The evaluation results are shown in Table 2.

[0689] <Evaluation of the presence or absence of foreign substances in the coating film (evaluation of leveling property)>

[0690] · Preparation of solution

[0691] Prepare a solution (negative resist composition) obtained by mixing 5 parts of a propylene glycol monomethyl ether acetate (PGMEA) solution containing 20% fluoropolymer (5), 10 parts of an acid generator (trip-tolylsulfonium trifluoromethanesulfonate), 1 part of a quencher (triethylamine), and 1000 parts of a solution in which a copolymer of 2-methyl-2-adamantyl methacrylate / γ-butyrolactone methacrylate / 3-hydroxy-1-adamantyl methacrylate (a resin whose polarity increases by the action of an acid and as a result its solubility in an organic solvent decreases) is dissolved in PGMEA at a concentration of 10%.

[0692] · Preparation of coating film

[0693] A coating film was produced by the same method as in Example 3.

[0694] · Evaluation method of coating film

[0695] For the film thickness of the obtained coating film, using FE-3000 manufactured by Otsuka Electronics Co., Ltd., 200 measurements were taken at 2 mm intervals in the central part of the coating film, and the standard deviation was measured. The larger the value of the standard deviation, the fewer the foreign substances in the coating film and the more excellent the leveling property.

[0696] Example 8 (resist composition)

[0697] Put 10 g of FASTOGEN Green A110 (manufactured by DIC Corporation) into a plastic bottle, add 60 g of PGMEA, 12 g of DISPERBYK LPN21116 (manufactured by BYK-Chemie GmbH), and 0.3 - 0.4 mm Φ SEPR beads (Sepulbeads), and disperse for 2 hours using a paint conditioner (manufactured by Toyo Seiki Seisaku-sho, Ltd.) to obtain a green pigment dispersion liquid.

[0698] With respect to 42 g of the pigment dispersion, 15 g of UNIDIC RS20-160 manufactured by DIC Corporation as a binder resin, 6 g of ARONIX M-402 manufactured by Toagosei Co., Ltd. as a photopolymerizable monomer, 0.5 g of Irgacure #369 manufactured by BASF Japan Ltd. as a photoinitiator, 0.06 g of a fluoropolymer (5) in terms of solid content, and 37 g of PGMEA were mixed to prepare a color resist composition. The same evaluation of liquid repellency as in Example 3 and the same evaluation of the presence or absence of foreign substances (leveling property) in the coating film as in Example 7 were carried out, and the results are shown in Table 3.

[0699] Comparative Example 1 (Synthesis of a fluoropolymer for comparative control)

[0700] In a glass flask equipped with a stirring device, a thermometer, a condenser, and a dropping device, 20 g of the above-mentioned perfluoropolyether compound (X-1) having hydroxyl groups at both ends, 10 g of diisopropyl ether as a solvent, 0.006 g of p-methoxyphenol as a polymerization inhibitor, and 3.3 g of triethylamine as a neutralizing agent were charged, and stirring was started under an air stream. While maintaining the temperature inside the flask at 10 °C, 3.1 g of methacryloyl chloride was added dropwise over 2 hours. After the addition was completed, the mixture was stirred at 10 °C for 1 hour, heated to 30 °C and stirred for 1 hour, and then heated to 50 °C and stirred for 10 hours to carry out the reaction. The disappearance of methacryloyl chloride was confirmed by gas chromatography measurement.

[0701] Next, the following washing method was repeated 3 times: After adding 72 g of diisopropyl ether as a solvent, 72 g of ion-exchanged water was mixed and stirred, then allowed to stand, and the water layer was separated and removed. Then, 8 g of magnesium sulfate as a dehydrating agent was added, allowed to stand for 1 day to complete dehydration, and then the dehydrating agent was filtered off to obtain a filtrate. The solvent of this filtrate was distilled off under reduced pressure to obtain 20.8 g of the monomer (a′) represented by the following formula.

[0702]

[0703] (In the formula, the average of a is 5, the average of b is 8, and the average number of fluorine atoms is 46.)

[0704] In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 260 g of methyl isobutyl ketone as a solvent was charged, and the temperature was raised to 105 °C with stirring under a nitrogen stream. Next, three dropping solutions, namely, a monomer solution prepared by mixing 20 g of monomer (a′), 80 g of tert-butyl methacrylate, and 80 g of methyl isobutyl ketone as a solvent, an initiator solution prepared by mixing 15 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 60 g of methyl isobutyl ketone as a solvent, were placed in their respective dropping devices, and while maintaining the temperature inside the flask at 105 °C, they were simultaneously dropped over 2 hours. After the dropping was completed, stirring was carried out at 105 °C for 10 hours to obtain a solution containing a fluoropolymer (1′) for comparative control. After the reaction was completed, the solvent was distilled off under reduced pressure and diluted with PGMEA to obtain a PGMEA solution containing 20% of the fluoropolymer (1′). The number-average molecular weight of the fluoropolymer (1′) was 1500, and the weight-average molecular weight was 2600. In addition, the fluorine content was 11%. Using the fluoropolymer (1′), except for this, the operation was the same as in Example 3 to prepare a coating film, the presence or absence of foreign substances in the coating film was confirmed, and the liquid repellency and developability were evaluated. The evaluation methods are shown below. In addition, the results of each evaluation are shown in Table 1.

[0705] Comparative Example 2 (same as above)

[0706] In a glass flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping device, 260 g of methyl isobutyl ketone as a solvent was charged, and the temperature was raised to 105 °C with stirring under a nitrogen stream. Next, three dropping solutions, namely, a monomer solution prepared by mixing 20 g of monomer (a′), 80 g of 2-methyl-2-adamantyl methacrylate, and 80 g of methyl isobutyl ketone as a solvent, an initiator solution prepared by mixing 15 g of tert-butyl peroxy-2-ethylhexanoate as a radical polymerization initiator and 60 g of methyl isobutyl ketone as a solvent, were placed in their respective dropping devices, and while maintaining the temperature inside the flask at 105 °C, they were simultaneously dropped over 2 hours. Two grams of tert-butyl peroxy-2-ethylhexanoate were added additionally 2 hours and 4 hours after the dropping was completed. Then, stirring was carried out at 105 °C for 10 hours to obtain a solution containing a fluoropolymer (2′) for comparative control. After the reaction was completed, the solvent was distilled off under reduced pressure and diluted with PGMEA to obtain a PGMEA solution containing 20% of the fluoropolymer (2′). The number-average molecular weight of the fluoropolymer (2′) was 600, and the weight-average molecular weight was 1100. In addition, the fluorine content was 11%. Using the fluoropolymer (2′), except for this, the operation was the same as in Example 3 to prepare a coating film, the presence or absence of foreign substances in the coating film was confirmed, and the liquid repellency and developability were evaluated. The evaluation methods are shown below. In addition, the results of each evaluation are shown in Table 1.

[0707] Comparative Example 3

[0708] Using the fluoropolymer (1′) obtained in Comparative Example 1, except for this, the operation was carried out in the same manner as in Example 7, the presence or absence of foreign substances in the coating film (leveling property) was confirmed, and the liquid repellency was evaluated. The evaluation results are shown in Table 2.

[0709] Comparative Example 4

[0710] Using the fluoropolymer (2′) obtained in Comparative Example 2, except for this, the operation was carried out in the same manner as in Example 7, the presence or absence of foreign substances in the coating film (leveling property) was confirmed, and the liquid repellency was evaluated. The evaluation results are shown in Table 2.

[0711] Comparative Example 5

[0712] Using the fluoropolymer (1′) obtained in Comparative Example 1, except for this, the operation was carried out in the same manner as in Example 8, the presence or absence of foreign substances in the coating film (leveling property) was confirmed, and the liquid repellency was evaluated. The evaluation results are shown in Table 3.

[0713] [Table 1]

[0714] Table 1

[0715] Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Fluoropolymer (1) (2) (3) (4) (1′) (2′) Contact Angle (degrees) 94 92 98 99 86 85 Foreign Matter in the Coating Film (Leveling Property) ○ ○ ○ ○ Δ × Developability ◎ ◎ ◎ ◎ ◎ ◎ Residual Film Ratio (%) 0 0 0 0 0 0

[0716] [Table 2]

[0717] Table 2

[0718] Example 7 Comparative Example 3 Comparative Example 4 Fluoropolymer (5) (1′) (2′) Contact Angle (degrees) 91 86 85 Leveling Property (Standard Deviation) 18.0 27 30

[0719] [Table 3]

[0720] Table 3

[0721] Example 8 Comparative Example 5 Fluoropolymer (5) (1′) Contact Angle (degrees) 90 86 Leveling Property (Standard Deviation) 19.7 28.7

Claims

1. A fluoropolymer (B), characterized in that, It is represented by the following general formula (I), wherein, PFPE is a poly(perfluoroalkylene ether) chain, R1 and R2 are each an alkylene group having 1 to 4 carbon atoms, R4 is a group that decomposes by the action of an acid to generate a carboxyl group, and in the group that decomposes by the action of an acid to generate a carboxyl group, the hydrogen atom of the carboxyl group is protected by a tert-butyl group, a 2-alkyl-2-adamantyl group or a 1-alkoxyethyl group, R5 and R6 are each a hydrogen atom or a methyl group, X is each a halogen atom, The total average of n1 and n2 is 1 to 800.

2. The fluoropolymer (B) according to claim 1, wherein, R1 and R2 are each a methylene group or an ethylene group.

3. A resist composition, characterized in that, It contains the fluoropolymer (B) described in claim 1.

4. The resist composition according to claim 3, which comprises the fluoropolymer (B) according to claim 1, an alkali-soluble resin (C), a polymerizable compound (D) other than the alkali-soluble resin (C), and a colorant (E).

5. The resist composition according to claim 4, wherein, It contains 0.01 to 10 parts by mass of the fluoropolymer (B) relative to 100 parts by mass of the alkali-soluble resin (C).

6. The resist composition according to claim 3, which comprises the fluoropolymer (B) according to claim 1, a resin (F) whose solubility in an alkaline solution increases by the action of an acid, and an acid generator component (G) that generates an acid upon exposure.

7. The resist composition according to claim 6, wherein, It contains 0.01 to 10 parts by mass of the fluoropolymer (B) relative to 100 parts by mass of the resin (F) whose solubility in an alkaline solution increases by the action of an acid.

8. The resist composition according to claim 3, which comprises the fluoropolymer (B) according to claim 1, a resin (H) whose solubility in an organic solvent decreases by the action of an acid, and an acid generator component (G) that generates an acid upon exposure.

9. The resist composition according to claim 8, wherein, It contains 0.01 to 10 parts by mass of the fluoropolymer (B) relative to 100 parts by mass of the resin (H) whose solubility in an organic solvent decreases by the action of an acid.

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