Method for producing organic halogen compound, compound, acid generator, base generator, quencher, polymer, composition, and method for forming resist pattern

Abstract

The present invention provides a method for producing an organic halogen compound, with which it is possible to produce an organic halogen compound with high selectivity and high yield. Disclosed is a method for producing an organic halogen compound, the method including a halogenation step for halogenating a compound represented by formula (1α), which is a starting material, to obtain an organic halogen compound A represented by formula (1). In the halogenation step, halogenation is carried out in a multiphase system which includes an organic phase that contains an organic solvent as a solvent and an aqueous phase that contains water as a solvent.

Description

Method for producing organic halogen compounds, compounds, acid generators, base generators, quenchers, polymers, compositions, and methods for forming resist patterns

[0001] The present invention relates to a method for producing an organic halogen compound, a compound, an acid generator, a base generator, a quencher, a polymer, a composition, and a method for forming a resist pattern.

[0002] Various compounds such as thionyl halides, phosphorus halides, and hydrogen halides are known as raw materials for synthesizing organic halogen compounds from alcohols.

[0003] For example, Patent Document 1 and Non-Patent Document 1 describe a method for producing an iodine compound by reacting an alcohol with hydroiodic acid. Patent Document 2 describes a method for producing an iodine compound by carrying out an iodination reaction using an alcohol and hydroiodic acid while distilling off water from the reaction system. It also describes carrying out the iodination reaction while distilling off water from the reaction system so that the concentration of hydroiodic acid in the aqueous layer falls within a specific range.

[0004] JP 2000-256231 A JP 2010-159223 A

[0005] J. Chem. Soc. 636, 1943.

[0006] Organohalogen compounds can be easily synthesized by mixing thionyl halide with alcohol and adjusting the reaction temperature to suit the structure of the alcohol, within the range from room temperature to the boiling point. However, because thionyl halide reacts violently with water, it is necessary to remove water from the reaction system, which tends to make the process complicated.

[0007] Halogenation using phosphorus halides has a low tendency to isomerize and produce alkenes. Therefore, from the viewpoint of synthesizing organic halogen compounds from secondary and tertiary alcohols, halogenation using phosphorus halides is suitable and generally has a high yield. On the other hand, halogenation using phosphorus halides is likely to produce organic phosphorus compounds as by-products, which may make purification difficult.

[0008] Furthermore, as in the case of thionyl halide, the halogenation also reacts violently with water, so it is necessary to remove water from the reaction system.

[0009] Examples of halogenation using hydrogen halide include a method of reacting an alcohol with hydriodic acid to produce an iodine compound, as described in Patent Document 1 and Non-Patent Document 1.

[0010] Hydrogen halides are stable in aqueous solution and therefore easier to handle than thionyl halides and phosphorus halides, but they also tend to result in lower yields and the formation of by-products.

[0011] In halogenation using hydrogen halide, there is also a method of specifying the concentration range of hydrogen halide in the reaction system, as described in Patent Document 2. For example, when the above method is used for a polyhydric alcohol, there is a concern that the reaction purity will decrease and an improvement in yield will not be achieved.

[0012] Therefore, when producing an organic halogen compound by halogenating an alcohol using hydrogen halide, a method for improving the yield of the product organic halogen compound is desired.

[0013] An object of one embodiment of the present invention is to provide a method for producing an organic halogen compound, which can produce an organic halogen compound with high selectivity and high yield.

[0014] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that when producing an organohalogen compound using an alcohol and an aqueous hydrogen halide solution as raw materials, the above-mentioned problems can be solved by carrying out the halogenation in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent, thereby completing the present invention.

[0015] The present invention includes the following aspects: <1> A method for producing an organic halogen compound, comprising a halogenation step of halogenating a raw material compound represented by the following formula (1α) to obtain an organic halogen compound A represented by the following formula (1), wherein the halogenation step is carried out in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.

[0016]

[0017] (In formula (1α), RG is a group containing at least one cyclic structure, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. １ At least one of these is a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. m' is an integer of 2 to 10.

[0018]

[0019] (In formula (1), RG is a group containing at least one cyclic structure, X is F, Cl, Br or I, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5, provided that m' ≠ m and m' - m ≧ 1.

[0020] <2> In the formula (1α), all R １ At least two of the X's are hydroxy groups, and in the formula (1), at least one of all X's is I, and all R's are １ At least one of the groups is a hydroxy group.

[0021] <3> The method for producing an organic halogen compound according to <1> or <2>, wherein a halogenating agent is used in the halogenation step.

[0022] <4> The method for producing an organic halogen compound according to <3>, wherein the halogenating agent is at least one selected from the group consisting of hydrogen halide, phosphorus halide, a combination of a sulfonyl halide and a halogen source, thionyl halide, Vilsmeier reagent, and a combination of triphenylphosphine and a halogen source.

[0023] <5> The method for producing an organic halogen compound according to <3> or <4>, wherein the halogenating agent is a water-soluble halogenating agent.

[0024] <6> The method for producing an organic halogen compound according to any one of <3> to <5>, wherein the halogenating agent is an aqueous hydrogen halide solution.

[0025] <7> The method for producing an organic halogen compound according to <6>, wherein the aqueous hydrogen halide solution is hydroiodic acid.

[0026] <8> The method for producing an organic halogen compound according to any one of <3> to <7>, wherein the halogenation step includes a step of distilling off water from the aqueous phase to concentrate the halogenating agent.

[0027] <9> The method for producing an organic halogen compound according to any one of <3> to <8>, wherein the halogenation step further comprises a step of adding an additional halogenating agent.

[0028] <10> The method for producing an organic halogen compound according to any one of <1> to <9>, wherein the organic solvent includes an organic solvent that forms an azeotrope with water.

[0029] <11> The method for producing an organic halogen compound according to any one of <1> to <10>, wherein the compound represented by formula (1α) is a secondary or tertiary alcohol.

[0030] <12> The method for producing an organic halogen compound according to any one of <1> to <11>, wherein the compound represented by formula (1α) is a compound represented by the following formula (1α-1):

[0031]

[0032] (In formula (1α-1), R ２ , R ３ and R ４ are each independently a hydrogen atom, a hydroxy group, a nitro group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may have at least one substituent, the substituent being one or more groups selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, a nitro group, and -NRR', and R and R' are each independently a hydrogen atom, a hydroxy group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may have at least one substituent.

[0033] <13> A compound produced by the production method according to any one of <1> to <12>.

[0034] <14> An acid generator comprising a structure derived from the compound according to <13>.

[0035] <15> A base generator or quencher comprising a structure derived from the compound according to <13>.

[0036] <16> A polymer containing a structural unit derived from the compound according to <13> in the main chain or side chain.

[0037] <17> A composition comprising one or more selected from the group consisting of the compound according to <13>, the acid generator according to <14>, the base generator or quencher according to <15>, and the polymer according to <16>.

[0038] <18> The composition according to <17>, which is for forming a film.

[0039] <19> A method for forming a resist pattern, comprising: a step of applying the composition according to <18> onto a substrate to form a resist film; a step of exposing the resist film to a pattern; and a step of developing the exposed resist film.

[0040] According to the present invention, there is provided a method for producing an organic halogen compound, which can produce an organic halogen compound with high selectivity and high yield.

[0041] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, an embodiment of the present invention (hereinafter also referred to as the present embodiment) will be described in detail.

[0042] <<Method for Producing Organohalogen Compound>> The method for producing an organohalogen compound of the present embodiment (also simply referred to as the production method of the present embodiment in this specification) includes a halogenation step of halogenating a compound represented by the following formula (1α), which is a raw material, to obtain organohalogen compound A represented by the following formula (1). The halogenation step is a step of performing halogenation in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.

[0043]

[0044] (In formula (1α), RG is a group containing at least one cyclic structure, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. １ At least one of these is a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. m' is an integer of 2 to 10.

[0045]

[0046] (In formula (1), RG is a group containing at least one cyclic structure, X is F, Cl, Br or I, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5, provided that m' ≠ m and m' - m ≧ 1.

[0047] The method for producing an organic halogen compound according to the present embodiment includes the above-described configuration, and thus can produce an organic halogen compound with high selectivity and high yield.

[0048] <Halogenation Step> In the present embodiment, the halogenation step is a step of halogenating a compound represented by the following formula (1α), which is a raw material, to obtain an organic halogen compound A represented by formula (1). The halogenation step is a step of performing halogenation in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.

[0049] (Compound Represented by Formula (1α)) In the halogenation step, the compound represented by the following formula (1α), which is a raw material, is halogenated.

[0050]

[0051] (In formula (1α), RG is a group containing at least one cyclic structure, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. １ At least one of these is a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. m' is an integer of 2 to 10.

[0052] In formula (1α), RG is a group containing at least one cyclic structure. The valence of RG may be appropriately adjusted depending on the number of substituents, etc. The cyclic structure may contain an aromatic ring, an alicyclic ring, or a heterocyclic ring.

[0053] RG is preferably a group having 6 to 60 carbon atoms, more preferably a group having 6 to 30 carbon atoms, still more preferably a group having 7 to 15 carbon atoms, and particularly preferably a group having 8 to 12 carbon atoms.

[0054] RG is preferably a group derived from benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, fluorene, cyclohexane, cyclododecane, dicyclopentane, norbornane, decahydronaphthalene, tricyclodecane, or adamantane.

[0055] Among the above, from the viewpoint of availability and the like, RG is more preferably a group derived from benzene, naphthalene, phenanthrene, fluorene or adamantane, and even more preferably a group derived from adamantane.

[0056] R １ are each independently preferably a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, and further having at least one substituent selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, and a thioether group, and more preferably a hydroxy group, a carboxyl group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, and further having at least one substituent selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, and an amino group.

[0057] There are no particular restrictions on the monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. For example, examples of alkyl groups having 1 to 30 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. For example, examples of aryl groups having 6 to 30 carbon atoms include a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group.

[0058] In formula (1α), the monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond may contain at least one substituent.

[0059] In the present embodiment, unless otherwise defined, the term "polymerizable unsaturated bond" refers to, for example, a carbon-carbon double bond or a carbon-carbon triple bond. Examples of carbon-carbon double bonds include vinyl groups, vinyloxy groups, (meth)allyl groups, (meth)allyloxy groups, 1-propenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, 1-hexenyl groups, 2-hexenyl groups, 3-hexenyl groups, 4-hexenyl groups, 5-hexenyl groups, 1-octenyl groups, 2-octenyl groups, 1-undecenyl groups, 1-pentadecenyl groups, 3-pentadecenyl groups, 7-pentadecenyl groups, 1-octadecenyl groups, 2-octadecenyl groups, 1-undecenyl groups, 1-pentadecenyl groups, 3-pentadecenyl groups, 7-pentadecenyl groups, 1-octadecenyl groups, 2-octadecenyl groups, 1-pentadecen ... Examples of the carbon-carbon triple bond include an ethynyl group, a propargyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 3-pentynyl group, a 4-pentynyl group, and a 1,3-butadiynyl group.

[0060] In this embodiment, unless otherwise defined, the term "substituted" means that one or more hydrogen atoms in a functional group are substituted with a substituent. The substituent may be, for example, one or more groups selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, a nitro group, and -NRR'.

[0061] In the above-mentioned —NRR′, the above-mentioned R and R′ are each independently a hydrogen atom, a hydroxy group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one substituent.

[0062] Examples of the substituent include a halogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a cyano group, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, a heterocyclic group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, and an amino group having 0 to 30 carbon atoms.

[0063] The alkyl group may be any of a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.

[0064] The alkyl group having 1 to 30 carbon atoms is not particularly limited, but examples thereof include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, an n-dodecyl group, and a valeric group. The aryl group having 6 to 30 carbon atoms is not particularly limited, but examples thereof include a phenyl group, a naphthalene group, a biphenyl group, an anthracyl group, a pyrenyl group, and a perylene group.

[0065] When the product, organohalogen compound A represented by formula (1), is used by further linking it to another resin, R １ As the alkyl group, it is preferable that the alkyl group is at least one selected from the group consisting of a hydroxy group, an acetal group, a carbonate ester group (including an alkoxycarbonyloxy group which may further have a substituent, an aryloxycarbonyloxy group which may further have a substituent, and groups having these groups as a substituent), a glycidyl group, a carboxyl group, a carboxylic acid halide group, and an alkyl group having 1 to 30 carbon atoms which may have a substituent or an aryl group having 1 to 30 carbon atoms, wherein the substituent is at least one selected from the group consisting of an alcohol group, an acetal group, a carbonate ester group (including an alkoxycarbonyloxy group which may further have a substituent, an aryloxycarbonyloxy group which may further have a substituent, and groups having these groups as a substituent), a glycidyl group, a carboxyl group, and a carboxylic acid halide group.

[0066] R １ may be a group (hydrolyzable group) represented by the following formula (Y-1):

[0067]

[0068] In formula (Y-1), L ２ is a group that is cleaved by the action of an acid or a base. ２ is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, ２ The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent.

[0069] Examples of the group that is cleaved by the action of an acid or a base include an ester group [* １ -O-(C=O)-* ２ or * １ -(C=O)-O-* ２ ], acetal group [* １ -O-(C(R ２１ ) ２ )-O-* ２ (R ２１ are each independently H or a hydrocarbon group having 1 to 10 carbon atoms.) ], a carboxyalkoxy group [* １ -O-R ２２ -(C=O)-O-* ２ (R ２２ is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], an oxycarbonyl group [* １ -O-(C=O)-* ２ (R ２３ is a divalent hydrocarbon group having 1 to 10 carbon atoms. )], and a carbonate group [* １ -O-(C=O)-O-* ２ In terms of achieving high sensitivity when used in a resist, the ester group is preferably a tertiary ester group. １ is the binding site for A, * ２ is R ２This is the binding site for

[0070] Among these, L ２ From the viewpoint of achieving high sensitivity when used in combination with a copolymer or additive for a resist resin, the group is preferably a tertiary ester group, an acetal group, a carbonate ester group or a carboxyalkoxy group, more preferably an acetal group, a carbonate ester group or a carboxyalkoxy group, and even more preferably an acetal group or a carboxyalkoxy group.

[0071] In addition, from the viewpoint of stable quality polymer production by radical polymerization, L ２ As another effect, when the organic halogen compound A in this embodiment is used as a polymerization unit of a copolymer, from the viewpoint of controlling the polymerizability of the resin and setting the degree of polymerization in a desired range, R １ is preferably a group represented by formula (Y-1).

[0072] By having the group represented by formula (Y-1) as a protecting group for the hydrophilic group in the organohalogen compound A represented by formula (1), variations in copolymer formation and polymerization inhibition resulting from the hydrophilic group can be suppressed.

[0073] L ２ is a carboxyalkoxy group [* １ -O-R ２２ -(C=O)-O-* ２ ], then R ２２ is a divalent hydrocarbon having 1 to 10 carbon atoms, or R ２２ is R ２ Alternatively, it may have a ring structure linked to the organic halogen compound A represented by formula (1).

[0074] R ２ is a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a linear, branched or cyclic aliphatic group having 1 to 30 carbon atoms and containing a heteroatom, or a linear, branched or cyclic aromatic group having 1 to 30 carbon atoms and containing a heteroatom, ２The aliphatic group, aromatic group, aliphatic group containing a hetero atom, and aromatic group containing a hetero atom may further have a substituent. ２ The details of specific examples and preferred specific examples of the substituents in the above are the same as the details of specific examples and preferred specific examples of the substituents described above.

[0075] R ２ The substituent in is preferably a linear, branched or cyclic aliphatic group having 1 to 20 carbon atoms, or an aromatic group having 6 to 20 carbon atoms.

[0076] R ２ Among these, an aliphatic group is more preferable. ２ The aliphatic group in the formula (I) is more preferably a branched or cyclic aliphatic group.

[0077] The aliphatic group preferably has 1 or more and 20 or less carbon atoms, more preferably 3 or more and 10 or less carbon atoms, and even more preferably 4 or more and 8 or less carbon atoms.

[0078] The aliphatic group is not particularly limited, but examples thereof include a methyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a cyclohexyl group, a methylcyclohexyl group, and an adamantyl group. Among these, a tert-butyl group, a cyclohexyl group, and an adamantyl group are preferred.

[0079] L ２ but* １ -(C=O)-O-* ２ Alternatively, in the case of a carboxyalkoxy group, when cleaved by the action of an acid or a base, a carboxylic acid group is formed, which increases the difference in solubility and dissolution rate between the dissociated portion and the non-dissociated portion during development, thereby improving the resolution and suppressing residues at the bottom of a fine line pattern, which is preferable.

[0080] R ２ Specific examples of the group include, but are not limited to, the following: * represents a bonding position.

[0081]

[0082] L ２When is an oxycarbonyl group, specific examples of formula (Y-1) include, but are not limited to, the following: * represents the bonding position.

[0083]

[0084] Specific examples of the group represented by formula (Y-1) include the following groups: * indicates the bonding position.

[0085]

[0086]

[0087]

[0088] Examples of alkoxy groups that can be used as the group represented by formula (Y-1) include alkoxy groups having 1 or more carbon atoms. From the viewpoint of the solubility of a resin after being combined with other monomers to form a resin, the alkoxy group is preferably an alkoxy group having 2 or more carbon atoms, more preferably an alkoxy group having 3 or more carbon atoms, still more preferably an alkoxy group having 3 to 13 carbon atoms, and particularly preferably an alkoxy group having a cyclic structure and having 3 to 13 carbon atoms.

[0089] Specific examples of alkoxy groups that can be used as the group represented by formula (Y-1) include, but are not limited to, the following: * represents the bonding position.

[0090]

[0091]

[0092] Examples of amino groups and amide groups that can be used as the group represented by formula (Y-1) include primary amino groups, secondary amino groups, tertiary amino groups, groups with a quaternary ammonium salt structure, and amides having a substituent. Specific examples of amino groups or amide groups include, but are not limited to, the following. * indicates a bonding position.

[0093]

[0094] In formula (1α), m′ is preferably an integer of 2 to 6, and more preferably an integer of 3 or 4.

[0095] The compound represented by formula (1α) is preferably a compound represented by the following formula (1α-1), and more preferably a compound represented by the following formula (1α-2).

[0096]

[0097]

[0098] (In formula (1α-1) and formula (1α-2), R ２ , R ３ and R ４ are each independently a hydrogen atom, a hydroxy group, a nitro group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may have at least one substituent, the substituent being one or more groups selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, a nitro group, and -NRR', and R and R' are each independently a hydrogen atom, a hydroxy group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may have at least one substituent.

[0099] In formula (1α-1) and formula (1α-2), R ２ , R ３ and R ４ Specific examples of the group include a hydrogen atom, a hydroxy group, a nitro group, —COOH, and —CH ３ , -CH ２ OH, -OCH ３ , -OCH ２ OH, -CH ２ CH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ OH, -CH ２ CH ２ CH ３ , -OCH ２ CH ２ CH ３ , -OCH ２ CH(OH)CH ３ , -OCH ２ CH(OH)CH ２ OH, etc. Preferably, R ２ and R３ is a hydroxy group, and R ４ is a hydrogen atom.

[0100] The halogenation step in this embodiment is a step of performing halogenation in a multi-phase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. As a result, in the multi-phase system, the halogenation of the hydroxy group proceeds well in the aqueous phase, and the substituent R in the compound represented by formula (1α) as the raw material is oxidized. １ Among these, R that remains without being substituted by X in the halogenation step １ is transferred to the organic phase in the presence of at least one

[0101] In particular, when a polyhydric alcohol is used as a raw material, there is a risk that multiple hydroxy groups may be halogenated in multiple stages, which makes the problem of improving the purity and yield of the resulting product more apparent and tends to make it difficult to achieve the problem. The method for producing an organic halogen compound of this embodiment is particularly effective when a polyhydric alcohol is used as a raw material. That is, when the raw material is a polyhydric alcohol, the raw material is present in the aqueous layer, but as the halogenation reaction progresses and the hydroxy groups decrease below a certain amount, its solubility in the aqueous layer decreases, and the product migrates to the organic layer. This keeps the halogen content of the product constant, making it possible to suppress yield reduction due to side reactions.

[0102] The compound represented by formula (1α), which is the raw material, may contain only one hydroxy group or two or more hydroxy groups in the molecule. From the above-mentioned viewpoint, it is preferable that it contains two or more hydroxy groups, and more preferably contains three to ten hydroxy groups.

[0103] The carbon atom to which the hydroxy group to be halogenated is bonded may be any of a primary carbon atom, a secondary carbon atom, and a tertiary carbon atom. From the viewpoints of the purity improvement effect and the yield, however, a secondary carbon atom or a tertiary carbon atom is preferred, and a tertiary carbon atom is more preferred.

[0104] The compound represented by formula (1α) is preferably a secondary or tertiary alcohol, more preferably a tertiary alcohol.

[0105] (Organohalogen Compound A Represented by Formula (1)) In the halogenation step, the product, organohalogen compound A represented by the following formula (1), is obtained.

[0106]

[0107] (In formula (1), RG is a group containing at least one cyclic structure, X is F, Cl, Br or I, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, m is an integer of 1 to 5, and n+m is an integer of 2 to 5, provided that m' ≠ m and m' - m ≧ 1.

[0108] In formula (1), the details of specific embodiments, preferred embodiments, etc. of RG are the same as the details of specific embodiments, preferred embodiments, etc. of RG in formula (1α).

[0109] In formula (1), R １ The specific embodiments and preferred embodiments of the monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond are described in detail in R １ and the specific and preferred aspects of the monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond are the same as those of the specific and preferred aspects of the monovalent group having 0 to 30 carbon atoms.

[0110] In formula (1), n ​​is an integer of 1 to 5, and m is an integer of 1 to 5, provided that m' ≠ m, and m' - m ≥ 1. In other words, m' in formula (1α) and m in formula (1) are not the same, and the value obtained by subtracting m from m' is at least 1 or more, and preferably 1 or more and 9 or less.

[0111] In formula (1), n ​​is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 2.

[0112] In formula (1), m is an integer of 1 to 5. In this embodiment, when m is an integer of 1 or more, the substituent R １Among these, R that remains without being substituted by X in the halogenation step １ But there is at least one.

[0113] That is, in a multi-phase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent, the substituent R １ Among these, R that remains without being substituted by X in the halogenation step １ is transferred to the organic phase in the presence of at least one

[0114] In formula (1), m is preferably an integer of 1 to 3, and more preferably 1.

[0115] The organic halogen compound A represented by formula (1) is preferably an organic halogen compound represented by the following formula (1-1), and more preferably an organic halogen compound represented by the following formula (1-2).

[0116]

[0117]

[0118] (In formula (1-1) and formula (1-2), X is F, Cl, Br or I, and R ２ , R ３ and R ４ are each independently a hydrogen atom, a hydroxy group, a nitro group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one substituent, and the substituent is one or more groups selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, a nitro group, and -NRR', and R and R' are each independently a hydrogen atom, a hydroxy group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one substituent and does not contain a polymerizable unsaturated bond.

[0119] In formula (1-1) and formula (1-2), R ２ , R ３ and R ４ Specific examples of the group include a hydrogen atom, a hydroxy group, a nitro group, —COOH, and —CH ３ , -CH ２ OH, -OCH ３ , -OCH２ OH, -CH ２ CH ３ , -OCH ２ CH ３ , -OCH ２ CH ２ OH, -CH ２ CH ２ CH ３ , -OCH ２ CH ２ CH ３ , -OCH ２ CH(OH)CH ３ , -OCH ２ CH(OH)CH ２ Examples include, but are not limited to, OH and the like.

[0120] In formula (1-2), preferably, R ３ is a hydroxy group, and R ４ is a hydrogen atom, and X is I (iodine).

[0121] In formula (1α), all R １ Preferably, at least two of the groups are hydroxy groups, and more preferably, at least three of the groups are hydroxy groups.

[0122] In formula (1), X is preferably I from the viewpoint of excellent sensitivity when used by bonding to a copolymer or additive for a resist resin.

[0123] In formula (1), at least one of all X is I, and all R １ It is preferred that at least one of X is a hydroxy group, at least two of all X are I (iodine), and all R １ It is more preferable that at least one of the groups is a hydroxy group.

[0124] (Halogenating Agent) In the method for producing an organic halogen compound of this embodiment, a halogenating agent is preferably used in the halogenation step.

[0125] In this embodiment, since it is preferable that the raw material is present in the aqueous layer and the product is present in the organic layer, the halogenating agent is preferably a water-soluble halogenating agent.

[0126] The halogenating agent is preferably at least one selected from the group consisting of hydrogen halide, phosphorus halide, a combination of a sulfonyl halide and a halogen source, thionyl halide, Vilsmeier reagent, and a combination of triphenylphosphine and a halogen source, more preferably hydrogen halide, and even more preferably an aqueous hydrogen halide solution, and the aqueous hydrogen halide solution is preferably hydroiodic acid.

[0127] Hydrogen halide, which is one of the halogenating agents, refers to hydrogen chloride, hydrogen bromide, and hydrogen iodide.

[0128] In this embodiment, it is preferable to use an aqueous solution of hydrogen halide as the raw material.

[0129] The hydrogen halide concentration in the reaction solution is preferably 10% by mass or more, more preferably 25% by mass or more, even more preferably 40% by mass or more, particularly preferably 45% by mass or more, and even more preferably 50% by mass or more. The upper limit of the hydrogen halide concentration in the reaction solution is not particularly limited, but is, for example, 58% by mass or less. When the reaction solution is separated into two or more phases, it is preferable that the hydrogen halide concentration of the aqueous phase containing hydrogen halide is within the above concentration range.

[0130] The concentration of hydrogen halide in the reaction solution is preferably high. On the other hand, hydrogen halide itself is a gas and is therefore distilled off from the reaction system along with water. Therefore, the halogenating agent used as a raw material for the reaction is preferably hydrogen bromide or hydrogen iodide, and more preferably hydrogen iodide.

[0131] The amount of hydrogen halide used relative to the hydroxy groups to be halogenated is preferably 1.01 equivalents or more, more preferably 1.1 equivalents or more, even more preferably 1.3 equivalents or more, and particularly preferably 1.5 equivalents or more, in terms of the molar ratio of the substance, and preferably 10.0 equivalents or less, more preferably 7.0 equivalents or less, and even more preferably 5.0 equivalents or less, in terms of the molar ratio of the substance, relative to the hydroxy groups to be halogenated.

[0132] The halogenation step preferably includes a step of further adding an additional halogenating agent. By adding the halogenating agent in portions, the purity of the resulting product can be improved.

[0133] (Multiphase System) The halogenation step is a step in which halogenation is carried out in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.

[0134] In this embodiment, it is preferable to use an alcohol having two or more hydroxy groups in the molecule as a reaction raw material, and in this case, it is preferable that one or more hydroxy groups remain after the halogenation step.

[0135] The reaction raw material, an alcohol having two or more hydroxy groups in its molecule, is mainly present in the aqueous layer. By extracting the organic halogen compound with one or more remaining hydroxy groups from the reaction raw material, an organic halogen compound with one or more remaining hydroxy groups, into the organic layer (e.g., the hydrophobic solvent phase), can be obtained.

[0136] When a polyhydric alcohol is used as a raw material, the halogenation degree of the resulting product varies due to the presence of multiple hydroxy groups as reaction sites, which makes it necessary to improve the purity and yield of the resulting product.

[0137] In the halogenation step of this embodiment, halogenation is carried out in a multiphase system, so that even when a polyhydric alcohol is used as a raw material, the solubility of the raw material in the aqueous layer decreases and the raw material migrates to the organic layer when multiple hydroxy groups in the raw material are halogenated at a certain ratio, resulting in a constant degree of halogenation in the resulting product. This improves the purity of the resulting product and suppresses a decrease in yield due to side reactions.

[0138] (Organic Solvent) The organic solvent may be any solvent that can be used without particular limitation, but is preferably a hydrophobic solvent. As a method for leaving one or more hydroxy groups, for example, a method of using a hydrophobic solvent as the organic solvent may be mentioned.

[0139] The organic solvent preferably contains an organic solvent that forms an azeotrope with water, and more preferably contains a hydrophobic solvent that forms an azeotrope with water.

[0140] Examples of hydrophobic solvents that form an azeotrope with water include dichloromethane, chloroform, carbon tetrachloride, nitromethane, 1,2-dichloroethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, pentane, cyclohexane, hexane, benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, nitrobenzene, phenol, s-butanol, cyclopentyl methyl ether, and cyclohexanone.

[0141] Among the above, the hydrophobic solvent that forms an azeotropic mixture with water preferably includes hexane, toluene, o-xylene, m-xylene, or p-xylene.

[0142] The organic solvent may be used alone or in combination of two or more hydrophobic solvents.

[0143] The amount of the organic solvent is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, relative to 1 part by mass of the raw material alcohol. The amount of the organic solvent is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and even more preferably 15 parts by mass or more, relative to 1 part by mass of the raw material alcohol.

[0144] (Acid) In the halogenation step, an acid may further be used.

[0145] Examples of the acid include sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, malic acid, lactic acid, glycolic acid, succinic acid, chromic acid, and boric acid.

[0146] (Metal Halide) In the halogenation step, a metal halide may further be used.

[0147] When hydrogen chloride is used as the halogenating agent, examples of the metal halide include LiCl, NaCl, KCl, and MgCl. ２ , CaCl ２ , AlCl３ etc. may also be used.

[0148] When hydrogen bromide is used as the halogenating agent, examples of the metal halide include LiBr, NaBr, KBr, and MgBr. ２ , CaBr ２ , AlBr ３ etc. may also be used.

[0149] When hydrogen iodide is used as the halogenating agent, examples of the metal halide include LiI, NaI, KI, and MgI. ２ , CaI ２ , AlI ３ etc. may also be used.

[0150] From the viewpoint of preventing bumping during the reaction, it is preferable to stir the reaction liquid.

[0151] The shape of the stirring blade is not particularly limited, and examples include flat paddle blades, inclined paddle blades, turbine blades, disc turbine blades, propeller blades, three-bladed swept blades, anchor blades, helical ribbon blades, screw blades, anchor blades, Max Blend, Full Zone, Twin Star, etc.

[0152] The stirring speed can be any speed.

[0153] When a hydrophobic solvent is used to separate the reaction liquid into two liquid-liquid phases, the stirring speed may be set to a level at which the interface fluctuates, at which some oil droplets or water droplets are generated and dispersed, or at which a completely dispersed state is achieved.

[0154] The reaction temperature is preferably 0 to 150°C, more preferably 20 to 150°C, and even more preferably 50 to 120°C.

[0155] [Concentration Step] In the method for producing an organic halogen compound of this embodiment, the halogenation step preferably includes a step of concentrating the halogenating agent by distilling off water from the aqueous phase (also referred to as a concentration step). This allows the reaction solution to be concentrated, and the product to be obtained with higher purity.

[0156] In the concentration step, the water to be distilled off may be only the water in the aqueous phase, or may be both the water in the aqueous phase and the water in the organic phase. From the viewpoint that by distilling off the water in the organic phase, the reaction in the organic phase can be further suppressed and a product with higher purity can be obtained, it is preferable to distill off both the water in the aqueous phase and the water in the organic phase.

[0157] From the viewpoint of efficiently distilling off water, it is preferable that the reaction temperature of the halogenation is the same as the boiling point of the reaction solution. When the boiling point varies due to the use of a hydrophobic solvent, the reaction temperature can be controlled by carrying out the reaction under reduced pressure or increased pressure.

[0158] The reaction temperature of the halogenation can also be controlled by changing the stirring speed.

[0159] Generally, when a hydrophobic solvent forms an azeotrope with water, the azeotropic point is lower than the boiling point of the solvent. When a hydrophobic solvent that forms an azeotrope with water is used to separate a reaction solution into two liquid-liquid phases, the two phases approach a completely dispersed state as the stirring speed increases, and the boiling point also approaches the azeotropic point, so the reaction temperature can be controlled by the stirring speed.

[0160] When concentrating the reaction solution, all of the water distilled by simple distillation may be distilled off, or a required amount may be distilled off using a Dean-Stark apparatus or the like, but it is preferable to distill off the required amount using a Dean-Stark apparatus or the like.

[0161] The amount of water to be distilled off is preferably determined so as to maintain the concentration of the halogenating agent at a predetermined concentration or higher. The concentration is preferably at least 15% by mass lower than the concentration of the halogenating agent charged, more preferably at least 10% by mass lower than the concentration of the halogenating agent charged, even more preferably at least 5% by mass lower than the concentration of the halogenating agent charged, and particularly preferably at least the concentration of the halogenating agent charged. In addition, a certain amount of water may be distilled off continuously, or may be distilled off all at once at predetermined time intervals.

[0162] During the reaction, elemental halogen may be generated by oxidation of the halogenating agent (e.g., hydrogen halide). If elemental halogen remains, it may cause coloration, etc., and therefore it is preferable to reduce it to hydrogen halide using a reducing agent. The type of reducing agent is not particularly limited, and examples thereof include sodium sulfite, sodium hydrogen sulfite, and phosphinic acid.

[0163] The reducing agent may be added directly to the reaction solution or may be added as an aqueous solution. The reducing agent may be added while hydrogen halide remains in the reaction solution, or may be added after neutralizing the hydrogen halide with a base. The base used in the neutralization step is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.

[0164] After the reaction is completed, the organic halogen compound product may be purified and isolated.

[0165] (Purification) When a hydrophobic solvent is used, the hydrophobic solvent phase can be purified by washing with water. For example, pure water, an aqueous sodium chloride solution, an aqueous nitric acid solution, an aqueous oxalic acid solution, an aqueous sulfuric acid solution, an aqueous hydrogen chloride solution, etc. can be suitably used for washing with water. Alternatively, after completion of the reaction, a hydrophobic solvent can be added and washed with water. The hydrophobic solvent added after completion of the reaction may be the same as or different from the hydrophobic solvent used in the reaction.

[0166] Generally, washing with water is carried out at around room temperature, but if the product precipitates when washing with water at room temperature, washing with water may be carried out while heating. The temperature for washing with water is preferably not higher than the azeotropic temperature of the hydrophobic solvent and water.

[0167] The purification may be carried out by passing the reaction solution through an ion exchange resin, a chelating resin, a metal removal filter, a particulate removal filter, or the like.

[0168] The above-mentioned purification using resins and filters may be carried out alone or in combination with an operation such as washing with water.

[0169] Examples of the ion exchange resin include a strongly acidic ion exchange resin, a weakly acidic ion exchange resin, a strongly basic ion exchange resin, and a weakly basic ion exchange resin.

[0170] Examples of cation exchange groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Examples of anion exchange groups include secondary, tertiary, and quaternary ammonium groups.

[0171] Examples of the chelating resin include those containing iminodiacetic acid, thiol, polyamine, sulfonic acid, primary amine, phosphonic acid, methylglucamine, aminophosphate, amidoxime, isothiouronium, bispicolylamine, semithiocarbamic acid, and the like as functional groups.

[0172] Examples of metal removal filters include cation exchange filters, anion exchange filters, and chelate filters. The functional groups of these filters are not particularly limited, and examples of cation exchange filters include sulfonic acid groups, carboxyl groups, and phosphate groups. Examples of anion exchange filters include secondary, tertiary, and quaternary ammonium groups. Examples of chelate filters include iminodiacetic acid, thiol, polyamine, sulfonic acid, primary amine, phosphonic acid, methylglucamine, aminophosphate, amidoxime, isothiouronium, bispicolylamine, and semithiocarbamic acid.

[0173] Adsorption filters can also be used for the purpose of removing metals. Examples of adsorption filters include nylon, polyethersulfone, and cellulose.

[0174] The particle removal filter preferably has a pore size of 1000 nm or less, more preferably 500 nm or less, even more preferably 100 nm or less, and particularly preferably 10 nm or less. The lower limit of the pore size is not particularly limited, but is, for example, 1 nm or more.

[0175] The material of the particulate removal filter is not particularly limited, but examples thereof include nylon, polyethylene, polypropylene, polyfluorocarbon, polyethersulfone, cellulose, and the like.

[0176] The metal removal filter and the particulate removal filter may be a membrane type filter or a hollow fiber type filter.

[0177] (Isolation) The organic halogen compound can be isolated by distillation, crystallization, or the like.

[0178] When isolating by distillation, the distillation method is not particularly limited, and examples thereof include simple batch distillation, equilibrium flash distillation, batch rectification, and continuous rectification.

[0179] The organic halogen compounds may be recovered by distillation or as bottoms or bottoms.

[0180] When isolating by crystallization, the hydrophobic solvent used in the reaction may be used as is, or a new solvent may be added. The solvent may be a single solvent or two or more solvents may be used in combination.

[0181] The amount of the solvent used during crystallization is, in mass ratio, preferably 20 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, per part by mass of the organic halogen compound.

[0182] The amount of the solvent used during crystallization may be 0.5 parts by mass or more, or may be 1 part by mass or more, relative to 1 part by mass of the organic halogen compound.

[0183] The ratio of the solvent to the organic halogen compound can also be adjusted by distilling off the solvent.

[0184] The crystals may be precipitated by adding seed crystals, or by cooling the solution without adding seed crystals. After the crystals are precipitated, it is preferable to cool the slurry to improve the yield.

[0185] The cooling rate is preferably 30°C / h or less, more preferably 20°C / h or less, even more preferably 10°C / h or less, and particularly preferably 5°C / h or less. The cooling rate may be 1°C / h or less, or may be 0.5°C / h or less. The lower limit of the cooling rate is not particularly limited, but is, for example, 0.1°C / h or more.

[0186] The temperature at which the slurry is subjected to solid-liquid separation after cooling is preferably −50 to 40° C., more preferably −20 to 30° C., and even more preferably −20 to 10° C. The holding time from when the slurry temperature reaches the solid-liquid separation temperature until solid-liquid separation occurs is not particularly limited, but is preferably within 24 hours, more preferably within 10 hours.

[0187] The method for solid-liquid separation is not particularly limited, but examples thereof include Nutsche filtration, centrifugation, and pressure filtration.

[0188] <<Compound>> The compound of this embodiment is an organohalogen compound produced by the production method of this embodiment. The compound of this embodiment may be organohalogen compound A represented by formula (1).

[0189] The compound of this embodiment can be used in a variety of applications, for example, as an acid generator, a base generator, a quencher, etc.

[0190] <Acid Generator> The acid generator of this embodiment includes a structure derived from the compound of this embodiment. The acid generator of this embodiment may be an acid generator including a structure derived from organohalogen compound A represented by formula (1).

[0191] <Base Generator, Quencher> The base generator or quencher of this embodiment includes a structure derived from the compound of this embodiment.

[0192] The base generator or quencher of this embodiment may be a base generator or quencher containing a structure derived from the organohalogen compound A represented by formula (1).

[0193] <Polymer> The polymer of this embodiment contains a structural unit derived from the compound of this embodiment in the main chain or side chain.

[0194] As described above, the compound of this embodiment can be used, for example, as an acid generator, a base generator, a quencher, etc. Therefore, for example, when a polymerization reaction is carried out using the acid generator or base generator of this embodiment, the resulting polymer contains a structural unit derived from the compound of this embodiment in the main chain or side chain.

[0195] <Composition> The composition of the present embodiment includes one or more members selected from the group consisting of the compound of the present embodiment, the acid generator of the present embodiment, the base generator or quencher of the present embodiment, and the polymer of the present embodiment.

[0196] The composition of the present embodiment can be used for a variety of purposes. For example, the composition of the present embodiment may be used for forming a film.

[0197] <<Method of Forming Resist Pattern>> The method of forming a resist pattern of the present embodiment includes a step of applying the composition of the present embodiment onto a substrate to form a resist film (also referred to herein as a film formation step), a step of exposing the resist film to a pattern (also referred to herein as an exposure step), and a step of developing the exposed resist film (also referred to herein as a development step).

[0198] <Film Forming Step> The film forming step is a step of applying the composition of this embodiment onto a substrate to form a resist film.

[0199] The method for applying the composition of this embodiment onto a substrate is not particularly limited, and it may be applied by coating.

[0200] The method for applying the composition of this embodiment onto a substrate is not particularly limited, but examples thereof include a spin coater, a dip coater, and a roller coater.

[0201] The substrate is not particularly limited, but examples thereof include silicon wafers, metals, plastics, glass, and ceramics.

[0202] After forming the resist film, it may be subjected to a heat treatment at a temperature of about 50° C. to 200° C. The thickness of the resist film is not particularly limited, but may be, for example, 0.1 to 20 μm, and preferably 0.3 to 2 μm.

[0203] <Exposure Step> The exposure step is a step of exposing the resist film to a pattern. In the exposure step, exposure may be performed through a predetermined mask pattern, or shot exposure may be performed without a mask.

[0204] For exposure, light rays of various wavelengths, such as ultraviolet rays and X-rays, can be used. As the light source, for example, far ultraviolet rays such as F2 excimer laser (wavelength 157 nm), ArF excimer laser (wavelength 193 nm), and KrF excimer laser (wavelength 248 nm), extreme ultraviolet rays (wavelength 13 nm), X-rays, electron beams, etc. can be appropriately selected and used. Among these, extreme ultraviolet rays are preferred.

[0205] The exposure conditions, such as the exposure dose, can be appropriately selected depending on the blending composition of the resin and / or compound, the type of each additive, and the like.

[0206] In this embodiment, in order to stably form a highly accurate fine pattern, it is preferable to perform a heat treatment after exposure at a temperature of 50 to 200° C. for 30 seconds or more. By setting the temperature at 50° C. or higher, it is possible to suppress variations in sensitivity due to the type of substrate.

[0207] <Developing Step> The developing step is a step of developing the exposed resist film.

[0208] Specifically, in the development treatment step, the resist film may be developed using an alkaline developer, typically at 10 to 50°C for 10 to 200 seconds, preferably at 20 to 25°C for 15 to 90 seconds, to form a predetermined resist pattern.

[0209] The alkaline developer may be, for example, an alkaline aqueous solution in which an alkaline compound such as an alkali metal hydroxide, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene is dissolved to a concentration of typically 1 to 10% by mass, preferably 1 to 3% by mass. Furthermore, a water-soluble organic solvent, a surfactant, or the like may also be appropriately added to the alkaline aqueous developer.

[0210] The composition of this embodiment can also be used as a composition for forming optical components using lithography techniques.

[0211] The optical component can be used in various shapes such as a film or a sheet.

[0212] Examples of optical components include plastic lenses (prism lenses, lenticular lenses, microlenses, Fresnel lenses, viewing angle control lenses, contrast enhancement lenses, etc.), retardation films, electromagnetic wave shielding films, prisms, optical fibers, solder resists for flexible printed wiring, plating resists, interlayer insulating films for multilayer printed wiring boards, photosensitive optical waveguides, liquid crystal displays, organic electroluminescence (EL) displays, optical semiconductor (LED) elements, solid-state imaging elements, organic thin-film solar cells, dye-sensitized solar cells, and organic thin-film transistors (TFTs).

[0213] The composition of the present embodiment can be suitably used as a composition for forming a filling film and a planarizing film on a photodiode, planarizing films before and after a color filter, a microlens, and a planarizing film and a conformal film on a microlens, which are components used in a solid-state imaging device that requires a high refractive index.

[0214] The composition of the present embodiment can be used as a patterning material for lithography applications.

[0215] Lithography processes are used in semiconductors, liquid crystal display panels, display panels using OLEDs (organic light emitting diodes), power devices, sensors such as CCDs, and the like.

[0216] In the process of forming device elements on a silicon wafer in integrated circuit applications such as semiconductors and devices, a pattern may be formed on an insulating film on the substrate side by etching based on a pattern formed using the composition of this embodiment. Furthermore, a metal film, a semiconductor material, or the like may be laminated based on the formed insulating film pattern to form a circuit pattern, thereby constructing a semiconductor element or other device.

[0217] The present embodiment will be specifically described below with reference to examples, but the present embodiment is not limited to these examples.

[0218] Example 1 A 300 mL four-neck flask equipped with a Dean-Stark tube was charged with 5.0 g of 1,3,5-adamantanetriol (hereinafter also referred to as ADT) [a compound represented by formula (1α)] and 156 mL of toluene (specific gravity 0.87). After replacing the atmosphere in the flask with nitrogen, 25.0 g of 55% by mass hydroiodic acid was added while stirring at a stirring rate of 70 rpm (revolutions per minute) using a plate-shaped blade (crescent-shaped) approximately half the length of the maximum inner diameter of the flask. The mixture was then heated under reflux to allow a reaction to occur. The reaction mixture separated into two liquid-liquid phases: a toluene phase and an aqueous phase; however, there was no residual raw material and the mixture was homogeneous. The toluene phase was analyzed by gas chromatography (hereinafter also referred to as GC) every hour or every two hours, and the concentration and reaction yield of 3,5-diiodo-1-adamantanol (hereinafter also referred to as DIADOH) extracted into the toluene phase were calculated, and distillate water was removed. Five hours after the start of reflux, it was confirmed that the GC area percentage value of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was stopped by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0219] The reaction solution was cooled to 56 ° C., and 108 mL of water was added. Thereafter, a 10% by mass aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. The amount of 10% by mass aqueous sodium sulfite solution used was 0.8 mL. After removing the aqueous phase by separation, 108 mL of water was added, followed by stirring and separation. The toluene phase was concentrated using a rotary evaporator. After concentration, a slurry was obtained, with a mass of 19.8 g. The slurry was filtered, and the separated crystals were dried under reduced pressure to obtain DIADOH [organohalogen compound A represented by formula (1)] with a GC area percentage of 99.4% and an isolation yield of 89.2%.

[0220] <DIADOH Concentration in Toluene Phase> The DIADOH concentration in the toluene phase, reaction yield, and amount of distillate extracted were calculated by the following method: A 0.5 mass % DIADOH methanol solution (sample 1) was analyzed by GC, and a factor was calculated from the following formula 1.

[0221]

[0222] The toluene phase of the reaction solution was collected and diluted 10 to 20 times with methanol to prepare an analytical sample (sample 2). The sample was analyzed by GC, and the concentration (%) of DIADOH in the toluene phase was calculated using the following formula 2.

[0223]

[0224] <Reaction Yield> The reaction yield was calculated from the following formula 3.

[0225]

[0226] <Amount of Distillate Water Withdrawn> The amount of hydrogen iodide consumed (g) and the amount of water produced (g) were calculated from the following formulas 4 and 5, and the total amount of distillate water withdrawn (g) was calculated from the following formula 6.

[0227]

[0228]

[0229]

[0230] The amount of distillate water withdrawn during the reaction was determined for each GC analysis so that the total amount of distillate water withdrawn would be the total amount of distillate water obtained by Equation 6.

[0231] Example 2: A 300 mL four-neck flask equipped with a Dean-Stark tube was charged with 6.6 g of ADT and 181 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 25.0 g of 55% by mass hydroiodic acid was added while stirring at a stirring speed of 70 rpm using a plate-shaped blade (crescent-shaped) approximately half the length of the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases, a toluene phase and an aqueous phase, but was homogeneous with no residual raw materials. During the reaction, the amount of distillate withdrawn was determined every 1 or 2 hours using the same method as in Example 1, and the distillate was withdrawn. Seven hours after the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was terminated by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0232] The reaction solution was cooled to 61 ° C., and 143 mL of water was added. Thereafter, a 10% by mass aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. The amount of 10% by mass aqueous sodium sulfite solution used was 0.8 mL. After removing the aqueous phase by separation, 143 mL of water was added, followed by stirring and separation. The toluene phase was concentrated using a rotary evaporator. After concentration, the mixture was in a slurry state, with a mass of 25.5 g. The slurry was filtered, and the separated crystals were dried under reduced pressure to obtain DIADOH with a GC area percentage of 99.2% and an isolation yield of 90.9%.

[0233] Example 3: A 5-L separable flask equipped with a Dean-Stark tube was charged with 105.6 g of ADT and 3,333 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 400.0 g of 55% by mass hydroiodic acid was added while stirring at a speed of 70 rpm using a blade with a length approximately half the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases, a toluene phase and an aqueous phase, but was homogeneous with no residual raw materials. During the reaction, the amount of distillate withdrawn was determined every two hours using the same method as in Example 1, and the distillate was withdrawn. After 8 hours from the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was terminated by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0234] The reaction solution was cooled to 34 ° C., and 1667 mL of water was added. Then, a 10% by weight aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. The amount of 10% by weight aqueous sodium sulfite solution used was 4.0 mL. After removing the aqueous phase by separation, 1667 mL of water was added, and stirring and separation were performed. The toluene phase was concentrated using a rotary evaporator. After concentration, the mixture was in a slurry state, with a mass of 279.9 g. The slurry was filtered, and the separated crystals were dried under reduced pressure to obtain DIADOH with a GC area percentage of 99.1% and an isolation yield of 94.8%.

[0235] Example 4: A 1000 mL separable flask equipped with a Dean-Stark tube was charged with 31.7 g of ADT and 465 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 120 g of 55% by mass hydroiodic acid was added while stirring at a stirring speed of 70 rpm using a blade with a length approximately half the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases: a toluene phase and an aqueous phase; however, the reaction was homogeneous with no residual raw materials remaining. During the reaction, the amount of distillate withdrawn was determined every two hours using the same method as in Example 1, and the distillate was withdrawn. Six hours after the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was terminated by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0236] The reaction solution was cooled to room temperature (25°C) and 268 mL of water was added. Then, a 10% by weight aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. 38 mL of 10% by weight aqueous sodium sulfite solution was used. 47.8 g of precipitated crystals were filtered off, and the toluene phase was recovered by separating the filtrate. The toluene phase was then washed twice with 268 mL of water. The filtered precipitated crystals were dissolved in 526.7 g of ethyl acetate, and 293 mL of water was added. A 10% by weight aqueous sodium sulfite solution was added until both the aqueous and ethyl acetate phases became transparent. 1.3 mL of 10% by weight aqueous sodium sulfite solution was used. After removing the aqueous phase by separation, the ethyl acetate phase was washed twice with 293 mL of water. The toluene and ethyl acetate phases were mixed and concentrated using a rotary evaporator. After concentration, the mixture was in a slurry state, with a mass of 117.2 g. The slurry was filtered and the separated crystals were dried under reduced pressure to give DIADOH with a GC area percentage value of 99.2% and an isolated yield of 90.6%.

[0237] Example 5: A 500 mL separable-neck flask equipped with a Dean-Stark tube was charged with 15.8 g of ADT and 233 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 60.0 g of 55% by mass hydroiodic acid was added while stirring at a stirring speed of 70 rpm using a blade with a length approximately half the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases, a toluene phase and an aqueous phase, but was homogeneous with no residual raw materials. During the reaction, the amount of distillate withdrawn was determined every two hours using the same method as in Example 1, and the distillate was withdrawn. Six hours after the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was terminated by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0238] After cooling the reaction solution to 75 ° C., 134 mL of water was added while controlling the temperature so that the liquid temperature was 70 to 80 ° C. A 50% by mass aqueous phosphinic acid solution was added under stirring until the reaction solution became colorless. The amount of 50% by mass aqueous phosphinic acid solution used was 6.0 mL. After removing the aqueous phase by separation, the toluene phase was washed twice with 134 mL of water while controlling the temperature so that the liquid temperature was 70 to 80 ° C. Thereafter, the toluene phase was concentrated using a rotary evaporator. After concentration, the product was in a slurry state, and its mass was 25.5 g. The slurry was filtered, and the filtered crystals were dried under reduced pressure to obtain DIADOH with a GC area percentage of 99.2% and an isolation yield of 90.1%.

[0239] Example 6: A 5-L separable flask equipped with a Dean-Stark tube was charged with 105.6 g of ADT and 3,333 mL of toluene. After replacing the atmosphere in the flask with nitrogen, 400.0 g of 55% by mass hydroiodic acid was added while stirring at a stirring speed of 250 rpm using a blade with a length approximately half the maximum inner diameter of the flask. The reaction was carried out by heating under reflux. The reaction solution separated into two liquid-liquid phases, a toluene phase and an aqueous phase, but was homogeneous with no residual raw materials. During the reaction, the amount of distillate withdrawn was determined every two hours using the same method as in Example 1, and the distillate was withdrawn. After 12 hours from the start of reflux, it was confirmed that the GC area percentage of 5-iodo-1,3-adamantanediol in the toluene phase was 1.0% or less, and the reaction was terminated by terminating heating. No ADT remained in the aqueous phase after the reaction was completed. Furthermore, almost all of the DIADOH was dissolved in the toluene phase, and no 1,3,5-triiodoadamantane was produced.

[0240] The reaction solution was cooled to 34 ° C., and 1667 mL of water was added. Then, a 10% by weight aqueous sodium sulfite solution was added while stirring until the reaction solution became colorless. The amount of 10% by weight aqueous sodium sulfite solution used was 4.0 mL. After removing the aqueous phase by separation, 1667 mL of water was added, and stirring and separation were performed. The toluene phase was concentrated using a rotary evaporator. After concentration, the mixture was in a slurry state, with a mass of 266.0 g. The slurry was filtered, and the separated crystals were dried under reduced pressure to obtain DIADOH with a GC area percentage of 99.2 and an isolation yield of 92.1%.

[0241] Comparative Example 1: 6.6 g of ADT was placed in a 300 mL four-neck flask. After replacing the atmosphere in the flask with nitrogen, 25.0 g of 55% by mass hydroiodic acid was added. The mixture was stirred at a stirring speed of 70 rpm using a plate-shaped blade approximately half the length of the maximum inner diameter of the flask. The mixture was heated to an internal temperature of 115°C in an oil bath and heated under reflux to cause a reaction. The reaction was stopped by stopping heating 5 hours after the start of reflux.

[0242] After cooling the reaction solution to room temperature (25°C), a 10% by weight aqueous sodium sulfite solution was added under stirring until the reaction solution became colorless. The amount of 10% by weight aqueous sodium sulfite solution used was 0.3 mL. The precipitate obtained by the reaction was collected by filtration, dissolved in 100 mL of toluene, and 100 mL of ion-exchanged water was added. The mixture was stirred and separated for washing, and the aqueous phase was discarded. This procedure was repeated twice. The resulting toluene phase was concentrated using a rotary evaporator to obtain a slurry. The slurry was filtered, and the filtered crystals were dried under reduced pressure. Based on GC area percentage, 82.9% of the target product, DIADOH, and 17.1% of the by-product, triiodoadamantane, were obtained. The synthesis yield of DIADOH was 62.3%. The results of each example and comparative example are shown in Table 1.

[0243]

[0244] As shown in Table 1, the examples using the method for producing an organic halogen compound, which includes a halogenation step of halogenating a raw material compound represented by the following formula (1α) to obtain organic halogen compound A represented by the following formula (1), in which the halogenation step is performed in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent, were excellent in both isolation yield and GC purity. On the other hand, Comparative Example 1, in which the halogenation was performed in a single phase rather than in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent, was inferior in both isolation yield and GC purity compared to the examples in which the halogenation was performed in the above multiphase system.

[0245] This application is based on a Japanese patent application (Patent Application No. 2023-176206) filed on October 11, 2023, the contents of which are incorporated herein by reference.

Claims

1. A method for producing an organic halogen compound, comprising a halogenation step of halogenating a raw material compound represented by the following formula (1α) to obtain an organic halogen compound A represented by the following formula (1), wherein the halogenation step is carried out in a multi-phase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent. In formula (1α), RG is a group containing at least one cyclic structure, １ are each independently a hydrogen atom, a hydroxyl group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. １ At least one of the groups is a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond. m' is an integer of 2 to 10. In formula (1), RG is a group containing at least one cyclic structure, X is F, Cl, Br or I, and R １ are each independently a hydrogen atom, a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, an amino group, a nitro group, a thiol group, a thioalkyl group, a thioether group, or a monovalent group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, n is an integer of 1 to 5, and m is an integer of 1 to 5, provided that m' ≠ m and m'-m ≧ 1.

2. In the formula (1α), all R １ At least two of X are hydroxy groups, and in the formula (1), at least one of all X is I, and all R １ The method for producing an organic halogen compound according to claim 1 , wherein at least one of the above is a hydroxy group.

3. The method for producing an organic halogen compound according to claim 1, wherein a halogenating agent is used in the halogenation step.

4. The method for producing an organic halogen compound according to claim 3, wherein the halogenating agent is at least one selected from the group consisting of hydrogen halides, phosphorus halides, a combination of a sulfonyl halide and a halogen source, a thionyl halide, a Vilsmeier reagent, and a combination of triphenylphosphine and a halogen source.

5. The method for producing an organic halogen compound according to claim 3, wherein the halogenating agent is a water-soluble halogenating agent.

6. The method for producing an organic halogen compound according to claim 3, wherein the halogenating agent is an aqueous hydrogen halide solution.

7. The method for producing an organic halogen compound according to claim 6, wherein the aqueous hydrogen halide solution is hydroiodic acid.

8. The method for producing an organic halogen compound according to claim 3, wherein the halogenation step includes a step of distilling off water from the aqueous phase to concentrate the halogenating agent.

9. The method for producing an organic halogen compound according to claim 3, wherein the halogenation step further comprises a step of adding an additional halogenating agent.

10. The method for producing an organic halogen compound according to claim 1, wherein the organic solvent comprises an organic solvent which forms an azeotrope with water.

11. The method for producing an organic halogen compound according to claim 1, wherein the compound represented by formula (1α) is a secondary or tertiary alcohol.

12. The method for producing an organic halogen compound according to claim 1, wherein the compound represented by formula (1α) is a compound represented by the following formula (1α-1): (In formula (1α-1), R ２ , R ３ and R ４ are each independently a hydrogen atom, a hydroxy group, a nitro group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may contain at least one substituent, the substituent being one or more groups selected from the group consisting of a hydroxy group, an ether group, an ester group, a carboxyl group, a halogen atom, a nitro group, and -NRR', and R and R' are each independently a hydrogen atom, a hydroxy group, or a monovalent group having 1 to 12 carbon atoms and not containing a polymerizable unsaturated bond which may contain at least one substituent.

13. A compound produced by the process of claim 1.

14. An acid generator comprising a structure derived from the compound of claim 13.

15. A base generator or quencher comprising a structure derived from the compound of claim 13.

16. A polymer containing a structural unit derived from the compound according to claim 13 in the main chain or side chain.

17. A composition comprising one or more members selected from the group consisting of the compound according to claim 13, the acid generator according to claim 14, the base generator or quencher according to claim 15, and the polymer according to claim 16.

18. The composition according to claim 17, which is for forming a film.

19. A method for forming a resist pattern, comprising the steps of: applying the composition according to claim 18 onto a substrate to form a resist film; exposing the resist film to a pattern; and developing the exposed resist film.

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