JP2014047329A - Acid proliferation agent, and acid reactive resin composition containing the acid proliferation agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: an acid proliferation agent with which a super strong acid is generated in a proliferation manner and a cation UV hardening material can be efficiently cured, regarding an acid proliferation agent with which a new acid can be generated by existence of an acid, and a proliferative response progresses; and an acid reactive resin composition containing the acid proliferation agent.SOLUTION: An acid proliferation agent uses a counter anion of a super strong acid as a composing anion Xto thereby become an acid proliferation agent that can proliferate or generate a super strong acid in a chain reaction. Therefore, an acid reactive resin composition in which an acid proliferation agent is made to coexist with an acid reactive compound that reacts with an acid proliferation agent is that in which a reaction between a super strong acid generated from an acid proliferation agent and an acid reactive compound that becomes a cation UV hardening material progresses in a chain reaction, a curing speed and reaction efficiency are excellent, and the curing is satisfactorily performed.

Description

  The present invention relates to an acid proliferating agent and an acid-reactive resin composition containing the acid proliferating agent. More specifically, the present invention relates to an acid proliferating agent that can be decomposed by the action of an acid to generate a new acid in a proliferative manner, and an acid reactive resin composition containing the acid proliferating agent.

  Lithography is often used to manufacture fine structures in various electronic devices such as semiconductor devices and liquid crystal devices. However, with the miniaturization of device structures, it is required to make finer resist patterns in the lithography process.

  In addition, a chemically amplified resist known as a resist pattern forming method, for example, irradiates an acid generator with light to generate a strong acid serving as a catalyst or the like, thereby chemically modifying a resin component. Then, a pattern is formed by the change in solubility of the chemically modified resin component. In such a chemically amplified positive resist, the acid generated in the irradiated portion of active energy rays such as light, X-rays, and electron beams diffuses by subsequent heat treatment (to remove protective groups such as resin, By regenerating the acid, the irradiated part becomes alkali-soluble.In addition, the chemically amplified negative resist diffuses the acid generated at the irradiated part by the subsequent heat treatment and acts on the crosslinking agent. The matrix resin at the irradiated part is cured.

  Combined with an active energy ray-acid reaction that generates an acid in a resist by irradiation with an active energy ray, an acid multiplication reaction that generates an acid proliferatively by decomposing in an autocatalytic manner in the resist by the action of an acid. Thus, it has been shown that the use of an acid proliferating agent is effective for improving curability, and a method for greatly accelerating the acid-catalyzed reaction and various acid proliferating agents used in such a method have been proposed, and cationic UV It is applied to curing of a curable material (see, for example, Patent Document 1 and Patent Document 2).

JP-A-8-248561 JP 2000-35665 A

  By the way, in order to cure the cationic UV curable material, it is necessary to bond constituent groups such as epoxy groups in the cured material to extend the chain (bonded chain). The acid generated from is good at cleaving protecting group bonds in chemically amplified resists, but it is difficult to bond the constituent groups in the cured material and extend the chain (bonded chain). In order to improve the sensitivity, it is required to generate a stronger acid so as to extend the chain between the constituent groups (bonded chain). Furthermore, a cationic UV curable material made of an epoxy resin or the like requires a super strong acid having a low nucleophilicity of the counter anion, and has been demanded for improvement.

  The present invention has been made in view of the above problems, and in an acid proliferating agent capable of generating a new acid by the presence of an acid and in which an acid proliferating reaction proceeds, a super strong acid is generated proliferatively, An object of the present invention is to provide an acid proliferating agent capable of efficiently curing a cationic UV curable material and an acid-reactive resin composition containing the acid proliferating agent.

  In order to solve the above-mentioned problems, the acid proliferating agent according to the present invention is represented by the following formula (I).

（式（Ｉ）中、Ｒ_１、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５及びＲ_６は、それぞれ独立して、炭素数１〜２０のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、または炭素数６〜１２の芳香族基を示し、これらは、直鎖構造、枝分かれ構造、あるいは環構造でもよくヘテロ原子を含んでいてもよい。Ｒ_７及びＲ_８は、それぞれ独立して、水素原子、あるいは炭素数１〜２０のアルキル基、炭素数２〜１２のアルケニル基、炭素数２〜１２のアルキニル基、または炭素数６〜１２の芳香族基を示す。ｍ_１、ｍ_２は、それぞれ独立して、１〜１０の整数を示す。Ｘ⁻は対アニオンであり、Ｈａｍｍｅｔｔの酸度関数Ｈ_０が−１２以下の超強酸の対アニオンを示す。）

(In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or carbon. An alkynyl group having 2 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms, which may have a straight chain structure, a branched structure, or a ring structure, and may contain a hetero atom, R ₇ and R _8; Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. M ₁ and m ₂ each independently represents an integer of 1 to 10. X ⁻ represents a counter anion, and represents a counter anion of a super strong acid having a Hammett acidity function H ₀ of −12 or less.

  The acid proliferation agent according to the present invention is represented by the following formula (I ′) in the above-described present invention.

（式（Ｉ’）中、Ｒ_２、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、ｍ_１、ｍ_２、Ｘ⁻は、前記式（Ｉ）と共通する。）

(In formula (I ′), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , m ₁ , m ₂ , and X ⁻ are the same as those in formula (I).)

In the acid proliferation agent according to the present invention, in the above-described present invention, the X ⁻ is HSO ₄ ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ⁻ , CF ₃ CF ₂ CF ₂ SO ₃ ⁻ , CF ₃ CF _2. Selected from the group consisting of SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ and B (C ₆ F ₅ ) ₄ ⁻ It is characterized by being one kind.

  The acid-reactive resin composition according to the present invention is characterized by containing the above-described acid proliferating agent and acid-reactive compound of the present invention.

  The acid-reactive resin composition according to the present invention is characterized by containing the above-described acid proliferating agent of the present invention, an acid generator and an acid-reactive compound.

  In the acid-reactive resin composition according to the present invention, in the above-described present invention, the acid-reactive compound is at least one selected from the group consisting of an epoxy compound, a silicon compound, an oxetane compound, and a vinyl ether compound. It is characterized by.

Since the acid proliferating agent according to the present invention uses a counter anion of a super strong acid as the anion X ⁻ constituting the acid proliferating agent, it becomes an acid proliferating agent capable of generating a super strong acid in a proliferative manner. Therefore, when the acid proliferating agent of the present invention is allowed to coexist with an acid-reactive compound that reacts with an acid, the acid-reactive compound can be efficiently cured by a super strong acid generated in a proliferative manner. The acid proliferating agent of the present invention can also be applied to a frontal polymerization system based on cationic polymerization.

  In addition, the acid-reactive resin composition according to the present invention includes the acid proliferating agent of the present invention or the acid proliferating agent of the present invention, an acid generator, and an acid-reactive compound, so The reaction between the strong acid and the acid-reactive compound serving as the cationic UV-curing material proceeds in a chain manner, resulting in an excellent curing speed and reaction efficiency, and an acid-reactive resin composition that is sufficiently cured. The acid-reactive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like.

In Experiment 2, it is the figure which showed the relationship between a heating time and the production | generation rate of a sulfide. In Experiment 4, it is the figure which showed the relationship between a heating time and the peak derived from 1, 3- dioxolane. In Experiment 5, it is the figure which showed the UV spectrum change of the acid multiplication agent obtained in Example 1. FIG. In Experiment 6, it is the figure which showed the UV spectrum change of the test film | membrane containing the acid multiplication agent and coumarin obtained in Example 1. FIG. In Experiment 7, it is the figure which showed the result of the pencil hardness measurement of the comparative example 1. FIG. In Experiment 7, it is the figure which showed the result of the pencil hardness measurement of Example 4. FIG.

  Hereinafter, one embodiment of the present invention will be described. The acid proliferating agent according to the present invention is a compound represented by the following formula (I).

In the acid proliferating agent represented by the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms. An organic group such as an alkenyl group having 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms is illustrated. These organic groups may have a straight chain structure, a branched structure, or a ring structure, and may contain a hetero atom. R _{1 to} R ₆ may contain a polymerizable group such as a silyl group, an acrylic group, or a methacryl group, and may be a monomer or a polymer obtained by polymerizing them. The alkyl group preferably has 1 to 12 carbon atoms.

In formula (I), R ₇ and R ₈ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an alkynyl group having 2 to 12 carbon atoms. Or an organic group such as an aromatic group having 6 to 12 carbon atoms. The alkyl group preferably has 1 to 12 carbon atoms.

In Formula (I), m ₁ and m ₂ each independently represent an integer of 1 to 10. m ₁ and m ₂ are preferably integers of 1 to 3, respectively.

In _the case _{R 1, R 2, R 3} , R 4, R 5 and _{R 6} is an aromatic group, these aromatic groups may have 1 to 5 substituents. Examples of the substituent include a hydrogen atom, halogen, hydroxyl group, sulfide group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, carboxyl group, Examples include a carbonyl group, an ester group, a formyl group, an acyl group, a cyano group, an alkoxy group, an amino group, an amide group, an aryl group, an allyl group, and an ammonio group. Such substituents may be the same or different. Furthermore, it may contain a polymerizable group such as a silyl group, an acryl group or a methacryl group as a substituent of the aromatic group, and may be a monomer or a polymer obtained by polymerizing them. A preferred example of formula (I) is shown as formula (I ′). In formula (I ′), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , m ₁ , m ₂ , and X ⁻ are the same as those in formula (I). It is.

In addition, as X ⁻ constituting the acid proliferating agent represented by the formula (I), a counter anion of an acid generally called a super strong acid can be used, and Hammett's acidity function H ₀ is less than −12. It is a counter anion of a strong acid. For example, as a super strong acid and its counter anion, H ₂ SO ₄ (the counter anion is HSO ₄ ⁻ ), CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ H (same CF ₃ CF ₂ CF ₂ CF _{^{2 SO 3 -), CF 3}} CF 2 CF 2 SO 3 H ( the ^{_{CF 3 CF 2 CF 2 SO 3}} -), CF 3 CF 2 SO 3 H ( the ^{_{CF 3 CF 2 SO 3 -)}} , CF 3 SO 3 H (same CF ₃ SO ₃ ⁻ ), HBF ₄ (same BF ₄ ⁻ ), HPF ₆ (same PF ₆ ⁻ ), HAsF ₆ (same as AsF ₆ ⁻ ), HSbF ₆ (same SbF ₆ ⁻ ), HB (C ₆ ) H _{5) 4} ( ^{_{B (C 6 H 5) 4}} -), HB (C 6 F 5) 4 ( same _{B (C 6 F 5) 4} -) is preferably set to such, HBF ₄ (the _BF ⁴ -), _HPF 6 ( PF ₆ ⁻ ), HAsF ₆ (AsF ₆ ⁻ ), HSbF ₆ (SbF ₆ ⁻ ), HB (C ₆ H ₅ ) ₄ (B (C ₆ H ₅ ) ₄ ⁻ ), HB (C ₆ F ₅ ) ₄ (same as B (C ₆ F ₅ ) ₄ ⁻ ) and the like are particularly preferable. Table 1 lists the Hammett acidity functions H ₀ of these representative examples.

(Hammett acidity function H ₀ )

  The acid proliferating agent of the present invention has the property of being decomposed by the action of an acid and generating an acid proliferatively. Therefore, the acid proliferating agent of the present invention is decomposed by self-proliferation by allowing a smaller equivalent amount of acid to act on the constant amount, and finally the total amount is decomposed. A large amount of acid corresponding to In addition, since the acid proliferating agent of the present invention can itself be a photoacid generator, it is also possible to multiply the acid in a self-proliferating manner by the subsequent heating triggered by an acid (super strong acid) generated by light irradiation. is there. Regarding the reaction behavior, in the case of only thermochemical reaction in scheme 1, scheme 2 shows the case in which a super strong acid is generated by light itself by scheme 2 and the acid is propagated by subsequent heating. The acid that acts on the acid proliferating agent is preferably the same acid as the acid constituting the acid proliferating agent (acid that is generated or propagated), but there is no problem even if a different acid is used.

(Scheme 1)

(Scheme 2)

In the present invention, since the counter-anion of the super strong acid described above is used as the anion X ⁻ constituting the acid proliferating agent, the reaction efficiency at the time of polymerization of the acid reactive compound when used in combination with the acid reactive compound. It acts as an excellent acid that is high, and can generate strong and strong acids by the growth reaction according to the scheme described above. Therefore, by making the acid proliferating agent of the present invention capable of generating a strong acid coexist in an acid-reactive compound such as an epoxy compound that reacts with an acid, the constituent groups of the acid-reactive compound are bonded together to form a chain (bonded chain). ) Can be extended, and the acid-reactive compound that becomes the cationic UV curable material can be efficiently cured. The acid proliferating agent of the present invention can also be applied to a frontal polymerization system based on cationic polymerization.

Incidentally, X ^- is a counter anion of the superacid, the cation portion of the acid amplifier are sulfonium, cation portion may be iodonium. Since sulfonium and iodonium are photodegradable and generate an acid corresponding to the counter anion, they also have a function as a photoacid generator.

  Specific examples of the acid proliferating agent represented by the formula (I) are shown below.

  In order to produce the acid proliferating agent represented by the formula (I), for example, it can be easily produced by the following synthesis scheme. That is, a sulfide is obtained by reacting a β-haloketone with a thiol compound. Next, a diol is reacted in the presence of an acid catalyst to synthesize a ketal, and further, a trialkyloxonium salt is reacted to obtain a target sulfonium salt.

(Synthesis scheme)

  Moreover, the acid growth agent according to the present invention can be used as an acid growth agent composition in combination with an acid generator. Here, the acid generator is generally a substance that generates an acid when irradiated with active energy rays such as light or heated. Although it does not specifically limit as an acid generator, The photo-acid generator which generate | occur | produces an acid by irradiation of active energy rays, such as light, and the thermal acid generator (thermal latent acid generator) which generate | occur | produces an acid by heating are used. It is preferable to do. Among these, it is particularly preferable to use a photoacid generator because it is not necessary to perform heat treatment at a high temperature in order to generate an acid.

Although it does not specifically limit as a photo-acid generator, For example, it was disclosed by Unexamined-Japanese-Patent No. 8-248561, Unexamined-Japanese-Patent No. 2000-35665, Unexamined-Japanese-Patent No. 2001-81138, Unexamined-Japanese-Patent No. 2012-104697 etc. Photoacid generators can be used. Specifically, salts of aromatic onium compounds (aromatic onium salts) such as diazonium, ammonium, iodonium, sulfonium, and phosphonium, such as BF ₄ , PF ₆ , AsF ₆ , SbF ₆ , and CF ₃ SO ₃ are listed. be able to.

  As the photoacid generator, other sulfonium salts include, for example, triphenylsulfonium hexafluorophosphate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide bishexafluorophosphate, 4,4′-bis [di (β -Hydroxyethoxy) phenylsulfonio] hexafluorophosphate-based sulfonium salts such as diphenylsulfide bishexafluorophosphate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenylsulfide hexafluorophosphate; triphenylsulfonium hexafluoroantimonate, 4 , 4′-bis [di (β-hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 7- [di (p-toluyl) sulfoni O] -2-Isopropylthioxanthone hexafluoroantimonate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfonio-diphenylsulfide hexafluoroantimonate and other hexafluoroantimonate-based sulfonium salts; triphenylsulfonium Tetrakis (pentafluorophenyl) borate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4- (p-tert-butylphenylcarbonyl) -4′-di (p -Toluyl) sulfonio-diphenyl sulfide tetrakis (pentafluorophenyl) borate and other tetrakis (pentafluorophenyl) borate-based sulfonium salts, etc. For example, UVI-6970, UVI-6974 (manufactured by Union Carbide), SP-170, SP-171, SP-172, SP-150, SP-151 (manufactured by ADEKA), CPI-210S ( San Apro Co., Ltd.).

  Further, as a photoacid generator, as other iodonium salts, for example, diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate As a commercial item, PI2074 (made by Rhodia) etc. are mentioned, for example.

  Further, the thermal acid generator is not particularly limited, but examples thereof include the thermal acid generator disclosed in JP2011-80044A and JP2011-207948A, and the above-described photoacid generator. Hexafluoroantimonate-based sulfonium salts and the like can be mentioned, and examples of commercially available products include Sun Aid SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L (Sanshin Chemical Industry CI-2624 (manufactured by Nippon Soda Co., Ltd.) and the like.

  In the case where the acid proliferating agent and the acid generator are used in combination as an acid proliferating agent composition, it is preferable that the acid constituting the acid proliferating agent and the acid constituting the acid generating agent are common. By using the acid in common, the acid proliferating agent is efficiently decomposed.

  When the acid proliferator and the acid generator are used in combination as an acid proliferator composition, the compounding ratio of the acid proliferator and the acid generator is, by mass ratio, acid proliferator / acid generator = 40 / 1-5 / It is preferable to be within the range of 20. If the amount of the acid proliferating agent is too small, the acid is not efficiently generated, and the acid-reactive compound may not be allowed to react rapidly. On the other hand, if the amount of the acid proliferating agent is too large, the amount of the acid generator used increases, and the acid generator itself may adversely affect the solubility of the acid-reactive compound. It is not preferable. The mixing ratio of the acid proliferator and the acid generator is particularly preferably in the range of acid proliferator / acid generator = 20/1 to 1/1 by mass ratio.

  Next, the acid-reactive resin composition of the present invention will be described. The acid-reactive resin composition of the present invention comprises, as an essential component, an acid-reactive compound that undergoes a curing reaction in the presence of an acid and an acid-growing agent or an acid-generating agent (acid-growing agent composition). contains.

  The acid-reactive compound constituting the acid-reactive resin composition of the present invention reacts with the action of an acid generated by an acid proliferating agent, or an acid proliferating agent and an acid generator (acid proliferating agent composition), and crosslinks. For example, the following No. 4-1. 6-4 compounds and the like can be used. In particular, for example, an epoxy compound having at least one epoxy group, a silicon compound having at least one alkoxysilyl group or silanol group, an oxetane compound containing an oxetane ring, and a cationically polymerizable compound such as a vinyl ether compound Is preferably used. Such acid reactive compounds may be used alone or in combination of two or more.

  Moreover, with respect to the acid-reactive compound, one type of acid proliferating agent may be used alone, or two or more types may be used in combination. Moreover, when using an acid growth agent and an acid generator together as an acid growth agent composition, one type of acid generator may be used alone, or two or more types may be used in combination. It may be used.

  The acid-reactive compound is not particularly limited, and examples thereof include acid-reactive substances disclosed in JP-A-8-248561, JP-A-2000-35665, JP-A-2001-81138, and the like. Cationic polymerizable compounds disclosed in JP2011-207948, etc., and cationic curable monomers disclosed in JP2012-104697A can be used.

  Specifically usable epoxy compounds (epoxy resins) include, for example, diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, diethylene glycol diglycidyl ether. Glycerol polyglycidyl ether, diglycerol polyglycidyl ether, sorbitol polyglycidyl ether, allyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, alkylphenol glycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,6-hexanedio Rudiglycidyl ether, glycerin polyglycidyl ether, diglycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, cresyl glycidyl ether, aliphatic diglycidyl ether, polyfunctional glycidyl ether, tertiary fatty acid monoglycidyl ether, spiroglycol diglycidyl ether And glycidylpropoxytrimethoxysilane. These epoxy compounds may be halogenated or hydrogenated, and these epoxy compounds include derivatives. And these epoxy compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Moreover, as a silicon-type compound (silicon-type resin), an alkoxysilane compound, a silane coupling agent, etc. can be used, for example. Examples of alkoxysilane compounds include trimethylmethoxysilane, dimethyldimethoxysilane, methyltrimethoxysilane, tetramethoxysilane, methyldimethoxysilane, trimethylethoxysilane, dimethyldiethoxysilane, methyltriethoxysilane, tetraethoxysilane, diphenyldimethoxysilane, phenyl Examples include trimethoxysilane, diphenyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. These alkoxysilane compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the silane coupling agent include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like. Examples of the vinyl silane include vinyl trichlorosilane, vinyl tris (β-methoxyethoxy) silane, vinyl triethoxysilane, and vinyl trimethoxysilane. Examples of the acrylic silane include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, and the like. Examples of the epoxy silane include β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. As aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- γ-aminopropyltrimethoxysilane and the like can be mentioned. Examples of other silane coupling agents include γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane. These silane coupling agents may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the oxetane compound (oxetane resin), a monomeric oxetane compound, a dimer oxetane compound, or the like can be used. Usable oxetane compounds include, for example, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl, 1,4-benzenedicarboxylic acid bis [(3-ethyl-3-oxetanyl) Methyl] ester, xylylene oxetane such as 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene, 3-ethyl-3-((((3-ethyloxetane-3-yl) methoxy) methyl ) Oxetane (or 3-(((3-ethyloxetane-3-yl) methoxy) methyl) -3-ethyloxetane), 3-ethylhexyloxetane, 3-ethyl-3-hydroxyoxetane, 3-ethyl- 3-hydroxymethyl oxetane, oxetated phenol novolak, etc. are mentioned. These oxetane compounds may be used alone or in combination of two or more.

  Examples of the vinyl ether compound (vinyl ether resin) include 2-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, 2-hydroxybutyl vinyl ether, 4-hydroxybutyl vinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, 1,4-butane. Examples thereof include diol divinyl ether. These vinyl ether compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

  Specific examples of acid-reactive compounds that can be used in the present invention will be given below.

  As the acid-reactive compound constituting the acid-reactive resin composition of the present invention, an epoxy-based compound having at least one epoxy group can be used. Moreover, an epoxy compound can be made into a polymer by ring-opening polymerization of an epoxy group by allowing an acid to act on an epoxy compound having at least two epoxy groups. Further, by adding an acid to the epoxy compound, the epoxy compound can be chemically modified. An example of an epoxy compound showing polymerization reactivity is shown below.

  Other examples of the epoxy compound (polymer) exhibiting polymerization reactivity are shown below.

  As the acid-reactive compound, a silicon compound having at least one silanol group or alkoxysilyl group can be used. Further, by allowing an acid to act on a silicon compound having at least two silanol groups or alkoxysilyl groups, the silicon compound can be made into a polymer by polycondensation of silanol groups or alkoxysilyl groups. Specific examples of silicon compounds showing polymerization reactivity (No. 5-2 to No. 5-4 are polymers) are shown below.

  Specific examples of structures of other acid-reactive compounds (lactone and cyclic siloxane) are shown below.

The above-mentioned photoacid generator, or an acid-reactive resin composition containing an acid multiplier and a photoacid generator in combination with the acid multiplier of the present invention and a photoacid generator (as an acid multiplier composition) ( The range of the wavelength of the irradiation light and the exposure amount in the photosensitive resin composition) include the type and amount of the photoacid generator and the acid reactive compound constituting the acid reactive resin composition (photosensitive resin composition). What is necessary is just to determine suitably according to a kind etc., For example, what is necessary is just to select and apply from the range of 6.0-400 nm as a wavelength, and 5-10000 mJ / cm < ² > as an exposure amount, The sensitizer mentioned later is used. Therefore, it is possible to use a higher wavelength region. Although irradiation time of irradiation light may be possible even for several seconds, it may be about 10 seconds or more, and is preferably 0.5 to 20 minutes.

  The heating conditions when using the thermal acid generator depend on the type and amount of the thermal acid generator used and the type of the acid reactive compound constituting the acid reactive resin composition (photosensitive resin composition). The heating temperature may be approximately 50 to 150 ° C. and the heating time may be 1 to 1800 minutes. On the other hand, in the case where an acid generator is not used in combination and the main components are an acid proliferating agent and an acid-reactive compound to form an acid-reactive resin composition, a desired acid that can be decomposed by the acid proliferating agent is added. You can do it. As described above, the acid acting on the acid proliferating agent is preferably the same acid as the acid constituting the acid proliferating agent (acid generated or propagated), but there is a problem even if a different acid is used. Absent.

  The content of the acid proliferating agent in the acid-reactive resin composition of the present invention is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the acid-reactive compound. If the content of the acid proliferating agent is less than 0.1 parts by mass, the acid-reactive compound may not be allowed to react rapidly. On the other hand, if the content of the acid proliferating agent exceeds 60 parts by mass, The presence of the agent may adversely affect the solubility of the acid-reactive compound in the solvent, and the presence of an excessive amount of the acid proliferating agent leads to high costs. The content of the acid proliferating agent is preferably 1 to 60 parts by mass, more preferably 2 to 30 parts by mass, and more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the acid-reactive compound. Is more preferable, and 2 to 15 parts by mass is particularly preferable.

  In addition, when the acid proliferating agent and the acid generator are used in combination and contained in the acid-reactive compound as an acid proliferating agent composition, the content of the acid generating agent is that of the acid proliferating agent and the acid generating agent described above. It is preferable to include an acid generator so as to correspond to the blending ratio. Moreover, it is preferable to set it as 0.5-30 mass parts with respect to 100 mass parts of acid-reactive compounds. If the content of the acid generator is less than 0.5 parts by mass, it may not act on the acid proliferating agent and the acid-reactive compound may not be allowed to react rapidly, whereas the content of the acid generator is 30. When the amount exceeds 50 parts by mass, the presence of the acid generator may adversely affect the solubility of the acid-reactive compound in the solvent, and the presence of an excessive amount of the acid generator leads to high costs. It will be. The content of the acid generator is more preferably 2 to 30 parts by mass and particularly preferably 5 to 20 parts by mass with respect to 100 parts by mass of the acid-reactive compound.

  The acid-reactive resin composition of the present invention is an acid-reactive compound having the above-described No. 4-1. No. 4-13 and other epoxy compounds exhibiting polymerization reactivity (polymerizable epoxy compounds) 5-1 to No. It is preferable to use a silicon compound (polymerizable silicon compound) exhibiting polymerization reactivity such as 5-6. Such an acid-reactive resin composition is polymerized by the action of light or heat to give a polymer. Among these, an acid-reactive resin composition (photosensitive resin composition) containing an acid-reactive compound that initiates a polymerization reaction by light is preferable.

  In order to form a pattern using the acid-reactive resin composition according to the present invention, for example, the resin composition is dissolved in an organic solvent to prepare a coating solution, and the prepared coating solution is applied to an appropriate substrate or the like. Apply to a solid surface and dry to form a coating. The formed coating film is subjected to pattern exposure to generate an acid, and then subjected to a heat treatment under predetermined conditions to polymerize an acid-reactive compound contained in the acid-reactive resin composition. To encourage.

  Since the acid-reactive resin composition of the present invention contains the acid proliferating agent of the present invention, the polymerization reaction proceeds even at room temperature, but it is preferable to perform a heat treatment in order to allow the polymerization reaction to proceed efficiently. The conditions for the heat treatment may be appropriately determined depending on the exposure energy, the type of acid generated from the acid proliferator used, and the type of acid-reactive compound such as an epoxy compound or silicon compound, but the heating temperature is 50 ° C. to 50 ° C. It is preferable to be within the range of 150 ° C, and it is particularly preferable to be within the range of 60 ° C to 130 ° C. The heating time is preferably 10 seconds to 60 minutes, particularly preferably 60 seconds to 30 minutes. The pattern can be obtained by immersing this in a solvent that causes a difference in solubility between the exposed part and the unexposed part and developing.

  When the acid-reactive resin composition of the present invention is used as a photosensitive resin composition, a sensitizer can be added to expand the photosensitive wavelength region and increase sensitivity. The sensitizer that can be used is not particularly limited. For example, benzophenone, p, p′-tetramethyldiaminobenzophenone, p, p′-tetraethylaminobenzophenone, 2-chlorothioxanthone, anthrone, 9-ethoxyanthracene, anthracene. , Pyrene, perylene, phenothiazine, benzyl, acridine orange, benzoflavin, cetoflavin-T, 9,10-diphenylanthracene, 9-fluorenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-chloro -4-nitroaniline, N-acetyl-p-nitroaniline, p-nitroaniline, N-acetyl-4-nitro-1-naphthylamine, picramide, anthraquinone, 2-ethylanthraquinone, 2 tert-butylanthraquinone, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9-benzanthrone, dibenzalacetone, 1,2-naphthoquinone, 3,3′-carbonyl-bis (5 , 7-dimethoxycarbonylcoumarin) or coronene. These sensitizers may be used alone or in combination of two or more.

  When the acid-reactive resin composition of the present invention is used as a photosensitive resin composition, the amount of the sensitizer added depends on the acid proliferation agent, photoacid generator or acid-reactive compound used, and the required sensitivity. Although it may determine suitably by etc., it is preferable that it is the range of 1-30 mass% with respect to the whole acid-reactive resin composition. If the sensitizer is less than 1% by mass, the sensitivity may not be sufficiently increased. On the other hand, if the sensitizer exceeds 30% by mass, the sensitivity may be excessive. The addition amount of the sensitizer is particularly preferably in the range of 5 to 20% by mass with respect to the entire acid-reactive resin composition.

  When the acid-reactive resin composition of the present invention is applied to a predetermined substrate, a solvent may be appropriately contained as necessary. By including a solvent in the acid-reactive resin composition, the coating ability can be increased and workability is improved. The solvent is not particularly limited. For example, aromatic hydrocarbon compounds such as benzene, xylene, toluene, ethylbenzene, styrene, trimethylbenzene, and diethylbenzene; cyclohexane, cyclohexene, dipentene, n-pentane, isopentane, n-hexane, Saturated or unsaturated hydrocarbon compounds such as isohexane, n-heptane, isoheptane, n-octane, isooctane, n-nonane, isononane, n-decane, isodecane, tetrahydronaphthalene, squalane; diethyl ether, di-n-propyl ether, Di-isopropyl ether, dibutyl ether, ethyl propyl ether, diphenyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibuty Ether, diethylene glycol methyl ethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol dibutyl ether, dipropylene glycol methyl ethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, ethylene glycol methyl ethyl Ether, tetrahydrofuran, 1,4-dioxane, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol monoethyl ether acetate, ethylcyclohexane, methylcyclohexane, p-menthane, o- Ethers such as dipropyl ether and dibutyl ether; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, dipropyl ketone, methyl amyl ketone, cyclopentanone, cyclohexanone and cycloheptanone; Examples thereof include esters such as ethyl acetate, methyl acetate, butyl acetate, propyl acetate, cyclohexyl acetate, methyl cellosolve, ethyl acetate cellosolve, butyl cellosolve, ethyl lactate, propyl lactate, butyl lactate, isoamyl lactate, and butyl stearate. One of these solvents may be used alone, or two or more of these solvents may be used in combination.

  In the acid-reactive resin composition of the present invention, the content of the solvent is uniform when, for example, the acid-reactive resin composition is applied on a predetermined substrate to form a layer of the acid-reactive resin composition. What is necessary is just to select suitably so that it may be applied to.

  In addition, you may make it add an additive suitably to the acid-reactive resin composition of this invention in the range which does not inhibit the objective and effect of this invention. Examples of additives that can be used include fillers, pigments, dyes, leveling agents, antifoaming agents, antistatic agents, ultraviolet absorbers, pH adjusters, dispersants, dispersion aids, surface modifiers, Examples thereof include a plasticizer, a plastic accelerator, an anti-sagging agent, a curing accelerator, and a filler. One of these may be used alone, or two or more may be used in combination.

  The acid-reactive resin composition according to the present invention described above is generated from the acid-growing agent by containing the acid-growing agent of the present invention or the acid-growing agent, the acid generator and the acid-reactive compound according to the present invention. The reaction between the super strong acid and the acid-reactive compound that becomes the cationic UV curable material proceeds in a chain, and the reaction rate is excellent in the curing rate and the reaction efficiency, and the acid-reactive resin composition is sufficiently cured.

  The acid-reactive resin composition of the present invention exhibiting such effects can be suitably used for, for example, a highly sensitive photocuring material, resist material (pattern forming material), and the like. In general, a chemically amplified resist is produced from a photoacid generator and an acid-decomposable (high) molecule (acid-reactive compound). Such a chemically amplified resist is attracting attention as a highly sensitive resist material because an acid generated from a photoacid generator by the action of light serves as a catalyst and can react repeatedly with acid-decomposable (high) molecules. On the other hand, as the pattern formed by the chemically amplified resist becomes finer, the exposure wavelength is shortened, the output of the light source used is lowered, and the light reaching the resist is weak. In order to maintain the production amount per unit time in the semiconductor manufacturing process, it is required to increase the output of the light source or improve the sensitivity of the resist. Has reached its limit.

(Conventional chemically amplified resist)

  Therefore, the acid-reactive resin composition incorporating the acid proliferating agent according to the present invention into the system can thermochemically increase the small amount of acid generated from the photoacid generator, so that High sensitivity can be achieved.

(Chemically amplified resist using the acid multiplication agent of the present invention)

  Examples of acid-decomposable (high) molecules and photoacid generators used in chemically amplified resists are shown below.

(Example of acid-decomposable (high) molecule (acid-reactive compound))

(Example of photoacid generator)

  The acid-reactive resin composition according to the present invention can be used as various photo-curing materials, and when applied as a photo-curing material, the molded body made of such a material has heat resistance, dimensional stability, insulation, etc. For example, paints or printing inks, color filters, flexible display films, semiconductor devices, electronic components, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, etc. Widely used as antireflection film, hologram, optical member or building material component, printed matter, color filter, flexible display film, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, optical circuit component An antireflection film, a hologram, an optical member, a building member, or the like is provided. In addition, the formed pattern has heat resistance and insulation, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, reflective It can be advantageously used as a protective film, other optical member or electronic member.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example etc., this invention is not limited to this Example at all.

[Example 1]
Production of acid proliferator (1):
The acid proliferating agent represented by the formula (Ia) was produced using the following operations (1) to (3).

(1) Production of intermediate (1):
In a four-necked flask, 14.9 g (88.4 × 10 ⁻³ mol) of 3-chloropropiophenone and 9.1 g (90.0 × 10 ⁻³ mol) of triethylamine as a base were added, and tetrahydrofuran (THF) was added. Dissolved in 10 ml. To this, 12.4 g (88.4 × 10 ⁻³ mol) of 4-methoxybenzenethiol dissolved in 10 ml of tetrahydrofuran (THF) was added dropwise from a dropping funnel. After stirring the mixture in the four-necked flask at room temperature for 30 minutes, add an appropriate amount of dichloromethane (CH ₂ Cl ₂ ), extract in the order of aqueous sodium hydrogen carbonate solution and aqueous sodium chloride solution, and recrystallize with a mixed solution of hexane / dichloromethane. As a result, 12.7 g (46.8) of a white solid of intermediate (1) (3- (4-methoxyphenylthio) -1-phenylpropan-1-one) represented by the following formula (H-1) was obtained. × 10 ⁻³ mol), and the yield was 58%.

(2) Production of intermediate (2):
In a four-necked flask equipped with a Dean-Stark apparatus, 5.0 g (18 of intermediate (1) (3- (4-methoxyphenylthio) -1-phenylpropan-1-one) obtained in (1) was obtained. .4 × 10 ⁻³ mol), 2.0 g (31.2 × 10 ⁻³ mol) of ethylene glycol, 0.5 g (2.9 × 10 ⁻³ mol) of p-toluenesulfonic acid, and 120 ml of benzene And refluxed for 12 hours. After refluxing, distilling off the solvent and concentrating, the product was separated by column chromatography using a developing solvent of ethyl acetate: hexane = 1: 20, and intermediate (2) (2- (2 A white solid (-(4-methoxyphenylthio) ethyl) -2-phenyl-1,3-dioxolane) was obtained in a yield of 5.39 g (17.1 × 10 ⁻³ mol) in a yield of 93%.

(3) Production of acid proliferator:
In a four-necked flask, 2.4 g of intermediate (2) (2- (2- (4-methoxyphenylthio) ethyl) -2-phenyl-1,3-dioxolane) obtained in (2) (5. 73 × 10 ⁻³ mol), 0.19 g (1.91 × 10 ⁻³ mol) of trimethyloxonium tetrafluoroborate and 10 ml of dehydrated acetonitrile (dry-CH ₃ CN) were added and stirred at room temperature for 15 minutes. 5 ml of methanol was added to the mixture after stirring and mixing, and after further stirring and mixing, the mixture was concentrated under reduced pressure with an evaporator and separated by column chromatography using a developing solvent of ethyl acetate: hexane = 1: 1. The following formula (I-a ) Was obtained in a yield of 0.23 g (0.55 × 10 ⁻³ mol) in a yield of 44%.

[Example 2]
Production of acid proliferator (2)
Using the following procedure, an acid proliferating agent represented by the formula (Ib) was produced.

0.38 g of intermediate (2) (2- (2- (4-methoxyphenylthio) ethyl) -2-phenyl-1,3-dioxolane) obtained in Example 1 (2) was added to a four-necked flask. (1.2 × 10 ⁻³ mol) and 10 ml of dehydrated dichloromethane (dry-CH ₂ Cl ₂ ) were added. To this, 0.1 g (0.61 × 10 ⁻³ mol) of methyl trifluoromethanesulfonate was added dropwise in an ice bath, and the mixture was stirred and mixed at room temperature for 30 minutes. The mixture after stirring and mixing was separated by column chromatography using a developing solvent of ethyl acetate: hexane = 1: 1, and the yield of the acid proliferating agent of the present invention represented by the formula (Ib) was 0.1 g (0. 33 × 10 ⁻³ mol), and the yield was 55%.

[Example 3]
Production of acid multiplier (3):
Using the procedures (1) to (3) below, an acid proliferating agent represented by the formula (Ic) was produced.

(1) Production of intermediate (3):
In a four-necked flask, 1.0 g (5.9 × 10 ⁻³ mol) of 3-chloropropiophenone and 0.86 g (8.6 × 10 ⁻³ mol) of triethylamine as a base were added, and tetrahydrofuran (THF) was added. Dissolved in 10 ml. To this, 4-nitrobenzenethiol dissolved in 10 ml of tetrahydrofuran (THF) was added dropwise from a dropping funnel of 1.0 g (7.12 × 10 ⁻³ mol). The mixture in the four-necked flask was stirred at room temperature for 30 minutes, and then dichloromethane (CH ₂ Cl ₂ ) was added thereto, followed by extraction with an aqueous sodium hydrogen carbonate solution and an aqueous sodium chloride solution in this order, and then again with a mixed solution of hexane and tetrahydrofuran (THF). Crystallization yielded a yellow solid of intermediate (3) (3- (4-nitrophenylthio) -1-phenylpropan-1-one) represented by the following formula (H-3) in a yield of 0.79 g (2. 75 × 10 ⁻³ mol), and the yield was 46%.

(2) Production of intermediate (4):
In a four-necked flask, 3.57 g (12.4 × 10 ⁻³ mol) of intermediate (3) (3- (4-nitrophenylthio) -1-phenylpropan-1-one) obtained in (1) was added. ), 1.49 g (23.2 × 10 ⁻³ mol) of ethylene glycol, 0.86 g (5.0 × 10 ⁻³ mol) of p-toluenesulfonic acid, and 100 ml of benzene were refluxed for 12 hours. After refluxing and concentration, separation was performed by column chromatography using a developing solvent of ethyl acetate: hexane = 1: 20, and intermediate (4) (2- (2- (4-nitro) shown in formula (H-4) was obtained. Phenylthio) ethyl) -2-phenyl-1,3-dioxolane) was obtained in a yield of 1.5 g (4.53 × 10 ⁻³ mol) in a yield of 37%.

(3) Production of acid proliferator:
In a four-necked flask, 2.4 g of intermediate (4) (2- (2- (4-nitrophenylthio) ethyl) -2-phenyl-1,3-dioxolane) obtained in (2) (5. 73 × 10 ⁻³ mol), 0.19 g (1.91 × 10 ⁻³ mol) of trimethyloxonium tetrafluoroborate and 10 ml of dehydrated acetonitrile (dry-CH ₃ CN) were added and stirred at room temperature for 15 minutes. 5 ml of methanol was added to the mixture after stirring and mixing, and the mixture was further stirred and mixed, and then concentrated under reduced pressure with an evaporator to obtain the acid growth agent of the present invention represented by the formula (Ic).

[Production Example 1]
Production of photoacid generator:
In a four-necked flask, 1.0 g (6.48 × 10 ⁻³ mol) of (4-methoxyphenyl) (methyl) sulfane and 0.32 g (2.16 × 10 ⁻³ mol) of trimethyloxonium tetrafluoroborate Then, 10 ml of dehydrated acetonitrile (dry-CH ₃ CN) was added and mixed with stirring at room temperature for 15 minutes. 5 ml of methanol was added to this mixture, and further stirred and mixed at room temperature for 5 minutes. The mixture after stirring and mixing was concentrated under reduced pressure using an evaporator, and separated by column chromatography using a developing solvent of ethyl acetate: hexane = 1: 1 to yield a white solid of the photoacid generator represented by the following formula (A). Obtained 0.23 g (0.9 × 10 ⁻³ mol) in a yield of 42%.

[Test Example 1]
Check storage stability:
When the acid proliferation agent obtained in Example 1 was allowed to stand at room temperature for 10 days to confirm the presence or absence of decomposition, the decomposition did not occur and excellent storage stability was exhibited.

[Test Example 2]
Confirmation of degradation behavior of acid multiplier in solution of acid multiplier:
As shown in the above-mentioned Scheme 1 and Scheme 2, the acid proliferating agent undergoes a decomposition reaction by the addition of an acid, and an acid (tetrafluoroboric acid in the acid proliferating agent of Example 1) and sulfide are generated ( A scheme in the case of the acid proliferating agent of Example 1 is shown, which leads to the scheme 1). The degradation behavior of the acid proliferating agent was confirmed using the following method.

(Scheme for acid growth in Example 1)

In an NMR sample tube, 72 × 10 ⁻³ mol / l of the acid proliferating agent obtained in Example 1, 4.7 × 10 ⁻³ mol of p-toluenesulfonic acid, 2.7 μl of water, 5.3 μl of heavy water, Methylene 20 μl and acetonitrile-d ₃ 1 ml were added, sealed, and heated at 100 ° C. for a predetermined time. Then, by analyzing the sulfide peak by ¹ H-NMR, the decomposition behavior (sulfide formation) of the acid proliferating agent was confirmed, and compared with the case where no acid (acetonitrile) was added. The relationship between the heating time and the sulfide generation rate is shown in FIG. The generation rate of sulfide was calculated from a ¹ H-NMR spectrum.

  As shown in FIG. 1, in the system in which no acid (acetonitrile) was added, the acid proliferating agent was not decomposed even if the heating time was prolonged, and the sulfide was not generated and was stable. On the other hand, in the system to which acid is added, the acid proliferating agent is rapidly decomposed to produce sulfide quantitatively, and a curve of nonlinear reaction peculiar to the growth reaction is obtained, and sulfide is generated proliferatively. Was confirmed.

[Test Example 3]
Neutralization titration:
A 6.58 × 10 ⁻³ N NaOH standard solution (H ₂ O was subjected to nitrogen bubbling with 20 ml of ion-exchanged water) was added to the burette. In the NMR tube in which the acid proliferating agent was decomposed in Test Example 2, 10 ml of dioxane was added, diluted and divided into two equal parts, 4.9 × 10 ⁵ mol of methyl orange was added, and neutralization titration (n = 2). Went. The results are shown in Table 2. The amount of acid generated (%) was calculated by dividing the amount of acid (measured value) (ml) by the amount of acid (theoretical value), and converted to% (100 times).

(result)

  As shown in Table 2, it was confirmed that the acid proliferating agent of Example 1 was decomposed autocatalytically by the action of acid, and new acid was quantitatively generated.

[Test Example 4]
Confirmation of degradation behavior of acid multiplier in polymer solid:
In polyisobutylene resin (PIB) (Tg: -64 ° C), 30 mol of the acid proliferating agent obtained in Example 1 with respect to PIB, 30 mol of p-toluenesulfonic acid with respect to PIB was added to 1.0 g of acetonitrile. The sample solution was dissolved. This sample solution was spin-coated on a silicon wafer at 1000 rpm for 30 seconds, and pre-baked on a hot plate at 80 ° C. for 30 seconds to prepare a test film. This test film was heated at 100 ° C., and the change with time in the FT-IR spectrum (change from 1,3-dioxolane) was confirmed. In addition, it confirmed also when not adding p-toluenesulfonic acid, and the presence or absence of the acid was compared. The relationship between the heating time and the peak derived from 1,3-dioxolane is shown in FIG.

  As shown in FIG. 2, in the system to which acid (p-toluenesulfonic acid) was added, decomposition of the acid proliferating agent progressed with heating at 100 ° C., and the change in the peak derived from 1,3-dioxolane decreased. After 30 minutes, it was almost zero. As described above, it was confirmed that the acid proliferation reaction according to the above-described scheme occurred due to the decomposition by the addition of acid as a trigger by heating.

[Test Example 5]
Confirmation of decomposition behavior of acid proliferator (1):
Irradiate light having a wavelength of 254 nm to the methanol solution of 2.0 × ⁻³ mol / l of the acid proliferating agent obtained in Example 1, and an ultraviolet-visible spectrophotometer (MultiSpec-1500 / manufactured by Shimadzu Corporation). The change of the UV spectrum with time was confirmed. The results are shown in FIG.

  FIG. 3 is a graph showing changes in the UV spectrum of the acid proliferator obtained in Example 1. As shown in FIG. 3, the acid proliferator obtained in Example 1 was photodegraded by light irradiation at 254 nm, the absorption changed with the exposure amount, and the photodegradation behavior could be confirmed. Moreover, it has confirmed that a decomposition product had absorption in the long wavelength side (300 nm).

[Test Example 6]
Confirmation of degradation behavior of acid proliferator (2):
To the polymethyl methacrylate resin (PMMA) (M _w : 12000, Tg: 99 ° C.) 0.1 g, the acid proliferating agent obtained in Example 1 0.0063 g (1.5 mol% with respect to PMMA), the following formula ( The sample solution was prepared by dissolving 0.0052 g of coumarin shown in C) (1.5 mol% with respect to PMMA) in 2.0 g of chloroform. This sample solution was spin-coated on quartz glass at 1000 rpm for 30 seconds and prebaked on a hot plate at 80 ° C. for 30 seconds to prepare a test film having a thickness of 0.3 μm. The test film was irradiated with monochromatic light of 254 nm, and the change with time of the UV spectrum was confirmed using an ultraviolet-visible spectrophotometer (MultiSpec-1500 / manufactured by Shimadzu Corporation).

  FIG. 4 is a diagram showing a change in UV spectrum of a test film containing the acid proliferating agent and coumarin obtained in Example 1. As shown in FIG. 4, it was confirmed that the absorption at 457 nm derived from coumarin decreased and the absorption at 533 nm indicating acidity increased according to the exposure dose. From this result, it was confirmed that acid was generated by photolysis.

[Example 4]
Production of acid-reactive resin composition (1):
The acid proliferating agent obtained in Example 1 with respect to 0.1 g of pentaerythritol polyglycidyl ether (DENACOL EX-411: manufactured by Nagase Chemtech Co., Ltd.), which is an epoxy compound represented by the formula (4-13) Was contained (0.035 g (35 parts by mass with respect to 100 parts by mass of EX-411)) (30 mol% with respect to the monomer of EX-411) to obtain the acid-reactive resin composition of the present invention.

[Comparative Example 1]
Production of resin composition (1):
Photoacid generation obtained in Production Example 1 with respect to 0.1 g of pentaerythritol polyglycidyl ether (Denacol EX-411: manufactured by Nagase Chemtech Co., Ltd.), which is an epoxy compound represented by the formula (4-13) The resin composition was obtained by containing 0.021g (21 mass parts with respect to 100 mass parts of EX-411) (30 mol% with respect to the monomer of EX-411) of an agent.

[Test Example 7]
Confirmation of cationic UV curing (1):
The acid-reactive resin composition (photosensitive resin composition) obtained in Example 4 was dissolved in 0.05 g of acetonitrile (CH ₃ CN) to obtain a sample solution. This sample solution was bar-coated on a glass substrate to form a film, heated at 100 ° C. for 30 seconds and prebaked to prepare a coating film having a thickness of 5 μm. 254 nm monochromatic light was applied to this coating film, the exposure amount was 0 (blank), 100, 250, 500 and 1000 mJ / cm ² , and the coating film was heated at 100 ° C. for 0 (blank), 5, 10, 20 minutes. The hardness was measured in accordance with JIS K5600-5-4, and compared and evaluated. The same operation was performed on the resin composition obtained in Comparative Example 1. The results are shown in FIGS.

FIG. 5 is a diagram showing the results of pencil hardness measurement of Comparative Example 1. FIG. 6 is a diagram showing the results of pencil hardness measurement of Example 4. As shown in FIG. 5, in Comparative Example 1 in which the photoacid generator of Production Example 1 was added, no increase in hardness was observed even when the temperature was heated to 100 ° C. after exposure, and exposure of 500 mJ / cm ² When heated for 5 minutes, the coating did not cure and remained liquid. Further, even when the exposure amount was 1000 mJ / cm ² , the hardness increased only by about 3B.

On the other hand, as shown in FIG. 6, in Example 4 to which the acid proliferating agent of Example 1 was added, the hardness increased to 3H by heating for 5 minutes after irradiation with 500 mJ / cm ² . At this time, the unexposed portion remained liquid. From this, the high hardness in the system of Example 4 was caused by a small amount of super strong acid (HBF ₄ ) generated from the acid proliferating agent of Example 1 by light irradiation, and the acid proliferating agent by subsequent heating. This is thought to be due to the fact that the growth reaction progressed and a large amount of super strong acid was generated, which reacted with the epoxy compound.

  INDUSTRIAL APPLICABILITY The present invention can be advantageously used as a material for providing a highly sensitive photocuring material, resist material (pattern forming material) and the like, and has high industrial applicability.

Claims (6)

An acid growth agent represented by the following formula (I):

(In the formula (I), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or carbon. An alkynyl group having 2 to 12 carbon atoms or an aromatic group having 6 to 12 carbon atoms, which may have a straight chain structure, a branched structure, or a ring structure, and may contain a hetero atom, R ₇ and R _8; Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkynyl group having 2 to 12 carbon atoms, or an aromatic group having 6 to 12 carbon atoms. M ₁ and m ₂ each independently represents an integer of 1 to 10. X ⁻ represents a counter anion, and represents a counter anion of a super strong acid having a Hammett acidity function H ₀ of −12 or less. The acid growth agent according to claim 1, which is represented by the following formula (I ').

(In formula (I ′), R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , m ₁ , m ₂ , and X ⁻ are the same as those in formula (I).) X ⁻ is HSO ₄ ⁻ , CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ ⁻ , CF ₃ CF ₂ CF ₂ SO ₃ ⁻ , CF ₃ CF ₂ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , BF ₄ ⁻ , PF _The claim 1 or claim 1, which is one selected from the group consisting of ₆ ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ and B (C ₆ F ₅ ) ₄ ^−. Item 3. The acid proliferating agent according to Item 2.   An acid-reactive resin composition comprising the acid proliferating agent according to any one of claims 1 to 3 and an acid-reactive compound.   An acid-reactive resin composition comprising the acid proliferating agent according to any one of claims 1 to 3, an acid generator, and an acid-reactive compound. 6. The acid-reactive resin according to claim 4, wherein the acid-reactive compound is at least one selected from the group consisting of an epoxy-based compound, a silicon-based compound, an oxetane-based compound, and a vinyl ether compound. Composition.

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