JP5814074B2 - Method for producing polymer membrane and polymer membrane - Google Patents

Description

  The present invention relates to a method for producing a polymer film. Furthermore, the present invention relates to a polymer film produced by the polymer film production method.

Conventionally, in a positive photosensitive resin composition, a photoacid generator is irradiated with light to generate an acid, and only the irradiated portion is alkali developed (Patent Documents 1 and 2). ). However, such a positive photosensitive resin composition has a problem of low stability to light. Therefore, when the positive photosensitive composition is stored under a white light or a yellow light for a certain period (for example, 10 days or longer), there is a problem that some of the photoacid generator generates an acid during the storage. It was.
On the other hand, Patent Document 3 describes forming a cured film by plasma irradiation. However, there is no description about using it for a positive resist.

JP 2007-328093 A JP 2008-158339 A JP 2005-523803 A

  An object of the present invention is to produce a polymer film in which a specific portion is removed by dissolving in an alkaline solution without using a photoacid generator in a positive photosensitive resin composition.

Under such circumstances, the inventor of the present application studied to generate an acid by a method other than light irradiation and remove the portion with an alkaline solution. Specifically, the above-mentioned problems have been solved by the following means <1>, preferably <2> to <9>.
<1> Applying a composition containing (A) an onium salt having a nitrogen cation and (B) a hardly alkali-soluble resin on a support to form a film;
And a method for producing a polymer film, comprising irradiating a part or all of the surface of the film with plasma and dissolving and removing the plasma-irradiated part with an alkaline solution.
<2> (A) The method for producing a polymer film according to <1>, wherein the onium salt having a nitrogen cation is at least one selected from a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt.
<3> (A) The polymer membrane method according to <1> or <2>, wherein the onium salt having a nitrogen cation has a partial structure represented by any one of the following general formulas (1) to (3): .
(In the above general formulas (1) to (3), R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may each have an alkyl group or a substituent that may have a substituent. Each of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be bonded to each other to form a ring, and R ⁵¹ , R ⁷¹ and R ⁸¹ are each a substituent; R ⁶¹ and R ⁹¹ each represents an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. An alkoxy group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have or a halogen atom, where n is an integer of 0 to 3. If .n indicated is 2 or more, R ⁶¹ may combine with each other, may form a ring .m For .m is 2 or more represents an integer of 0 to 3, R ⁹¹ are linked to each other X ⁻ may be Cl ⁻ , Br ⁻ , I ⁻ , R ¹ —SO ₃ ⁻ , NO ₃ ⁻ , R ¹ —COO ⁻ , AlO ₂ ⁻ , ClO ₄ ⁻ , B ( C ₆ H ₅ ) ₄ ⁻ , R ¹ —O ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ (wherein R ¹ is an optionally substituted alkyl group) Or an aryl group which may have a substituent.), And R ^{11 to} R ⁹¹ may form a chemical bond with R ¹ via a divalent organic group.
<4> (A) The method for producing a polymer film according to <1> or <2>, wherein the onium salt having a nitrogen cation is represented by the following general formula (4).
(In the general formula (4), R ⁷² , R ⁸² , and R ⁹² each represents an alkyl group having 4 or less carbon atoms,
Y ⁻ represents R ¹ —SO ₃ ⁻ , ClO ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ . m shows the integer of 0-3. When m is 2 or more, R ⁹¹ may be bonded to each other to form a ring. )
<5> (A) The method for producing a polymer film according to any one of <1> to <4>, wherein the onium salt having a nitrogen cation is an ionic liquid.
<6> (B) The hardly alkali-soluble resin contains at least one of an acetal-modified hydroxystyrene repeating unit, an acetal-modified (meth) acrylic repeating unit, and a tertiary ester-modified (meth) acrylic repeating unit as a partial structure. The method for producing a polymer film according to any one of <1> to <5>, wherein:
<7> The method for producing a polymer film according to any one of <1> to <6>, wherein the support is a polymer film.
<8> The method for producing a polymer film according to any one of <1> to <7>, wherein the plasma is low-temperature atmospheric pressure plasma.
<9> A polymer membrane produced by the polymer membrane production method according to any one of <1> to <8>.

  The onium salt having a nitrogen cation according to the present invention is extremely stable against light, rapidly decomposes by plasma, and generates an acid, so that acid decomposition of an alkali poorly soluble resin triggered by this proceeds to change polarity. As a result, the solubility in alkali can be increased.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The present invention applies (A) a composition containing an onium salt having a nitrogen cation and (B) a hardly alkali-soluble resin on a support to form a film, and a part of the surface of the film or In all, a method for producing a polymer film comprising irradiating plasma and dissolving and removing a portion irradiated with plasma with an alkaline solution is disclosed.
Conventionally, in a positive resin composition, a film is formed by applying on a support, and then an acid generator is generated by light irradiation on part or all of the film surface, and dissolved and removed with an alkaline solution. Was. However, such a positive resin composition has a demerit that it is unstable to light. In the present invention, an onium salt having a nitrogen cation is used as the acid generator, and plasma irradiation is employed as the acid generation source, thereby succeeding in avoiding the problems of the prior art. That is, the onium salt having a nitrogen cation used in the present invention is rapidly decomposed by plasma having high energy and high reducibility, and generates an acid. A polarity change occurs and the solubility in alkali can be increased.
Furthermore, the onium salt having a nitrogen cation in the present invention is extremely stable against light and heat, and has high solubility in organic substances, and thus has excellent storage stability (decomposition and precipitation suppression) in a white lamp. In addition, since the applied film is stable against light and heat, it can be used as a substrate protective agent.
Hereinafter, the present invention will be described in detail.

(A) Onium salt having nitrogen cation The onium salt having a nitrogen cation used in the present invention serves as a so-called plasma acid generator. That is, by irradiating plasma, an acid is generated only in an onium salt onium salt having a nitrogen cation in the irradiated portion.
The onium salt having a nitrogen cation is preferably at least one selected from quaternary ammonium salts, alkylpyridinium salts, and alkylimidazolium salts, and at least one selected from alkylpyridinium salts and alkylimidazolium salts. It is more preferable that it is alkyl imidazolium salt. Since the imidazole after decomposition is a weak base and does not neutralize the generated acid, the function as an acid generator is more easily maintained.
The onium salt is preferably an ionic liquid (melting point: 100 ° C. or lower) from the viewpoint of suppressing crystal precipitation during storage at room temperature.
For use in polarity conversion accompanying acid decomposition of a poorly alkali-soluble resin, anions include Cl ⁻ , Br ⁻ , I ⁻ , R ¹ —SO ₃ ⁻ , NO ₃ ⁻ , R ¹ —COO ⁻ , AlO ₂ ⁻ , ClO ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , R ¹ —O ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ (where R ¹ has a substituent) An alkyl group which may be substituted or an aryl group which may have a substituent.), R ¹ —SO ₃ ⁻ , ClO ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , PF _{6 ^{-, SbF 6 -, GaF 6}} - or AsF ₆ ^-, more preferably, R ¹ -SO ₃ ^- is more preferred. From the viewpoint of acid strength, R ¹ is preferably a fluoroalkyl group, more preferably a fluoromethyl group.

(A) The onium salt having a nitrogen cation preferably has a partial structure represented by any one of the following general formulas (1) to (3).
(In the above general formulas (1) to (3), R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may each have an alkyl group or a substituent that may have a substituent. Each of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be bonded to each other to form a ring, and R ⁵¹ , R ⁷¹ and R ⁸¹ are each a substituent; R ⁶¹ and R ⁹¹ each represents an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. An alkoxy group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have or a halogen atom, where n is an integer of 0 to 3. If .n indicated is 2 or more, R ⁶¹ may combine with each other, may form a ring .m For .m is 2 or more represents an integer of 0 to 3, R ⁹¹ are linked to each other X ⁻ may be Cl ⁻ , Br ⁻ , I ⁻ , R ¹ —SO ₃ ⁻ , NO ₃ ⁻ , R ¹ —COO ⁻ , AlO ₂ ⁻ , ClO ₄ ⁻ , B ( C ₆ H ₅ ) ₄ ⁻ , R ¹ —O ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ (wherein R ¹ is an optionally substituted alkyl group) Or an aryl group which may have a substituent.), And R ^{11 to} R ⁹¹ may form a chemical bond with R ¹ via a divalent organic group.
As the substituent that R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may have, a phenyl group, an acetylcarbonyl group, a vinyl group, an anion, or a group containing a cation is preferable. The cation is preferably a nitrogen cation, and the anion is preferably an anion represented by X ⁻ .
R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ are preferably an unsubstituted alkyl group, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, and further an unsubstituted alkyl group having 2 to 4 carbon atoms. preferable.
The substituent that R ⁵¹ , R ⁷¹ , and R ⁸¹ may have is the same as the substituent that R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may have, and the preferred range is also the same. It is.
R ⁵¹ , R ⁷¹ , and R ⁸¹ are each preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably an unsubstituted alkyl group having 2 to 4 carbon atoms. The substituent that R ⁶¹ and R ⁹¹ may have is the same as the substituent that R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may have, and the preferred range is also the same.
R ⁶¹ and R ⁹¹ are each preferably an alkyl group which may have a substituent, more preferably an unsubstituted alkyl group having 1 to 10 carbon atoms, and an unsubstituted alkyl group having 2 to 4 carbon atoms. More preferred is an alkyl group. X ⁻ is preferably in the same range as the anion described above.

(A) The onium salt having a nitrogen cation is more preferably represented by the following general formula (4).
(In the general formula (4), R ⁷² , R ⁸² , and R ⁹² each represents an alkyl group having 4 or less carbon atoms,
Y ⁻ represents R ¹ —SO ₃ ⁻ , ClO ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ . m shows the integer of 0-3. When m is 2 or more, R ⁹¹ may be bonded to each other to form a ring. )
The preferred ranges of R ⁷² , R ⁸² , R ⁹² and Y ⁻ are the same as R ⁷¹ , R ⁸¹ , R ⁹¹ and Y ^{− in the} general formula (3), respectively, and the preferred ranges are also the same.

  Furthermore, since the conventionally known photoacid generators (sulfonium salts, iodonium salts) deteriorate the storage stability under white light and the stability of the coating film against light and heat, the composition used in the present invention. Is preferably substantially free of a photoacid generator. “Substantially not contained” means not containing within the range that affects the effect of the present invention, for example, 0.1% by weight or less.

  As the ionic liquid, an imidazolium salt, a pyrrolidinium salt, a pyridinium salt, or an ammonium salt commercially available from Tokyo Chemical Industry Co., Ltd. can be used. For example, 1,3-dimethylimidazolium chloride, 1,3-dimethylimidazolium dimethyl phosphate, 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methyl Imidazolium iodide, 1-ethyl-3-methylimidazolium methanesulfonate, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluorotrifluoromethylborate, 1-ethyl-3 Methyl imidazolium hydrogen sulfate, 1-ethyl-3 methyl imidazolium ethyl sulfate, 1-ethyl-3 methyl imidazolium 2- (2-methoxyethoxy) ethyl sulfate, 1-ethyl-3 methyl imidazole Umdicyanamide, 1-ethyl-3methylimidazolium tetrafluoroborate, 1-ethyl-3methylimidazolium hexafluorophosphate, 1-ethyl-3methylimidazolium bis (trifluoromethanesulfonyl) imide, 1-ethyl-3methyl Imidazolium p-toluenesulfonate, 1-ethyl-3-methylimidazolium tetrachloroferrate, 1-methyl-3-propylimidazolium iodide, 1-butyl-3 methylimidazolium chloride, 1-butyl-3-methylimidazolium Bromide, 1-butyl-3methylimidazolium iodide, 1-butyl-3methylimidazolium trifluoromethanesulfonate, 1-butyl-3methylimidazolium trifluorotrifluoromethylborate, 1-butyl 3 methyl imidazolium tetrafluoroborate, 1-butyl-3 methyl imidazolium hexafluorophosphate, 1-butyl-3 methyl imidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-3 methyl imidazolium tetrachloroferrate, 1 -Hexyl-3-methylimidazolium chloride, 1-hexyl-3-methylimidazolium bromide, 1-hexyl-3-methylimidazolium tetrafluoroborate, 1-hexyl-3-methylimidazolium hexafluorophosphate, 1-methyl-3-octyl Imidazolium chloride, 1-methyl-3-octylimidazolium bromide, 1-methyl-3-octylimidazolium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazole Lithium bis (trifluoromethanesulfonyl) imide, 1,2-dimethyl-3-propylimidazolium iodide, 1-butyl-2,3-dimethylimidazolium chloride, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium hexafluorophosphate, 1-butyl-2,3-dimethylimidazolium bis (trifluoromethanesulfonyl) imide, 1-butyl-2,3-dimethylimidazolium polyethylene glycol hexadecyl ether Sulfate coated lipase, 1-methyl-1-propylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-butyl-1-methylpyrrolidinium chloride, 1-butyl-1-methylpyrrolidinium bromide 1-butyl-1-methylpyrrolidinium bis (trifluoromethanesulfonyl) imide, 1-ethylpyridinium chloride, 1-ethylpyridinium bromide, 1-butylpyridinium chloride, 1-butylpyridinium bromide, 1-butylpyridinium tetrafluoroborate, 1-butylpyridinium hexafluorophosphate, 1-butyl-3-methylpyridinium chloride, 1-butyl-3-methylpyridinium bromide, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-ethyl-3-methylpyridinium bis ( Trifluoromethanesulfonyl) imide, 1-ethyl-3- (hydroxymethyl) pyridinium ethyl sulfate, 1-butyl-4-methylpyridinium chloride, 1-butyl-4-methylpyridi Umbromide, 1-butyl-4-methylpyridinium hexafluorophosphate, amyltriethylammonium bis (trifluoromethanesulfonyl) imide, tributylmethylammonium bis (trifluoromethanesulfonyl) imide, tetrabutylammonium chloride, tetrabutylammonium bromide, methyltri-n- Octylammonium bis (trifluoromethanesulfonyl) imide, cyclohexyltrimethylammonium bis (trifluoromethanesulfonyl) imide, etc.

Although the onium salt which has (A) nitrogen cation used by this invention below is illustrated, it cannot be overemphasized that this invention is not restricted to these.

  (A) The onium salt having a nitrogen cation is preferably contained in the resin composition used in the present invention in a proportion of 0.5 to 50% by weight of all components excluding the solvent. It is more preferable that it is contained.

(B) Alkali-poorly soluble resin The alkali-poorly soluble resin used in the present invention is one or more acid-dissociable groups capable of dissociating part or all of the alkali-affinity functional groups in the alkali-soluble resin in the presence of an acid. The resin protected with
As the alkali hardly soluble resin, the acid dissociable group introduction rate with respect to the alkali soluble resin is preferably 16 to 60 mol%, and more preferably 18 to 50 mol%. By setting the introduction rate to 16 mol% or more, the development speed can be kept moderate, and appropriate pattern formation can be performed more effectively. By setting the amount to 60 mol% or less, it is possible to more effectively suppress that developability is too slow and sufficient sensitivity cannot be obtained. The introduction rate is a ratio of the number of moles of the acid-dissociable group in the total value of the number of moles of the acid-dissociable group and the number of moles of the alkali-affinity functional group in the hardly alkali-soluble resin. .
As a method for measuring the introduction rate of the acid dissociable group in the hardly alkali-soluble resin, for example, after reacting the acid dissociable group, the unreacted acid dissociable group is detected by gas chromatography, and the acid Examples thereof include a method for calculating the introduction rate of the dissociable group, a method for measuring the introduction rate of the acid dissociable group by measuring the reaction product by proton NMR measurement, and the like.
In the present invention, it is particularly preferable that at least one of an acetal-modified hydroxystyrene repeating unit, an acetal-modified (meth) acrylic repeating unit, and a tertiary ester-modified (meth) acrylic repeating unit is included as a partial structure.

  Examples of the acid dissociable group in the hardly alkali-soluble resin include a substituted alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a saturated cyclic group.

  Examples of the substituted alkyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a vinyloxymethyl group, a vinylthiomethyl group, a benzyloxymethyl group, a benzylthiomethyl group, Phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, triphenylmethyl group, diphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl Group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group 1,1- Ethoxyethyl group, 1-vinyloxyethyl group, 1-vinylthioethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzyl Thioethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl Group, 2-vinyloxyethyl group, 2-vinylthioethyl group, 2-methyladamantane, 2-ethyladamantane, 2-isopropyladamantane, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylethyl group, 2- (1-adamantyl) An isopropyl group etc. can be mentioned.

  Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, methylditert- Examples thereof include a butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  Examples of the germyl group include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, tert- Examples thereof include a butyldimethylgermyl group, a methylditert-butylgermyl group, a tritert-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

  Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, tert-butoxycarbonyl group and the like.

  As the acyl group, for example, acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioyl group, methacryl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, camphoroyl group, benzoyl Group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonico Hexanoyl group, p- toluenesulfonyl group, and mesyl group.

  Examples of the saturated cyclic group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydrothiofuranyl group. , 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, S, S-dioxide group, 2-1,3-dioxolanyl group, 2-1,3-dithiooxolanyl group Benzo-2-1,3-dioxolanyl group, benzo-2-1,3-dithiooxolanyl group and the like.

The alkali-soluble resin is a resin that is soluble in an alkali developer composed of an aqueous alkali solution, and has at least one functional group having an affinity for the aqueous alkali solution.
There is no restriction | limiting in particular as a functional group which shows affinity with the said alkaline aqueous solution, It can select suitably from well-known things, For example, a phenolic hydroxyl group, a carboxyl group, etc. are mentioned.

  Specific examples of the alkali-soluble resin include vinyl resins and novolac type phenol resins, and examples include polyhydroxystyrene resins, (meth) acrylic resins, and novolac type phenol resins.

The vinyl resin and the novolak resin are preferably resins having a structural unit derived from a monomer containing an acidic functional group.
Examples of the monomer containing an acidic functional group include hydroxystyrene, vinyl benzoic acid, styryl acetic acid, styryloxyacetic acid, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, And mesaconic acid.

The vinyl resin can further have a structural unit composed of a monomer other than the monomer containing the acidic functional group.
Examples of the monomer other than the monomer containing an acidic functional group include a monomer having a polymerizable double bond.
Examples of the monomer having a polymerizable double bond include styrene, α-methylstyrene, p-acetoxystyrene, p-tert-butoxystyrene, p-ethoxyethoxystyrene, vinyltoluene, maleic anhydride, (meta ) Acrylonitrile, (meth) acrylic acid, (meth) acrylic acid ester, maleinonitrile, fumaronitrile, mesaconitrile, citraconitrile, itacone nitrile, (meth) acrylamide, crotonamide, maleinamide, fumaramide, mesaconamide, citraconic amide, itacone Examples include amide, vinylaniline, vinylpyridine, vinyl-ε-caprolactam, vinylpyrrolidone, and vinylimidazole.
As a method for producing an alkali-soluble resin comprising the vinyl resin, for example, a required monomer or monomer mixture may be produced by polymerization or copolymerization using a polymerization initiator or a polymerization catalyst. it can.
The polymerization initiator or the polymerization catalyst is not particularly limited and may be appropriately selected depending on the type of the monomer and the reaction catalyst. For example, a radical polymerization initiator, an anionic polymerization catalyst, a coordination anionic polymerization catalyst , Cationic polymerization catalyst, and the like.
The polymerization or copolymerization method is not particularly limited and may be appropriately selected depending on the type of the vinyl resin. For example, bulk polymerization, solution polymerization, precipitation polymerization, emulsion polymerization, suspension polymerization, bulk -Suspension polymerization etc. are mentioned.

-Alkali poorly soluble resin composed of novolac type phenol resin-
The hardly alkali-soluble resin composed of the novolak resin can be obtained by reacting the side chain of the novolak resin with one of a vinyl ether compound and an isopropenyl ether compound.

  Examples of the method for producing the novolak resin include a method in which 0.6 to 1.0 mol of aldehydes are addition-condensed with 1 mol of phenol under an acidic catalyst.

Examples of the phenols include phenol, p-cresol, m-cresol, o-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, 2,4,5-trimethylphenol, Methylene bisphenol, methylene bis p-cresol, resorcin, catechol, 2-methyl resorcin, 4-methyl resorcin, o-chlorophenol, m-chlorophenol, p-chlorophenol, 2,3-dichlorophenol, p-methoxyphenol, m -Methoxyphenol, p-bu Xylphenol, o-ethylphenol, m-ethylphenol, p-ethylphenol, 2,3-diethylphenol, 2,5-diethylphenol, p-isopropylphenol, p-tert-butylphenol, α-naphthol, β-naphthol -4-phenylphenol etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, plural mixtures of alkylphenols such as cresol, dimethylphenol, and trimethylphenol are preferable.
Moreover, as said phenols, it can use as substituted phenols further substituted by the substituent. Examples of the substituted phenols include monomethylolated products and dimethylolated products of the phenols.

  Examples of the aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, glyoxal, chloroacetaldehyde, dichloroacetaldehyde, and bromoaldehyde. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the acidic catalyst include hydrochloric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, and the like.

  The novolak type phenol resin preferably has a relatively narrow molecular weight distribution in order to obtain a photoresist having a wide development latitude. Such spread of the molecular weight distribution can be generally expressed by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), that is, the Mw / Mn value (dispersion degree). The degree of dispersion becomes larger as the molecular weight distribution is wider, and becomes 1 when there is no molecular weight distribution. The novolak resin used in a typical positive type photoresist has a relatively wide molecular weight distribution. For example, as shown in Japanese Patent Publication No. 62-172341, the degree of dispersion is generally 5-10. Between. Also, in SPIE Brocade Dink “Advanceds in Resist Technology and Processing V”, Volume 920, page 349, the value of 4.55 to 6.75 is higher than that of 3.0. It has been suggested to give value.

  The dispersion degree of the novolac type phenol resin is different from the above dispersion degree (Mw / Mn), preferably 1.5 to 4.0, and more preferably 2.0 to 3.5. When the degree of dispersion is less than 1.5, it is inappropriate for synthesizing the novolak type phenol resin and a high-level purification step is required, so that it is not suitable for lacking practical reality. , Wide development latitude may not be obtained.

  Various methods are conceivable for producing the novolac type phenol resin having the above-described degree of dispersion. For example, it can be obtained by a method such as selection of a specific phenolic monomer, selection of condensation reaction conditions, and fractional precipitation of a normal novolak type phenol resin having a high degree of dispersion. May be manufactured.

  The mass average molecular weight (Mw) of the novolak resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,000 to 50,000 is preferable, and 2,000 to 30,000 is more preferable. . When the mass average molecular weight (Mw) exceeds 50,000, the sensitivity may decrease or the resolution may deteriorate, and when it is less than 1,000, the developer resistance may be poor. In some cases, an appropriate pattern cannot be obtained.

Examples of the vinyl ether compound include methyl vinyl ether, ethyl vinyl ether, methylthiomethyl vinyl ether, ethylthiomethyl vinyl ether, n-propyl vinyl ether, isopropyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, and the like. It is done. Among these, methyl vinyl ether, ethyl vinyl ether, and benzyl vinyl ether are preferable in terms of heat resistance.
Examples of the isopropenyl ether compound include methyl isopropenyl ether, ethyl isopropenyl ether, methylthiomethyl isopropenyl ether, n-propyl isopropenyl ether, benzyl isopropenyl ether, tert-butyl isopropenyl ether, n-butyl vinyl ether, Etc. Among these, methyl isopropenyl ether, ethyl isopropenyl ether, and benzyl isopropenyl ether are preferable from the viewpoint of heat resistance.

  Examples of the method of reacting the side chain of the novolak resin with any one of the vinyl ether compound and the isopropenyl ether compound include organic solvents such as tetrahydrofuran, acetone, 1,4-dioxane, methylene chloride, and dimethoxyethane. In the presence of a suitable acid (eg sulfuric acid, hydrochloric acid, p-toluenesulfonic acid, chlorosulfonic acid or pyridine salt, sulfuric acid or pyridine salt, p-toluenesulfonic acid or pyridine salt, etc.) at 10-100 ° C. The method of making it react for 1 to 20 hours, etc. are mentioned.

  Examples of the acid dissociable group in the hardly alkali-soluble resin made of the novolak resin include the same as the acid dissociable group.

  Specific examples of the alkali poorly soluble resin composed of the novolak resin include, for example, a novolak resin having a 1-methoxy-1-methylethoxy group as an acid dissociable group, and a 1-benzyloxy-1-methylethoxy group as an acid dissociating property. And a novolak resin based on 1-ethoxyethoxy group and an acid dissociable group.

-Poor alkali-soluble resin made of polyhydroxystyrene resin-
The alkali poorly soluble resin comprising the polyhydroxystyrene resin can be obtained by reacting the polyhydroxystyrene resin with any one of a vinyl ether compound and an isopropenyl ether compound.

  Examples of the polyhydroxystyrene resin include alkali-soluble resins having a hydroxyl group (—OH) and a carboxyl group (—COOH) in the side chain. Among these, alkali-soluble resins having an aryloxy group (—Ar—OH) are preferable. Ar represents a monocyclic or polycyclic aromatic group, which may be further substituted with a substituent.

Examples of the base resin of the polyhydroxystyrene resin include alkali-soluble resins having a phenolic hydroxyl group.
The alkali-soluble resin having a phenolic hydroxyl group preferably contains, for example, 30 mol% or more of any repeating unit of hydroxystyrene and hydroxy-α-methylstyrene, more preferably contains 50 mol% or more. preferable.
Examples of the hydroxystyrene include o-hydroxystyrene, m-hydroxystyrene, and p-hydroxystyrene.
Examples of the hydroxy-α-methylstyrene include o-hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, and p-hydroxy-α-methylstyrene.
Examples of the alkali-soluble resin having a phenolic hydroxyl group include a copolymer and a homopolymer.
The alkali-soluble resin having a phenolic hydroxyl group is preferably a resin in which the benzene nucleus in the repeating unit is partially hydrogenated, and more preferably a p-hydroxystyrene homopolymer.
When the alkali-soluble resin having a phenolic hydroxyl group is a copolymer, examples of the monomer other than the hydroxystyrene and hydroxy-α-methylstyrene include acrylic esters, methacrylic esters, acrylamides, and methacrylamides. , Acrylonitrile, methacrylonitrile, maleic anhydride, styrene, α-methylstyrene, acetoxystyrene, alkoxystyrenes and alkylstyrenes are preferable, and styrene, acetoxystyrene and tert-butylstyrene are more preferable.

  There is no restriction | limiting in particular as a mass mean molecular weight (Mw) of the said polyhydroxy styrene resin, According to the objective, it can select suitably, For example, 2,000-50,000 are preferable, 3,000-30,000 Is more preferable. If the mass average molecular weight (Mw) is too large, the sensitivity may decrease or the resolution may deteriorate.

The alkali poorly soluble resin comprising polyhydroxystyrene can be obtained by reacting the vinyl ether compound with polyhydroxystyrene dissolved in an appropriate solvent such as tetrahydrofuran by a known method. The reaction is preferably performed in the presence of an acidic catalyst.
Examples of the acidic catalyst include acidic ion exchange resins, hydrochloric acid, p-toluenesulfonic acid, and pyridinium tosylate.
Specific examples of the vinyl ether compound include, for example, methyl vinyl ether, ethyl vinyl ether, methylthiomethyl vinyl ether, ethylthiomethyl vinyl ether, n-propyl vinyl ether, isopropyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, phenyl vinyl ether, benzyl vinyl ether, Etc. Among these, methyl vinyl ether, ethyl vinyl ether, and benzyl vinyl ether are preferable in terms of heat resistance.
As a method for synthesizing the vinyl ether, for example, a method of synthesizing from an active raw material such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction can be employed. As a method of synthesizing from an active raw material such as chloroethyl vinyl ether by a method such as a nucleophilic substitution reaction, it can be synthesized using mercury or a palladium catalyst.
Examples of the method for synthesizing the vinyl ether include a method for synthesizing by an acetal exchange method using alcohol and vinyl ether.
The method for acetal exchange using the alcohol and vinyl ether is a method in which a substituent to be introduced into the alcohol is added and reacted with the vinyl ether in the presence of an acid. As the vinyl ether, it is preferable to mix a relatively unstable vinyl ether such as tert-butyl vinyl ether. Examples of the acid include p-toluenesulfonic acid and pyridinium tosylate.

  Examples of the acid dissociable group in the poorly alkali-soluble resin made of the polyhydroxystyrene resin include a substituted alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a saturated cyclic group.

  Examples of the substituted alkyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a vinyloxymethyl group, a vinylthiomethyl group, a benzyloxymethyl group, and a benzylthiomethyl group. Phenacyl group, bromophenacyl group, methoxyphenacyl group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, triphenylmethyl group, diphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxy Benzyl group, methylthiobenzyl group, ethoxybenzyl group, ethylthiobenzyl group, piperonyl group, 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl Group 1, -Diethoxyethyl group, 1-vinyloxyethyl group, 1-vinylthioethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1 -Benzylthioethyl group, 1-phenylethyl group, 1,1-diphenylethyl group, isopropyl group, sec-butyl group, tert-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1- Examples thereof include a dimethylbutyl group, a 2-vinyloxyethyl group, and a 2-vinylthioethyl group.

  Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, isopropyldimethylsilyl group, methyldiisopropylsilyl group, triisopropylsilyl group, tert-butyldimethylsilyl group, methylditert- Examples thereof include a butylsilyl group, a tri-tert-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

  Examples of the germyl group include trimethylgermyl group, ethyldimethylgermyl group, methyldiethylgermyl group, triethylgermyl group, isopropyldimethylgermyl group, methyldiisopropylgermyl group, triisopropylgermyl group, tert- Examples thereof include a butyldimethylgermyl group, a methylditert-butylgermyl group, a tritert-butylgermyl group, a phenyldimethylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

  The alkali-insoluble resin composed of the polyhydroxystyrene resin can also be obtained by copolymerizing a monomer previously reacted with a protecting group as described in JP-A No. 05-249682.

  Specific examples of the alkali poorly soluble resin composed of the polyhydroxystyrene resin include, for example, p-1-methoxy 1 methylethoxystyrene-p-hydroxystyrene polymer, p-1-benzyloxy-1-methylethoxystyrene-p. -Hydroxystyrene polymer, p-1-ethoxyethoxystyrene-p-hydroxystyrene polymer, p-1-methoxyethoxystyrene-p-hydroxystyrene polymer, p-1-n-butoxyethoxystyrene-p-hydroxystyrene Polymer, p-1-isobutoxyethoxystyrene-p-hydroxystyrene polymer, p-1- (1,1-dimethylethoxy) -1-methylethoxystyrene-p-hydroxystyrene polymer, m-1- ( 2-chloroethoxy) ethoxystyrene-m-hydroxystyrene heavy P-tert-butoxycarbonyloxystyrene-p-hydroxystyrene polymer, p-1-methoxy-n-propyloxystyrene-p-hydroxystyrene polymer, p-tetrahydropyranyloxystyrene-p-hydroxystyrene heavy Polymer, p-1-cyclohexyloxyethoxystyrene-p-hydroxystyrene polymer, m-1- (2-ethylhexyloxy) ethoxystyrene-m-hydroxystyrene polymer, p-1-methoxy-1-methylethoxy-α -Methylstyrene-p-hydroxy-α-methylstyrene polymer, p-1-ethoxyethoxystyrene-p-hydroxystyrene-acrylonitrile polymer, p-1-ethoxyethoxystyrene-p-hydroxystyrene-fumaronitrile polymer, p -1-n-but Xoxyethoxystyrene-p-hydroxystyrene-methyl methacrylate polymer, p-1-cyclohexyl-1-ethoxyethoxystyrene-p-hydroxystyrene-tert-butyl methacrylate polymer, p-1-methoxycyclohexyloxystyrene-p -Hydroxystyrene polymer, p-1-ethoxy 1-methylethoxystyrene-p-hydroxystyrene polymer, p-1-cyclopentyloxyethoxystyrene-p-hydroxystyrene polymer, p-1- (2-chloroethoxy) ethoxy Examples thereof include styrene-p-hydroxystyrene-tert-butyl methacrylate polymer and m-1-cyclohexyloxyethoxystyrene-m-hydroxystyrene-maleic anhydride polymer.

-Alkali poorly soluble resin made of (meth) acrylic resin-
The hardly alkali-soluble resin composed of the (meth) acrylic resin can be obtained by radical copolymerization of a (meth) acrylic monomer having an acid dissociable group. Examples of the acid dissociable group include a substituted alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a saturated cyclic group.

  The (B) alkali poorly soluble resin in the present invention is preferably contained in the range of 50 to 99% by weight, and in the range of 70 to 95% by weight, based on all components except the solvent in the composition. More preferred.

  The composition used in the present invention includes (A) an onium salt having a nitrogen cation and (B) a hardly alkali-soluble resin, as long as it does not depart from the spirit of the present invention, a solvent, a crosslinking agent, a silane coupling agent, an interface An activator, an antioxidant and the like may be included.

Solvent The composition in the present invention usually contains a solvent. The solvent is basically not particularly limited as long as the solubility and coating properties of each component are satisfied. As the solvent, one or more organic solvents can be used. Moreover, water and the mixed solvent of water and 1 or more types of organic solvents can also be used as a solvent.

  Examples of the solvent include various solvents described in paragraph [0187] of JP-A-2008-32803. Specific examples of organic solvents that can be used as the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, and butyl butyrate. , Methyl lactate, ethyl lactate, alkyl oxyacetate (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (specifically, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethoxyacetic acid And ethyl 3-oxypropionate (eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (specifically, methyl 3-methoxypropionate, 3-methoxy). Ethyl propionate, methyl 3-ethoxypropionate, 3- And 2-oxypropionic acid alkyl esters (eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (specifically, And methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, etc.)), 2-oxy-2-methylpropion Acid methyl, ethyl 2-oxy-2-methylpropionate (specifically, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate , Ethyl pyruvate, propyl pyruvate, methyl acetoacetate, acetovinegar Ethyl, methyl 2-oxobutanoate, esters such as ethyl 2-oxobutanoate.

  Examples of organic solvents that can be used as the solvent include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether. , Propylene glycol monomethyl ether (PGME: alias 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate (PGMEA: alias 1-methoxy-2-acetoxypropane), propylene glycol monoethyl ether acetate, Propylene glycol monopro They include ethers such as ether acetate.

Examples of organic solvents that can be used as the solvent include ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Examples of organic solvents that can be used as the solvent include aromatic hydrocarbons such as toluene and xylene.

  Two or more of these organic solvents may be mixed from the viewpoints of solubility of each component, improvement of the coating surface condition, and the like. In this case, particularly preferably, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol It is a mixed solvent composed of two or more selected from acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

  Moreover, as content of the solvent in the said composition, it is preferable to set it as the quantity from which a total solid content concentration in a composition becomes 1-50 mass% from a viewpoint of applicability | paintability, 2 mass%-40 mass%. More preferable is an amount of 5% by mass to 30% by mass.

Surfactant The composition used in the present invention may contain one or more surfactants from the viewpoint of further improving applicability. As the surfactant, any surfactant such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. Two or more kinds may be used in combination.

  In particular, when the composition contains a fluorosurfactant, the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved. can do. In an embodiment in which a film is formed using a coating liquid comprising the above-described composition containing a fluorosurfactant, the interfacial tension between the coated surface of the support and the coated liquid is reduced, and the wettability to the coated surface is reduced. It improves and the applicability | paintability to a coated surface improves. For this reason, in the said aspect, even if it is a case where a thin film about several nanometers-several micrometers is formed with a small amount of liquids, since the film of uniform thickness with small thickness nonuniformity can be formed, it is more effective in formation of a thin film. .

  The fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. . A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.

  Examples of the fluorosurfactant include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC-101, Same SC-103, Same SC-104, Same SC-105, Same SC1068, Same SC-381, Same SC-383, Same S393, Same KH-40 (above, manufactured by Asahi Glass Co., Ltd.), Solsperse 20000 (Japan Rouble) Zole Co., Ltd.).

  Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol dilaurate. Stearate, sorbitan fatty acid ester (pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, manufactured by BASF, Tetronic 304, 701, 704, 901, 904, 150R1, etc. are mentioned.

  Specific examples of the cationic surfactant include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid ( Co) polymer polyflow no. 75, no. 90, no. 95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.) and the like.

  Examples of the silicone surfactant include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, “Toray Silicone” manufactured by Toray Dow Corning Co., Ltd. “Silicone SH29PA”, “Toresilicone SH30PA”, “Toresilicone SH8400”, “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF” manufactured by Momentive Performance Materials, Inc. -4552 "," KP341 "," KF6001 "," KF6002 "manufactured by Shin-Etsu Silicone Co., Ltd.," BYK307 "," BYK323 "," BYK330 "manufactured by Big Chemie.

  In the present invention, the composition may or may not contain a surfactant, but when it is contained, the content of the surfactant is 0 with respect to the total solid mass of the composition. It is preferably 0.001% by mass or more and 1% by mass or less, and more preferably 0.01% by mass or more and 0.1% by mass or less.

A method for producing a polymer film using the composition of the present invention will be described.
The method for producing a polymer film of the present invention comprises (A) applying a composition containing an onium salt having a nitrogen cation and (B) a hardly alkali-soluble resin on a support to form a film, and The method includes irradiating a part or all of the film with plasma and dissolving and removing the plasma-irradiated part with an alkaline solution.
More preferably, the method for producing a polymer film of the present invention includes the following (1) to (4).
(1) The step of applying the composition on the support (2) The step of removing the solvent from the applied composition (3) The step of plasma irradiation (4) The step of developing

In the application step (1), the composition is usually applied (usually applied) on a support to form a wet film containing a solvent. Examples of the application method include spin coating, extrusion coating, direct gravure coating, reverse gravure coating, and die coating. Moreover, you may utilize an inkjet.
About a support body, there is no restriction | limiting in particular in any viewpoints, such as a shape and material. Any form of a tubular body, a planar shape, or a strip shape may be used. Further, it may be a support having pores such as a porous body, and a film may be formed on the inner surface of the pores. In addition, any support made of an organic material, an inorganic material, and a hybrid material thereof can be used. Specifically, a polymer film is preferable. Further, the surface on which the film of the support is formed may be either a flat surface or a curved surface, or may be a surface having fine irregularities. Specifically, examples of the support for forming the membrane include films, substrates, sheets, filter paper, membrane filters, resin tubes, fabrics, cotton, felts, feathers, and the like. It is not limited.

  In the solvent removing step (2), the solvent is removed from the applied film by vacuum (vacuum) and / or heating to form a dry film on the substrate.

  (3) In the plasma irradiation step, the formed film is irradiated with plasma to generate an acid. It is preferable to use a low-temperature atmospheric pressure plasma generated under conditions near atmospheric pressure. For example, a non-equilibrium plasma jet, low-temperature plasma by AC pulse discharge, or the like can be used, and it is preferable to use plasma generated under conditions near atmospheric pressure.

Various atmospheric pressure plasma apparatuses can be used for plasma irradiation. For example, a device that can generate low-temperature plasma by performing intermittent discharge while passing an inert gas at a pressure close to atmospheric pressure between electrodes covered with a dielectric is preferable, and any device can be used. Various modification examples can be selected according to the purpose of use. More specifically, in Japanese Patent Application Laid-Open No. 2008-60115, an apparatus used for substrate plasma processing, an atmospheric pressure plasma apparatus described in Japanese Patent Application Laid-Open No. 2004-228136, Japanese Patent Application Laid-Open No. 2006-21972, Japanese Patent Application Laid-Open No. 2007-188690, And plasma devices described in the specifications of International Publication WO2005 / 062338, WO2007 / 024134, WO2007 / 145513, and the like. The atmospheric pressure plasma apparatus is also available as a commercial product. For example, ATMP-1000 from Arios Co., Ltd., atmospheric pressure plasma apparatus from HEIDEN LABORATORIES, INC., S5000 type atmospheric pressure low-temperature plasma from Sakai Semiconductor Co., Ltd. An atmospheric pressure plasma apparatus currently on the market such as a jet apparatus, MyPL100, ILP-1500 of Well Co., Ltd., and RD550 of Sekisui Chemical Co., Ltd. can also be suitably used. However, in order to avoid non-uniform concentration (streamer) of plasma and reduce damage to the film, for example, the energization to the discharge part described in each specification of WO / 2005/062338 and WO2007 / 024134 is performed. It is preferable to use a device with a devised electrical circuit, such as via a pulse control element.
In the present invention, “pressure near atmospheric pressure” in “atmospheric pressure plasma” refers to a range of 70 kPa to 130 kPa, preferably 90 kPa to 110 kPa.

As a discharge gas used at the time of generating atmospheric pressure plasma, any gas of nitrogen, oxygen, hydrogen, carbon dioxide, helium, and argon, or a mixed gas of two or more of these can be used. It is preferable to use an inert gas such as He and Ar, or a nitrogen gas (N ₂ ), and Ar or He is particularly preferable. By applying plasma to the film surface, the reductive decomposition of the onium salt, the accompanying acid generation, and the deprotection reaction of the alkali-insoluble resin proceed rapidly.

  Note that the plasma treatment may be performed by a batch method or an in-line method connected to other processes.

  From the viewpoint of suppressing damage to the film surface, the plasma action site is separated from the discharge site, or local plasma concentration (streamer) is suppressed by devising the discharge circuit to generate a uniform plasma. In particular, the latter is preferable in that a uniform plasma treatment over a large area can be performed. As the former, a method in which the plasma generated by the discharge is brought into contact with the surface of the film by an inert gas stream is preferable, and a so-called plasma jet method is particularly preferable. In this case, the path (conducting tube) for transporting the inert gas containing plasma is preferably a dielectric such as glass, porcelain, or organic polymer. As the latter, a method of generating uniform glow plasma in which streamers are suppressed by energizing an electrode covered with a dielectric via a pulse control element described in WO / 2005/062338 and WO2007 / 024134. Is preferred.

The distance from the supply nozzle of the inert gas containing plasma to the film surface is preferably 0.01 mm to 100 mm, and more preferably 1 mm to 20 mm.
Even in the case of a transport system using an inert gas, plasma can be applied to the film surface by an in-line system, similar to the system described in WO2009 / 096785. In other words, an organic thin film can be formed continuously by forming a film for forming an organic thin film by a coating method and providing a blowing nozzle that can apply an inert gas and plasma to the downstream side of the coating process. It becomes.

  Note that, from the viewpoint of reducing the intake of chemical species derived from oxygen, an inert gas may be sufficiently supplied to the region where the plasma treatment is performed, or the region may be filled with the inert gas. When carrying the plasma using such an inert gas, it is preferable that an inert gas is allowed to flow through the plasma generation site before the plasma is turned on, and the inert gas is allowed to continue even after the plasma is extinguished.

  The inert gas after the plasma treatment may be exhausted without performing any special treatment because the plasma has a short life, but the inert gas that has been treated by providing an inlet in the vicinity of the treatment region. May be recovered.

  The temperature at the time of plasma irradiation can be selected according to the characteristics of the material in the film irradiated with plasma, but damage can be reduced if the temperature rise caused by irradiation with atmospheric pressure and low temperature plasma is smaller. preferable. The effect is further improved by separating the plasma application area from the plasma generator.

In the above method, by selecting and irradiating the atmospheric low temperature plasma, the supply of thermal energy from the plasma can be reduced, and the temperature rise of the film can be suppressed. The temperature rise of the film due to the plasma irradiation is preferably 50 ° C. or less, more preferably 40 ° C. or less, and particularly preferably 20 ° C. or less.
The temperature at the time of plasma irradiation is preferably equal to or lower than the temperature that can be withstood by the material in the film irradiated with plasma, and is generally preferably −196 ° C. or higher and lower than 150 ° C., more preferably −21 ° C. or higher and 100 ° C. or lower. preferable. Particularly preferred is the vicinity of room temperature (25 ° C.) under an ambient temperature atmosphere.

  By the said method, an alkali-soluble film | membrane is formed in at least one part of the surface of a support body. The thickness of the alkali-soluble film to be formed is not particularly limited, but the method of the present invention using plasma is advantageous for forming a thin film. Specifically, the thickness of the cured film produced by the method of the present invention is not limited. The thickness is preferably 1 to 500 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm. In particular, in the present invention, since the reaction can be started by performing plasma treatment only on the extreme surface, there is an advantage that it does not mix with adjacent layers when applied in multiple layers.

  In the developing step (4), the alkali-soluble film generated by the plasma irradiation is developed using an alkaline developer. A positive image is formed by removing the region irradiated with plasma.

The polymer film produced by the method for producing a polymer film of the present invention is useful as a planarizing film or an interlayer insulating film for use in organic EL display devices and liquid crystal display devices.
In addition to the planarization film and the interlayer insulating film, the polymer film of the present invention is a color filter protective film, a spacer for keeping the thickness of the liquid crystal layer in a liquid crystal display device constant, and a color in a solid-state imaging device. It can be suitably used for a microlens or the like provided on a filter.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Preparation of plasma reactive composition containing onium salt with nitrogen cation (1) Example 1
Components of the following component amounts were mixed, and the mixed solution was filtered through a 0.1 μm tetrafluoroethylene filter to prepare the plasma reactive coating solution of Example 1.
-(A) Onium salt having a nitrogen cation (Exemplary Compound A-1) 5 parts by mass-(B) Alkali-soluble resin (B-1 below) 95 parts by mass-Surfactant (polyoxyethylene lauryl ether) 0. 1 part by weight / solvent: 900 parts by mass of propylene glycol monomethyl ether (PGME)

(2) Other Examples and Comparative Examples Coating solutions were prepared in the same manner as in Example 1 except that the compositions shown in the following table were changed.

(3-1) Preparation of residual film by partial plasma treatment (Examples 1-7, Comparative Examples 1-3)
(Formation of coating film)
Each coating solution obtained above was applied onto a polyethylene terephthalate substrate (PET substrate) by a spin coating method, and then heated on a hot plate at 60 ° C. for 1 minute to obtain a plasma-reactive coating film. . The film thickness was 500 nm.

(Plasma treatment)
The coating film was scanned with a S5000 type atmospheric pressure low temperature plasma jet apparatus (discharge gas: nitrogen) manufactured by Sakai Semiconductor Co., Ltd., and irradiated with low temperature N ₂ plasma at a rate of 1 mm / second for 30 seconds. The decomposition reaction of the acid dissociable group was allowed to proceed, immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds, rinsed with water for 30 seconds, and dried. A positive pattern film in which the plasma irradiation portion was alkali-developed was formed.
However, in Example 8, instead of N ₂ plasma, Ar plasma was irradiated by scanning an S5000 type atmospheric pressure low temperature plasma jet apparatus (discharge gas: argon).

(3-2) Preparation of residual film by partial plasma treatment (Comparative Example 4)
In the same manner as described above, a coating film having a thickness of 500 nm is formed, UV UV SOURCE EX250 (manufactured by HOYA-SCHOTT) is used as a UV lamp instead of atmospheric pressure plasma, and UV is passed through a photomask (1 cm × 3 cm). Irradiation was performed so that the irradiation amount was 1 J / cm ² . It was immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. A positive pattern film in which the UV irradiated portion was alkali-developed was formed.

<Performance evaluation>
The following evaluations were performed for each coating composition and each film.
(1) Storage stability (white light, heating test)
Each coating composition prepared above was placed in a thermocellco set at 60 ° C. under a white lamp and stored for 1 month. An onium salt that is unstable to light and heat is decomposed at this stage, and an acid or a radical is generated, so that the coexisting alkali-insoluble resin is decomposed and lowered in molecular weight, which is not preferable. This solution was subjected to GPC measurement to observe changes in molecular weight. Evaluation was performed based on the following criteria.
○: No change in molecular weight is observed.
Δ: Molecular weight change was less than 5%.
X: Molecular weight change was 5% or more.

(2) Storage stability Yellow lamp, refrigeration test Each coating composition prepared above was placed in a thermocellco set at 0 ° C under a yellow lamp and stored for 1 month. Onium salts with low solvent solubility are not preferred because crystals precipitate at this stage or the solution becomes cloudy, and a uniform composition cannot be obtained. This solution was visually observed. Evaluation was performed based on the following criteria.
(Double-circle): Crystal precipitation and cloudiness are not recognized at all.
○: Slight cloudiness is observed.
(Triangle | delta): A cloudiness is recognized notably.
X: Crystal precipitation is recognized simultaneously with cloudiness.

(3) Irradiation part alkali solubility The alkali-developed positive pattern formed above was visually observed.
○: Rapid development, no development residue is observed Δ: Development residue is slightly seen ×: No development

(4) Pattern film light resistance Each of the formed pattern films was subjected to a forced light resistance test (LUX time) and then immersed in an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution for 60 seconds and then water for 30 seconds. Rinse and dry. The change in weight before and after the light resistance test was measured. The smaller the change in weight, the higher the light stability of the pattern film, and it can be used as a PET protective agent under severe conditions such as outdoors.
◎: 90% or more remaining ○: 60% or more and less than 90% △: 30% or more and less than 60% remaining ×: less than 30% remaining

The compounds used are shown below.

<Synthesis Method of B-1>
5 g of polyhydroxystyrene (Mw 15000) was dissolved in 30 mL of propylene glycol monomethyl ether acetate, 0.05 g of pyridinium p-toluenesulfonate and 1.2 g of ethyl vinyl ether were added, and the mixture was stirred at room temperature for 4 hours. After being diluted with ethyl acetate, it was washed with 100 mL of pure water three times. The organic layer was distilled off under reduced pressure to 30 mL and crystallized with 200 mL of hexane. 4.8 g (Mw 15600) of the obtained white powder B-1 was obtained.
<Synthesis Method of B-2>
3 g of p-acetoxystyrene and 1.3 g of t-butyl methacrylate were dissolved in 50 mL of propylene glycol monomethyl ether acetate and heated and stirred at 80 ° C. under N 2 stream. To this was added 0.25 g of dimethyl azobisisobutyrate, and the mixture was further stirred for 6 hours. The obtained polymer was crystallized with 200 mL of hexane. This powder was collected by filtration and redissolved in 50 mL of tetrahydrofuran. To this, 5 g of 28% sodium methoxide methanol solution was added and stirred at room temperature for 2 hours. This was added to 200 mL of 1% hydrochloric acid aqueous solution to obtain 3.8 g (Mw 8900) of white powder B-2.
<Synthesis Method of B-3>
7.2 g of benzyl methacrylate and 3.5 g of 2- (1-adamantane) propyl-2-methacrylate were dissolved in 50 mL of propylene glycol monomethyl ether acetate, and the mixture was heated and stirred at 80 ° C. under N 2 stream. To this was added 0.25 g of dimethyl azobisisobutyrate, and the mixture was further stirred for 6 hours. The obtained polymer was crystallized with 200 mL of hexane.
The obtained white powder B-3 was obtained in 7.1 g (Mw 10200).
<Synthesis Method of B-4>
12.6 g of benzyl methacrylate and 2.4 g of methacrylic acid were dissolved in 50 mL of propylene glycol monomethyl ether acetate, and the mixture was heated and stirred at 80 ° C. in a N 2 stream. To this was added 0.25 g of dimethyl azobisisobutyrate, and the mixture was further stirred for 6 hours. The obtained polymer was crystallized with 200 mL of hexane. This was collected by filtration, redissolved in 30 mL of propylene glycol monomethyl ether acetate, added with 0.05 g of pyridinium p-toluenesulfonate and 3.8 g of cyclohexaneethyl vinyl ether, and stirred at room temperature for 4 hours. After being diluted with ethyl acetate, it was washed with 100 mL of pure water three times. The organic layer was distilled off under reduced pressure to 30 mL and crystallized with 200 mL of hexane. The obtained white powder B-4 was obtained in 10.5 g (Mw12300).
(A′-1) Bis (p-tert-butyl) phenyliodonium hexafluorophosphate (manufactured by TCI Corporation)
(A′-2) Tris (p-tolyl) sulfonium hexafluorophosphate (manufactured by TCI Corporation)

  As is clear from the above table, it was possible to form a film partially removed with an alkaline solution by irradiating an onium salt having a nitrogen cation with plasma to generate an acid. In particular, it was found that the storage stability under a yellow lamp is further improved by using an onium salt having a nitrogen cation represented by the general formula (3).

Claims (8)

(A) applying a composition containing an onium salt having a nitrogen cation and (B) a hardly alkali-soluble resin on a support to form a film;
And a method for producing a polymer film, comprising irradiating a part or all of the surface of the film with plasma and dissolving and removing the plasma-irradiated part with an alkaline solution. (A) The method for producing a polymer film according to claim 1, wherein the onium salt having a nitrogen cation is at least one selected from a quaternary ammonium salt, an alkylpyridinium salt, and an alkylimidazolium salt. (A) The method for producing a polymer film according to claim 1 or 2, wherein the onium salt having a nitrogen cation has a partial structure represented by any one of the following general formulas (1) to (3).
(In the above general formulas (1) to (3), R ¹¹ , R ²¹ , R ³¹ , and R ⁴¹ may each have an alkyl group or a substituent that may have a substituent. Each of R ¹¹ , R ²¹ , R ³¹ and R ⁴¹ may be bonded to each other to form a ring, and R ⁵¹ , R ⁷¹ and R ⁸¹ are each a substituent; R ⁶¹ and R ⁹¹ each represents an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. An alkoxy group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an alkoxycarbonyl group which may have a substituent, a substituent An aryloxycarbonyl group which may have or a halogen atom, where n is an integer of 0 to 3. If .n indicated is 2 or more, R ⁶¹ may combine with each other, may form a ring .m For .m is 2 or more represents an integer of 0 to 3, R ⁹¹ are linked to each other X ⁻ may be Cl ⁻ , Br ⁻ , I ⁻ , R ¹ —SO ₃ ⁻ , NO ₃ ⁻ , R ¹ —COO ⁻ , AlO ₂ ⁻ , ClO ₄ ⁻ , B ( C ₆ H ₅ ) ₄ ⁻ , R ¹ —O ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ (wherein R ¹ is an optionally substituted alkyl group) Or an aryl group which may have a substituent.), And R ^{11 to} R ⁹¹ may form a chemical bond with R ¹ via a divalent organic group. (A) The manufacturing method of the polymer film of Claim 1 or 2 with which the onium salt which has a nitrogen cation is represented by following General formula (4).
(In the general formula (4), R ⁷² , R ⁸² , and R ⁹² each represents an alkyl group having 4 or less carbon atoms,
Y ⁻ represents R ¹ —SO ₃ ⁻ , ClO ₄ ⁻ , B (C ₆ H ₅ ) ₄ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , GaF ₆ ⁻ or AsF ₆ ⁻ . m shows the integer of 0-3. When m is 2 or more, R ⁹¹ may be bonded to each other to form a ring. ) (A) The manufacturing method of the polymer film of any one of Claims 1-4 whose onium salt which has a nitrogen cation is an ionic liquid. (B) The poorly alkali-soluble resin contains at least one of an acetal-modified hydroxystyrene repeating unit, an acetal-modified (meth) acrylic repeating unit, and a tertiary ester-modified (meth) acrylic repeating unit as a partial structure. The manufacturing method of the polymer film of any one of Claims 1-5. The method for producing a polymer film according to claim 1, wherein the support is a polymer film. The method for producing a polymer film according to claim 1, wherein the plasma is low-temperature atmospheric pressure plasma.