JP2013091741A - Method for producing cured product, and cured product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cured product with excellent curability.SOLUTION: A method for manufacturing a cured product includes irradiating, with plasma, a composition including (A) an onium salt having nitrogen cations, and (B) a curable compound.

Description

The present invention relates to a method for producing a cured product. Furthermore, it is related with the hardened | cured material manufactured by the manufacturing method of this hardened | cured material.
The present invention also relates to a plasma polymerization initiator using an onium salt. The present invention also relates to a method for generating at least one of radicals, acids and bases by irradiating plasma to an onium salt.

Conventionally, organic cured films have been used for various applications such as optical materials and electrical materials. In general, the organic cured film is polymerized and crosslinked to form a polymer network structure by irradiating a polymerizable composition containing a polymerizable monomer or a polymer having a crosslinking group and a polymerization initiator with light. Is formed. However, conventional organic cured films such as instability of polymerizable monomers (corrosion, progress of polymerization during storage), handleability of the raw material polymerizable composition, and inability to store in the presence of a polymerization initiator. There were various problems with formation. In particular, a polymerizable composition containing a photopolymerization initiator has a problem of stability against light during storage. However, there are many cases where it is not practical to cure the polymerizable composition immediately after preparing it, such as when the seller of the polymerizable composition is different from the manufacturer of the cured film.
On the other hand, Patent Document 1 describes that a curable composition is irradiated with plasma. In patent document 1, it has succeeded in forming a cured film on the three-dimensional base material which ultraviolet rays do not reach using plasma irradiation. However, even in Patent Document 1, the problem of light stability of the curable composition remains.
Patent Document 2 describes an acid generator composition containing a cation. However, since the acid is generated by irradiating light in Patent Document 2, the problem of light stability of the composition remains.

JP 2005-523803 A JP 2005-239877 A

  The present invention is intended to solve the problems of the prior art, and can provide a curable composition that can maintain high polymerizability without using a curing reaction initiator and has excellent storage stability. It is related with the manufacturing method of the used hardened | cured material.

Under the circumstances, the present inventor has conducted intensive studies, and as a result, the present inventor generates at least one of radical, acid and base by a method other than light irradiation, thereby starting a curing reaction. It was investigated. Specifically, the above-mentioned problems have been solved by the following means <1>, preferably <2> to <15>.
<1> A method for producing a cured product, comprising irradiating a composition containing (A) an onium salt having a nitrogen cation and (B) a curable compound with plasma.
<2> (A) The method for producing a cured product 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 cured product 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 cured product 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 ⁹² may be bonded to each other to form a ring. )
<5> (A) The method for producing a cured product according to any one of <1> to <4>, wherein the onium salt having a nitrogen cation is an ionic liquid.
<6> (B) The method for producing a cured product according to any one of <1> to <5>, wherein the curable compound contains at least one of a cationic polymerizable monomer and a radical polymerizable monomer.
<7> Forming a film on a support by applying a composition containing (A) an onium salt having a nitrogen cation, (B) a curable compound and (C) a solvent, and applying plasma to the film Irradiation to decompose (A) an onium salt having a nitrogen cation, and (B) to cure the curable compound by radical or cationic polymerization,
The manufacturing method of the hardened | cured material of any one of <1>-<6> containing this.
<8> The method for producing a cured product according to <7>, wherein the support is a polymer film.
<9> The method for producing a cured product according to any one of <1> to <8>, wherein the plasma is low-temperature atmospheric pressure plasma.
<10> The method for producing a cured product according to any one of <1> to <9>, wherein the cured product is a film.
<11> A cured product produced by the method according to any one of <1> to <10>.
<12> A cured film produced by the method according to any one of <1> to <10>.
<13> A method of initiating a reaction by irradiating an onium salt having a nitrogen cation with plasma to decompose the onium salt to generate at least one of a radical, an acid, and a base.
<14> A plasma acid generator comprising an onium salt having a nitrogen cation.
<15> (A) The plasma acid generator according to <14>, 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.
<16> A plasma polymerization initiator comprising an onium salt having a nitrogen cation.
<17> (A) The plasma polymerization initiator according to <16>, 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.

  The onium salt having a nitrogen cation in the present invention is extremely stable against light and heat, and is rapidly decomposed by plasma to generate an acid or a radical. The acid crosslinking reaction proceeds to increase the molecular weight, and it has become possible to achieve a high degree of curing without using a photocuring reaction initiator such as a photopolymerization initiator.

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.
Further, in the present specification, the terms “cured film” and “film” are used to include both a self-supporting film, and a layer and a film formed on the support.
The curing reaction initiator in the present invention refers to a compound that initiates a curing reaction by light irradiation.
The plasma acid generator in the present invention refers to a compound that generates an acid when irradiated with plasma.
The plasma polymerization initiator in the present invention refers to a compound that initiates polymerization of a polymerizable compound by irradiation with plasma.

This invention discloses the manufacturing method of hardened | cured material including irradiating a plasma to the composition containing (A) onium salt which has a nitrogen cation, and (B) curable compound.
Conventionally, for curing a composition containing a curable compound, for example, when the curable compound is a radical polymerizable compound, the photo radical polymerization initiator is used, and when the curable compound is a cationic polymerizable compound, the photo cationic polymerization is performed. An initiator was employed. However, these photopolymerization initiators have a problem that they are weak in light stability. For this reason, when the curable 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 a part of the curable compound starts to be polymerized. The onium salt having a nitrogen cation according to the present invention is extremely stable against light and heat and has high solubility in organic matter, and thus has excellent storage stability (decomposition and precipitation suppression) in a white light or a yellow light. .
In the present invention, high-energy and high-reducibility plasma rapidly decomposes to generate acids and radicals, so that cationic polymerization, radical polymerization, or acid cross-linking reaction of these curable compounds as a trigger proceeds, increasing the molecular weight. And succeeded in obtaining a high degree of cure.

  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 initiator.
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 a plasma 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 ^- is more preferable. From the viewpoint of acid strength, R ¹ is preferably a fluoroalkyl group, more preferably a fluoromethyl group.
In particular, when the curing reaction is radical polymerization or cationic polymerization, the anion is preferably a Lewis acid (PF ₆ ⁻ , BF ₄ ⁻ , SbF ₄ ⁻ , BPh ₄ ⁻ or the like).
When the curing reaction is acid crosslinking, it is preferable to use a Bronsted acid as an anion rather than a Lewis acid, and particularly a sulfonic acid that is a strong acid is preferably used. The anion is preferably a Bronsted acid (R ¹ SO ₃ ^— or the like). R ¹ has the same meaning as above, and the preferred range is also the same.

(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), and has a partial structure represented by the general formula (3). It is more preferable.
(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 ⁹² 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, conventionally known photopolymerization initiators and photoacid generators deteriorate the storage stability under white light, and the stability of the coating film against light and heat deteriorates. It is preferable that the photopolymerization initiator and the photoacid generator are substantially not contained. “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-octylimidazolium 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- Examples include octylammonium bis (trifluoromethanesulfonyl) imide, cyclohexyltrimethylammonium bis (trifluoromethanesulfonyl) imide, and the like.

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 20% by weight of all components excluding the solvent. It is more preferable that it is contained.
When the curing reaction is radical polymerization, it is preferable from the viewpoint of the degree of curing that the onium salt is decomposed more efficiently and radicals are generated. The radical generation amount increases in the order of ammonium salt, pyridinium salt, and imidazolium salt. Accordingly, in the case of radical polymerization, (A) the onium salt having a nitrogen cation is preferably a pyridinium salt or an imidazolium salt, and more preferably an imidazolium salt.

(B) Curable compound As long as the curable compound in the present invention is a compound that initiates a curing reaction by irradiating the above-mentioned (A) onium salt having a nitrogen cation with plasma, the type thereof is not particularly defined. , Polymerization reaction, condensation reaction and the like can be used. In the case of a polymerization reaction, conventionally known radically polymerizable compounds and cationically polymerizable compounds can be used. In the case of the condensation reaction, conventionally known acid crosslinkable compounds can be used.
The presumed mechanism in which radical polymerization reaction, cation polymerization reaction, and acid cross-linking reaction occur by an onium salt having a nitrogen cation will be described.
When the onium salt having a nitrogen cation of the present invention is irradiated with plasma, the onium salt is reduced by one electron by a strong reducing action such as electrons of the plasma to form an excited state, and the carbon atom adjacent to the nitrogen cation is desorbed in a homolytic manner. Separates to form radical carbon. On the other hand, the nitrogen radical cation thus obtained radically extracts active hydrogen in the system and forms a corresponding acid HX by donating a proton to the counter anion X ⁻ .
Radical polymerization proceeds by radicals generated in this mechanism. Cationic polymerization and acid crosslinking reaction proceed with the acid HX produced.
For the subsequent reaction after the onium salt having a nitrogen cation forms an excited state by plasma, the same mechanism as that of the photoexcitable sulfonium salt or iodonium salt can occur.
Hereinafter, these will be described in detail.

Radical polymerizable compound The radical polymerizable compound used in the present invention is not particularly limited as long as it is a compound that cures by causing radical polymerization reaction by plasma irradiation of nitrogen cation.
The radical polymerizable compound that can be used in the present invention is preferably an addition polymerizable compound having at least one ethylenically unsaturated double bond, and preferably has at least one terminal ethylenically unsaturated bond, preferably two. It is selected from the compounds having the above. It is preferable that 2-10 terminal ethylenically unsaturated bonds are contained in 1 molecule. These compounds include those having chemical forms such as prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof, in addition to monomers.
Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like. Of these, a mixture of pentaerythritol triacrylate and dipentaerythritol hexaacrylate is also preferably used.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include, for example, aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. Those having an aromatic skeleton described in JP-A-2-226149, those containing an amino group described in JP-A-1-165613, and the like are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(In the general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in JP 17654, JP-B 62-39417, and JP-B 62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Depending on the case, it is possible to obtain a composition excellent in sensitivity speed.

  Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates reacted with acrylic acid. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, and vinylphosphonic acid compounds described in JP-A-2-25493 Etc. can also be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

A commercially available product may be used as the polymerizable compound. Examples of the commercially available product used in the present invention include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 ”(Shin Nakamura Chemical). DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
As the polymerizable compound, ethylenically unsaturated compounds having an acid group are also preferably used.
The ethylenically unsaturated compounds having an acid group can be obtained by, for example, converting (meth) acrylate a part of the hydroxy group of the polyfunctional alcohol and adding an acid anhydride to the remaining hydroxy group to form a carboxy group. can get. Examples of commercially available products include TO-756, which is a carboxy group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and TO-1382 including a carboxy group-containing pentafunctional acrylate.

About these addition polymerizable compounds, the details of usage methods such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured product (particularly, a cured film), it is preferable to have a tri- or higher functional group, and further, different functional number / different polymerizable group (for example, acrylate ester, methacrylate ester, styrene compound). The method of adjusting both sensitivity and strength is also effective by using a combination of a vinyl ether compound).

  The content of the radical polymerizable compound in the curable composition used in the present invention is preferably 10 to 99% by mass, more preferably 20 to 97% by mass, and 50 to 95% by mass with respect to the total solid content of the composition. Further preferred. Only one type of radical polymerizable compound may be used, or two or more types may be used in combination.

Cationic polymerizable compound The cationic polymerizable compound used in the present invention is not particularly limited as long as it is a compound that cures by causing a cationic polymerization reaction by plasma irradiation of nitrogen cation.
As the cationically polymerizable compound used in the present invention, various known cationically polymerizable compounds known as photocationic polymerizable compounds can be used. Examples of the cationic polymerizable compound include JP-A-6-9714, JP-A-2001-31892, JP-A-2001-40068, JP-A-2001-55507, JP-A-2001-310938, JP-A-2001-310937, and JP-A-2001-2001. Examples thereof include epoxy compounds, vinyl ether compounds, oxetane compounds and the like described in each publication such as No. 220526.

Examples of the epoxy compound include aromatic epoxides, alicyclic epoxides, and aromatic epoxides.
Aromatic epoxides include di- or polyglycidyl ethers produced by the reaction of polyphenols having at least one aromatic nucleus or their alkylene oxide adducts and epichlorohydrin, such as bisphenol A or its alkylene oxides. Examples thereof include di- or polyglycidyl ethers of adducts, di- or polyglycidyl ethers of hydrogenated bisphenol A or its alkylene oxide adducts, and novolak-type epoxy resins. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

  As the alicyclic epoxide, cyclohexene oxide obtained by epoxidizing a compound having at least one cycloalkane ring such as cyclohexene or cyclopentene ring with a suitable oxidizing agent such as hydrogen peroxide or peracid. Or a cyclopentene oxide containing compound is mentioned preferably.

  Examples of the aliphatic epoxide include an aliphatic polyhydric alcohol or a di- or polyglycidyl ether of an alkylene oxide adduct thereof. Typical examples include diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol or diglycidyl ether of 1,6-hexanediol, diglycidyl ether of alkylene glycol, glycerin or its alkylene oxide adduct di- or tri- Polyglycidyl ethers of polyhydric alcohols such as glycidyl ether, diglycidyl ethers of polyethylene glycol or alkylene oxide adducts thereof, diglycidyl ethers of polyalkylene glycols typified by diglycidyl ethers of polypropylene glycol or alkylene oxide adducts thereof, etc. Can be mentioned. Here, examples of the alkylene oxide include ethylene oxide and propylene oxide.

The epoxy compound may be monofunctional or polyfunctional.
Examples of monofunctional epoxy compounds that can be used in the present invention include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3 -Vinylcyclohexene oxide etc. are mentioned.

  Examples of polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, and brominated bisphenol. S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxy 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclo) Xylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6 '-Methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylenebis (3,4-epoxycyclohexanecarboxylate) , Epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether Glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2,7,8- Examples include diepoxyoctane and 1,2,5,6-diepoxycyclooctane.

  Among these epoxy compounds, aromatic epoxides and alicyclic epoxides are preferable from the viewpoint of excellent curing speed, and alicyclic epoxides are particularly preferable.

  Examples of the vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, propylene glycol divinyl ether, dipropylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, cyclohexanedimethanol divinyl ether, Di- or trivinyl ether compounds such as methylolpropane trivinyl ether, ethyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexane dimethanol monovinyl ether, n-propyl Pills vinyl ether, isopropyl vinyl ether, isopropenyl ether -o- propylene carbonate, dodecyl vinyl ether, diethylene glycol monovinyl ether, and octadecyl vinyl ether.

The vinyl ether compound may be monofunctional or polyfunctional.
Specifically, examples of the monofunctional vinyl ether include, for example, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tert-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether , Methoxy polyethylene Recall vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, Examples include chloroethoxyethyl vinyl ether, phenylethyl vinyl ether, phenoxypolyethylene glycol vinyl ether, and the like.

  Examples of the polyfunctional vinyl ether include, for example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F. Divinyl ethers such as alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol Hexavinyl ether, ethylene oxide-added trimethylolpropane trivinyl ether, propylene oxide-added trimethylolpropane trivinyl ether, ethylene oxide-added ditrimethylolpropane tetravinyl ether, propylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide-added pentaerythritol tetravinyl ether, propylene oxide Examples thereof include polyfunctional vinyl ethers such as addition pentaerythritol tetravinyl ether, ethylene oxide addition dipentaerythritol hexavinyl ether, and propylene oxide addition dipentaerythritol hexavinyl ether.

  As the vinyl ether compound, a di- or trivinyl ether compound is preferable from the viewpoints of curability, adhesion to a recording medium, surface hardness of the formed image, and the like, and a divinyl ether compound is particularly preferable.

The oxetane compound in the present invention refers to a compound having an oxetane ring, and a known oxetane compound is arbitrarily selected as described in JP-A Nos. 2001-220526, 2001-310937, and 2003-341217. Can be used.
As the compound having an oxetane ring, a compound having 1 to 4 oxetane rings in its structure is preferable. By using such a compound, it becomes easy to maintain the viscosity of the composition in a favorable range of handling properties, and high adhesion between the cured composition and the support can be obtained. .

  Examples of the compound having 1 to 2 oxetane rings in the molecule include compounds represented by the following general formulas (1) to (3).

In the general formulas (1) to (3), R ^a1 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a fluoroalkyl group having 1 to 6 carbon atoms, an allyl group, an aryl group, a furyl group, or a thienyl group. Represents. When two Ra1 are present in the molecule, they may be the same or different. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. Preferred examples of the fluoroalkyl group include those in which any hydrogen of these alkyl groups is substituted with a fluorine atom.

In the general formula (1), R ^a2 is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a group having an aromatic ring, or an alkylcarbonyl having 2 to 6 carbon atoms. Group, an alkoxycarbonyl group having 2 to 6 carbon atoms, and an N-alkylcarbamoyl group having 2 to 6 carbon atoms. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkenyl group include 1-propenyl group, 2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-butenyl group, 2-butenyl group and 3-butenyl group. It is done. Examples of the group having an aromatic ring include a phenyl group, a benzyl group, a fluorobenzyl group, a methoxybenzyl group, and a phenoxyethyl group. Examples of the alkylcarbonyl group include an ethylcarbonyl group, a propylcarbonyl group, and a butylcarbonyl group. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a propoxycarbonyl group, and a butoxycarbonyl group.
Examples of the N-alkylcarbamoyl group include an ethylcarbamoyl group, a propylcarbamoyl group, a butylcarbamoyl group, and a pentylcarbamoyl group.

In the general formula (2), R ^a3 represents a linear or branched alkylene group, a linear or branched poly (alkyleneoxy) group, a linear or branched unsaturated hydrocarbon group, a carbonyl group or a carbonyl group. An alkylene group containing a group, an alkylene group containing a carboxyl group, an alkylene group containing a carbamoyl group, or a group shown below is represented. Examples of the alkylene group include an ethylene group, a propylene group, and a butylene group. Examples of the poly (alkyleneoxy) group include a poly (ethyleneoxy) group and a poly (propyleneoxy) group. Examples of the unsaturated hydrocarbon group include a propenylene group, a methylpropenylene group, and a butenylene group.

In the polyvalent group, R ^a4 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, a mercapto group, a lower alkyl carboxyl group, Represents a carboxyl group or a carbamoyl group.
R ^a5 represents an oxygen atom, a sulfur atom, a methylene group, NH, SO, SO ₂ , C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ .
Ra6 represents an alkyl group having 1 to 4 carbon atoms or an aryl group, and n is an integer of 0 to 2000.
R ^a7 represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a monovalent group having the following structure.

In the monovalent group, R ^a8 is an alkyl group having 1 to 4 carbon atoms or an aryl group, and m is an integer of 0 to 100.

  Examples of the compound having 3 to 4 oxetane rings include compounds represented by the following general formula (4).

In the general formula (4), R ^a1 is synonymous with R ^a1 in the formula (1). R ^a9 is a polyvalent linking group, for example, a branched alkylene group having 1 to 12 carbon atoms such as groups represented by A to C below, or a branched poly (alkylene group such as a group represented by D below. (Oxy) group or a branched polysiloxy group such as a group represented by E below. j is 3 or 4.

In the above A, R ^a10 represents a methyl group, an ethyl group, or a propyl group. Moreover, in said D, p is an integer of 1-10.

  Another embodiment of the oxetane compound that can be suitably used in the present invention includes a compound represented by the following general formula (5) having an oxetane ring in the side chain.

In the general formula (5), R ^a1 has the same meaning as R ^a1 in Formula (1), R ^a8 has the same meaning as R ^a8 in the general formula (4). R ^a11 is an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, or a butyl group, or a trialkylsilyl group, and r is 1 to 4.

The compound having such an oxetane ring is described in detail in JP-A No. 2003-341217, paragraph numbers [0021] to [0084], and the compounds described herein can be suitably used in the present invention. .
Among the oxetane compounds used in the present invention, it is preferable to use a compound having one oxetane ring from the viewpoint of the viscosity and tackiness of the composition.

  The content of the cationically polymerizable compound in the composition of the present invention is suitably 10 to 99% by mass, preferably 20 to 97% by mass, more preferably 50 to 95% by mass, based on the total solid content of the composition. % Range.

Acid Crosslinkable Compound The acid crosslinkable compound that can be used in the present invention is a crosslinker that is crosslinked with an acid (hereinafter, referred to as “acid crosslinker” or simply “crosslinker” as appropriate). A crosslinking agent may be used independently and may be used in combination of 2 or more types.

Examples of the crosslinking agent preferably used in the present invention include the following crosslinking agents (i) to (iv).
(I) Compound substituted with alkoxymethyl group or hydroxymethyl group (ii) Compound having nitrogen atom bonded to hydroxymethyl group, alkoxymethyl group, acyloxymethyl group or methylol group (iii) Epoxy compound (iv) General formula Compounds described later as phenol derivatives represented by (5) These cross-linking agents are described in detail below.

<(I) Compound substituted with alkoxymethyl group or hydroxymethyl group>
(I) Examples of the compound substituted with an alkoxymethyl group or a hydroxymethyl group include aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group, an acetoxymethyl group, or an alkoxymethyl group. Moreover, methylated melamine resin and methylated urea resin can also be mentioned.

  Among the aromatic compounds and heterocyclic compounds poly-substituted with a hydroxymethyl group or an alkoxymethyl group, compounds having a hydroxymethyl group or an alkoxymethyl group at a position adjacent to the hydroxy group can be mentioned as preferred examples. In the case of an alkoxymethyl group, the alkoxymethyl group is preferably a compound having 18 or less carbon atoms. Particularly preferred examples include compounds represented by the following general formulas (1) to (4).

In the general formulas (1) to (4), L ^{1 to} L ⁸ each independently represents a hydroxymethyl group or an alkoxymethyl group substituted with an alkoxy group having 18 or less carbon atoms such as methoxymethyl and ethoxymethyl. Show.

  The compounds represented by the general formulas (1) to (4) are more preferable. These crosslinking agents may be used alone or in combination of two or more.

<(Ii) Compound having nitrogen atom bonded to hydroxymethyl group, alkoxymethyl group, acyloxymethyl group or methylol group>
(Ii) Examples of the compound having an N-hydroxymethyl group or an N-acyloxymethyl group include European Patent (hereinafter referred to as EP-A) No. 0,133,216, West German Patent No. 3,634, Examples thereof include monomers and oligomers, melamine-formaldehyde condensates, urea-formaldehyde condensates and the like disclosed in Nos. 671 and 3,711,264.

  Examples of the acid crosslinking agent include compounds having a nitrogen atom bonded to a methylol group and / or an alkoxymethyl group described in JP2010-210851A, such as melamine, glycoluril, urea, alkyleneurea, benzoguanamine, and the like. And a compound in which formaldehyde or formaldehyde and an alcohol are reacted with the amino group-containing compound, and a hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Moreover, the oligomer formed by self-condensing methylol groups of these compounds may be sufficient. Two or more of these may be contained.

  Among the above amino group-containing compounds, those using melamine are melamine-based crosslinking agents, those using glycoluril are glycoluril-based crosslinking agents, those using urea are urea-based crosslinking agents, and those using alkylene urea Is an alkylene urea type cross-linking agent, and one using benzoguanamine is called a benzoguanamine type cross-linking agent.

  Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine and the like.

  Specific examples of the glycoluril-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated glycoluril, mono, di, tri and / or tetramethoxymethylated glycoluril, mono, di, tri and / or Examples include tetraethoxymethylated glycoluril, mono, di, tri and / or tetrapropoxymethylated glycoluril, mono, di, tri and / or tetrabutoxymethylated glycoluril.

  Specific examples of the urea crosslinking agent include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, bisbutoxymethylurea and the like.

  Specific examples of alkylene urea-based crosslinking agents include mono and / or dihydroxymethylated ethylene urea, mono and / or dimethoxymethylated ethylene urea, mono and / or diethoxymethylated ethylene urea, mono and / or dipropoxymethylated Ethylene urea based crosslinkers such as ethylene urea, mono and / or dibutoxymethylated ethylene urea, mono and / or dihydroxymethylated propylene urea, mono and / or dimethoxymethylated propylene urea, mono and / or diethoxymethylated propylene Propylene urea-based crosslinking agents such as urea, mono and / or dipropoxymethylated propylene urea, mono and / or dibutoxymethylated propylene urea, 1,3-di (methoxymethyl) 4,5-dihydroxy-2- Midazorijinon, 1,3-di (methoxymethyl) -4,5-dimethoxy-2-imidazolidinone.

  Specific examples of the benzoguanamine-based crosslinking agent include, for example, mono, di, tri and / or tetrahydroxymethylated benzoguanamine, mono, di, tri and / or tetramethoxymethylated benzoguanamine, mono, di, tri and / or tetraethoxymethyl. Benzoguanamine, mono, di, tri and / or tetrapropoxymethylated benzoguanamine, mono, di, tri and / or tetrabutoxymethylated benzoguanamine and the like.

<(Iii) Epoxy compound>
(iii) Examples of the epoxy compound include monomer, dimer, oligomer, and polymer epoxy compounds containing one or more epoxy groups. For example, the reaction product of bisphenol A and epichlorohydrin, the reaction product of low molecular weight phenol-formaldehyde resin and epichlorohydrin, etc. are mentioned. Other examples include epoxy resins described and used in US Pat. No. 4,026,705 and British Patent 1,539,192.

<(Iv) Phenol Derivative Represented by General Formula (5)>
As a crosslinking agent in this invention, the phenol derivative represented by following General formula (5) is also preferable.

In General Formula (5), Ar ¹ represents an aromatic hydrocarbon ring which may have a substituent. In view of availability of raw materials, the aromatic hydrocarbon ring is preferably a benzene ring, a naphthalene ring or an anthracene ring. Preferred substituents include a halogen atom, a hydrocarbon group having 12 or less carbon atoms, an alkoxy group having 12 or less carbon atoms, an alkylthio group having 12 or less carbon atoms, a cyano group, a nitro group, or a trifluoromethyl group. Etc. For the reason of high sensitivity, Ar ¹ includes a benzene ring or naphthalene ring having no substituent, a halogen atom, a hydrocarbon group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, carbon A benzene ring or naphthalene ring having an alkylthio group or a nitro group of several 6 or less as a substituent is particularly preferred.

In general formula (5), R ¹ and R ² may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. From the reason that synthesis is easy, R ¹ and R ² are preferably a hydrogen atom or a methyl group.

In general formula (5), R ³ represents a hydrogen atom or a hydrocarbon group having 12 or less carbon atoms. R ³ is preferably a hydrocarbon group having 7 or less carbon atoms such as a methyl group, an ethyl group, a propyl group, a cyclohexyl group, or a benzyl group because of its high sensitivity.

In general formula (5), m represents an integer of 2 to 4, and is preferably 2.
In general formula (5), n represents an integer of 1 to 3, and is preferably 1.

  The phenol derivative represented by the general formula (5) can be synthesized according to the method described in JP-A No. 11-254850.

  The compounding quantity of a crosslinking agent is 10-99 mass% in the total solid of the composition used by this invention, Preferably it is 20-97 mass%.

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.

Furthermore, examples of the organic solvent 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 will be 5-80 mass% from a viewpoint of applicability | paintability, 5 mass%-60 mass%. More preferable is an amount of 10% by mass to 50% 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 to-be-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.

Binder The composition used in the present invention may contain a binder. The binder that can be used in the present invention is not particularly limited, and a suitable type can be selected according to the type of the curable compound to be used in combination. A polymer having a molecular weight of about 1,000 to 1,000,000 is preferable. Specifically, polystyrene, poly (meth) acrylate, polyester, polyethylene terephthalate, nylon, vinylon, polyamide, polyimide, polyurethane, polyethylene, polypropylene, polyvinyl chloride, Fluorinated polyethylene, fluorinated polypropylene, phenol resin, polyvinyl acetate, polyethylene oxide, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral, polycarbonate, butadiene rubber, silicone rubber, silicone oil, cellulose, and the like can be used. Two or more kinds may be used in combination.
In the present invention, the composition may or may not contain a binder, but when it is included, the content of the surfactant is 10 to 90 with respect to the total solid mass of the composition. It is preferable that it is mass%, and it is more preferable that it is 30-70 mass%.

The composition used in the present invention is preferable in terms of storage stability so that general thermal polymerization and photopolymerization do not proceed at room temperature. It is more preferable from the same viewpoint that general thermal polymerization or photopolymerization does not proceed at 60 ° C.
The presence or absence of the progress of polymerization can be confirmed by placing in a thermocellco set at 60 ° C. and storing for one month, then measuring the GPC and observing the change in molecular weight. If no change in molecular weight is observed, the polymerization does not proceed. If the molecular weight change is 5% or more, it can be said that the polymerization proceeds.

Manufacturing method of cured film In the manufacturing method of the present invention, the composition is applied to the surface of a support to form a film. For example, it can be performed by a spin coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, or a die coating method. Moreover, you may utilize an inkjet. Depending on the application, it may be applied in a pattern such as a stripe or a lattice. Alternatively, the polymerizable composition may be prepared as an immersion liquid, and the support may be immersed in the liquid to form a film. The solvent may be removed by heating after application. The heating temperature can be determined according to the boiling point of the solvent used.

  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. In the present invention, a polymer film is preferred. In the method of the present invention, it is not necessary to be exposed to an excessively high temperature for the progress of the polymerization reaction. 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.

  Next, the formed film is irradiated with plasma to initiate and advance the curing reaction of the curable compound. 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 polymerization reaction starts and proceeds quickly. In the polymerization by plasma irradiation, active species (for example, radicals) contained in the plasma adhere to the film surface, and polymerization (for example, radical polymerization) starts from the surface.

  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.
In the case of a plasma generation method using an inert gas, since the polymerization and curing reaction start and proceed efficiently by direct action of the plasma directly on the plasma polymerizable compound present in the film, it is usually aimed at suppressing oxygen inhibition As described above, even when a polymerization reaction that requires a closed system environment in an inert gas atmosphere is performed in an open system, there is an advantage that good curability can be achieved without being affected by oxygen inhibition.

  From the viewpoint of reducing the intake of oxygen-derived chemical species during the polymerization reaction, the plasma treatment region may be sufficiently supplied with an inert gas, 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 from −196 ° C. to less than 150 ° C., more preferably from −21 ° C. to 100 ° C. preferable. Particularly preferred is the vicinity of room temperature (25 ° C.) under an ambient temperature atmosphere.

  By the said method, a cured film is formed in at least one part of the surface of a support body. The thickness of the cured 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 preferably 1 to 500 nm, more preferably 1 to 200 nm, and even more preferably 1 to 100 nm.

  The cured product and cured film produced by the production method of the present invention can be used for various applications such as optical materials, electrical materials, medical materials, electronics materials, aerospace materials, gas barrier materials, and the like. In particular, since it has a high degree of curing and excellent durability such as heat resistance and moisture resistance, it is useful for gas barrier materials and the like.

  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 curable 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 nitrogen cation (Exemplary Compound A-1) 5 parts by mass-(B) Curing Compound (Denacol EX-614B (Nagase ChemteX Corporation) (B-1))
95 parts by mass-surfactant (polyoxyethylene lauryl ether) 0.1 parts by weight-solvent: 900 parts by mass of propylene glycol monomethyl ether (PGME)

(2) Examples 2 to 17 and Comparative Examples 1 to 4
The composition was changed to the composition shown in the following table, and coating solutions were prepared in the same manner as in Example 1.

(3) Preparation of cured film by plasma treatment (3-1) Examples 1-1 and Comparative Examples 1-3
(Formation of coating film)
Each coating solution obtained above was applied onto a 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.

(Plasma treatment)
The coating film was irradiated with low-temperature N ₂ plasma for 30 seconds using an S5000 type atmospheric pressure low-temperature plasma jet apparatus (discharge gas: nitrogen) manufactured by Sakai Semiconductor Co., Ltd., and the polymerization reaction was allowed to proceed to be cured to a film thickness of 500 nm. A plasma polymerization film was formed.
However, in Example 18, 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) Comparative Example 4
In the same manner as described above, a coating film having a thickness of 500 nm is formed, UV light source EX250 (manufactured by HOYA-SCHOTTT) is used as a UV lamp instead of atmospheric pressure plasma, and the UV irradiation amount is 1 J / cm ^2. Irradiated.

4). Performance Evaluation The following evaluation was 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. The onium salt that is unstable to light and heat is decomposed at this stage, and an acid or radical is generated, so that the coexisting curable compound becomes high 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 light, refrigeration test-
Each coating composition prepared above was placed in a thermocellco set at 0 ° C. under a yellow light 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) Degree of curing Each cured film formed was immersed in propylene glycol monomethyl ether acetate (PGMEA) for 60 seconds, and the weight change of the film was measured. The smaller the change in weight, the higher the degree of cure and the better.
The evaluation was made on a scale of 10 and almost no change in weight of “10” was observed. From “9” to “2”, the weight change was recognized in this order, and “1” had the largest change in weight.

The compounds in the above table are as follows.
(B-1) Denacol EX-614B (manufactured by Nagase ChemteX Corporation)
(B-2) A-DPH (manufactured by Shin-Nakamura Chemical Co., Ltd.)
(B-3) Nikarac MX-270 (manufactured by Sanwa Chemical Co., Ltd.)
(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 apparent from the above table, it was possible to start the polymerization of the curable composition by irradiating the onium salt having a nitrogen cation with plasma. 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).
Moreover, when radically polymerizable compounds were used, it turned out that storage stability improves especially (Examples 8-13 and Comparative Example 3).

Claims (17)

(A) The manufacturing method of hardened | cured material including irradiating plasma to the composition containing the onium salt which has a nitrogen cation, and (B) curable compound. (A) The method for producing a cured product 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 cured product method 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 hardened | cured material 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 ⁹² may be bonded to each other to form a ring. ) (A) The manufacturing method of the hardened | cured material of any one of Claims 1-4 whose onium salt which has a nitrogen cation is an ionic liquid. (B) The manufacturing method of the hardened | cured material of any one of Claims 1-5 in which a curable compound contains at least one of a cationically polymerizable monomer and a radically polymerizable monomer. A film is formed by applying a composition containing (A) an onium salt having a nitrogen cation, (B) a curable compound, and (C) a solvent on the support, and the film is irradiated with plasma. (A) decomposing an onium salt having a nitrogen cation, and (B) curing the curable compound by radical or cationic polymerization,
The manufacturing method of the hardened | cured material of any one of Claims 1-6 containing these. The manufacturing method of the hardened | cured material of Claim 7 whose said support body is a polymer film. The manufacturing method of the hardened | cured material of any one of Claims 1-8 whose plasma is low temperature atmospheric pressure plasma. The manufacturing method of the hardened | cured material of any one of Claims 1-9 whose said hardened | cured material is film form. Hardened | cured material manufactured by the method of any one of Claims 1-10. The cured film manufactured by the method of any one of Claims 1-10. A method of initiating a reaction by irradiating an onium salt having a nitrogen cation with plasma and decomposing the onium salt to generate at least one of a radical, an acid, and a base. A plasma acid generator comprising an onium salt having a nitrogen cation. (A) The plasma acid generator according to claim 14, 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 plasma polymerization initiator comprising an onium salt having a nitrogen cation. (A) The plasma polymerization initiator according to claim 16, 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.