JP2018204010A - Composition, method for producing cured film and electronic component - Google Patents

Abstract

To provide a composition that can form a cured film that can maintain insulating performance even under a severe environment such as a high temperature-high humidity environment, and a method for producing the cured film.SOLUTION: A composition contains a radical polymerizable compound, a photoradical generating agent, and a photocation generating agent. When the total mass of the composition is 100 mass%, the content of halogen atoms is 0.5 ppm or more and 100 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a composition, a method for producing a cured film, and an electronic component.

  Various components such as wiring and electrodes are used for electronic components such as circuit boards, and insulating films are used to prevent electrical shorts between the metals. As the insulating film, a patterned cured film formed from a composition such as a solder resist by exposure and development is used (for example, see Patent Documents 1 and 2).

JP 2006-028497 A JP 2006-243161 A

  With the recent miniaturization of electronic components, the distance between wirings has become narrower, and the insulation of insulating films used between wirings has become increasingly important for the miniaturization of electronic components. In particular, electronic components such as circuit boards are sometimes used in harsh environments such as high temperatures and high humidity, and insulating films used for electronic components maintain insulation even under such harsh environments. It needs to be possible. However, the materials described in Patent Document 1 and Patent Document 2 are prone to insulation deterioration when used in severe environments such as high temperature and high humidity, and further improvements have been demanded.

  Accordingly, some embodiments according to the present invention provide a composition capable of forming a cured film capable of maintaining insulation even under a severe environment such as high temperature and high humidity by solving at least a part of the above problems. And a method for producing the cured film.

  SUMMARY An advantage of some aspects of the invention is to solve at least a part of the problems described above, and the invention can be implemented as the following aspects or application examples.

[Application Example 1]
One aspect of the composition according to the present invention is:
A composition containing a radical polymerizable compound, a photo radical generator, and a photo cation generator,
When the total mass of the composition is 100% by mass, the halogen atom is contained in an amount of 0.5 ppm to 100 ppm.

[Application Example 2]
In the composition of the above application example,
Furthermore, when the total mass of the said composition is 100 mass%, water can be contained 0.01 mass% or more and 1 mass% or less.

[Application Example 3]
In any composition of the above application examples,
The radical polymerizable compound can contain a (meth) acrylate having a radical polymerizable group and a polymer having a radical polymerizable group.

[Application Example 4]
In any composition of the above application examples,
Furthermore, a cation reactive compound can be contained.

[Application Example 5]
One aspect of the method for producing a cured film according to the present invention is as follows.
Applying the composition of the above application example on a substrate to form a coating film;
Exposing the coating film;
including.

[Application Example 6]
One aspect of the electronic component according to the present invention is:
It has the cured film created using the composition in any one of the said application example.

According to the composition of the present invention, it is possible to form a cured film that can maintain insulation even under a harsh environment such as high temperature and high humidity. Further, according to some embodiments of the composition of the present invention, in addition to the above effects, a cured film having excellent storage stability and excellent curability and adhesion (with a substrate or the like). Can be formed.
The electronic component according to the present invention has the cured film, so that the circuit pattern can be protected from the external environment such as dust, heat, moisture, etc., and has excellent insulation reliability between the circuit patterns, and can be operated stably for many years. Is possible.

It is a top view which shows typically the board | substrate which has a copper wiring used by <insulation evaluation> of the Example. It is sectional drawing along the A-A 'line of FIG.

  Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited only to the embodiments described below, and includes various modifications that are implemented within a scope that does not change the gist of the present invention. In this specification, “(meth) acrylic acid” is a concept encompassing both “acrylic acid” and “methacrylic acid”. Further, “˜ (meth) acrylate” is a concept encompassing both “˜acrylate” and “˜methacrylate”.

  In the present specification, a numerical range described using “to” means that numerical values described before and after “to” are included as a lower limit value and an upper limit value.

1. Composition The composition according to the present invention is a composition containing a radical polymerizable compound, a photo radical generator, and a photo cation generator. When the total mass of the composition is 100% by mass, a halogen atom From 0.5 ppm to 100 ppm. Hereinafter, each component contained in the composition according to the present embodiment will be described.

1.1. Radical polymerizable compound A radical polymerizable compound is a compound having a radical polymerizable group (functional group) and reacting with radicals generated by irradiation with light such as ultraviolet rays in the presence of a photo radical generator. . The radical polymerizable group possessed by the radical polymerizable compound is preferably a group having a radical polymerizable unsaturated bond. Moreover, it is preferable that the composition which concerns on this embodiment uses 2 or more types of radically polymerizable compounds together, and it is more preferable to use together the (meth) acrylate which has a radically polymerizable group, and the polymer which has a radically polymerizable group. preferable.

  When the composition according to the present embodiment contains a polymer having a radical polymerizable group, the content of the polymer having a radical polymerizable group is 10 to 10 parts by mass with respect to 100 parts by mass of the solid content contained in the composition. 80 mass parts is preferable and 20-70 mass parts is more preferable.

  When the composition according to this embodiment uses a (meth) acrylate having a radical polymerizable group and a polymer having a radical polymerizable group in combination, the content ratio of the compound having a radical polymerizable group is included in the composition. 10-80 mass parts is preferable with respect to 100 mass parts of solid content, and 20-70 mass parts is more preferable.

1.1.1. (Meth) acrylate having radically polymerizable group In the present specification, “(meth) acrylate having a radically polymerizable group” means a polyfunctional (meth) acrylate having two or more radically polymerizable groups. Examples of such polyfunctional (meth) acrylates include polyfunctional (meth) acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and alkylene oxide-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting (meth) acrylate having hydroxyl group and polyfunctional isocyanate, and polyfunctional (meth) acrylate having hydroxyl group and acid anhydride are reacted And a polyfunctional (meth) acrylate having a carboxy group. These polyfunctional (meth) acrylates may have an epoxy group that is a cationically polymerizable group.

  Specific examples of the (meth) acrylate having a radical polymerizable group include 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate , Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol A bis (acryloyloxyethyl) ether, bisphenol A di (meth) acryloyloxymethyl Cyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, propoxy modified bisphenol A di (meth) acrylate, ethoxy-propoxy modified Bisphenol A di (meth) acrylate, propoxy-modified bisphenol F di (meth) acrylate, ethoxylated neopentyl glycol di (meth) acrylate, 3-methylpentanediol di (meth) acrylate, trimethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and bisphenol A di Difunctional acrylates such as epoxy (meth) acrylate obtained by adding the glycidyl ether (meth) acrylate;

Trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tetramethylolpropane tetra (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) Acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth)
Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol Octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, tripentaerythritol hepta (meth) acrylate and acid anhydride Reaction product, propoxy-modified pentaerythritol tetra (meth) acrylate, propoxy-modified dipentaerythritol poly (meth) acrylate, butoxy modification Pentaerythritol tetra (meth) acrylate, butoxy-modified dipentaerythritol poly (meth) acrylate, caprolactone-modified trimethylolpropane tri (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanate Nurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, Caprolactone-modified tripentaerythritol penta (meth) acrylate Caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride Trifunctional or higher functional acrylates such as a reaction product, a reaction product of caprolactone-modified dipentaerythritol penta (meth) acrylate and an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritol hepta (meth) acrylate and an acid anhydride; and By reaction of epoxy (meth) acrylate with carboxylic acids such as oxalic acid, malonic acid, succinic acid, and hydrogenated phthalic acid, alcoholic compounds, or phenolic compounds. And a reaction product of alkylene glycol diglycidyl ether or polyalkylene glycol diglycidyl ether and (meth) acrylic acid.

  Among these, bifunctional (meth) acrylates such as ethoxylated bisphenol A di (meth) acrylate and tricyclodecane dimethanol (meth) acrylate; dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Tripentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, propoxy-modified pentaerythritol tetra (meth) acrylate, propoxy-modified dipentaerythritol poly (meth) acrylate , Butoxy-modified pentaerythritol tetra (meth) acrylate, butoxy-modified dipentaerythritol poly (meth) acrylate , And even under trifunctional or higher (meth) acrylate is high temperature and high humidity, such as caprolactone-modified tripentaerythritol hexa (meth) acrylate preferred because easily form a cured film capable of maintaining the insulating property.

1.1.2. Polymer having radical polymerizable group The polymer having a radical polymerizable group preferably has a (meth) acryloyl group, for example, preferably has a repeating unit represented by the following general formula (1) or (9). .

In formula (1), R ¹ , R ² and R ³ are each independently a hydrogen atom or a methyl group, and R ⁴ is a branched or chain having 1 to 12 carbon atoms which may have a substituent. They are an alkyl group, a C5-C20 alicyclic alkyl group which may have a substituent, a heterocyclic group containing a nitrogen atom, a sulfur atom or an oxygen atom, a benzyl group, a naphthyl group, or an anthranyl group. X is the formula (2)
To any one of groups represented by (4), wherein n is an integer of 2 to 6, and the bond of * in each of formulas (2) to (4) is bonded to oxygen To do. Y is any of the groups represented by the formulas (5) to (8). In the formula (5), m is an integer of 2 to 6, and in the formula (7), p1 and p2 are respectively Independently, it is 2 or 3, and in formula (8), R ⁵ is a hydrogen atom or a methyl group, and the bond of * is bonded to oxygen. In Formula (9), R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or a halogen atom, L is an integer of 1 to 5, r is an integer of 2 to 12, and R ⁸ is a hydrogen atom or a methyl group.

In the repeating units of the formulas (1) and (9), R ¹ , R ² , R ³ , R ⁴ and R ⁵ , and R ⁶ , R ⁷ and R ⁸ include plural kinds in the polymer. May be. That is, the ethylenically unsaturated bond-containing monomer and the monomer having a (meth) acryloyl group, which are constituent materials of these polymers, can each be a mixture of plural types of monomers.

  These polymers can be synthesized according to the following reaction formulas. A polymer having a repeating unit represented by formula (18) or (19), which is a raw material of a polymer having a repeating unit represented by formulas (11) to (17), is methacrylic acid and methyl methacrylate, or methacrylic acid. It can be obtained by heating and polymerizing methyl and 2-hydroxyethyl methacrylic acid ester in the presence of a polymerization initiator. Moreover, with respect to the polymer which has a repeating unit shown by Formula (18) or (19), the meta (acryloyl) group which has a glycidyl group, an epoxycyclohexyl group, or an isocyanate group shown by Formula (20)-(26) is contained. The polymer which has a repeating unit shown by Formula (11)-(17) can be obtained by making a compound react. This reaction is considered to proceed by the oxygen anion derived from the carboxyl group or hydroxyl group or the unpaired electron on the oxygen atom nucleophilically attacking epoxy carbon or isocyanate carbon, and a bond is formed between them. In addition, the meta (acryloyl) group-containing compounds having an isocyanate group represented by the formulas (22) to (25) are trade names of Karenz MOI, Karenz AOI, Karenz MOI-EG and Karenz BEI, respectively (manufactured by Showa Denko KK). ).

  When the polymer having a radical polymerizable group has a (meth) acryloyl group, for example, the method described in JP2011-90163A, JP2010-128007A, JP2015-184675A, etc. Can be synthesized. The polymer having a radically polymerizable group contains a repeating unit having a radically polymerizable group (preferably a group having a radically polymerizable unsaturated bond). If a cured film can be formed, the other repeating units are There is no particular limitation.

  Monomers that can be used to synthesize a polymer having a radical polymerizable group include, for example, mono [(meth) acryloyloxyalkyl] esters of monocarboxylic acid, dicarboxylic acid, and polyvalent carboxylic acid. Mono (meth) acrylate of polymer having carboxy group and hydroxyl group, polycyclic compound having carboxy group and its anhydride, unsaturated compound having phenolic hydroxyl group, unsaturated compound having oxiranyl group, unsaturated compound having oxetanyl group Examples thereof include saturated compounds, maleimide compounds, unsaturated aromatic compounds, unsaturated carboxylic acid esters, and macromonomers.

  As monocarboxylic acid, (meth) acrylic acid, crotonic acid, etc. can be used, for example. As the dicarboxylic acid, for example, maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, cyclohexene dicarboxylic acid and the like can be used. As an anhydride of dicarboxylic acid, the anhydride of the compound illustrated as said dicarboxylic acid etc. are mentioned, for example.

Examples of mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids include, for example, succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] Etc.

  Examples of the mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends include ω-carboxypolycaprolactone mono (meth) acrylate.

  Examples of the polycyclic compound having a carboxy group and anhydrides thereof include 5-carboxybicyclo [2.2.1] hept-2-ene and 5-carboxy-5-methylbicyclo [2.2.1] hept. 2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy Examples include -6-ethylbicyclo [2.2.1] hept-2-ene and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene.

  Examples of the unsaturated compound having a phenolic hydroxyl group include p-isopropenylphenol, hydroxystyrene, N-hydroxyphenylmaleimide, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, and the like.

  Examples of unsaturated compounds having an oxiranyl group include glycidyl (meth) acrylate, glycidyl α-ethyl (meth) acrylate, glycidyl α-n-propyl (meth) acrylate, α-n-butyl (meth) acrylic. Glycidyl acid, (meth) acrylic acid-3,4-epoxybutyl, (meth) acrylic acid-6,7-epoxyheptyl, α-ethyl (meth) acrylic acid-6,7-epoxyheptyl, o-vinylbenzylglycidyl Examples include ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like.

  Examples of the unsaturated compound having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -2-methyloxetane, and 3-((meth) acryloyloxymethyl). -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2-trifluoromethyloxetane, 3-((meth) acryloyloxymethyl) -2-pentafluoroethyloxetane, 3-((meth) acryloyloxy Methyl) -2-phenyloxetane, 3-((meth) acryloyloxymethyl) -2,2-difluorooxetane, 3-((meth) acryloyloxymethyl) -2,2,4-trifluorooxetane, 3- ( (Meth) acryloyloxymethyl) -2,2,4,4-tetra Ruorookisetan, 3- (2- (meth) acryloyloxyethyl) oxetane, and the like.

  Examples of the maleimide compound include N-phenylmaleimide and N-cyclohexylmaleimide.

  Examples of the unsaturated aromatic compound include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, p-hydroxy-α-methylstyrene, and the like.

Examples of the unsaturated carboxylic acid ester include methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, and benzyl (meta ) Acrylate, polyethylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, Polypropylene glycol (n = 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate,
Isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, ethylene oxide of paracumylphenol Examples thereof include modified (meth) acrylate.

  As the macromonomer, for example, a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane or the like. Etc.

  The polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography of the polymer having a radical polymerizable group is preferably 1,000 to 1,000,000, more preferably 2,000 to 50,000. preferable.

1.2. Photoradical generator A photoradical generator is a compound that generates radicals by light irradiation and initiates radical polymerization of a radically polymerizable compound. The maximum absorption wavelength of the photo radical generator is preferably 150 nm to 380 nm. Two or more photoradical generators may be used in combination.

  In this specification, the maximum absorption wavelength of a compound can be observed as the wavelength at which absorption is maximum when the absorbance of a solution obtained by dissolving the compound in a good solvent is measured, for example.

  Examples of the photo radical generator include JP 2008-276194 A, JP 2003-241372 A, JP 2009-519991 A, JP 2009-531730 A, International Publication No. 2010/001691, International Publication No. Examples thereof include compounds described in 2010/146833, JP 2011-132215 A, JP 2008-506749 A, JP 2009-519904 A, and the like.

  Examples of the photoradical generator include biimidazole compounds, acylphosphine oxide compounds, alkylphenone compounds, oxime compounds, benzoin compounds, benzophenone compounds, and thioxanthone compounds.

  Examples of the biimidazole compound include 2,2′-bis (2,4-dichlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 '-Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dimethylphenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole, 2 , 2′-bis (2-methylphenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-diphenyl-4,5,4 ′, 5′- Examples include tetraphenyl-1,2'-biimidazole.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the alkylphenone compounds include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl]- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one,
1-hydroxycyclohexyl phenyl ketone, 1-hydroxy-4-methoxyphenyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (dimethylamino) -2- {(4-methylphenyl) methyl} -1- {4- (4-morpholinyl) phenyl} -1-butanone, 2- (2-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone 2- (3-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2 -(2-ethylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-propyl) Njiru) 2-dimethylamino-1- (4-morpholinophenyl) butanone, 2- (2-butyl-benzyl) -2-dimethylamino-1- (4-morpholinophenyl) butanone and the like.

  Examples of the oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-ethoxycarbonyloxy-1-phenylpropane-1-one-2-imine, N -Benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H -Carbazol-3-yl] ethane-1-imine, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzo Oxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6 -(2-Methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), and ethanone, 1- [9-ethyl-6- {2-methyl- 4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bis (diethylamino) benzophenone, 4,4′-tetra (tert -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and the like.

  Examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 , 4-diisopropylthioxanthone and the like.

  Among these, alkylphenone compounds are preferable because they easily form a cured film that can maintain insulation even under high temperature and high humidity.

  The content ratio of the photo radical generator contained in the composition according to the present embodiment is preferably 0.1 to 40 parts by mass, and 0.5 to 30 parts by mass with respect to 100 parts by mass of the radical polymerizable compound. More preferably, it is a part.

1.3. Photocation generator The photocation generator is a compound that generates cations by light irradiation and initiates crosslinking of the cation-reactive compound by reaction with the cations. The maximum absorption wavelength of the photocation generator is preferably in the ultraviolet region, and more preferably from 150 nm to 380 nm. Two or more photocation generators may be used in combination.

  Examples of the photocation generator include onium salt compounds, halogen-containing compounds, sulfone compounds, sulfonic acid compounds, sulfonimide compounds, and diazomethane compounds.

  Examples of onium salt compounds include iodonium salts, sulfonium salts, phosphonium salts, diazonium salts, and pyridinium salts. Specific examples of the onium salt compounds include diphenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, triphenylsulfonium trifluoromethanesulfonate, triphenyl Sulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, 4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium p-toluenesulfonate, 4,7-di-n-butoxynaphthyltetrahydro Thiophenium trifluoromethane Sulfonate, 4,7-di-n-butoxynaphthyltetrahydrothiophenium nonafluorobutanesulfonate, 4- (phenylthio) phenyldiphenylsulfonium tris (pentafluoroethyl) trifluorophosphate, 4- (phenylthio) phenyldiphenylsulfonium hexafluorophos Examples include fert. Specific product names of the onium salt compounds include CPI-101A, CPI-100P, CPI-200K, CPI-210S (above, manufactured by San Apro Co., Ltd.); SP-056, SP-140, SP-082, SP- 606, SP-171 (above, manufactured by ADEKA Corporation); WPI-113, WPI-116, WPI-169, WPI-170, WPI-124 (above, manufactured by Wako Pure Chemical Industries, Ltd.).

  Examples of the halogen-containing compound include haloalkyl group-containing hydrocarbon compounds and haloalkyl group-containing heterocyclic compounds. Specific examples of the halogen-containing compound include 1,10-dibromo-n-decane; 1,1-bis (4-chlorophenyl) -2,2,2-trichloroethane; phenyl-bis (trichloromethyl) -s-triazine, 4-methoxyphenyl-bis (trichloromethyl) -s-triazine, styryl-bis (trichloromethyl) -s-triazine, naphthyl-bis (trichloromethyl) -s-triazine, and 2- [2- (5-methylfuran) -2-yl) ethenyl] -4,6-bis- (trichloromethyl) -1,3,5-triazine and other s-triazine derivatives.

  Examples of the sulfone compounds include β-ketosulfone compounds, β-sulfonylsulfone compounds, and α-diazo compounds of these compounds. Specific examples of the sulfone compound include 4-trisphenacylsulfone, mesitylphenacylsulfone, bis (phenacylsulfonyl) methane, and the like.

  Examples of the sulfonic acid compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates. Specific examples of the sulfonic acid compound include benzoin tosylate, pyrogallol tris trifluoromethane sulfonate, o-nitrobenzyl trifluoromethane sulfonate, and o-nitrobenzyl p-toluene sulfonate.

Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (trifluoromethylsulfonyl). And oxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and N- (trifluoromethylsulfonyloxy) naphthylimide.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, and the like.

  Among these, an onium salt compound is preferable because it can easily form a cured film that can maintain insulation even under high temperature and high humidity.

  The content ratio of the photocation generator contained in the composition according to the present embodiment is preferably 0.1 to 40 parts by mass, and 0.5 to 30 parts by mass with respect to 100 parts by mass of the cation reactive compound. More preferably, it is a part.

1.4. Halogen Atom The composition according to the present embodiment contains a halogen atom of 0.5 ppm or more and 100 ppm or less when the total mass of the composition is 100% by mass. The halogen atom may exist in an ionic state or a nonionic state. Since the insulating film prevents current leakage from the wiring, it is one of important functions to suppress corrosion and diffusion of the wiring material. From such a viewpoint, it is generally considered that the smaller the ionic component in the insulating material or the component that is easily ionized, especially the halogen content, the better. However, as a result of studies by the present inventors, it has been found that not only a sufficient insulating performance is exhibited but also an excellent curability is exhibited within a specific halogen content range.

  The content of halogen atoms in the composition according to this embodiment is 0.5 ppm or more and 100 ppm or less, and 0.5 ppm or more and 80 ppm or less as a concentration in the non-volatile component excluding the organic solvent in the composition. It is preferably 1 ppm or more and 60 ppm or less. When the halogen atom content is not more than the above upper limit, the insulation durability is excellent, and when it is not less than the above lower limit, a cured film having sufficient curability can be formed. In addition, it is preferable that the halogen atom contained in the composition which concerns on this embodiment does not contain a fluorine atom but is at least 1 sort (s) selected from the group which consists of a chlorine atom and a bromine atom.

  The halogen atom content may be controlled by using a raw material having a halogen content such that the halogen atom content falls within the above range, or by adjusting the composition by purification with an adsorbent, etc. You may add and adjust a compound. Examples of the halogen-containing compound include chlorobenzene, dichlorobenzene, dichloroethane, benzyl chloride, bromobenzene, dibromobenzene, benzyl bromide, epichlorohydrin, epibromohydrin, and the like.

1.5. Water The composition according to the present embodiment preferably contains 0.01% by mass to 1% by mass of water when the total mass of the composition is 100% by mass. When the composition which concerns on this embodiment contains a cation-reactive component, it discovered not only that insulation but maintaining sclerosis | hardenability by containing an appropriate amount of water.

  The water content in the composition according to the present embodiment is preferably 0.01% by mass or more and 1% by mass or less, and preferably 0.03% by mass or more and 1% by mass or less as the concentration in the composition. More preferably, it is 0.05 mass% or more and 0.5 mass% or less is especially preferable.

  The water content may be controlled by using raw materials containing water such that the water content is in the above range, or may be adjusted by purification of the composition by adsorbent treatment, etc. May be.

1.6. Other components In addition to the above components, the composition according to the present embodiment includes a cation reactive compound, an amine, a solvent, a thermal polymerization inhibitor, an adhesion assistant, a monofunctional (meth) acrylate, a leveling agent, a surfactant, Known components such as sensitizers and fillers can be blended within a range that does not impair the object and characteristics of the present invention.

1.6.1. Cationic Reactive Compound As used herein, “cation reactive compound” refers to a compound having at least two cation reactive groups. The cationic reactive compound may have one radical polymerizable group in addition to the cationic reactive group, but the compound having two or more radical polymerizable groups (that is, a polyfunctional radical reactive compound) is Not included. Two or more cationic reactive compounds may be used in combination.

  Examples of cationic reactive compounds include compounds having a methylolated amino group, compounds having an alkyl etherified amino group, compounds having an active methylene such as a methylol group-containing aromatic compound, and an alkyl etherified aromatic compound; oxazoline compounds, oxiranes Cyclic ether compounds such as ring-containing compounds (epoxy compounds), oxetane ring-containing compounds, and cyclic thioether compounds; isocyanate group-containing compounds (including those blocked); aldehyde group-containing phenol compounds; vinyl ether compounds; and dipropenyl An ether compound is mentioned. Of these, oxirane ring-containing compounds are preferred.

  The oxirane ring-containing compound only needs to contain an oxirane ring (also referred to as an oxiranyl group) in the molecule, such as a phenol novolac epoxy resin, a cresol novolac epoxy resin, a bisphenol epoxy resin, or a trisphenol epoxy resin. Tetraphenol type epoxy resin, phenol-xylylene type epoxy resin, naphthol-xylylene type epoxy resin, phenol-naphthol type epoxy resin, phenol-dicyclopentadiene type epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, etc. Can be mentioned. Among these, bisphenol type epoxy resins are preferable because they easily form a cured film that can maintain insulation even under high temperature and high humidity.

  Examples of the bisphenol type epoxy resin include resins having bisphenol A type, bisphenol F type, bisphenol S type, etc. as the main skeleton and having glycidyl ether groups bonded to both ends. Examples of commercially available bisphenol-type epoxy resins include JER806, JER807, JER825, JER825, and JER828, ADEKA EP series manufactured by Japan Epoxy Resin, and Epicron 850S manufactured by Dainippon Ink & Chemicals, Inc.

  It is preferable that the content rate of the cation reactive compound contained in the composition which concerns on this embodiment is 1-60 mass parts with respect to 100 mass parts of solid content contained in the said composition, and 2-50 masses. More preferably, it is a part. Moreover, it is preferable that it is 1-100 mass parts with respect to 100 mass parts of radically polymerizable compounds, and, as for the content rate of a cation reactive compound, it is more preferable that it is 2-50 mass parts.

1.6.2. Amine An amine is a compound in which the hydrogen atom of ammonia is substituted with an arbitrary number of substitutable hydrocarbon groups. The amine having a protecting group is a hydrogen atom of a primary amine or a secondary amine, t -A compound substituted with a group that can be easily substituted with a hydrogen atom by light or heat, such as a butoxycarbonyl group or a benzyloxycarbonyl group.

  It is presumed to have a function of capturing cations generated from the photocation generator by exposure (step (b) described later), and by curing the cations, the insulation can be maintained even under high temperature and high humidity. It is presumed that a film can be formed. Even when an acidic compound having an alkali-developable group and a cationic curable compound coexist, excellent storage stability can be obtained. Two or more amines may be used in combination.

  The amine has a function of trapping cations generated from the photoacid generator, while promoting the curing reaction of the epoxy compound or the like. Furthermore, when the amine is protected by a protecting group and does not react with an epoxy compound or the like, the storage stability of the composition can be further improved.

  Examples of the protecting group for amine include t-butoxycarbonyl group, benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, allyloxycarbonyl group, phthaloyl group, tosyl group and Examples include 2-nitrobenzenesulfonyl group.

  Examples of the amine having a protecting group include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, and Nt-butoxy. Carbonyldicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4′-diaminodiphenylmethane, N, N′-di-t-butoxycarbonylhexamethylenediamine, N, N, N ′, N′-tetra-t-butoxycarbonylhexamethylenedia N, N-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl -1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′- Di-t-butoxycarbonyl-4,4′-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, Nt-butoxycarbonyl-pyrrolidine, Nt-butoxycarbonyl-piperidine, Nt-butoxycarbonyl -4-hydroxy - piperidine, N-t-butoxycarbonyl - morpholine.

  In addition, trioctylamine, triethylamine, 1,4-diazabicyclo [2.2.2. An amine having no protecting group such as octane, diazabicycloundecene, N, N-dimethylbenzylamine, pyridine and the like can also be suitably used.

  It is preferable that the content rate of the amine contained in the composition which concerns on this embodiment is 1-50 mass parts with respect to 100 mass parts of photocation generators, and it is more preferable that it is 5-40 mass parts. .

1.6.3. Solvent Solvents include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, propylene glycol dibutyl ether, propylene glycol monomethyl ether acetate Alkylene glycol alkyl ethers such as tate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate; carbitols such as butyl carbitol; methyl lactate, ethyl lactate, n-propyl lactate, Lactic acid esters such as isopropyl lactate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, isopropyl propionate, n-butyl propionate, isobutyl propionate, etc. Aliphatic carboxylic acid esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, Other esters such as methyl rubinate and ethyl pyruvate; ketones such as 2-heptanone, 3-heptanone, 4-heptanone, and cyclohexanone; N, N-dimethylformamide, N-methylacetamide, N, N-dimethyl Examples include amides such as acetamide and N-methylpyrrolidone; lactones such as γ-butyrolacun; and aromatic hydrocarbons such as toluene and xylene.

  Among these, lactic acid esters, propylene glycol monoalkyl ether acetates, ethylene glycol monoalkyl ethers, and propylene glycol monoalkyl ethers are preferable.

  The content of the solvent contained in the composition according to this embodiment is preferably 1 to 80 parts by mass and more preferably 10 to 75 parts by mass in 100 parts by mass of the composition.

1.6.4. Surfactant As the surfactant, a commercially available surfactant can be used. Specific examples of the surfactant include, for example, NBX-15, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218, FTX-220D, FX-222D (above, manufactured by Neos Co., Ltd.) ), BM-1000, BM-1100 (above, manufactured by BM Chemie), MegaFuck F142D, F172, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (above, manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 (above Manufactured by Asahi Glass Co., Ltd.), SH-28PA, -190, -193, SZ-6032, SF-8428 (above, Toray Dow Corning Silicone ( ) Ltd.) and the like. Among these, FTX-216D, FTX-218, and FTX-220D are preferable.

  It is preferable that content of surfactant contained in the composition which concerns on this embodiment is 0.0001-10 mass parts in 100 mass parts of compositions.

1.6.5. Adhesion aid As the adhesion aid, a functional silane coupling agent is preferred. The functional silane coupling agent includes a silane coupling agent having a reactive substituent such as a carboxy group, a (meth) acryloyl group, a vinyl group, an isocyanate group, or an epoxy group (however, the above radical polymerizable compound and cation) Specifically, trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ -Glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 1,3,5-N-tris (trimethoxysilylpropyl) isocyanurate and the like.

  It is preferable that content of the adhesion support agent contained in the composition which concerns on this embodiment is 0.5-30 mass parts in 100 mass parts of compositions.

1.6.6. Monofunctional (meth) acrylate As the monofunctional (meth) acrylate, the above radical polymerizable compound, cation reactive compound and adhesion aid are excluded. Specific examples of the monofunctional (meth) acrylate include, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, isobornyl acrylate, isobornyl methacrylate, 3- Methoxybutyl acrylate, 3-methoxybutyl methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate, ω-carboxypolycaprolactone monoacrylate, ethoxylation o-Phenylphenol (meth) acrylate, isostearyl (meth) acrylate, methoxypolyethylene glycol (meta Acrylate, phenoxy polyethylene glycol (meth) acrylate, and 2- (meth) acryloyloxyethyl succinate and the like. As commercial products, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toa Gosei Co., Ltd.); KAYARAD TC-110S, TC-120S ( As mentioned above, Nippon Kayaku Co., Ltd.); Biscoat 158, 2311 (above, Osaka Organic Chemical Industry Co., Ltd.) and the like can be mentioned.

  It is preferable that content of the monofunctional (meth) acrylate contained in the composition which concerns on this embodiment is 0-30 mass parts in 100 mass parts of compositions.

1.7. Manufacturing method of composition The composition which concerns on this embodiment can be manufactured by mixing each above-mentioned component. Moreover, in order to remove a foreign material, after mixing each component, you may filter the obtained mixture with a filter etc.

2. Cured film and its manufacturing method The cured film which concerns on this embodiment is formed from the above-mentioned composition, and can maintain insulation even under high temperature, high humidity. For this reason, the cured film according to the present embodiment can be suitably used as a surface protective film, a rewiring layer, or a planarizing film included in an electronic component such as a circuit board (semiconductor element), a semiconductor package, or a display board.

  The manufacturing method of the cured film which concerns on this embodiment is the process (process (a)) which apply | coats the above-mentioned composition on a board | substrate, and forms a coating film, and the process of exposing the said coating film (process (b)). And including. Moreover, the manufacturing method of the cured film which concerns on this embodiment develops the said coating film, and forms the pattern (process (c)), and the process (process (process (c)) after a process (c). d)) may be included.

2.1. Step (a)
Step (a) is a step of applying the composition described above onto a substrate to form a coating film. Examples of the substrate include a wafer having elements (semiconductor elements, optical elements, liquid crystal display elements, etc.).

The coating film is formed by applying the above-described composition by a coating method such as a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, or an inkjet method, and the coated film as necessary Can be formed by heating and drying. In the case of the spin coating method, the rotation speed is preferably 600 to 3000 rpm, and the rotation time is preferably 1 to 300 seconds. The heating and drying conditions are preferably 50 to 250 ° C. and about 1 to 30 minutes.

  Although the film thickness of the said coating film is not specifically limited, 0.1-100 micrometers is preferable and 1-30 micrometers is more preferable.

  The coating film may be formed by coating the composition twice or more on the substrate. For example, the coating film may be formed by coating the composition once on the substrate, further coating the composition on the coated film, and then drying by heating.

2.2. Step (b)
Step (b) is a step of exposing the coating film formed in step (a). In the exposure, the coating film is exposed through a desired mask pattern using a contact aligner, a stepper, a scanner, or the like. The light beam wavelength of the exposure light is preferably 200 to 500 nm. The irradiation amount of actinic rays varies depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, and the like. However, when i-line (365 nm) is used for exposure light, the exposure amount is 10-10. 1,000 mJ / cm ² is preferable.

  In order to promote the radical polymerization reaction of the radical polymerizable compound in the coating film and the cation reaction of the cation reactive compound, the coating film after exposure can be heated. As heating conditions, it is preferable to heat at 80 to 150 ° C. for 90 to 300 seconds.

2.3. Step (c)
Step (c) is a step of developing the coating film after exposure to form a pattern. A desired resist pattern can be formed by leaving a latent image generated in the coating film by development and removing the remaining image. Development is performed, for example, by bringing a known developer such as an alkaline aqueous solution into contact with the coating film after exposure.

  The development time varies depending on the type of each component in the composition, the blending ratio, the thickness of the coating film, etc., but is preferably 30 to 600 seconds. Examples of the developing method include a liquid piling method, a dipping method, a paddle method, a spray method, and a shower developing method. After development, the substrate may be washed with water and dried.

2.4. Step (d)
Step (d) is a step of exposing the pattern (hereinafter also referred to as “post-exposure”). The unreacted cation-reactive compound can be reacted by post-exposure, thereby easily forming a cured film that can maintain insulation even under high temperature and high humidity.

As post-exposure light, ultraviolet rays are preferable, and ultraviolet rays having a wavelength of 150 to 380 nm are more preferable. For example, when a high-pressure mercury lamp is used, the integrated irradiation amount of the post-exposure light is preferably 10 to 10,000 mJ / cm ² . Heat treatment may be performed after the post-exposure, and the heat treatment condition is preferably 100 to 250 ° C. for 30 minutes to 10 hours.

3. Electronic component The electronic component which concerns on this embodiment has the cured film produced using the above-mentioned composition. Examples of the electronic component according to the present embodiment include a circuit board, a semiconductor package, and a display board. The cured film can be used as a surface protective film, a rewiring layer, or a planarizing film of these electronic components. Since the cured film can maintain insulation even under high temperature and high humidity, the electronic component according to the present embodiment can protect the circuit pattern from the external environment such as dust, heat, and humidity, and can also provide insulation reliability between the circuit patterns. It can be operated stably for many years.

  For example, the substrate and the metal wiring are formed by filling the metal between the patterns of the cured film by plating or the like, forming a rewiring layer by repeatedly laminating the cured film and filling the metal as necessary. In addition, an electronic component having a rewiring layer including an insulating film can be manufactured.

4). Examples Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples. In the following examples, “parts” and “%” are based on mass unless otherwise specified.

4.1. Synthesis example 4.1.1. Synthesis example 1
163.1 parts by mass of propylene glycol monomethyl ether was weighed into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while replacing with nitrogen, and heated to 120 ° C. Next, 56.3 parts by mass of methacrylic acid, 72.89 parts by mass of dicyclopentanyl methacrylate (trade name “FA-513M” manufactured by Hitachi Chemical Co., Ltd.), 1.55 parts by mass of styrene, and t-hexylhydro 6.46 parts by mass of peroxide (manufactured by NOF Corporation, trade name “Perhexyl O”) was mixed to prepare a dropping composition. This dropping composition was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours after the completion of dropping. Next, 29.0 parts by mass of glycidyl methacrylate (manufactured by NOF Corporation, trade name “Blenmer GS”), 0.4 part by mass of trisdimethylaminomethylphenol and 0.1 part by mass of hydroquinone are mixed to modify the side chain. A composition was prepared. The inside of the flask was purged with air, and the prepared side chain modification mixture was dropped and reacted at 120 ° C. for 6 hours to obtain a polymer P1 having a radical polymerizable group.

Using a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, the weight average molecular weight (Mw) of the polymer P1 was measured in terms of polystyrene, and the measuring device “HLC-8220-GPC”. (Tosoh Co., Ltd.) was used for measurement. As a result, the weight average molecular weight of the polymer P1 was 1.9 × 10 ⁴ .

4.1.2. Synthesis Examples 2-7
Except having changed into the composition of Table 1, the polymer P2-P7 which has a radically polymerizable group similarly to the synthesis example 1 was synthesize | combined. Further, the weight average molecular weights of these polymers were measured in the same manner as in Synthesis Example 1. The results are shown in Table 1.

4.1.3. Synthesis Example 8
The polymer P1 prepared in Synthesis Example 1 was reprecipitated in methanol and further vacuum dried at 25 ° C. to obtain a polymer P8 having a radical polymerizable group. The weight average molecular weight (Mw) of the polymer P8 measured in the same manner as in Synthesis Example 1 was 2.4 × 10 ⁴ .

In addition, the symbol of the glycidyl methacrylate in Table 1 represents the glycidyl methacrylate of the following brand name, respectively.
・ G: NOF Corporation, trade name "Blemmer G"
・ GH-LC: NOF Corporation, trade name “Blemmer GH-LC”
・ GS: Product name "Blemmer GS", manufactured by NOF Corporation

4.2. Example 4.2.1. Example 1
<Preparation of composition>
100 parts by mass of a polymer P1 having a radical polymerizable group as a radical polymerizable compound, and 100 parts by mass of a trade name “KAYARAD DPHA” (manufactured by Nippon Kayaku Co., Ltd.) as a (meth) acrylate having a radical polymerizable group. 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone as a photo radical generator, 1 part by weight of a trade name “CPI-210S” (manufactured by San Apro Co., Ltd.) as a photo cation generator, and a cation reactive compound as an additive. (ADEKA Co., Ltd., trade name “ADEKA RESIN EP-4000L”) 20 parts by mass, amine (trioctylamine from Wako Pure Chemical Industries, Ltd.) 0.1 part by mass, surfactant (Neos Co., Ltd.) Product name “FTX-218”), 0.1 part by mass of propylene glycol monomethyl ether, As needed, a propylene glycol monomethyl ether solution containing 0.1% by mass of dichlorobenzene or a propylene glycol monomethyl ether solution containing 0.1% by mass of dibromobenzene and / or 0.1% by mass of water is contained. A propylene glycol monomethyl ether solution was added, and the composition was obtained by controlling the halogen content and water content shown in Table 2.

  The halogen content in the composition was determined by the FP method using a MagiX PRO (program: Uni Quant5) manufactured by PANalytical fluorescent X-ray apparatus in a helium atmosphere using a loose powder data container. It was measured and confirmed to have a halogen content described in Table 2.

  The water content in the composition was measured using a Karl Fischer moisture meter (manufactured by Metrohm, KF Coulometer 756), and the water content shown in Table 2 was confirmed.

<Evaluation of insulation>
First, the board | substrate 100 which has the copper wiring 10 shown in FIG.1 and FIG.2 was prepared. FIG. 1 is a plan view schematically showing the substrate 100, and FIG. 2 is a cross-sectional view taken along the line AA 'in FIG. As shown in FIGS. 1 and 2, the substrate 100 has a SiO ₂ film 12 formed on silicon (Si) 14, and a copper wiring 10 is formed on the SiO ₂ film 12 with a thickness of 8 μm. Yes. Line / Space on the substrate 100 = 20 μm.

The composition obtained above was applied onto the substrate 100 shown in FIGS. 1 and 2 and heated on a hot plate at 110 ° C. for 3 minutes to form a coating film. The entire surface of the coating film was exposed (apparatus name “MA8”, manufactured by Suss MicroTec, wavelength 365 nm, irradiation amount 600 mJ / cm ² ), and then heated in an oven at 120 ° C. for 1 hour to form a cured film on the substrate 100 ( A cured film having a thickness of 20 μm was formed from the surface of SiO ₂ . A substrate having this cured film was used as an evaluation substrate.

The cured resin on the electrodes at both ends of the wiring shown in FIGS. 1 and 2 was scraped off with a cutter knife and connected to a HAST evaluation apparatus (apparatus name “EHS-211”, manufactured by ESPEC) by soldering. The substrate was placed in a HAST apparatus and tested under conditions of a temperature of 121 ° C., a humidity of 85%, and an applied voltage of 5V. The evaluation was made according to the following criteria based on the time when the insulation was lowered and the resistance value was less than 10 ⁶ Ω.
(Evaluation criteria)
A: The time when the resistance value falls below 10 ⁶ Ω exceeds 168 h, and it can be judged that the resistance value is very good.
B: The time when the resistance value falls below 10 ⁶ Ω is 168 h or less and more than 100 h, and can be judged as good.
C: The time when the resistance value falls below 10 ⁶ Ω is 100 h or less and 50 h or more, and it can be determined that the level can be practically used.
D: Since the time when the resistance value falls below 10 ⁶ Ω is less than 50 h and cannot be put to practical use, it can be judged as defective.

<Evaluation of curability>
The composition obtained above was spin-coated on a silicon substrate and heated on a hot plate at 110 ° C. for 3 minutes to form a coating film. The coating film was exposed through a mask (device name “MA8”, manufactured by Suss MicroTec, wavelength 365 nm, irradiation amount 600 mJ / cm ² ). After the exposure, the film was developed with a developer (trade name “OPD5262”, manufactured by Fuji Film Co., Ltd.) and washed with water to form a cured film (1 L / 1S pattern having a height of 20 μm and a line width of 40 μm). The cured film was observed with an optical microscope, and the obtained cured film was further immersed in propylene glycol monomethyl ether acetate (PGMEA) for 5 minutes, then again observed with an optical microscope and evaluated according to the following criteria.
(Evaluation criteria)
A: It can be judged that the cured film is peeled off and the appearance is not changed before and after immersion in PGMEA and is very good.
B: Slight swelling is observed before and after immersion in PGMEA, but no change is observed in the peeling or appearance of the cured film, which can be judged as good.
C: Swelling was observed before and after immersion in PGMEA, and slight changes were observed in the peeling and appearance of the cured film, but it can be judged as a level that can be put to practical use.
D: Peeling of the cured film was observed before and after immersion in PGMEA, and it could not be put to practical use, so it can be judged as defective.

<Evaluation of adhesion>
The composition obtained above was applied onto a silicon wafer and heated on a hot plate at 110 ° C. for 3 minutes to form a coating film. The coated film was exposed on the entire surface (manufactured by Suss MicroTec, apparatus name “MA8”, wavelength 365 nm, irradiation amount 600 mJ / cm ² ), and then heated in an oven at 120 ° C. for 1 hour to form an evaluation substrate. Using an evaluation substrate stud pull tester (manufactured by Phototechnica Co., Ltd., device name “Romulus”), the adhesion was evaluated according to the following criteria.
(Evaluation criteria)
A: Adhesiveness is over 20 MPa, and it can be judged that it is very good.
B: Adhesiveness is 20 MPa or less and more than 15 MPa, which can be judged as good.
C: Adhesiveness is 15 MPa or less and more than 10 MPa, and it can be determined that it can be put to practical use.
D: Since the adhesiveness is 10 MPa or less and cannot be put into practical use, it can be judged as defective.

<Evaluation of storage stability>
The composition obtained above was stored at 25 ° C. in a dark place for 168 hours, and the viscosity change rate before and after storage was evaluated.
A: Viscosity change rate is less than 5%, and can be judged to be very good.
B: Viscosity change rate is 5% or more and 10% or less, which can be used practically and can be judged to be good.
C: Viscosity change rate is over 10%, and since it cannot be put to practical use, it can be judged as defective.

4.2.2. Examples 2-14 and Comparative Examples 1-5
A composition was prepared and evaluated in the same manner as in Example 1 except that the composition used was changed to the composition described in Table 2. The results are shown in Table 2.

4.3. Evaluation results Table 2 below shows the compositions and evaluation results of the compositions used in the examples and comparative examples.

  In Table 2 above, the numerical value of each component excluding water represents parts by mass. The numerical value in the row of water represents the mass% of water in 100 mass% of the composition. Moreover, the abbreviations in Table 2 above represent the following components, respectively.

<(Meth) acrylate having radical polymerizable group>
・ B1: Trade name “KAYARAD DPHA”, Nippon Kayaku Co., Ltd. ・ B2: Trade name “NK Ester CBZ-SA”, Shin-Nakamura Chemical Co., Ltd. ・ B3: Trade name “NK Ester A-TMM-” 3LM-N ", Shin-Nakamura Chemical Co., Ltd. B4: Trade name" NK Ester A-DPH-6E ", Shin-Nakamura Chemical Co., Ltd. B5: Trade name" NK Ester A-BPE-2 " Manufactured by Shin-Nakamura Chemical Co., Ltd. <Photoradical generator>
C1: 1-hydroxycyclohexyl phenyl ketone, manufactured by Wako Pure Chemical Industries, Ltd. C2: Trade name “Irgacure 379EG”, manufactured by BASF <cation reactive compound>
・ D1: Trade name “Adeka Resin EP-4000L”, manufactured by ADEKA Corporation ・ D2: Trade name “Denacol EX-321L”, manufactured by Nagase ChemteX Corporation ・ D3: Trade name “Denacol EX-810P”, Nagase Chem Made by Tex Co., Ltd. D4: Trade name “Blemmer GS”, made by NOF Co., Ltd. <Photocation generator>
E1: Trade name “CPI-210S”, manufactured by San Apro Co., Ltd. E2: Trade name “WPI-113”, manufactured by Wako Pure Chemical Industries, Ltd. <Amine>
F1: Trioctylamine, manufactured by Wako Pure Chemical Industries, Ltd. <Surfactant>
・ H1: Product name “FTX-218”, manufactured by Neos Co., Ltd.

  According to Table 2 above, by forming a cured film on the substrate 100 using the compositions of Examples 1 to 14 of the present invention, the circuit board can be obtained even in a severe environment such as high temperature and high humidity. It can be seen that insulation can be maintained. Moreover, it turns out that the composition of Examples 1-14 of this invention is excellent also in storage stability, and can form the cured film excellent also in sclerosis | hardenability and adhesiveness with a board | substrate.

  On the other hand, a cured film is formed on the substrate 100 using the composition of Comparative Example 1 that does not contain a radical polymerizable compound and a photo radical generator, or the composition of Comparative Example 2 that does not contain a photo cation generator. However, it can be seen that the insulation reliability of the circuit board cannot be obtained under a severe environment such as high temperature and high humidity. In particular, since the composition of Comparative Example 2 does not contain a cation-reactive compound, it can be seen that not only the insulation reliability cannot be obtained but also the curability is lowered.

  In addition, the composition of Comparative Example 3 containing 0.1 ppm of halogen atoms was unable to form a good cured film on the substrate due to reduced curability. It can be seen that the composition of Comparative Example 4 containing 150 ppm of bromine atoms and the composition of Comparative Example 5 containing 128 ppm of chlorine atoms cannot form a cured film excellent in insulation reliability because the halogen content is too high.

  The present invention is not limited to the above embodiment, and various modifications can be made. The present invention includes configurations that are substantially the same as the configurations described in the embodiments (for example, configurations that have the same functions, methods, and results, or configurations that have the same objects and effects). The present invention also includes a configuration in which a non-essential part of the configuration described in the above embodiment is replaced with another configuration. Furthermore, the present invention includes a configuration that achieves the same effects as the configuration described in the above embodiment or a configuration that can achieve the same object. Furthermore, the present invention includes a configuration obtained by adding a known technique to the configuration described in the above embodiment.

10 ... copper wiring, 12 ... _SiO 2, 14 ... silicon (Si), 100 ... substrate

Claims (6)

A composition containing a radical polymerizable compound, a photo radical generator, and a photo cation generator,
A composition containing a halogen atom in an amount of 0.5 ppm to 100 ppm when the total mass of the composition is 100% by mass.   Furthermore, the composition of Claim 1 which contains 0.01 mass% or more and 1 mass% or less of water when the total mass of the said composition is 100 mass%.   The composition according to claim 1 or 2, wherein the radical polymerizable compound contains a (meth) acrylate having a radical polymerizable group and a polymer having a radical polymerizable group.   Furthermore, the composition as described in any one of Claim 1 thru | or 3 containing a cation reactive compound. Applying the composition according to any one of claims 1 to 4 on a substrate to form a coating film;
Exposing the coating film;
A method for producing a cured film, comprising: The electronic component which has a cured film produced using the composition as described in any one of Claims 1 thru | or 4.