JP2021138916A - Curable resin composition, dry film, cured product and electronic component - Google Patents

Abstract

To provide a curable resin composition which can prevent yellow discoloration in thermosetting, and can also prevent long-term yellow discoloration by ultraviolet rays, and a dry film, a cured product and an electronic component having a resin layer obtained from the composition.SOLUTION: A curable resin composition contains (A) a hindered phenolic antioxidant, and (B) a thermosetting component. The (A) hindered phenolic antioxidant contains at least (A1) a hindered phenolic antioxidant having a vapor pressure at 20°C of 1.0×10-7 Pa or less and having an ester skeleton, and (A2) a hindered phenolic antioxidant having an isocyanurate structure. The curable resin composition can prevent yellow discoloration in thermosetting and long-term yellow discoloration by ultraviolet rays.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and a dry film thereof, a cured product thereof, and an electronic component having the cured product thereof.

In the printed wiring board, a solder resist is formed on a substrate having a conductor layer of a circuit pattern. Not limited to solder resists, various curable resin compositions have been conventionally proposed as materials for permanent protective films such as interlayer insulating materials for printed wiring boards and coverslays for flexible printed wiring boards.

Among them, in consideration of environmental problems, there are many alkaline-developable curable resin compositions that use a dilute alkaline aqueous solution as a developer, but the present invention is not limited to this, and ink is extruded onto a panel through a mesh of a printing plate for printing. There are also curable resin compositions for screen printing.

There are various uses of such a curable resin composition, and as an example thereof, a high reflectance suitable as an insulating layer of a printed wiring board on which a light emitting element such as a light emitting diode (LED) is mounted. White curable resin compositions are known. By using an insulating layer with high reflectance, the efficiency of using light from a light source such as an LED can be improved. In order to obtain a white curable resin composition, it is common to add a white colorant such as titanium dioxide. However, in the case of white, there is a problem that deterioration is easily visible when the color is changed by heat. Further, this problem applies not only to the white cured product but also to the transparent cured product and the cured product in which the amount of the colorant added is small.

Patent Document 1 discloses a photosensitive and thermosetting resin composition containing Irganox 1010 as a phenolic antioxidant. According to this resin composition, the effect of suppressing yellowing under heating conditions assuming solder reflow during manufacturing is exhibited.

Japanese Unexamined Patent Publication No. 2012-108523

However, according to the resin composition of Patent Document 1, although the effect of suppressing yellowing under the heating conditions at the time of production is shown, it cannot be said that this effect is sufficient as the effect of suppressing yellowing. Specifically, in a printed wiring board on which a light emitting element such as a light emitting diode (LED) is mounted, a long-term yellowing is caused by exposing an insulating layer using a curable resin composition to the light of an LED light source for a long period of time. It has become clear from the examination of the inventors that there is a strange problem.

An object of the present invention in view of the above problems is a curable resin composition capable of preventing yellowing during thermosetting and also preventing long-term yellowing due to ultraviolet rays, and a resin obtained from the curable resin composition. It is an object of the present invention to provide a dry film having a layer, a cured product thereof, and an electronic component having the cured product thereof.

The inventors have made diligent studies to achieve the above objectives. As a result, they have found that the above object can be achieved by adopting a combination of a specific antioxidant in the curable resin composition, and have completed the present invention.

That is, the above object of the present invention is
A composition containing (A) a hindered phenolic antioxidant and (B) a thermosetting component.
(A) Hindered phenolic antioxidant
(A1) A hindered phenolic antioxidant having an ester skeleton and a vapor pressure of 1.0 × ^{10-7 Pa or less at 20 ° C.}
(A2) A hindered phenolic antioxidant having an isocyanurate structure and
It has been found that this is achieved with a curable resin composition characterized by containing at least.

The curable resin composition of the present invention also preferably contains (C) an alkali-soluble resin and (D) a photopolymerization initiator, and (C) the alkali-soluble resin contains a carboxyl group-containing fluororesin. Is even more preferable.

Further, (A1) a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having a vapor pressure of 20 ° C. of 1.0 × ^{10-7 Pa or less and (A2) an isocyanurate structure.} Is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, respectively, with respect to 100 parts by mass of the total of (B) thermosetting component and (C) alkali-soluble resin in terms of solid content. ..

Further, the above object is a dry film having the curable resin composition of the present invention as a resin layer.
It can also be achieved by the curable resin composition of the present invention, a cured product obtained by curing the resin of a dry film, and an electronic component having the cured product.

According to the curable resin composition of the present invention, it is possible to suppress yellowing of the curable resin composition during thermosetting and yellowing of the cured product after curing due to ultraviolet irradiation. Therefore, for example, when applied to a cured product that is white, transparent, translucent, and has a small amount of colorant added, it is possible to form a cured product that is less affected by yellowing.

<Curable resin composition>
The curable resin composition of the present invention is
A composition containing (A) a hindered phenolic antioxidant and (B) a thermosetting component.
(A) Hindered phenolic antioxidant
(A1) A hindered phenolic antioxidant having an ester skeleton and a vapor pressure of 1.0 × ^{10-7 Pa or less at 20 ° C.}
(A2) A hindered phenolic antioxidant having an isocyanurate structure and
At least include.

[(A) Hindered phenolic antioxidant]
(A) The hindered phenolic antioxidant is used to suppress yellowing due to deterioration due to heat applied to the coating film and yellowing due to deterioration due to long-term exposure to ultraviolet rays on the cured product (A1). At least a hindered phenolic antioxidant having an ester skeleton and (A2) isocyanurate structure having a vapor pressure of 1.0 × ^{10-7 Pa or less at 20 ° C.} It is incorporated into the curable resin composition in the form of inclusion. By using these (A1) and (A2) components in combination, it is possible to suppress yellowing in thermosetting when forming a cured product, and also to suppress yellowing due to long-term exposure to ultraviolet rays to the cured product. .. Due to these actions, a white cured product having little yellowing and high reflectance can be maintained even after being exposed to ultraviolet rays for a long period of time.

(A1) As a hindered phenol-based antioxidant having an ester skeleton and a vapor pressure of 20 ° C. of 1.0 × ^10-7 Pa or less, for example, pentaerythritol tetrakis [3- (3,5-di-) tert-Butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propioquinyloxy] -1,1-dimethyl Ethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, ethylenebis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate), Hexamethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), And so on.

(A1) Commercially available products of hindered phenolic antioxidants having a vapor pressure of 20 ° C. of 1.0 × ^10-7 Pa or less and having an ester skeleton include ADEKA STAB AO-60 and ADEKA STAB AO-80 (above, above, ADEKA), Irganox 245, Irganox 259, Irganox 1010 (above, manufactured by BASF Japan), and Sumilyzer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.) can be used, but are not limited thereto.

Further, (A1) the vapor pressure at 20 ° C. is 1.0 × ^10-7 Pa or less, and as a hindered phenolic antioxidant having an ester skeleton, the vapor pressure at 20 ° C. is 5.0 × ^10-8. It is preferable to use Pa or less from the viewpoint of preventing volatilization of the hindered phenolic antioxidant from the curable resin composition due to heating or heating, and the vapor pressure at 20 ° C. is 1.0 × ^10-9. It is more preferable to use one having Pa or less.

のイソシアヌレート構造を有するヒンダードフェノール系酸化防止剤であればどのようなものであってもよいが、
好ましくは、式（２）

（式（２）中、Ｒ_１、Ｒ_２、Ｒ_３は、それぞれ、水素原子、炭素数１個以上４個以下の直鎖状または分岐状の炭化水素基、および３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル基である（ただし、Ｒ_１〜Ｒ_３の少なくとも１個が３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル基である））
で表される化合物であり、なかでも、Ｒ_１〜Ｒ_３が全て３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジル基である式（２）で表される化合物であることが特に好ましい。 (A2) As a hindered phenolic antioxidant having an isocyanurate structure, the formula (1)

Any hindered phenolic antioxidant having the isocyanurate structure of
Preferably, equation (2)

(In formula (2), R ₁ , R ₂ , and R ₃ are hydrogen atoms, linear or branched hydrocarbon groups having 1 to 4 carbon atoms, and 3,5-di-tert, respectively. - butyl-4-hydroxybenzyl group (provided _that at least one of R 1 to R ₃ is 3,5-di -tert- butyl-4-hydroxybenzyl))
It is particularly preferable that the compound is represented by the formula (2) in which R _{1 to} R _{3 are all 3,5-di-tert-butyl-4-hydroxybenzyl groups.} ..

(A2) Commercially available products of hindered phenolic antioxidants having an isocyanurate structure include ADEKA STAB AO-20 (manufactured by ADEKA), Irganox 3114 (manufactured by BASF Japan), and K-NOX 014 (manufactured by Sanyo Trading Co., Ltd.). , Cyanox 1790 manufactured by Japan Cytec Industries Co., Ltd. and the like.

(A1) Blending of a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having an isocyanurate structure and a vapor pressure of 20 ° C. of 1.0 × ^{10-7 Pa or less.} The amount is 100 parts by mass in total of (B) thermosetting component and (C) alkali-soluble resin ((C) 100 parts by mass of thermosetting component when (C) alkali-soluble resin is not contained, in terms of solid content. ), Each is preferably 0.1 parts by mass or more and 5.0 parts by mass or less, more preferably 0.2 parts by mass or more and 4 parts by mass or less, and 0.4 parts by mass or more and 2 parts by mass, respectively. More preferably, it is less than or equal to a portion.

(A1) Formulation of a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having an isocyanurate structure and a vapor pressure of 20 ° C. of 1.0 × ^{10-7 Pa or less.} The total amount is 100 parts by mass of (B) thermosetting component and (C) alkali-soluble resin in terms of solid content (when (C) alkali-soluble resin is not contained, (B) 100 parts by mass of thermosetting component. ), It is expected that the amount of yellowing will be less noticeable in the white, transparent, translucent and curable resin compositions containing a small amount of pigments / colorants.

Further, (A1) a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having an isocyanurate structure and a steam pressure of 20 ° C. of 1.0 × ^{10-7 Pa or less.} In terms of solid content, the total amount of (B) thermosetting component and (C) alkali-soluble resin is 100 parts by mass (when (C) alkali-soluble resin is not contained, (B) thermosetting component 100 When the amount is 5 parts by mass or less with respect to (part by mass), the effect of preventing yellowing caused by the hindered phenolic antioxidant can be expected.

[(B) Thermosetting component]
(B) The thermosetting component is added to heat-cure the curable resin composition of the present invention.

As the thermosetting component, known and commonly used thermosetting components such as isocyanate compounds, amino resins, maleimide compounds, benzoxazine resins, carbodiimide resins, cyclocarbonate compounds, epoxy compounds, polyfunctional oxetane compounds, and episulfide resins can be used.

In the present invention, an epoxy resin is particularly preferably used.

As the epoxy resin, a known and commonly used polyfunctional epoxy resin having at least two epoxy groups in one molecule can be used. The epoxy resin may be liquid, solid or semi-solid. Here, the liquid, solid, and semi-solid refer to the state of the epoxy resin at 30 ° C., respectively.

Examples of the epoxy resin include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, EPICLON 840, 850, 850-S, 1050, 2055 manufactured by DIC Corporation, and Epototo YD-011 manufactured by Nittetsu Chemical & Materials Co., Ltd. YD-013, YD-127, YD-128, D.D. manufactured by Dow Chemical Corporation. E. R. 317, D.I. E. R. 331, D.I. E. R. 661, D.I. E. R. 664, Sumitomo Chemical's Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, etc. (all trade names) bisphenol A type epoxy resin; Mitsubishi Chemical's jERYL903, DIC's EPICLON 152, 165, Epototo YDB-400, YDB-500 manufactured by Nittetsu Chemical & Materials Co., Ltd., D.D. E. R. 542, Sumitomo Chemical's Sumi-Epoxy ESB-400, ESB-700, etc. (all trade names) brominated epoxy resins; Mitsubishi Chemical's jER152, jER154, Dow Chemical's D.D. E. N. 431, D.I. E. N. 438, EPICLON N-730, N-770, N-865 manufactured by DIC, EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo manufactured by Nippon Kayaku Co., Ltd. Sumi-epoxy ESCN-195X, ESCN-220 manufactured by Kagaku Co., Ltd., YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700 manufactured by Nittetsu Chemical & Materials Co., Ltd. Novolak type epoxy resins such as -10, YDCN-701, YDCN-704, YDCN-704A, EPICLON N-680, N-690, N-695 (all trade names) manufactured by DIC; EPICLON 830 manufactured by DIC. , Mitsubishi Chemical's jER807, Nittetsu Chemical & Material's Epototo YDF-170, YDF-175, YDF-2004, etc. (all trade names) bisphenol F type epoxy resin; Nittetsu Chemical & Material's Epototo Hydrophobic bisphenol A type epoxy resin such as ST-2004, ST-2007, ST-3000 (trade name), YX8034 manufactured by Mitsubishi Chemical Co., Ltd .; jER604 manufactured by Mitsubishi Chemical Co., Ltd., Epototo YH- manufactured by Nittetsu Chemical & Materials Co., Ltd. 434, Sumi-epoxy ELM-120 manufactured by Sumitomo Chemical Co., Ltd. (both trade names) glycidylamine type epoxy resin; hidden-in type epoxy resin; Daicel Co., Ltd. Formula epoxy resin; YL-933 manufactured by Mitsubishi Chemical Co., Ltd., EPPN-501, EPPN-502 manufactured by Nippon Kayaku Co., Ltd., etc. (all trade names) trihydroxyphenylmethane type epoxy resin; YL-6056 manufactured by Mitsubishi Chemical Co., Ltd. , YX-4000, YL-6121 (all trade names) and other bixilenol-type or biphenol-type epoxy resins or mixtures thereof; EBPS-200 manufactured by Nippon Kayaku Co., Ltd., EPX-30 manufactured by ADEKA Co., Ltd., EXA manufactured by DIC Co., Ltd. Bisphenol S type epoxy resin such as -1514 (trade name); Bisphenol A novolac type epoxy resin such as jER157S (trade name) manufactured by Mitsubishi Chemical Co., Ltd .; Tetra such as jERYL-931 manufactured by Mitsubishi Chemical Co., Ltd. (both trade names) Phenilol ethane type epoxy resin; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co., Ltd .; diglycidyl phthalate resin such as Blemmer DGT manufactured by Nichiyu Co., Ltd .; Nittetsu Chemical & Materials Tetraglycidyl xylenoyl ethane resin such as ZX-1063 manufactured by Nittetsu Chemical &Materials; Naphthalene group-containing epoxy such as ESN-190, ESN-360 manufactured by Nittetsu Chemical & Materials, HP-4032 manufactured by DIC, EXA-4750, EXA-4700, etc. Resin; Epoxy resin having a dicyclopentadiene skeleton such as HP-7200 and HP-7200H manufactured by DIC; Glycydyl methacrylate copolymer epoxy resin such as CP-50S and CP-50M manufactured by Nichiyu Co., Ltd .; Further, cyclohexyl maleimide and glycidyl. Copolymerized epoxy resin of metal acrylate; CTBN modified epoxy resin (for example, YR-102, YR-450 manufactured by Nittetsu Chemical & Materials Co., Ltd.) and the like can be mentioned, but the present invention is not limited thereto.

Among them, an epoxy resin containing no benzene ring in the resin is preferable, and for example, a heterocyclic epoxy resin of TEPIC-S, TEPIC-VL, TEPIC-PAS, TEPIC-UC, etc. (all manufactured by Nissan Chemical Co., Ltd.). , Celoxide 2000, Celoxide 2021, Celoxide 2081 and the like (all manufactured by Daicel Co., Ltd.) are preferably used as the (B) thermosetting component.

The blending amount of the (B) thermosetting component is defined by the total amount of the (C) alkali-soluble resin described later. That is, the total amount of the (B) thermosetting component and the (C) alkali-soluble resin described later is 5.5% by mass or more and 75% by mass or less of the curable composition in terms of solid matter, preferably 11% by mass. % Or more and 70% by mass or less, and more preferably 21.5% by mass or more and 58% by mass or less.

When the total amount of the thermosetting component (B) and the alkali-soluble resin (C) is 5.5% by mass or more and 75% by mass or less of the curable resin composition in terms of solid matter, good coating strength can be obtained. It is possible to obtain a curable resin composition having good viscosity and excellent coatability while ensuring it.

[(C) Alkali-soluble resin]
The alkali-soluble resin (C) is a resin that enables the curable resin composition to be dissolved in an alkaline developer, that is, developed with an alkaline solution, and the curable resin composition of the present invention is an alkali-developable type. In this case, (C) an alkali-soluble resin is blended.

As the alkali-soluble resin (C), it is preferable to use a carboxyl group-containing resin or a phenol resin. In particular, it is more preferable to use a carboxyl group-containing resin from the viewpoint of developability.

As the carboxyl group-containing resin, various conventionally known carboxyl group-containing resins having a carboxyl group in the molecule and not having an ethylenically unsaturated group (non-photosensitive) or having this (photosensitive) However, from the viewpoint of making the curable resin composition photocurable and developing resistance, it is preferable to use a curable resin composition having an ethylenically unsaturated group (photosensitive).

The ethylenically unsaturated group is a functional group having an ethylenically unsaturated bond, and examples thereof include a vinyl group and a (meth) acryloyl group. From the viewpoint of reactivity, the ethylenically unsaturated group is a (meth) acryloyl group. Is preferable. Here, the (meth) acryloyl group is a general term for an acryloyl group and a meta-acryloyl group.

Specific examples of the carboxyl group-containing resin that can be used in the curable resin composition of the present invention include compounds (either oligomers and polymers) listed below.

(1) A carboxyl group-containing resin obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α-methylstyrene, lower alkyl (meth) acrylate, or isobutylene.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a double addition reaction of a diol compound such as a polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic-based polyol, a bisphenol A-based alkylene oxide adduct diol, and a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An end carboxyl group-containing urethane resin obtained by reacting an acid anhydride at the end of a urethane resin by a double addition reaction of a diol compound such as an alkylene oxide adduct diol, a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenel type epoxy resin, biphenol type epoxy resin ( Meta) A photosensitive carboxyl group-containing urethane resin obtained by a double addition reaction of an acrylate or a modified partial acid anhydride thereof, a carboxyl group-containing dialcohol compound, and a diol compound.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (5). Meta) Acryloylated carboxyl group-containing urethane resin.

(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A carboxyl group-containing urethane resin that is terminal (meth) acrylicized by adding the compound to be possessed.

(7) Photosensitivity in which (meth) acrylic acid is reacted with a polyfunctional epoxy resin and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to a hydroxyl group existing in a side chain. Carboxyl group-containing resin.

(8) A photosensitive carboxyl group obtained by reacting a (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a bifunctional epoxy resin with epichlorohydrin, and adding a dibasic acid anhydride to the generated hydroxyl group. Containing resin.

(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin as described later with a dicarboxylic acid and adding a dibasic acid anhydride to the generated primary hydroxyl group.

(10) Reaction production obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid. A carboxyl group-containing photosensitive resin obtained by reacting a substance with a polybasic acid anhydride.

(11) Obtained by reacting an unsaturated group-containing monocarboxylic acid with a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive resin obtained by reacting a reaction product with a polybasic acid anhydride.

(12) An epoxy compound having a plurality of epoxy groups in one molecule, a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol, and (meth). Reacting with an unsaturated group-containing monocarboxylic acid such as acrylic acid, maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, adipine with respect to the alcoholic hydroxyl group of the obtained reaction product. A carboxyl group-containing photosensitive resin obtained by reacting a polybasic anhydride such as an acid.

(13) In addition to the resin according to any one of (1) to (12) above, one epoxy group and one or more (meth) acryloyl in the molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A photosensitive carboxyl group-containing resin obtained by adding a compound having a group.

Since the above-mentioned carboxyl group-containing resin has a large number of carboxyl groups in the side chain of the backbone polymer, it can be developed with a dilute alkaline aqueous solution.

Further, it is preferable that the alkali-soluble resin (C) contains a carboxyl group-containing fluororesin.

As the carboxyl group-containing fluororesin, a known fluororesin containing a carboxyl group can be used. Fluororesin refers to a polymer or oligomer having at least one fluorine atom. The presence of fluorine atoms in the alkali-soluble resin can improve the thermal discoloration resistance.

Specific examples of the carboxyl group-containing fluororesin that can be used in the curable resin composition of the present invention include compounds (either oligomers and polymers) listed below. The "fluorine-substituted product" described below refers to a compound in which one or more hydrogen atoms other than hydrogen atoms constituting the functional group of a predetermined compound are substituted with fluorine.

(1) Unsaturated carboxylic acid such as (meth) acrylic acid and styrene, α-methylstyrene, alkyl (meth) acrylate (alkyl is, for example, an alkyl having 2 to 15 carbon atoms, preferably 2 to 8 carbon atoms. A carboxyl group-containing fluororesin obtained by copolymerizing an unsaturated group-containing compound such as isobutylene with a fluorine-substituted compound.

(2) Diisocyanates such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates and aromatic diisocyanates, carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid, polycarbonate-based polyols and polyether-based compounds. Carboxyl group-containing urethane resin by double addition reaction of diol compounds such as polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, bisphenol A-based alkylene oxide adduct diols, compounds having phenolic hydroxyl groups and alcoholic hydroxyl groups. A fluororesin containing a carboxyl group and a urethane bond, wherein at least one of the described raw materials is a fluorine substitute.

(3) Diisocyanate compounds such as aliphatic diisocyanates, branched aliphatic diisocyanates, alicyclic diisocyanates, and aromatic diisocyanates, and polycarbonate-based polyols, polyether-based polyols, polyester-based polyols, polyolefin-based polyols, acrylic-based polyols, and bisphenol A-based An alkylene oxide adduct diol, a terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with an acid anhydride at the end of the urethane resin by a double addition reaction of a diol compound such as a compound having an alkylene oxide adduct diol, a phenolic hydroxyl group and an alcoholic hydroxyl group. A fluororesin containing a carboxyl group and a urethane bond, wherein at least one of the described raw materials is a fluorine substitute.

(4) Diisocyanate and bifunctional epoxy resin such as bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bixylenel type epoxy resin, biphenol type epoxy resin ( A photosensitive carboxyl group-containing urethane resin obtained by a double addition reaction of a meta) acrylate or a partially acid anhydride modified product thereof, a carboxyl group-containing dialcohol compound, and a diol compound, wherein at least one of the described raw materials is a fluorine substitute. A fluororesin containing a carboxyl group and an epoxy bond.

(5) During the synthesis of the resin of (2) or (4) above, a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule such as hydroxyalkyl (meth) acrylate is added to the terminal (5). Meta) A fluororesin containing an acrylicized carboxyl group and urethane bond.

(6) During the synthesis of the resin according to (2) or (4) above, one isocyanate group and one or more (meth) acryloyl groups are added to the molecule, such as an isophorone diisocyanate and pentaerythritol triacrylate equimolar reaction product. A fluororesin containing a carboxyl group and a urethane bond that are terminal (meth) acrylicized by adding the compound to be possessed.

(7) A (meth) acrylic acid is reacted with a fluoropolymer of a polyfunctional epoxy resin, and a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is added to a hydroxyl group existing in a side chain. Photosensitive carboxyl group-containing fluororesin.

(8) A (meth) acrylic acid was reacted with a fluorosubstituted product of a polyfunctional epoxy resin in which the hydroxyl group of a bifunctional epoxy resin was further epoxidized with epichlorohydrin, and a dibasic acid anhydride was added to the generated hydroxyl group. Photosensitive carboxyl group-containing fluororesin.

(9) A fluororesin containing a carboxyl group and an ester bond in which a dicarboxylic acid is reacted with a fluoropolymer of a polyfunctional oxetane resin as described later, and a dibasic acid anhydride is added to the generated primary hydroxyl group.

(10) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a fluorine substitute of a compound having a plurality of phenolic hydroxyl groups in one molecule with an alkylene oxide such as ethylene oxide or propylene oxide. A carboxyl group-containing photosensitive fluororesin obtained by reacting a obtained reaction product with a polybasic acid anhydride.

(11) An unsaturated group-containing monocarboxylic acid is reacted with a reaction product obtained by reacting a fluorine substitute of a compound having a plurality of phenolic hydroxyl groups in one molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate. A carboxyl group-containing photosensitive fluororesin obtained by reacting the obtained reaction product with a polybasic acid anhydride.

(12) A fluorine-substituted epoxy compound having a plurality of epoxy groups in one molecule, and a compound having at least one alcoholic hydroxyl group and one phenolic hydroxyl group in one molecule such as p-hydroxyphenethyl alcohol. , (Meta) Acrylic acid and other unsaturated group-containing monocarboxylic acids are reacted with each other, and maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and pyrochloride are used with respect to the alcoholic hydroxyl group of the obtained reaction product. Merit A carboxyl group-containing photosensitive fluororesin obtained by reacting a polybasic anhydride such as acid or adipic acid.

(13) In addition to the resin according to any one of (1) to (12) above, one epoxy group and one or more (meth) acryloyl in a molecule such as glycidyl (meth) acrylate and α-methylglycidyl (meth) acrylate. A photosensitive carboxyl group-containing fluororesin obtained by adding a compound having a group.

The above-mentioned fluorine substitution product can be obtained by fluorinating a predetermined compound. As the fluorination method, a known method may be used, and for example, low temperature fluorination, contact fluorination, aqueous solution fluorination, liquid phase fluorination, solid phase fluorination, vapor phase fluorination and the like can be adopted.

When a carboxyl group-containing fluororesin (C) is used as the alkali-soluble resin, examples of commercially available products include carboxyl group-containing fluororesins manufactured by Shin-Nakamura Chemical Co., Ltd. (product names: TIF-1, TIF-2, TIF-). 3) can be used.

The acid value of the alkali-soluble resin (C) is preferably in the range of 20 to 200 mgKOH / g, more preferably in the range of 40 to 150 mgKOH / g. When the acid value of the alkali-soluble resin (C) is 20 mgKOH / g or more, the adhesion of the coating film is good and the alkali development is good. On the other hand, when the acid value is 200 mgKOH / g or less, the dissolution of the exposed part by the developing solution can be suppressed, so that the line becomes thinner than necessary, and in some cases, the developing solution does not distinguish between the exposed part and the unexposed part. It is possible to draw a resist pattern satisfactorily by suppressing dissolution and peeling.

The weight average molecular weight of the alkali-soluble resin (C) used in the present invention varies depending on the resin skeleton, but is preferably in the range of 2,000 to 150,000, more preferably 5,000 to 100,000. When the weight average molecular weight is 2,000 or more, the tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss can be suppressed during development, and resolution deterioration can be suppressed. On the other hand, when the weight average molecular weight is 150,000 or less, the developability is good and the storage stability is also excellent.

When the curable resin composition of the present invention contains the (C) alkali-soluble resin, the blending amount thereof is preferably 5% by mass or more and 60% by mass or less in the curable resin composition in terms of solid matter. It is preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 60% by mass or less, and particularly preferably 20% by mass or more and 50% by mass or less. When it is 5% by mass or more and 60% by mass or less, the coating film strength is good, the viscosity of the composition is appropriate, and the coatability and the like are improved.

[(D) Photopolymerization Initiator]

When the curable resin composition of the present invention is an alkali-developed type, (D) a photopolymerization initiator is blended in the curable resin composition in order to enable photocuring of the composition in the exposure step. As the photopolymerization initiator (D), any known photopolymerization initiator or photoradical generator can be used.

Examples of the photopolymerization initiator (D) include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, and bis-. (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxide, bis- (2,6-dimethoxybenzoyl) phenylphosphine oxide, Bis- (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis- (2,4) , 6-trimethylbenzoyl) -bisacylphosphine oxides such as phenylphosphine oxide; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyl Monoacylphosphine oxides such as phenylphosphinic acid methyl ester, 2-methylbenzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; 1-hydroxy -Cyclohexylphenyl ketone, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-hydroxy-1- {4- [4- (2) -Hydroxy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propane-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other hydroxyacetophenones; benzoyl, benzyl , Benzoyl methyl ether, benzoin ethyl ether, benzoin n-propyl ether, benzoin isopropyl ether, benzoin n-butyl ether and other benzoins; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4'- Benzoyls such as dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl) -1- [4- (4-morpholinyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone, etc. Acetphenones; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone , 2-Methyl anthraquinone, 2-Ethyl anthraquinone, 2-tert-butyl anthraquinone, 1-chloroanthraquinone, 2-amyl anthraquinone, 2-aminoanthraquinone and other anthraquinones; acetphenone dimethyl ketal, benzyl dimethyl ketal and other ketals; ethyl Ethyl benzoates such as -4-dimethylaminobenzoate, 2- (dimethylamino) ethyl benzoate, p-dimethylbenzoic acid ethyl ester; 1,2-octanedione, 1- [4- (phenylthio)-, 2-( O-benzoyloxime)], etanone, oxime esters such as 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); (Η5-2,4-cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2 6-Difluoro-3- (2- (1-pyr-1-yl) ethyl) phenyl] Titanocentes such as titanium; phenyldisulfide 2-nitrofluorene, butyloin, anisoine ethyl ether, azobisisobutyronitrile, tetra Methylthiolam disulfide and the like can be mentioned. Among these, monoacylphosphine oxides and oxime esters are preferable, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole) −3-Il] −, 1- (O-acetyloxime) is more preferable. (D) As the photopolymerization initiator, one type may be used alone, or two or more types may be used in combination.

The blending amount of the (D) photopolymerization initiator is preferably 0.01 to 30 parts by mass, and more preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the (C) alkali-soluble resin. When the blending amount of the photopolymerization initiator (D) is 0.01 parts by mass or more, the photocurability is good, the coating film is hard to peel off, and the coating film characteristics are good, and (D) the photopolymerization initiator is blended. When the amount is 30 parts by mass or less, the light absorption of the (D) photopolymerization initiator is good, and the deep curability is improved.

[Compound having an ethylenically unsaturated group]
The curable resin composition of the present invention may contain a photopolymerizable monomer known and commonly used as a compound having an ethylenically unsaturated group. The compound having an ethylenically unsaturated group is a compound having one or more ethylenically unsaturated groups in the molecule, and assists photocuring of the alkali-soluble resin by irradiation with active energy rays to cure the curable resin composition. It is a thing.

Examples of the compound used as the compound having an ethylenically unsaturated group include commonly known polyester (meth) acrylate, polyether (meth) acrylate, urethane (meth) acrylate, carbonate (meth) acrylate, and epoxy (meth). Examples include acrylate. Specifically, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate; diacrylates of glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol; N, N-dimethylacrylamide. , N-methylolacrylamide, acrylamides such as N, N-dimethylaminopropylacrylamide; aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate; hexanediol, trimethylolpropane, Polyhydric alcohols such as pentaerythritol, dipentaerythritol, tris-hydroxyethyl isocyanurate or polyhydric acrylates such as ethireoxyside adducts, propylene oxide adducts, or ε-caprolactone adducts; phenoxyacrylates, bisphenol A di. Acrylate and polyvalent acrylates such as ethylene oxide adducts or propylene oxide adducts of these phenols; glycidyl ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, triglycidyl isocyanurate. Polyvalent acrylates; Not limited to the above, acrylates and melamine acrylates obtained by directly acrylated polyols such as polyether polyols, polycarbonate diols, hydroxyl group-terminated polybutadienes, and polyester polyols, or urethane acrylates via diisocyanates, and the acrylates. At least one of each methacrylate corresponding to the above can be mentioned.

Above all, it is preferable that the compound having an ethylenically unsaturated group is a monomer containing no benzene ring. Further, from the viewpoint of improving the strength of the cured product after photocuring, it is preferable that the compound having an ethylenically unsaturated group contains a cyclic compound (however, it does not contain a benzene ring).

Commercially available products of cyclic compounds (however, not containing a benzene ring) having an ethylenically unsaturated group include A-DCP, A-9300, A-9300YN, A-9300-1CL, and DCP (above, Shin-Nakamura Chemical Co., Ltd.), A1208, D3380, M0594, T2325 (above, Tokyo Chemical Industry), M-215, M-313, M-315 (above, Toagosei), Photomer4356 (above, IGM Resins) (Manufactured by Hitachi, Ltd.), FA-731A (all manufactured by Hitachi Kasei Co., Ltd.) and the like.

Further, the compound having an ethylenically unsaturated group is preferably a compound having two or more ethylenically unsaturated groups in the molecule.

When a compound having an ethylenically unsaturated group is blended, the blending amount is 10 parts by mass or more and 60 parts by mass or less in terms of solid content with respect to 100 parts by mass of the total of (C) alkali-soluble resin. The ratio is preferably 15 parts by mass or more and 50 parts by mass or less, and more preferably 20 parts by mass or more and 40 parts by mass or less.

The amount of the compound having an ethylenically unsaturated group (C) is within the range of 10 parts by mass or more and 60 parts by mass or less in terms of solid content with respect to 100 parts by mass of the total of (C) alkali-soluble resin. The curable resin composition has excellent photocurability, good patterning during development, and good tackiness (dryness to the touch).

[White colorant]
When the curable resin composition of the present invention is used for producing an insulating layer having a high reflectance, it is preferable that a white colorant is blended in the curable resin composition.

Examples of the white colorant include titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, white lead, zinc sulfide, lead titanate, etc., but titanium oxide has a high effect of suppressing discoloration due to heat. Is preferably used. By containing a white colorant, the composition of the present invention can be made white, and a high reflectance can be obtained.

The titanium oxide may be titanium oxide having any structure of rutile type, anatase type, and rams delight type, and one type may be used alone or two or more types may be used in combination. Of these, rams delite type titanium oxide is _{obtained by subjecting rams delite type Li 0.5} TiO ₂ to a lithium desorption treatment by chemical oxidation.

Of the above, when rutile-type titanium oxide is used, heat resistance can be further improved, discoloration due to light irradiation is less likely to occur, and quality is less likely to deteriorate even in a harsh usage environment. preferable. In particular, by using rutile-type titanium oxide whose surface is treated with aluminum oxide such as alumina or silica, deterioration with respect to light can be suppressed, and reflectance and heat resistance can be further improved. Further, another surface treatment can be applied on top of the above surface treatment. In particular, the reflectance can be further improved by surface-treating with alumina and then further surface-treating with zirconia. When titanium oxide is used as the white colorant, the content of rutile-type titanium oxide surface-treated with aluminum oxide in total titanium oxide is preferably 10% by mass or more, more preferably 30% by mass or more. The upper limit may be 100% by mass or less, that is, the total amount of titanium oxide may be rutile-type titanium oxide surface-treated with the above aluminum oxide. Examples of the rutile-type titanium oxide surface-treated with the aluminum oxide include CR-58 manufactured by Ishihara Sangyo Co., Ltd., which is rutile-type chlorine-type titanium oxide, and R, which is rutile-type sulfuric acid-type titanium oxide. -630 and the like can be mentioned. Further, it is also preferable to use rutile-type titanium oxide whose surface is treated with a silicon oxide, and in this case as well, the heat resistance can be further improved. Further, it is also preferable to use rutile-type titanium oxide surface-treated with both aluminum oxide and silicon oxide, and examples thereof include CR-90 manufactured by Ishihara Sangyo Co., Ltd., which is rutile-type chlorine-type titanium oxide. Be done.

Further, titanium oxide may contain sulfur, and the amount of sulfur thereof is preferably 100 ppm or less, more preferably 60 ppm or less. This is because when the amount of sulfur is 100 ppm or less, discoloration of the peripheral portion due to the generated sulfur gas does not occur.

The blending amount of such a white colorant is preferably 5 to 80 mass by mass with respect to the solid content in the curable resin composition (when the resin composition contains an organic solvent, the component excluding the organic solvent). %, More preferably 10 to 70% by mass.

[Silica powder]
The curable resin composition of the present invention may contain silica powder in order to impart thixotropy, if necessary. Thixotropy is a phenomenon in which the apparent viscosity of a fluid such as paint changes reversibly due to the flow and standing.

As the silica powder used in the present invention, both natural silica and synthetic silica can be used, but in general, synthetic silica having stable quality is used.

As the silica powder used in the present invention, a crushed product of synthetic or natural crystalline silica, a crushed product of molten silica, a spherically processed product of molten silica, synthetic spherical silica, synthetic fine powder silica and the like can be used.

Synthetic silica, that is, hydrous amorphous silicon dioxide (SiO ₂ · nH ₂ O) is produced by reacting a sodium silicate solution (water glass) with sulfuric acid in a reaction vessel, and has a shape and particle size depending on the reaction conditions. Can be controlled and made into synthetic spherical silica or synthetic fine powder silica.

Silica powders preferably used in the present invention include, for example, Aerosil 90, Aerosil 130, Aerosil 150, Aerosil 200, Aerosil 225, Aerosil 300, Aerosil 380, Aerosil OX50, Aerosil TT6600, Aerosil Aero10 R711, Aerosil R805, Aerosil R812, Aerosil R816, Aerosil R972, Aerosil R974, Aerosil R7200, Aerosil R8200, Aerosil R9200 (all manufactured by Nippon Aerosil) 82 (all manufactured by EVONIK DEGUSSA), E-200A, E-220A, K-500, E-1009, E-1011, E-1030, E-150J, E-170, E-200, E-220, E-743, E-75, HD, HD-2, L-250, L-300, G-300, SS-10, SS-50, SS-30P, SS-30V, SS-30X, SS-50, Synthetic fine silica such as SS-70 (manufactured by Tosoh Silica), FUSELEX RD-8, FUSELEX RD-8AL, FUSELEX RD-120, FUSELEX MCF-200C, FUSELEX GP-200TC, FUSELEX TZ-20, FUSELEX ZA Melted and crushed silica such as -30C, FUSELEX E-1, FUSELEX E-2, FUSELEX AS-1, FUSELEX X (above, manufactured by Ryumori), FS-3DC, FS-5DC (above, manufactured by Denka), FB -5D, FB-12D, FB-20D, FB-105, FB-940, FB-9454, FB-950, FB-105FC, FB-870FC, FB-875FC, FB-9454FC, FB-950FC, FB-300FC , FB-105FD, FB-970FD, FB-975FD, FB-950FD, FB-300FD, FB-400FD, FB-7SDC, FB-5SDC, FB-3SDC, FB-74X, FB-25SX, F B-35X, FB-302X, FB-105X, FB-940X, FB-950X, FB-105XFC, FB-950XFC, FB-100XFD, FB-950XFD, FB-7SDX, FB-5SDX, FB-3SDX (above, Made by Denka), MSR-2212, MSR-25, MSR-3512, MSR-2214M4, MSV-2212N, MSV-2212NH, MSV-2507NH, MSV-3512N, MSV-3512NH, MSS-7, MSS-6, EXR -4, EXR-3, AC-5VLD, B-21, A-21, MP-15EF, AC-5V, MP-8FS (all manufactured by Ryumori Co., Ltd.) and other molten spherical silica, SO-E1, SO- Synthetic spherical silica such as E2, SO-E3, SO-E5, SO-E6, SO-C1, SO-C2, SO-C3, SO-C5, SO-C6 (all manufactured by Admatex), CRYSTALITE 3K, CRYSTALITE 3K-S, CRYSTALITE C, CRYSTALITE TNC-1, CRYSTALITE NX-7, CRYSTALITE SMT-10, CRYSTALITE CMC-12S, CRYSTALITE XJ-7, CRYSTALITE C-BASE-1, CRYSTALITE C-BASE-1 Examples thereof include crystalline crushed silica such as CRYSTALITE VX-S2 (all manufactured by Ryumori Co., Ltd.).

When silica powder is blended, synthetic fine powder silica is preferably used from the viewpoint of dispersibility, but a mixture of synthetic fine powder silica and melt-ground silica may also be used.

The blending amount of the silica powder is preferably 0.01 parts by mass or more and 15 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass (solid content) of the curable resin composition. Particularly preferably, it is 0.5 parts by mass or more and 5 parts by mass or less. Within this range, the effect of the silica powder as a thixotropic agent, that is, the suppression of sedimentation separation of components (white agent powder, etc.) in the curable resin composition, and the suitable decrease in viscosity at the time of coating on a substrate. , And the effect of improving the leveling property after application is exhibited.

[Other ingredients]
The curable resin composition of the present invention may contain an antifoaming agent. Examples of the defoaming agent include silicone-based defoaming agents and non-silicone-based defoaming agents. Among them, from the viewpoints of being able to reduce contamination of the developing solution and being less likely to cause poor adhesion of the marking ink. , It is preferable to use a non-silicone antifoaming agent. One type of antifoaming agent may be used, or two or more types may be used in combination.

Examples of the silicon-based defoaming agent include KS-66 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like. Examples of the non-silicone antifoaming agent include FOAMKILLER NSI-0.00 (manufactured by Aoki Yushi Kogyo Co., Ltd.).

The amount of the defoaming agent to be blended is preferably 0.01 to 30.00 parts by mass with respect to 100 parts by mass of the (C) alkali-soluble resin in terms of solid content.

Yellowing of the cured product of the curable resin composition can be a problem not only in the white curable resin composition but also in a transparent, translucent, or cured film to which a small amount of a colorant is added. Therefore, the curable resin composition of the present invention may contain a colorant in addition to the white colorant. Specific examples of the colorant include phthalocyanine blue, phthalocyanine green, iodin green, disazo yellow, leuco crystal violet, carbon black, naphthalene black, solvent blue and the like. One type of colorant may be used, or two or more types may be used in combination.

Further, the curable resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applied to a substrate or a carrier film, and the like. Examples of the organic solvent include ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene and tetramethyl benzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol and propylene glycol monomethyl ether. , Dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether and other glycol ethers; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbi Esters such as tall acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; petroleum solvents such as petroleum ether, petroleum naphtha, and solvent naphtha are known. Conventional organic solvents can be used. These organic solvents can be used alone or in combination of two or more.

The curable resin composition of the present invention may further contain other additives known and commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, UV absorbers, silane coupling agents, thermoplastics, flame retardants, antistatic agents, antiaging agents, antibacterial / antifungal agents, leveling agents, thickeners, adhesions. Additives, release agents (excluding silica powder), photoinitiator aids, sensitizers, photobase generators, thermoplastic resins, elastomers, organic fillers such as urethane beads, barium sulfate, talc, silica (silica powder) Inorganic fillers such as (excluding), mold release agents, surface treatment agents, dispersants, dispersion aids, surface modifiers, stabilizers, phosphors, cellulose resins and the like can be mentioned.

The curable resin composition of the present invention may be used as a dry film or as a liquid. When used as a liquid, it may be one-component or two-component or more.

<Dry film>
The dry film of the present invention has a resin layer obtained by applying the curable resin composition of the present invention on a carrier film and drying it. When forming a dry film, first, the curable resin composition of the present invention is diluted with the above organic solvent to adjust the viscosity to an appropriate level, and then a comma coater, a blade coater, a lip coater, a rod coater, and a squeeze coater. , Reverse coater, transfer coater, gravure coater, spray coater, etc., and apply to a uniform thickness on the carrier film. Then, the applied composition is usually dried at a temperature of 50 to 130 ° C. for 1 to 30 minutes to form a resin layer. The coating film thickness is not particularly limited, but in general, the film thickness after drying is appropriately selected in the range of 10 to 150 μm, preferably 20 to 60 μm.

As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamide-imide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, but is generally selected as appropriate in the range of 10 to 150 μm.

After forming the resin layer made of the curable resin composition of the present invention on the carrier film, a peelable cover film is further formed on the surface of the film for the purpose of preventing dust from adhering to the surface of the film. It is preferable to stack them. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, surface-treated paper, or the like can be used. The cover film may be smaller than the adhesive force between the resin layer and the carrier film when the cover film is peeled off.

In the present invention, the curable resin composition of the present invention may be applied onto the cover film and dried to form a resin layer, and a carrier film may be laminated on the surface thereof. That is, either a carrier film or a cover film may be used as the film to which the curable resin composition of the present invention is applied when producing the dry film in the present invention.

<Cured product>
The case where the curable resin composition of the present invention is an alkali-developable type (that is, includes (C) an alkali-soluble resin and (D) a photopolymerization initiator) will be described first.

In this case, in order to form a cured product using the curable resin composition of the present invention, the composition is applied onto a substrate, and the resin layer obtained after volatilizing and drying the solvent is exposed (light irradiation). ), The exposed part (the part irradiated with light) is cured. Specifically, the unexposed portion is exposed to an alkaline aqueous solution (for example, by selectively exposing with active energy rays through a photomask in which a pattern is formed by a contact method or a non-contact method, or by directly exposing the pattern with a laser direct exposure machine. , 0.3 to 3 mass% sodium carbonate aqueous solution) to form a pattern of the cured product. Further, by heating to a temperature of about 100 to 180 ° C. and thermosetting (post-curing), a cured film (cured product) having excellent various properties such as heat resistance, chemical resistance, hygroscopicity, adhesion, and electrical characteristics is obtained. ) Can be formed.

When the curable resin composition of the present invention is not an alkali-developable type, the curable resin composition is, for example, a thermosetting type that does not contain (C) an alkali-soluble resin and (D) a photopolymerization initiator. .. In this case, in order to form a cured product, the composition is applied onto a substrate, and the resin layer obtained after volatilizing and drying the solvent is heated to a temperature of about 100 to 180 ° C. and thermally cured. Therefore, a cured film (cured product) can be obtained.

The curable resin composition of the present invention is, for example, adjusted to a viscosity suitable for the coating method using the above organic solvent, and is subjected to a dip coating method, a flow coating method, a roll coating method, a bar coater method, etc. on the substrate. After coating by a method such as a screen printing method or a curtain coating method, a tack-free resin layer is formed by volatilizing and drying (temporarily drying) the organic solvent contained in the composition at a temperature of about 60 to 100 ° C. be able to. Further, in the case of a dry film in which the above composition is applied on a carrier film or a cover film, dried and wound as a film, the layer of the composition of the present invention is brought into contact with the base material by a laminator or the like on the base material. A resin layer can be formed on the base material by peeling off the carrier film after the film is attached to the substrate.

The base material includes a printed wiring board and a flexible printed wiring board whose circuit is formed of copper or the like in advance, as well as paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, and glass cloth / paper epoxy. , Synthetic fiber epoxy, fluororesin / polyethylene / polyimideene ether, polyphenylene oxide / cyanate, etc. are used for high frequency circuit copper-clad laminates, etc., and all grades (FR-4, etc.) of copper-clad laminates are used. Examples thereof include a plate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.

The above-mentioned volatile drying or heat curing is performed by a hot air circulation type drying oven, an IR furnace, a hot plate, a convection oven, etc. It can be carried out by using a method of spraying on a support.

As the exposure machine used for the above-mentioned active energy ray irradiation, if it is a device equipped with a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, etc., and irradiates the active energy ray in the range of 350 to 450 nm. Often, a direct drawing device (eg, a laser direct imaging device that draws an image directly with a laser from CAD data from a computer) can also be used. The lamp light source or the laser light source of the direct drawing machine may have a maximum wavelength in the range of 350 to 410 nm. The amount of exposure for image formation varies depending on the film thickness and the like, but is generally 20 to 1000 mJ / cm ² , preferably 20 to 800 mJ / cm ² .

The development method can be a dipping method, a shower method, a spray method, a brush method, etc., and the developing solution includes potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, etc. Alkaline aqueous solutions such as ammonia and amines can be used.

The curable resin composition of the present invention is suitably used for forming a solder resist or a coverlay, particularly for forming a solder resist.

<Electronic components>
The present invention also provides an electronic component having a cured resin composition of the present invention or a cured product obtained by curing a resin layer of a dry film. By using the cured product of the curable resin composition of the present invention, an electronic component having high appearance, durability and productivity is provided. In the present invention, the electronic component means a component used in an electronic circuit, and includes active components such as printed wiring boards, transistors, light emitting diodes, and laser diodes, as well as passive components such as resistors, capacitors, inductors, and connectors. The cured product of the curable resin composition of the present invention exhibits the effect of the present invention as these insulating cured coating films.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

<1. Preparation of curable resin compositions of Examples 1 to 7 and Comparative Examples 1 to 5>
The various components shown in Examples and Comparative Examples in Table 1 below are premixed with a stirrer at the ratio (parts by mass) shown in Table 1 and then kneaded with a three-roll mill to prepare a curable resin composition. bottom. The numerical values in the table indicate parts by mass (nonvolatile content, that is, solid content conversion).

For each of the curable resin compositions, test samples were prepared as shown below, and developability, reflectance (initial value), b * value (initial value), reflectance (after UV irradiation), and UV treatment. ΔE (photochromic resistance) and openness of 250 μm were evaluated. The results are shown in Table 1.

<Synthesis example 1 of component (C-2)>
In a 2 liter separable flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen introduction tube, 900 g of diethylene glycol dimethyl ether as a solvent and t-butylperoxy-2-ethylhexanoate as a polymerization initiator (Japan). 21.4 g of perbutyl O manufactured by Yushi Co., Ltd. was added and heated to 90 ° C. After heating, 309.9 g of methacrylic acid, 116.4 g of methyl methacrylate, and 109.8 g of lactone-modified 2-hydroxyethyl methacrylate (Plaxel FM1 manufactured by Daicel Chemical Industry Co., Ltd.) were added thereto as a polymerization initiator. 4-t-Butylcyclohexyl) Peroxydicarbonate (Perloyl TCP manufactured by Nippon Oil & Fats Co., Ltd.) is added dropwise over 3 hours and aged for another 6 hours to obtain a carboxyl group-containing copolymer resin. rice field. The reaction was carried out in a nitrogen atmosphere.

Next, 363.9 g of 3,4-epoxycyclohexylmethyl acrylate (Cyclomer A200 manufactured by Daicel Chemical Co., Ltd.), 3.6 g of dimethylbenzylamine as a ring-opening catalyst, and polymerization inhibition were added to the obtained carboxyl group-containing copolymer resin. 1.80 g of hydroquinone monomethyl ether was added as an agent, heated to 100 ° C., and stirred to carry out an epoxy ring-opening addition reaction. After 16 hours, a solution containing a carboxyl group-containing resin having no aromatic ring ((C) alkali-soluble resin) having an acid value of 108.9 mgKOH / g and a weight average molecular weight of 25,000 was obtained.

<Evaluation method>
(1) Developable buff-polished (Scotch-Brite SF (equivalent to # 600) and UEF (equivalent to # 1000) double) FR-4 1.6 mm thick copper foil 18 μm thick copper-clad laminate, Examples 1 to Each of the curable resin compositions of 6 and Comparative Examples 1 to 5 was applied using an applicator and dried at 80 ° C. for 30 minutes to obtain a dry coating film having a film thickness of 20 μm. Then, it was immersed in a 1 wt% sodium carbonate aqueous solution, and the developability was evaluated according to the following criteria.

Since Example 7 does not contain an alkali-soluble resin, the developability has not been evaluated.

◯: Development time 90 seconds or more and less than 120 seconds ×: Development time 120 seconds or more −: Not evaluated

(2) Reflectance (initial value)
Examples 1 to 6 and Comparative Example 1 on a copper-clad laminate with a thickness of FR-4 1.6 mm thick copper foil 18 μm thick buffed (two series of Scotch-Brite SF (equivalent to # 600) and UEF (equivalent to # 1000)). Each of the curable resin compositions of to 5 was applied using an applicator and dried at 80 ° C. for 30 minutes to obtain a dry coating film having a film thickness of 20 μm. ^{Then, the active energy rays were irradiated with an exposure amount of 600 mJ / cm 2} through a negative mask having patterning using a metal halide lamp light source, and then immersed in a 1 wt% sodium carbonate aqueous solution. Then, the thermosetting treatment was carried out at 150 ° C. for 1 hour to obtain a substrate having a cured coating film.

The curable resin composition of Example 7 was applied to a substrate using an applicator, dried at 80 ° C. for 30 minutes, and then heat-cured at 150 ° C. for 1 hour to obtain a cured coating film. Was obtained. That is, the curable resin composition of Example 7 has not been subjected to alkaline development.

For each substrate having these cured coatings, a color difference meter (CR-400, manufactured by Konica Minolta) is used to measure the reflectance at a wavelength of 450 nm including specularly reflected light, so the material itself is measured regardless of the surface condition. It was measured by the SCI (specular reflection light included) method, which is a color evaluation. Here, the initial values are the initial values (before UV irradiation) compared with the values of (4) reflectance (after UV irradiation) and (5) UV treatment ΔE (light discoloration resistance) after UV irradiation, which will be described later. It shall mean that. The same applies to the initial value of (3) b * value described later. The evaluation criteria for reflectance (initial value) are as follows.

◯: 89% or more ×: less than 89%

(3) b * value (initial value)
Using a spectrophotometer (CM-2600d, manufactured by Konica Minolta) on the same substrate as the substrate used in the above (2) Reflectance (initial value) evaluation, CIE L * a * b * was used as the color system. (Using the standard light source D65), the measurement was performed by the SCI method. The evaluation criteria for the b * value (initial value) are as follows.

○: 1 or less ×: 2 or more

(4) Reflectance (after UV irradiation)
The same substrate as the substrate used in the above (2) reflectance (initial value) evaluation was prepared, and the surface of the cured coating film formed on the substrate was irradiated with ^{UV light of 20 J / cm 2 using a metal halide lamp as a light source.} The reflectance of the substrate after UV irradiation was measured by the same method as (2) reflectance (initial value) described above, except that the wavelength was changed to 451 nm. The evaluation criteria for reflectance (after UV irradiation) are as follows.

◯: 85% or more ×: less than 85%

(5) UV treatment ΔE (light discoloration resistance)
For the substrate of the above (4) reflectance (after UV irradiation) before and after UV irradiation, the amount of color change ΔE (ΔE * ab, color difference) from the initial value was calculated. The criteria for changing the UV treatment ΔE (photocolor change resistance) are as follows.

◯: 0.9 or less ×: 1.0 or more

(6) Example on a copper-clad laminate with a thickness of FR-4 1.6 mm thick copper foil 18 μm thick with 250 μm open buff polishing (two series of Scotch-Brite SF (equivalent to # 600) and UEF (equivalent to # 1000)). Each of the curable resin compositions of 1 to 6 and Comparative Examples 1 to 5 was applied using an applicator and dried at 80 ° C. for 30 minutes to obtain a dry coating film having a thickness of 20 μm. Then, after irradiating an active energy ray with an exposure amount of 600 mJ using a metal halide lamp light source through a negative having a pattern in which a plurality of 250 μm × 250 μm openings are formed, the film is immersed in a 1 wt% sodium carbonate aqueous solution for development. Then, it was heated at 150 ° C. for 60 minutes to perform a curing treatment. Since the curable resin composition of Example 7 cannot be alkaline-developed, this evaluation has not been performed. The evaluation criteria for the openness of 250 μm are as follows.

◯: An opening of 180 μm or more and less than 210 μm could be formed ×: An opening of less than 180 μm was formed −: Not evaluated

* 1: Pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (vapor pressure: 1.3 × 10E-10 Pa (20 ° C.)) (Irganox1010: BASF Japan Ltd. Made)
* 2: Ethylene bis (oxyethylene) bis- (3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate) (vapor pressure: 4.0 x 10E-8 Pa (20 ° C)) (Irganox245 : Made by BASF Japan)
* 3: Hexamethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (vapor pressure: 1.3 × 10E-8 Pa (20 ° C.)) (Irganox259: BASF Japan Ltd. Made)
* 4: 1,3,5-Tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (vapor pressure: 7.0 × 10E-13 Pa (20 ° C)) (Irganox3114: manufactured by BASF Japan Ltd.)
* 5: 2,4,6-tris (3', 5'-di-tert-butyl-4'-hydroxybenzyl) mesitylene (vapor pressure: 2.0 × 10E-11 Pa (20 ° C.)) (Irganox 1330: Made by BASF Japan)
* 6: Octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamate (vapor pressure: 1.5 × 10E-3 Pa (25 ° C)) (Irganox1135: manufactured by BASF Japan Ltd.)
* 7: Isocyanurate type epoxy resin (TEPIC-VL: manufactured by Nissan Chemical Industries, Ltd.)
* 8: Alicyclic epoxy resin (Ceroxide 2021P: manufactured by Daicel)
* 9: Carboxyl group-containing fluororesin (acid value 130 mgKOH / g) (TIF-3: manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 10: Carbosil group-containing copolymer (photosensitive) resin of Synthesis Example 1
* 11: 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Omnirad TPO H: manufactured by IGM Resins)
* 12: Bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Omnirad 819: manufactured by IGM Resins)
* 13: Ethoxylated isocyanuric acid triacrylate (A-9300YN: manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 14: Aliphatic bifunctional acrylate (A-DOD-N: manufactured by Shin-Nakamura Chemical Co., Ltd.)
* 15: Rutile type titanium oxide (PX-3788: manufactured by Sakai Chemical Industry Co., Ltd.)
* 16: Fine silica (Nippil (registered trademark) E-743: manufactured by Tosoh Silica)
* 17: Fine silica (AEROSIL (registered trademark) R974: manufactured by Aerosil Japan Co., Ltd.)

Compared with the curable resin compositions of Comparative Examples 1 to 5, the curable resin compositions of Examples 1 to 7 can prevent yellowing during thermosetting and can also suppress yellowing due to ultraviolet irradiation. It turns out that you can get things. In particular, (A1) a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having an isocyanurate structure and a ^{vapor pressure of 1.0 × 10-7 Pa or less at 20 ° C.} If both were not included, the above effect could not be obtained.

Further, according to the curable resin compositions of Examples 1 to 6, a curable resin composition exhibiting good alkali developability while exhibiting the effect of suppressing / preventing yellowing during the above-mentioned thermosetting and irradiation with ultraviolet rays can be obtained. It turned out to be.

Claims (7)

A curable resin composition containing (A) a hindered phenolic antioxidant and (B) a thermosetting component.
(A) Hindered phenolic antioxidant
(A1) A hindered phenolic antioxidant having an ester skeleton and a vapor pressure of 1.0 × ^{10-7 Pa or less at 20 ° C.}
(A2) A hindered phenolic antioxidant having an isocyanurate structure and
A curable resin composition comprising at least. Moreover,
(C) Alkali-soluble resin and
The curable resin composition according to claim 1, further comprising (D) a photopolymerization initiator. The curable resin composition according to claim 2, wherein the alkali-soluble resin (C) contains a carboxyl group-containing fluororesin. (A1) Formulation of a hindered phenolic antioxidant having an ester skeleton and (A2) a hindered phenolic antioxidant having an ester skeleton and a vapor pressure of 20 ° C. of 1.0 × ^{10-7 Pa or less.} The amount is 0.1 parts by mass or more and 5.0 parts by mass or less, respectively, with respect to 100 parts by mass of the total of (B) thermosetting component and (C) alkali-soluble resin in terms of solid content. The curable resin composition according to claim 2 or 3. A dry film comprising the curable resin composition according to any one of claims 1 to 4 as a resin layer. The curable resin composition according to any one of claims 1 to 4, or a cured product obtained by curing the resin layer of the dry film according to claim 5. An electronic component having the cured product according to claim 6.