JP2020052362A - Production method of cured product, photosensitive resin composition used for the same, dry film, cured product and electronic component - Google Patents

Abstract

To provide a production method of a cured product having excellent resolution and excellent adhesiveness regardless of types of IC packages or substrates.SOLUTION: The production method of a cured product includes: a step of exposing a photosensitive resin composition comprising (A) an alkali-soluble resin, (B) an epoxy resin, (C) a compound having an acryloyl group, (D) a photopolymerization initiator, (E) an inorganic filler, and (F) a thermosetting catalyst to active energy rays; a step of developing the photosensitive resin composition after exposed with an alkaline aqueous solution; and a step of heating to cure the photosensitive composition after developed. The method is characterized in that a reaction rate of acryloyl groups in the photosensitive resin composition after the exposure and before the development with respect to the whole unreacted acryloyl groups in the composition before the exposure is 10% or more and 40% or less and that a reaction rate of epoxy groups in the photosensitive resin composition after the exposure and before the development with respect to the whole epoxy groups in the composition before the exposure is 0.5% or more and 10% or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a cured product, a photosensitive resin composition used therefor, a dry film, a cured product, and an electronic component.

  In the manufacture of printed wiring boards, a photosensitive resin composition is generally used for forming a permanent film such as a solder resist, and a dry film or a liquid composition using such a photosensitive resin composition has been developed. I have. Among these, alkali development type photosensitive resin compositions using a dilute alkaline aqueous solution as a developing solution have become mainstream in consideration of environmental problems, and several composition systems have been proposed in the past.

On the other hand, in recent years, with the rapid progress of semiconductor components, electronic devices tend to be lighter and thinner, have higher performance, and have more functions. Following this trend, miniaturization, thinning, and increasing the number of pins of semiconductor packages have been put to practical use.
Specifically, instead of IC packages called QFP (Quad Flat Pack Package) and SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip Scale Package), etc. An IC package called “IC package” is used. In recent years, FC-BGA (flip chip ball grid array) has been put to practical use as an IC package with a higher density. In a printed wiring board (also called a package substrate) used for such an IC package, a circuit pattern tends to be miniaturized (made into a fine pattern).

In response to the miniaturization and thinning of these packages, high resolution and adhesion are required for permanent coatings such as solder resists used for their production.
Of the above, package substrates and the like for FC-BGA applications are extremely advanced especially for use as electronic components (semiconductor packages, modules, sensors, etc.) for PCs, servers, and vehicles. Reliability is required, and demand for high resolution is increasing.
Further, in application to a wafer level package (WLP) or the like, a substrate such as silicon or glass is often used, and it is difficult to obtain an anchor effect because the roughness of the substrate surface is small. That is, it is necessary to further improve the adhesion while further improving the resolution.

  Conventionally, as a technique for obtaining a resist pattern excellent in developability, for example, Patent Document 1 proposes increasing the reaction rate of a compound having an ethylenic double bond by exposure.

WO 2015/178462

  However, in the case of controlling the reaction rate of a compound having an ethylenic double bond as in the prior art, resolution and adhesion to a substrate may not yet be sufficiently obtained.

  Accordingly, an object of the present invention is to provide a method for producing a cured product having excellent resolution and excellent adhesion regardless of the type of substrate, a photosensitive resin composition used in the method, a dry film, and a cured product. And electronic components.

  The present inventors have achieved the above object of the present invention by (A) an alkali-soluble resin, (B) an epoxy resin, (C) a compound having an acryloyl group, (D) a photopolymerization initiator, (E) an inorganic filler, and (F) a step of exposing the photosensitive resin layer containing the thermosetting catalyst to active energy rays, a step of developing the exposed photosensitive resin layer with an aqueous alkali solution, and heating and curing the developed photosensitive resin layer. A method for producing a cured product, comprising: a reaction rate of acryloyl groups after the exposure and before the development with respect to all unreacted acryloyl groups in the photosensitive resin layer before the exposure, which is 10% or more and 40% or more. %, And the reaction rate of the epoxy group after the exposure and before the development with respect to all the epoxy groups in the photosensitive resin layer before the exposure is 0.5% or more and 10% or less. Of cured product It found to be achieved by the method.

  In the production method of the present invention, it is preferable to use, as the epoxy resin (B), a resin having three or more epoxy groups in one molecule.

  In the production method of the present invention, it is preferable to use the compound (C) having an acryloyl group in a proportion of 20% by mass or less based on the total mass of the solid content of the photosensitive resin layer.

  The above object of the present invention is achieved by a photosensitive resin composition used in the production method of the present invention, and a dry film having a photosensitive resin layer.

  Further, the object of the present invention is attained by a cured product obtained by the above-mentioned production method and an electronic component characterized by including these cured products.

  According to the present invention, a method for producing a cured product having excellent resolution and excellent adhesion regardless of the type of substrate, a photosensitive resin composition used for the method, a dry film, and a cured product thereof , And electronic components can be provided.

  The method for producing a cured product of the present invention comprises (A) an alkali-soluble resin, (B) an epoxy resin, (C) a compound having an acryloyl group, (D) a photopolymerization initiator, (E) an inorganic filler, and (F) A step of exposing the photosensitive resin layer containing the thermosetting catalyst to active energy rays, a step of developing the exposed photosensitive resin layer with an aqueous alkali solution, and a step of heat-curing the developed photosensitive resin layer. A method for producing a cured product, wherein a reaction rate of the acryloyl groups before the development after the exposure to all unreacted acryloyl groups in the photosensitive resin layer before the exposure is 10% or more and 40% or less. And a reaction rate of the epoxy group after the exposure and before the development with respect to all the epoxy groups in the photosensitive resin layer before the exposure is 0.5% or more and 10% or less.

(Preparation process of photosensitive resin composition, formation process of photosensitive resin layer)
In the production method of the present invention, first, the components (A) to (F) and other components are mixed and kneaded, dispersed, diluted, and the like to prepare a photosensitive resin composition. The obtained resin composition may be used in the form of a dry film or may be used in the form of a liquid. When the resin composition is used in the form of a liquid, it may be one-part or two-part or more.
In the case of a dry film, the obtained resin composition is adjusted to an appropriate viscosity such as 0.1 to 200 Ps (25 ° C.) and then uniformly spread on a carrier film by a comma coater, a blade coater, a lip coater or the like. Apply to a suitable thickness. The resin composition coated on the carrier film in this manner is dried at a temperature of 60 ° C. to 130 ° C. for about 10 minutes to 30 minutes by a hot-air circulating drying furnace or the like to obtain a photosensitive resin having a film thickness of about 5 μm to 50 μm. Form a layer.
The photosensitive resin layer thus obtained is generally laminated on a substrate using a conventional vacuum laminator or the like, and is subjected to smoothing and pressing.
The preparation, application, drying, etc. of the above-mentioned photosensitive resin composition are carried out by a known and commonly used method, and are not limited to the above-mentioned method and apparatus used, and can be appropriately changed and selected.

(Exposure process)
In the production method of the present invention, the reaction rate of the acryloyl group contained in the entire photosensitive resin layer after the exposure and before the development is changed, instead of suddenly exposing the photosensitive resin layer to cure the resin layer at once. 10% or more and 40% or less, preferably 15% or more and 30% or less, and the reaction rate of epoxy groups contained in the entire photosensitive resin layer after exposure and before development is 0.5% or more and 10% or less, preferably 0% or less. Exposure is performed while controlling the amount of exposure, the exposure time, and the like so as to be in the range of 0.5% to 5%.
Exposure is performed by using a commercially available high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, mercury short arc lamp, and an exposure machine equipped with an LED. , the resin layer, the entire surface is exposed through a photomask so that the light quantity ^{50J / cm 2 ~1000J / cm 2} . Note that direct exposure may be performed in a desired image shape.
For example, by using a direct exposure apparatus Di IMPACT Mms60 manufactured by Oak Co., Ltd. (using a cut filter of 355 nm or less), a 41-step step tablet is used to perform exposure at an exposure amount of 8 to 12 steps, thereby obtaining a photosensitive resin having the above reaction rate. Get the layers.

The type of the exposure machine used is not particularly limited as long as it can be adjusted so as to obtain the above reaction rate.
The reaction rate of the acryloyl group and the epoxy group in the photosensitive resin layer is measured and evaluated by the following method.

[Evaluation of reactivity]
Here, the evaluation of the reactivity of the present invention will be described.
First, a photosensitive resin layer of a dry film that has not been exposed (unexposed sample) and a photosensitive resin layer that has been exposed and left for at least 10 minutes (a sample to be evaluated for reaction rate) are prepared.
The acryloyl group and epoxy group abundance in both the unexposed sample (reference) and the exposed sample (reaction rate evaluation sample) are measured, and the reaction rate of the acryloyl group and epoxy group is determined from the comparison.
In the present invention, the peaks of an unexposed sample (reference) and a sample after exposure (a sample to be evaluated for reaction rate) are measured using infrared spectroscopy, particularly using a Fourier transform infrared spectrometer (FT-IR device). Is compared.

Specifically, an unexposed sample (reference) and an exposed sample (reaction rate evaluation target sample) are sequentially set in an FT-IR apparatus, and respective IR absorption spectra are obtained. From both spectra, the peak of the acryloyl group (peak top: 1350-1450 cm ^-1 ), the peak of the epoxy group (peak top: 850-950 cm ^-1 ), and the peak of the inorganic filler used (for example, when silica is used, peak top 800-1200Cm ^-1, the peak top) of 500-800Cm ^-1 if barium sulfate to obtain the respective peak intensity (peak height).

The reaction rate of the acryloyl group in the photosensitive resin layer can be determined by the following equations (1) to (3).
Intensity ratio of peak of acryloyl group in unexposed sample (C0 _Acr ):
C0 _Acr = A0 / R0. . . . . . (1)
In the above formula,
R0: peak intensity (Abs: absorbance) of the inorganic filler of the unexposed sample,
A0: Peak intensity of acryloyl group of unexposed sample (Abs)
Intensity ratio of peak of acryloyl group in sample after exposure (C1 _Acr ):
C1 _Acr = A1 / R1. . . . . . (2)
In the above formula,
R1: peak intensity (Abs) of the inorganic filler of the sample after exposure,
A1: Peak intensity of acryloyl group of sample after exposure (Abs)

Acryloyl group reaction rate (%) = [1-C1 _Acr / C0 _Acr )] × 100. . (3)

Similarly, the reaction rate of the epoxy group of the photosensitive resin layer can be determined by the following equations (4) to (6).
Intensity ratio of peak of epoxy group in unexposed sample (C0 _Epo ):
C0 _Epo = E0 / R0. . . . . . (4)
In the above formula,
R0: peak intensity (Abs) of the inorganic filler of the unexposed sample,
E0: peak intensity of the epoxy group of the unexposed sample (Abs)
Intensity ratio of peak of epoxy group in sample after exposure (C1 _Epo ):
C1 _Epo = E1 / R1. . . . . . (5)
In the above formula,
R1: peak intensity (Abs) of the inorganic filler of the sample after exposure,
E1: Peak intensity of the epoxy group of the sample after exposure (Abs)

Reaction rate (%) of epoxy group = [1- (C1 _Epo / C0 _Epo )] × 100. . (6)

(Development process and heat curing process)
Subsequent to the above-described exposure, development and heat curing are performed.
In the manufacturing method of the present invention, a pattern (pattern film) of the photosensitive resin layer is formed by developing the exposed photosensitive resin layer with a diluted alkaline aqueous solution (for example, a 0.3 to 3% by mass aqueous sodium carbonate solution). As a developing method, a dipping method, a shower method, a spray method, a brush method, or the like can be used. As a developing solution, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia And aqueous solutions of alkalis such as amines.
Furthermore, the photosensitive resin layer after development is irradiated with active energy rays and then cured by heating (for example, 100 to 220 ° C.), or irradiated with active energy rays after being cured, or finally cured only by heat curing (final curing). ) To form a cured pattern film having excellent properties such as adhesion and hardness.
Here, when the active energy ray irradiation is performed after the development and before the heat curing, the reaction rate of the acryloyl group contained in the entire photosensitive resin layer before the heat curing may be more than 40% and 90% or less. More preferably, it is set to 60% or more and 90% or less. Further, the reaction rate of the epoxy group is preferably more than 10% and 50% or less, more preferably 30% or more and 50% or less.

  In the production method of the present invention, when a liquid photosensitive resin composition is used, it is adjusted to a viscosity suitable for a coating method using the above-mentioned organic solvent, and a dip coating method and a flow coating method are applied on a substrate. After applying by a method such as a roll coating method, a bar coater method, a screen printing method, a curtain coating method, a spin coating method, etc., the organic solvent contained in the composition is volatilized and dried (temporary drying) at a temperature of 60 to 100 ° C. By doing so, a tack-free photosensitive resin layer (also referred to as a dry coating film) is formed. Thereafter, processes such as exposure, development, and heat curing are performed in the same manner as described above.

  Examples of the substrate (support) include a printed wiring board and a flexible printed wiring board in which a circuit is formed in advance using copper or the like, paper phenol, paper epoxy, glass cloth epoxy, glass polyimide, glass cloth / non-woven cloth epoxy, glass cloth. / Paper epoxy, synthetic fiber epoxy, materials such as copper-clad laminates for high frequency circuits using fluororesin, polyethylene, polyphenylene ether, polyphenylene oxide, cyanate, etc., of all grades (FR-4 etc.) Examples include a copper-clad laminate, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, and a wafer plate. The circuit may be pre-treated. For example, the circuit may be pre-treated with GliCAP manufactured by Shikoku Chemicals, New Organic AP (Adhesion promoter) manufactured by Mec, Nova Bond manufactured by Atotech Japan, or the like. The adhesion to a cured film such as a resist may be improved, or a pre-treatment with a rust inhibitor may be performed.

As is clear from the above description, in the production method of the present invention, not only (B) epoxy resin and (C) acryloyl group-containing compound but also (A) When the alkali-soluble resin and other components include an acryloyl group and an epoxy group, the reaction rate of all acryloyl groups and all epoxy groups in the photosensitive resin layer is set to 10% or more and 40%, respectively, in consideration of these. Hereinafter, it is set to 0.5% or more and 10% or less.
By controlling the reaction rate of the acryloyl group within the above range after the exposure and before the development, the development resistance can be obtained to a deep portion without causing halation at the time of exposure, and good patterning without development residue can be achieved. Furthermore, in the production method of the present invention, since the reaction rate of the acryloyl group is within the above range, surface curability can be exhibited, and thus the surface of the photosensitive resin layer is damaged by a transport roll of a developing machine or a developer. Not even. When the reaction rate of the epoxy group is in the above range, generation of a development residue is suppressed and the resolution is excellent, and the adhesion to the substrate and the electrical insulation reliability (B-HAST resistance) are also excellent.

Further, according to the production method of the present invention, a cured film having a smooth surface such as silicone or glass and having extremely good adhesion to a substrate on which an anchor effect is difficult to be obtained can be obtained.
Needless to say, the manufacturing method of the present invention can be used not only for a printed wiring board having a small circuit surface roughness, but also for a printed wiring board having a large circuit surface roughness.

  Hereinafter, each component of the photosensitive resin composition used in the production method of the present invention will be described. In this specification, the term “(meth) acrylate” is a general term for acrylate, methacrylate and mixtures thereof, and the same applies to other similar expressions.

[(A) Alkali-soluble resin]
(A) Examples of the alkali-soluble resin include a compound having two or more phenolic hydroxyl groups, a carboxyl group-containing resin, a compound having a phenolic hydroxyl group and a carboxyl group, and a compound having two or more thiol groups. Above all, it is preferable that the alkali-soluble resin is a carboxyl group-containing resin or a phenol resin because the adhesion to the base is improved. In particular, the alkali-soluble resin is more preferably a carboxyl group-containing resin because of excellent developability. The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group or a carboxyl group-containing resin having no ethylenically unsaturated group.

  Specific examples of the carboxyl group-containing resin include the compounds listed below (which may be oligomers or polymers).

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

(2) Diisocyanates such as aliphatic diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate; and carboxyl group-containing dialcohol compounds such as dimethylolpropionic acid and dimethylolbutanoic acid; and polycarbonate-based polyols and polyether-based compounds. A carboxyl group-containing urethane resin obtained by a polyaddition reaction of a diol compound such as a polyol, a polyester polyol, a polyolefin polyol, an acrylic 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 diisocyanate, branched aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate, and polycarbonate polyol, polyether polyol, polyester polyol, polyolefin polyol, acrylic polyol, bisphenol A A terminal carboxyl group-containing urethane resin obtained by reacting an acid anhydride with a terminal of a urethane resin by a polyaddition 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 a 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, bixylenol type epoxy resin, biphenol type epoxy resin, etc. (Meth) acrylate or a partial acid anhydride modified product thereof, a carboxyl group-containing urethane resin obtained by a polyaddition reaction of a carboxyl group-containing dialcohol compound and a diol compound.

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

  (6) During the synthesis of the resin (2) or (4), one isocyanate group and one or more (meth) acryloyl groups in a molecule such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate. Carboxyl group-containing urethane resin having terminal (meth) acrylated by adding a compound having the same.

  (7) A carboxyl group obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin and adding a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride to a hydroxyl group present in a side chain. Containing resin.

  (8) A carboxyl group-containing resin obtained by reacting (meth) acrylic acid with a polyfunctional epoxy resin obtained by further epoxidizing hydroxyl groups of a bifunctional epoxy resin with epichlorohydrin and adding a dibasic acid anhydride to the resulting hydroxyl groups. .

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

  (10) 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 is reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product. Carboxyl group-containing resin obtained by reacting a product with a polybasic acid anhydride.

  (11) 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 is reacted with an unsaturated group-containing monocarboxylic acid to obtain a reaction product. A carboxyl group-containing resin obtained by reacting a reaction product with a polybasic acid anhydride.

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

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

  It is preferable to include at least one of the carboxyl group-containing resins described in (7), (8), (10), (11), and (13) among the carboxyl group-containing resins. From the viewpoint of further improving insulation reliability, it is preferable to include the carboxyl group-containing resin described in the above (10) and (11).

  As the compound having a phenolic hydroxyl group, for example, a compound having a biphenyl skeleton or a phenylene skeleton or both skeletons, phenol, orthocresol, paracresol, metacresol, 2,3-xylenol, 2,4-xylenol, , 5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, catechol, resorcinol, hydroquinone, methylhydroquinone, 2,6-dimethylhydroquinone, trimethylhydroquinone, pyrogallol, phloroglucinol, etc. And phenolic resins having various skeletons.

  Examples of the compound having a phenolic hydroxyl group include phenol novolak resin, alkylphenol volak resin, bisphenol A novolak resin, dicyclopentadiene-type phenol resin, Xylok-type phenol resin, terpene-modified phenol resin, polyvinylphenols, and bisphenol F And phenol resins known in the art such as bisphenol S-type phenol resins, poly-p-hydroxystyrene, condensates of naphthol and aldehydes, and condensates of dihydroxynaphthalene and aldehydes.

  Commercially available phenolic resins include, for example, HF1H60 (manufactured by Meiwa Kasei Co., Ltd.), phenolite TD-2090, phenolite TD-2131 (manufactured by Dai Nippon Printing Co., Ltd.), Vesmall CZ-256-A (manufactured by DIC), and Shonool BRG-555, SHYONORU BRG-556 (manufactured by Showa Denko KK), CGR-951 (manufactured by Maruzen Sekiyu KK), and polyvinyl phenol CST70, CST90, S-1P, S-2P (manufactured by Maruzen Sekiyu KK).

  (A) The acid value of the alkali-soluble resin is suitably in the range of 40 to 200 mgKOH / g, and more preferably in the range of 45 to 120 mgKOH / g. When the acid value of the alkali-soluble resin is 40 mgKOH / g or more, alkali development becomes easy, and on the other hand, a normal cured product pattern of 200 mgKOH / g or less is easily drawn, which is preferable.

  (A) The weight average molecular weight of the alkali-soluble resin varies depending on the resin skeleton, but is preferably in the range of 1,500 to 150,000, more preferably 1,500 to 100,000. When the weight average molecular weight is 1,500 or more, tack-free performance is good, the moisture resistance of the coating film after exposure is good, film loss during development can be suppressed, and a decrease in resolution 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 excellent.

  (A) The alkali-soluble resin can be used alone or in combination of two or more.

[(B) epoxy resin]
The photosensitive resin composition of the present invention contains (B) an epoxy resin. As long as the effects of the present invention are not impaired, examples of other thermosetting resins may include an oxetane compound, a melamine resin, a silicone resin, and the like.

  As the epoxy resin (B), a known compound having one or more epoxy groups can be used, and examples thereof include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, and glycidyl (meth) acrylate. In addition to monoepoxy compounds (monofunctional epoxy compounds), bifunctional epoxy compounds such as neopentyl glycol diglycidyl ether and 1,6-hexanediol diglycidyl ether, and polyglycerol triglycidyl ether, sorbitol polyglycidyl ether, and pentaerythritol Examples include trifunctional epoxy compounds such as polyglycidyl ether.

  Further, bisphenols such as t-butylphenol type epoxy resin and other monophenol type epoxy resins, bisphenol A type epoxy resins, hydrogenated bisphenol A type epoxy resins, bisphenol S type epoxy resins, bisphenol F type epoxy resins, and bisphenol AP type epoxy resins Epoxy resin, novolak epoxy resin such as phenol novolak epoxy resin, cresol novolak epoxy resin, amino group-containing epoxy resin such as aminophenol epoxy resin, diphenyldiaminomethane epoxy resin, and trisphenol Aromatic group-containing epoxy resin such as methane type epoxy resin, cyclopentadiene type epoxy resin, dicyclopentadiene type epoxy resin, epoxy resin having cyclohexane skeleton Alicyclic epoxy resins such as alicyclic polyhydric alcohol polyglycidyl ether, trimethylolpropane polyglycidyl ether, phenyl-1,3-diglycidyl ether, biphenyl-4,4'-diglycidyl ether, 1,6- In one molecule of hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2,3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, etc. A compound having two or more epoxy groups (polyfunctional epoxy compound) can be used. These can be used alone or in combination of two or more in accordance with desired properties.

  Specific examples of the compound having two or more epoxy groups include jER828, jER834, jER1001, jER1004 manufactured by Mitsubishi Chemical Corporation, Epicron 840, Epicron 850, Epicron 1050, Epicron 2055 manufactured by DIC, and Nippon Steel & Sumitomo Metal Corporation. Epotototes YD-011, YD-013, YD-127, YD-128 manufactured by Dow Chemical Japan Co., Ltd. E. FIG. R. 317, D.E. E. FIG. R. 331; E. FIG. R. 661, D.C. E. FIG. R. 664, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESA-011, ESA-014, ELA-115, ELA-128, Asahi Kasei E-materials A. E. FIG. R. 330, A.I. E. FIG. R. 331, A.I. E. FIG. R. 661, A.I. E. FIG. R. Bisphenol A type epoxy resin such as 664; Mitsubishi Chemical Corporation's jERYL903, DIC's Epicron 152 and Epicron 165, Nippon Steel & Sumitomo Chemical's Epototh YDB-400, YDB-500, Dow Chemical Japan's D.C. E. FIG. R. 542, Sumi-Epoxy ESB-400 and ESB-700 manufactured by Sumitomo Chemical Co., Ltd., A.E. E. FIG. R. 711, A.I. E. FIG. R. Brominated epoxy resin such as 714; jER152 and jER154 manufactured by Mitsubishi Chemical Corporation, and D.C. E. FIG. N. 431; E. FIG. N. 438, DIC Epicron N-730, Epicron N-770, Epicron N-865, Nippon Steel & Sumitomo Chemical's Epototo YDCN-701, YDCN-704, Nippon Kayaku's EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, NC-3000, Sumitomo Chemical Co., Ltd. Sumi-Epoxy ESCN-195X, ESCN-220, Asahi Kasei E-materials A.M. E. FIG. R. ECN-235, ECN-299, YDCN-700-2, YDCN-700-3, YDCN-700-5, YDCN-700-7, YDCN-700-10, YDCN-704 YDCN-704A manufactured by Nippon Steel & Sumitomo Metal Corporation Novolac epoxy resins such as Epicron N-680, N-690, and N-695 (trade names) manufactured by DIC Corporation; Epicron 830 manufactured by DIC Corporation, jER807 manufactured by Mitsubishi Chemical Corporation, and Epototo manufactured by Nippon Steel & Sumitomo Metal Corporation Bisphenol F type epoxy resin such as YDF-170, YDF-175, YDF-2004; hydrogenated bisphenol A type epoxy resin such as Epototo ST-2004, ST-2007, ST-3000 manufactured by Nippon Steel & Sumikin Chemical; Mitsubishi Chemical Corporation JER604, Nippon Steel & Sumitomo Chemical's Epototo YH-4 4; Glycidylamine type epoxy resin such as Sumitomo Chemical Co., Ltd. Sumi-Epoxy ELM-120; Aminophenol type epoxy resin such as jER630 manufactured by Mitsubishi Chemical Corporation; Hydantoin type epoxy resin; Alicyclic ring such as Celloxide 2021 manufactured by Daicel Corporation Formula epoxy resin: YL-933 manufactured by Mitsubishi Chemical Corporation, T.D. E. FIG. N. , EPPN-501, EPPN-502 and the like; trihydroxyphenylmethane type epoxy resins such as YL-6056, YX-4000 and YL-6121 manufactured by Mitsubishi Chemical Corporation or a mixture thereof; Japan Bisphenol S type epoxy resin such as EBPS-200 manufactured by Kayaku Co., EPX-30 manufactured by ADEKA, EXA-1514 manufactured by DIC; bisphenol A novolak type epoxy resin such as jER157S manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation tetraphenylolethane-type epoxy resin such as jERYL-931; heterocyclic epoxy resin such as TEPIC manufactured by Nissan Chemical Co .; diglycidyl phthalate resin such as Blenmer DGT manufactured by Nissan Chemical; ZX-1063 manufactured by NSSMC Tetraglycidyloxy Noylethane resin; Naphthalene group-containing epoxy resin such as ESN-190 and ESN-360 manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., HP-7241, HP-4032, EXA-4750, EXA-4700 manufactured by DIC Corporation; HP-7200 manufactured by DIC And epoxy resins having a dicyclopentadiene skeleton such as HP-7200H; glycidyl methacrylate copolymer-based epoxy resins such as NOF CP-50S and CP-50M; and copolymerized epoxy resins of cyclohexylmaleimide and glycidyl methacrylate; CTBN-modified epoxy resin (for example, YR-102, YR-450, etc., manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.); dicyclopentadiene-type epoxy resin such as EP-4088L manufactured by ADEKA Corporation, etc., manufactured by Showa Denko KK PETG, etc. It includes aliphatic epoxy resins.

  In addition, epoxidized vegetable oil; hydroquinone type epoxy resin; thioether type epoxy resin; triphenylmethane type epoxy resin; epoxy resin having a silsesquioxane skeleton; glycidyl (meth) acrylate copolymerized epoxy resin; cyclohexylmaleimide and glycidyl ( A copolymerized epoxy resin of meth) acrylate; an epoxy-modified polybutadiene rubber derivative or the like can also be used.

The epoxy compound used in the present invention may be either solid or liquid at room temperature (25 ° C.), but it is trifunctional or more (having three or more epoxy groups in one molecule). It is preferable to use an epoxy resin that is trifunctional or more and has an ultraviolet transmittance of 80% or more, particularly 90% or more.
In the present invention, the ultraviolet transmittance was obtained by dissolving the epoxy compound to be measured in PMA (1,2-propanediol 1-monomethyl ether 2-acetate) at a ratio of 50% by mass. It refers to the transmittance of the epoxy solution when irradiated with ultraviolet light (UV) (center wavelength: 365 nm).
In the measurement of the above-mentioned ultraviolet transmittance, in the present invention, a 10-mm quartz cell containing a sample is set in a UV-visible-near-red spectrophotometer (JASCO, JA-670). In addition, the baseline was implemented by PMA.

  Examples of epoxy resins having three or more functions and having an ultraviolet transmittance of 80% or more include JER604 (diphenyldiaminomethane type epoxy resin) and JER630 (aminophenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and Nissan Chemical Industries, Ltd. TEPIC-PAS, TEPIC-VL, TEPIC-FL, TEPIC-UC (triazine ring-containing epoxy resin), Showa Denko's PETG (polyfunctional aliphatic epoxy resin), Showa Denko's BATG, Printec's BATG VG-3101, VG-3101M80, NC-6000 manufactured by Nippon Kayaku Co., Ltd., NC-6300 (polyfunctional aromatic epoxy resin) and the like.

Further, from the viewpoint of tack-drying property, it is preferable not to include a bifunctional or monofunctional epoxy resin, but it may be included within a range that does not impair the effects of the present invention. For example, even if a bifunctional epoxy resin having an ultraviolet transmittance of 80% or more (EP-4088S, L manufactured by ADEKA Corporation) is contained in a proportion of 30% by mass or less based on the total solid content of the epoxy resin (B). Good.
One of the above epoxy resins may be used alone, or two or more thereof may be used in combination.

The compounding amount of the epoxy resin (B) is, for example, 10 to 100 parts by mass, preferably 20 to 80 parts by mass, per 100 parts by mass of the alkali-soluble resin (A).

[(C) Compound having an acryloyl group]
In the photosensitive resin composition of the present invention, as the compound having an acryloyl group (C), a compound having one or more (C) acryloyl groups in a molecule is used. (C) As the compound having an acryloyl group, a (meth) acrylate oligomer or the like, which is a known and commonly used compound having an ethylenically unsaturated group, can be used. The compound having an acryloyl group (C) does not include the alkali-soluble resin (A) having an acryloyl group and the surface-treated (E) inorganic filler having a curable reactive group.

  Examples of the (meth) acrylate oligomer include epoxy (meth) acrylates such as phenol novolak epoxy (meth) acrylate, cresol novolak epoxy (meth) acrylate, and bisphenol-type epoxy (meth) acrylate, urethane (meth) acrylate, and epoxy urethane (meth). A) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.

  In addition, (meth) acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymethylacrylamide, N-ethoxymethylacrylamide, and N-butoxymethylacrylamide; 2-ethylhexyl (meth) ) Esters of (meth) acrylic acid such as acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate; hydroxyethyl ( Hydroxyalkyl (meth) acrylates such as (meth) acrylate, hydroxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate Alkoxyalkylene glycol mono (meth) acrylates such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate A) alkylene polyol poly (meth) acrylates such as acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate; Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylated Polyoxyalkylene glycol poly (meth) acrylates such as methylolpropane tri (meth) acrylate; poly (meth) acrylates such as neopentyl glycol ester hydroxypivalate di (meth) acrylate; tris [(meth) acryloxyethyl] And isocyanurate-type poly (meth) acrylates such as isocyanurate. These can be used alone or in combination of two or more according to required characteristics.

(C) The compounding amount of the compound having an acryloyl group is preferably 20% by mass or less, more preferably 1% by mass to 18% by mass, based on the photosensitive resin composition. By setting the amount of the compound (C) having an acryloyl group in the above range, the amount of unreacted components can be minimized while the curability of the photosensitive resin layer is maintained.
Further, even when the blending amount of the (C) acryloyl group is set to 20% by mass or less based on the photosensitive resin layer, the photosensitive resin layer can be formed by using (B) an epoxy resin having an ultraviolet transmittance of 80% or more as the epoxy resin. Has excellent curability, high sensitivity and excellent development resistance.

[(D) Photopolymerization initiator]
As the photopolymerization initiator, any photopolymerization initiator known as a photopolymerization initiator or a photoradical generator can be used.
(D) Examples of the photopolymerization initiator include bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, 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) -phenylphosphineoxo Bisacylphosphine oxides such as amides; 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylphosphinic acid methyl ester, 2-methyl Monoacylphosphine oxides such as benzoyldiphenylphosphine oxide, pivaloylphenylphosphinic acid isopropyl ester, and 2,4,6-trimethylbenzoyldiphenylphosphine oxide); 1-hydroxy-cyclohexylphenyl ketone, 1- [4 -(2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methyl-pro Onyl) -benzyl] phenyl} -2-methyl-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like; hydroxyacetophenones; benzoin, benzyl, benzoin methyl ether, benzoin ethyl Benzoins such as ether, benzoin n-propyl ether, benzoin isopropyl ether and benzoin n-butyl ether; benzoin alkyl ethers; benzophenone, p-methylbenzophenone, Michler's ketone, methylbenzophenone, 4,4′-dichlorobenzophenone, 4,4 ′ Benzophenones such as -bisdiethylaminobenzophenone; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1- Chloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 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. Acetophenones; thioxanthones such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; anthraquinone, chloroanthraquinone , Anthraquinones such as -methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone and 2-aminoanthraquinone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; ethyl-4 Benzoic acid esters such as -dimethylaminobenzoate, 2- (dimethylamino) ethylbenzoate and ethyl p-dimethylbenzoate; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O- Oxime esters such as benzoyl oxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); -2,4-cyclopentadiene -1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, bis (cyclopentadienyl) -bis [2,6-difluoro-3- (2- Titanocenes such as (1-pyr-1-yl) ethyl) phenyl] titanium; and phenyldisulfide 2-nitrofluorene, butyroin, anisoinethyl ether, azobisisobutyronitrile, tetramethylthiuram disulfide, and the like. . One photopolymerization initiator may be used alone, or two or more photopolymerization initiators may be used in combination.

  The amount of the photopolymerization initiator (D) is preferably 0.5 to 20 parts by mass based on 100 parts by mass of the alkali-soluble resin (A). When the amount is 0.5 parts by mass or more, the surface curability becomes good, and when the amount is 20 parts by mass or less, halation hardly occurs and good resolution is obtained.

[(E) Inorganic filler]
(E) The inorganic filler is not particularly limited, and known inorganic fillers such as silica, crystalline silica, Neuburg silicate, aluminum hydroxide, glass powder, talc, clay, magnesium carbonate, calcium carbonate, natural mica, and synthetic mica. Inorganic fillers such as mica, aluminum hydroxide, barium sulfate, barium titanate, iron oxide, non-fibrous glass, hydrotalcite, mineral wool, aluminum silicate, calcium silicate, and zinc white can be used. Among them, silica is preferable because it has a small specific gravity and can be highly filled in a cured product and can easily be made high in strength.

  (E) The inorganic filler is preferably a surface-treated inorganic filler (also referred to as “surface-treated inorganic filler”), and has been subjected to a surface treatment capable of introducing a curable reactive group to the surface of the inorganic filler. Is more preferred. Here, the curable reactive group is not particularly limited as long as it is a group that undergoes a curing reaction with (A) an alkali-soluble resin or (B) an epoxy resin, and may be a photocurable reactive group or a thermosetting reactive group. Examples of the photocurable reactive group include a methacryl group, an acrylic group, a vinyl group, and a styryl group. Examples of the thermosetting reactive group include an epoxy group, an amino group, a hydroxyl group, a carboxyl group, an isocyanate group, an imino group, and oxetanyl. Group, mercapto group, methoxymethyl group, methoxyethyl group, ethoxymethyl group, ethoxyethyl group, oxazoline group and the like. The method for introducing the curable reactive group on the surface of the inorganic filler is not particularly limited, and may be introduced using a known and commonly used method, and a surface treating agent having a curable reactive group, for example, an organic group having a curable reactive group. The surface of the inorganic filler may be treated with a coupling agent or the like having the above. As the coupling agent, a silane coupling agent (methacrylic type, diphenyldiamino type, etc.), a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent and the like can be used. As the surface-treated inorganic filler having no curable reactive group, for example, silica-alumina surface treatment, titanate-based coupling agent treatment, aluminate-based coupling agent treatment, organic-treated inorganic filler and the like No.

  (E) As the inorganic filler, one type can be used alone, or two or more types can be used in combination. (E) The compounding amount of the inorganic filler is preferably from 30 to 90% by mass, more preferably from 40 to 80% by mass, based on the solid content of the photosensitive resin composition.

[(F) thermosetting catalyst]
The photosensitive resin composition of the present invention further contains (F) a thermosetting catalyst. Examples of such a thermosetting catalyst include, for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenyl Imidazole derivatives such as imidazole and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole; dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, Amine compounds such as N-dimethylbenzylamine and 4-methyl-N, N-dimethylbenzylamine; hydrazine compounds such as adipic dihydrazide and sebacic dihydrazide; and phosphorus compounds such as triphenylphosphine. Guanamine, acetoguanamine, benzoguanamine, melamine, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino S-triazine derivatives such as -S-triazine / isocyanuric acid adduct and 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct can also be used, and preferably, these adhesion promoters are used. The compound which also functions is used in combination with the thermosetting catalyst (F).

  The compounding amount of the (F) thermosetting catalyst is preferably from 0.1 to 20 parts by mass, particularly preferably from 1 to 10 based on 100 parts by mass of the alkali-soluble resin (A).

(Curing agent)
The photosensitive resin composition of the present invention can contain a curing agent. Examples of the curing agent include a phenol resin, a polycarboxylic acid and an acid anhydride thereof, a cyanate ester resin, an active ester resin, a maleimide compound, and an alicyclic olefin polymer. As the curing agent, one type can be used alone, or two or more types can be used in combination.

(Colorant)
The photosensitive resin composition of the present invention may contain a colorant. As the coloring agent, known coloring agents such as red, blue, green, yellow, black, and white can be used, and any of pigments, dyes, and pigments may be used. However, it is preferable not to contain halogen from the viewpoint of reducing the environmental load and affecting the human body.

  The amount of the coloring agent is not particularly limited, but is preferably 10 parts by mass or less, more preferably 0.01 to 7 parts by mass, per 100 parts by mass of the alkali-soluble resin (A).

(Organic solvent)
The photosensitive resin composition of the present invention may contain an organic solvent for the purpose of preparing the composition, adjusting the viscosity when applying the composition 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 tetramethylbenzene; cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, and propylene glycol monomethyl ether. Glycol ethers such as dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate and tripropylene glycol monomethyl ether; ethyl acetate, butyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbine Tall acetate, propylene glycol monomethyl ether acetate, zip Propylene glycol monomethyl ether acetate, esters such as propylene carbonate; octane, aliphatic hydrocarbons decane; petroleum ether, petroleum naphtha, and petroleum solvents such as solvent naphtha, organic solvents conventionally known can be used. These organic solvents can be used alone or in combination of two or more.

(Other optional components)
Furthermore, the photosensitive resin composition of the present invention may contain other additives commonly used in the field of electronic materials. Other additives include thermal polymerization inhibitors, ultraviolet absorbers, silane coupling agents, plasticizers, flame retardants, antistatic agents, antioxidants, antioxidants, antibacterial and antifungal agents, defoamers, leveling Agent, thickener, adhesion promoter, thixotropy promoter, photoinitiator, sensitizer, photobase generator, thermoplastic resin, organic filler, release agent, surface treatment agent, dispersant, dispersing aid Agents, surface modifiers, stabilizers, phosphors and the like.

  Next, the dry film used in the production method of the present invention has a photosensitive resin layer obtained by applying and drying the photosensitive resin composition of the present invention on a carrier film. When a dry film is formed, the above-described method or a commonly used method may be used.

  As the carrier film, a plastic film is used, and for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide 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 appropriately selected in the range of 10 to 150 μm. More preferably, it is in the range of 15 to 130 μm.

  After forming the photosensitive resin layer on the carrier film, it is preferable to further laminate a peelable cover film on the surface of the resin layer for the purpose of preventing dust from adhering to the surface of the resin layer. 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 only needs to have a smaller adhesive strength between the resin layer and the carrier film when the cover film is peeled off.

  In the present invention, a photosensitive resin layer may be formed on the cover film, and a carrier film may be laminated on the surface. That is, any of a carrier film and a cover film may be used as a film on which the photosensitive resin composition of the present invention is applied when producing a dry film in the present invention.

  The manufacturing method of the present invention is suitably used for forming a cured film on a printed wiring board, more preferably, it is used for forming a permanent film, and still more preferably, a solder resist, an interlayer insulating layer, Used to form coverlay. Further, it is suitable for forming a printed wiring board provided with a fine pitch wiring pattern requiring high reliability, for example, a package substrate, particularly a permanent film (particularly a solder resist) for FC-BGA. For example, a fine pitch of L / S of 10/10 or less, that is, a line width L of 10 μm or less and a space S between lines of 10 μm or less can be suitably used. In addition, the manufacturing method of the present invention can be suitably used for a printed wiring board having a wiring pattern even if the surface roughness of the circuit is small, for example, a printed wiring board for high frequency. For example, even when the surface roughness Ra is 0.5 μm or less, particularly 0.3 μm or less, it can be suitably used.

  As described above, the present invention also provides an electronic component having a cured film obtained by the above manufacturing method. By using the manufacturing method of the present invention, an electronic component having high quality, durability and reliability is provided. In the present invention, the electronic component means a component used in an electronic circuit, and includes passive components such as a resistor, a capacitor, an inductor, and a connector in addition to active components such as a printed wiring board, a transistor, a light emitting diode, and a laser diode. Thus, the cured product obtained from the photosensitive resin composition of the present invention exerts the effects of the present invention as these insulating cured coating films.

  Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the following, “parts” and “%” are all based on mass unless otherwise specified.

[Examples 1 to 6, and Comparative Examples 1 to 7]
<Preparation of composition>
Each component was blended in the ratio (unit: parts by mass) shown in Table 1, and the viscosity thereof was appropriately adjusted so that the components could be dispersed in a bead mill. Then, the components were charged and dispersed in a bead mill (K-8, manufactured by Bühler). Thereby, the composition of the present invention (Examples 1 to 6) and the composition for comparison (Comparative Examples 1 to 7) were obtained.
In addition, the alkali-soluble resin A-1 in Table 1 was synthesized as follows.

[Synthesis of alkali-soluble resin A-1]
A flask equipped with a condenser and a stirrer was charged with 456 parts of bisphenol A, 228 parts of water and 649 parts of 37% formalin, kept at a temperature of 40 ° C. or lower, and added 228 parts of a 25% aqueous sodium hydroxide solution. Reaction was performed at 10 ° C. for 10 hours. After completion of the reaction, the mixture was cooled to 40 ° C., and neutralized to pH 4 with a 37.5% phosphoric acid aqueous solution while maintaining the temperature at 40 ° C. or lower. Thereafter, the mixture was allowed to stand, and the aqueous layer was separated. After the separation, 300 parts of methyl isobutyl ketone was added and uniformly dissolved, followed by washing three times with 500 parts of distilled water, and removing water, solvent and the like under a reduced pressure at a temperature of 50 ° C. or lower. The obtained polymethylol compound was dissolved in 550 parts of methanol to obtain 1230 parts of a methanol solution of the polymethylol compound.
A part of the obtained methanol solution of the polymethylol compound was dried in a vacuum dryer at room temperature, and the solid content was 55.2%.
In a flask equipped with a condenser and a stirrer, 500 parts of a methanol solution of the obtained polymethylol compound and 440 parts of 2,6-xylenol were charged and uniformly dissolved at 50 ° C. After uniform dissolution, methanol was removed under reduced pressure at a temperature of 50 ° C. or less. Thereafter, 8 parts of oxalic acid was added, and the mixture was reacted at 100 ° C. for 10 hours. After the reaction was completed, the distillate was removed at 180 ° C. under a reduced pressure of 50 mmHg to obtain 550 parts of novolak resin A.

In an autoclave equipped with a thermometer, a nitrogen introducing device, an alkylene oxide introducing device, and a stirring device, 130 parts of novolak resin A, 2.6 parts of a 50% aqueous sodium hydroxide solution, 100 parts by mass of toluene / methyl isobutyl ketone (mass ratio = 2/1). Then, the inside of the system was purged with nitrogen while stirring, then the temperature was increased by heating, and 60 parts of propylene oxide was gradually introduced at 150 ° C. and 8 kg / cm ² to cause a reaction. The reaction was continued for about 4 hours until the gauge pressure became 0.0 kg / cm ^2, and then cooled to room temperature. To this reaction solution, 3.3 parts of a 36% hydrochloric acid aqueous solution was added and mixed to neutralize sodium hydroxide. The neutralized reaction product was diluted with toluene, washed three times with water, and the solvent was removed with an evaporator to give a hydroxyl value of 189 g / eq. Of novolak resin A was obtained. This was one in which propylene oxide was added on average to 1 mole per equivalent of phenolic hydroxyl group.

  189 parts of propylene oxide adduct of the obtained novolak resin A, 36 parts of acrylic acid, 3.0 parts of p-toluenesulfonic acid, 0.1 part of hydroquinone monomethyl ether, and 140 parts of toluene were stirred with a stirrer, a thermometer, and an air blowing tube. The mixture was stirred while blowing in air, heated to 115 ° C., and allowed to react for another 4 hours while distilling off water formed by the reaction as an azeotrope with toluene. Cool. The obtained reaction solution was washed with a 5% aqueous NaCl solution, and toluene was removed by distillation under reduced pressure. Diethylene glycol monoethyl ether acetate was added to obtain an acrylate resin solution having a solid content of 67%.

  Next, 322 parts of the obtained acrylate resin solution, 0.1 part of hydroquinone monomethyl ether, and 0.3 part of triphenylphosphine were charged into a four-necked flask equipped with a stirrer and a reflux condenser. , 60 parts of tetrahydrophthalic anhydride was added, and the mixture was reacted for 4 hours. After cooling, the mixture was taken out. The photosensitive carboxyl group-containing resin solution thus obtained had a solid content of 70% and an acid value of the solid content of 81 mgKOH / g. Hereinafter, the solution of the carboxyl group-containing photosensitive resin is referred to as an alkali-soluble resin solution A-1.

From the composition thus obtained, a substrate for evaluation was produced as follows.

<Preparation of dry film>
300 g of methyl ethyl ketone was added to the total amount of the composition obtained above to dilute the mixture, and the mixture was stirred with a stirrer for 15 minutes to obtain a coating liquid. The coating liquid was applied on a 38 μm-thick polyethylene terephthalate film (carrier film: Emblet PTH-25 manufactured by Unitika) and dried at a temperature of 80 ° C. for 15 minutes to form a 20 μm-thick photosensitive resin layer. . Next, a biaxially stretched polypropylene film (cover film: OPP-FOA manufactured by Futamura Co., Ltd.) was laminated on the photosensitive resin layer to produce a dry film.

<Preparation of Evaluation Board A>
The above-mentioned dry film is placed in a first chamber at 100 ° C. of a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.), and copper foil is applied under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds. The laminate was laminated on the laminate substrate, and then further pressed in a second chamber at 70 ° C. under the conditions of a press pressure of 0.5 MPa and a press time of 30 seconds. The obtained substrate after the lamination process is also referred to as evaluation substrate A.

<Exposure>
Using the direct exposure machine Di IMPACT Mms60 (using a cut filter of 355 nm or less) manufactured by Oak Co., on the evaluation substrate A of Examples 1 to 6 and Comparative Examples 1 to 7, the surface of the photosensitive resin layer of the evaluation substrate A was used. Was exposed from a vertical direction with a step tablet having 41 steps of Stuffer at an exposure amount of 8 to 10 steps, and after standing for 10 minutes, the carrier film was peeled off to obtain an exposed sample.

The following evaluations were performed, and the results are shown in Table 1.
<Reaction rate evaluation>
The sample after exposure obtained as described above was allowed to stand for 10 minutes or longer to obtain a reaction rate evaluation target sample.
FT-IR (Fourier transform infrared spectroscopy) analysis of both the photosensitive resin layer of the dry film before lamination (unexposed reference) and the exposed photosensitive resin layer after lamination (sample for evaluation of reaction rate) An IR absorption spectrum was obtained by an ATR method (prism: diamond, window plate: KRS-5) using an apparatus (PerkinElmer, Spectrum100). Each sample was pressed against the prism such that the maximum peak on the vertical axis was 10 to 30% (using a UV-visible and near-red spectrophotometer V-670 manufactured by JASCO).
For each composition of each Example and Comparative Example, a reference and a spectrum of a sample to be evaluated for reaction rate were obtained, and a peak of both acryloyl groups (peak top: 1350-1450 cm ^-1 ) and a peak of epoxy group (peak top: 850) -950 cm ^-1 ) and a peak derived from SiO ₂ derived from the inorganic filler (peak range: 900-1100 cm ^-1 peak top). The measured values were introduced into the above formulas (1) to (3) and (4) to (6) to determine the conversion of the acryloyl group and the conversion of the epoxy group. In addition, the result shown in Table 1 is an average value of the values measured by repeating the above measurement three times.
<Resolution evaluation>
The laminating evaluation substrates A of Examples 1 to 6 and Comparative Examples 1 to 7 were processed using a direct exposure machine Di IMPACTMms60 (355 nm or less with a cut filter) manufactured by Oak Co., using a step tablet having 41 steps of stuffer and 4 to 10 steps. exposed with an exposure amount (mJ / cm ^2), allowed to stand for 10 minutes, using a 1 mass% sodium carbonate aqueous solution, 30 ° C., it was carried out for 60 seconds by development for spray pressure 0.2 MPa.
The thus-developed pattern film after development was visually observed and evaluated according to the following criteria.
〇: Development resistance was obtained to the deep part without halation, and no development residue was confirmed.
C: Any of halation shape, undercut shape, development residue, and surface layer damage was observed.

<Evaluation of adhesion to silicon wafer>
After washing a high-purity silicon wafer (manufactured by Mitsubishi Materials Trading Co., Ltd.) 17.5 mm × 300 μm with isopropyl alcohol, 10 cc of an amine-based adhesion promoter AP8000 (manufactured by Dow) is dropped on the silicon wafer and 2,500 rpm by a spin coater. For 1 minute. Thereafter, this was placed on a hot plate and dried at 80 ° C. for 10 minutes.
The photosensitive resin compositions of the present invention and the comparative examples were applied to the silicon wafer at a film thickness of 20 μm. The coating film on the silicon wafer thus obtained was exposed and developed in the same manner as in the evaluation of the resolution described above, and then heated at 160 ° C. for 60 minutes to obtain a cured product.
The HAST treatment was performed by holding the above cured product in a high-temperature and high-humidity tank under an atmosphere of 2 atm, 130 ° C., and 85% humidity for 100 hours.

According to JIS K5400, 100 cross-cuts of 1 mm square (10 × 10) are made on the cured product after the HAST treatment by a cross cutter so as to reach a silicon wafer according to JIS K5400. The tape was completely adhered and pulled apart. How many of the 100 pieces adhered was visually observed and evaluated as follows.
◎: 95 pieces or more adhered / 100 pieces
〇: 61 to 94 pieces adhered / 100 pieces
△: 11-60 close contact / 100
×: Adhesion of 10 or less / 100 pieces

<Evaluation of strength at break>
On the glossy side of the copper foil of GTS-MP foil (made by Furukawa Circuit Foil), a photosensitive resin layer of a dry film obtained from the composition of each of the examples and comparative examples was laminated after the cover film was peeled off. Using a vacuum laminator (CVP-300: manufactured by Nikko Materials Co., Ltd.), lamination was performed in a first chamber at 100 ° C. under the conditions of a vacuum pressure of 3 hPa and a vacuum time of 30 seconds, and a press pressure of 0.5 MPa. Pressing was performed under the condition of a pressing time of 30 seconds.

After exposing the photosensitive resin layer of the evaluation substrate B laminated in this way from an upper surface of the carrier film using an exposure device equipped with a high-pressure mercury lamp (short arc lamp), the exposure amount becomes 10 steps of sensitivity. The carrier film was peeled off from the photosensitive resin layer to expose the photosensitive resin layer.
Thereafter, development was performed for 60 seconds using a 1% by mass aqueous solution of sodium carbonate at 30 ° C. and a spray pressure of 0.2 MPa, and subsequently, an exposure amount of 1 J / cm ^{2 in} a UV conveyor furnace equipped with a high-pressure mercury lamp. After exposing the photosensitive resin layer by heating at 160 ° C. for 60 minutes, the photosensitive resin layer was completely cured to form a pattern cured film.

The pattern cured film produced as described above was cut out to a size of 3 mm × 10 mm × 0.04 mm, mounted on a solid analyzer (manufactured by TA Instrument, RSA-G2), and the breaking strength was measured. That is, the cured pattern film was subjected to a tensile test at a speed of 0.2 mm / min, and the strength when the cured pattern film was broken was determined. The measurement results are shown below.
〇: 80 MPa or more Δ: 50 MPa or more, less than 80 MPa ×: less than 50 MPa

<Tg (glass transition point) evaluation>
A cured product prepared in the same manner as in the evaluation of the breaking point strength was cut out in a size of 5 mm × 10 mm × 0.04 mm. This cured product was measured from 25 ° C. to 300 ° C. at a frequency of 1 Hz using a solid analyzer (manufactured by TA Instrument, RSA-G2), and the temperature at the peak top of the Tan δ value was confirmed to determine the glass transition point. The measurement results are shown below.
〇: 150 ° C or higher △: 130 ° C or higher but lower than 150 ° C ×: lower than 130 ° C

<B-HAST resistance evaluation>
A single-sided printed wiring board having a copper thickness of 18 μm and a comb pattern of L / S = 12/13 was prepared, and pre-processed using CZ8100 manufactured by MEC. Except for using this substrate, a pattern cured film was produced in the same manner as in the evaluation of the breaking point strength.
In a high acceleration life test device (HAST device) PC-R8D manufactured by Hirayama Seisakusho Co., Ltd., the pattern cured film prepared as described above is connected to an electrode and placed in a high-temperature and high-humidity tank at 130 ° C. and 85% humidity. A HAST test was performed by applying a voltage of 5 V for 300 hours or more.

The time when the electrical insulation became 1 × 10 ⁶ Ω or less was measured, and the insulation reliability of the cured film was evaluated as follows.
◎: 300 hours or more 〇: 200 hours or more and less than 300 hours Δ: 100 hours or more and less than 200 hours ×: less than 100 hours

* 1: NC-6000, manufactured by Nippon Kayaku Co., Ltd., 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2,3- Epoxypropoxy] phenyl)] ethyl] phenyl] propane * 2: PETG manufactured by Showa Denko KK, aliphatic epoxy resin * 3: EP-4088L manufactured by ADEKA, dicyclopentadiene epoxy resin * 4: manufactured by ADEKA ED-509S, t-butylphenol type epoxy resin * 5: DIC Corporation, HP-4710, naphthalene type epoxy resin * 6: Nippon Kayaku Co., Ltd., DPHA (dipentaerythritol hexaacrylate)
* 7: Omnirad TPO (2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide) manufactured by IGM Resins.
* 8: Irgacure OXE02 (1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone 1- (O-acetyloxime) manufactured by BASF Japan Ltd.
* 9: Spherical silica, SFP-30M manufactured by Denka Corporation (untreated material)
* 10: Filler obtained by surface-treating spherical silica, SFP-30M manufactured by Denka Co., Ltd. with methacrylsilane * 11: Filler obtained by surface-treating spherical silica, SFP-30M manufactured by Denka Co., Ltd. with phenylaminosilane * 12 : BARIACE B-30 (Barium) manufactured by Sakai Chemical Industry Co., Ltd.

From the results shown in the above table, it is understood that the cured film obtained by the production method of the present invention is excellent in all of resolution, adhesion, strength at break, and insulation reliability, and has a high glass transition point.

Claims (7)

Photosensitive resin layer containing (A) an alkali-soluble resin, (B) an epoxy resin, (C) a compound having an acryloyl group, (D) a photopolymerization initiator, (E) an inorganic filler, and (F) a thermosetting catalyst. Exposing the substrate with active energy rays,
A method for producing a cured product, comprising: a step of developing the exposed photosensitive resin layer with an aqueous alkali solution; and a step of heating and curing the developed photosensitive resin layer,
A reaction rate of the acryloyl group after the exposure and before the development with respect to all unreacted acryloyl groups in the photosensitive resin layer before the exposure is 10% or more and 40% or less, and the photosensitive resin before the exposure A method for producing a cured product, wherein a reaction rate of an epoxy group after the exposure and before the development with respect to all epoxy groups in a layer is 0.5% or more and 10% or less.   The method according to claim 1, wherein the epoxy resin (B) has three or more epoxy groups in one molecule.   3. The method according to claim 1, wherein the compound (C) having an acryloyl group is used in an amount of 20% by mass or less based on the total mass of the solid content of the photosensitive resin layer.   A photosensitive resin composition used in the production method according to claim 1.   A dry film comprising a photosensitive resin layer used in the production method according to claim 1.   A cured product obtained by the production method according to claim 1.   An electronic component comprising the cured product according to claim 6.