JP6658648B2 - Photosensitive resin composition - Google Patents

Description

  The present invention relates to a photosensitive resin composition. Furthermore, the present invention relates to a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition.

  In a printed wiring board, a solder resist is sometimes provided as a permanent protective film for preventing solder from adhering to unnecessary portions and preventing corrosion of a circuit board. As the solder resist, it is common to use a photosensitive resin composition as described in Patent Document 1, for example.

JP 2011-164304 A

  In general, a photosensitive resin composition for a solder resist has resolution, insulation, solder heat resistance, gold plating resistance, moisture and heat resistance, crack resistance (TCT resistance), and ultra-accelerated high temperature between fine wirings. HAST resistance to high humidity life test (HAST) is required. In recent years, in response to the increase in the density of printed wiring boards, workability and higher performance have also been required for solder resists. In particular, the demand for crack resistance is increasing year by year, and it is important to provide further durability.

  In order to increase the crack resistance, for example, a method of highly filling the photosensitive resin composition with an inorganic filler is conceivable. However, the adhesion to the adherend is reduced, and the light transmission is not sufficient because the light transmission is insufficient. There is a possibility that the sensitivity of the bottom is deteriorated, an undercut occurs, or the aperture is not sufficiently opened due to halation of light.

  In addition, from the viewpoint of workability and productivity, when producing a solder resist, the appearance of the photosensitive film is high, cracks are suppressed during handling, and cracks and resin are generated when cutting the solder resist. It is required to suppress scattering.

  Further, it has been required to increase the crack resistance and to impart flexibility to the photosensitive film. In order to increase the flexibility, it is generally considered to use a resin having a low glass transition temperature and a large weight average molecular weight, but there is a possibility that the heat resistance is significantly reduced. On the other hand, when a resin having a high glass transition temperature is used, heat resistance is excellent, but alkali solubility may be significantly reduced.

  An object of the present invention is to provide a photosensitive resin composition which has a low average linear thermal expansion coefficient, a high glass transition temperature, and is capable of obtaining a cured product having excellent crack resistance, excellent tackiness, flexibility and resolution. An object of the present invention is to provide a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using a photosensitive resin composition.

  In general, when a large amount of an inorganic filler having a large average particle diameter is contained, light is reflected, so that the resolution is deteriorated. For this reason, conventionally, a photosensitive resin composition contains a large amount of an inorganic filler having an average particle diameter of less than 0.5 μm. However, the present inventors have made it possible to use inorganic fillers that have been conventionally used by incorporating a predetermined (meth) acrylic copolymer having a high glass transition temperature and a predetermined (meth) acrylic copolymer having a low glass transition temperature. Even if a large amount of an inorganic filler larger than the average particle diameter of the material is contained, it has been found that light reflection is suppressed, resolution and the like are improved, and a cured product having excellent crack resistance can be obtained, and the present invention is completed. Reached.

That is, the present invention includes the following contents.
[1] (A-1) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a main chain glass transition temperature of 150 ° C. or higher,
(A-2) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of a main chain of −20 ° C. or less;
(B) an inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less,
A photosensitive resin composition containing (C) a photopolymerization initiator, and (D) an epoxy resin,
The weight average molecular weight of each of the component (A-1) and the component (A-2) is 30,000 or less,
(B) The photosensitive resin composition, wherein the content of the component is 60% by mass or more and 85% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass.
[2] The photosensitive resin composition according to [1], further comprising (A-3) a resin containing an ethylenically unsaturated group and a carboxyl group.
[3] The photosensitive resin composition according to [2], wherein the component (A-3) has a naphthalene skeleton.
[4] The photosensitive resin composition according to [2] or [3], wherein the component (A-3) is an epoxy (meth) acrylate having an acid-modified naphthalene skeleton.
[5] When the content of the component (A-1) is A1, the content of the component (A-2) is A2, and the content of the component (A-3) is A3, (A1 + A2) / A3 is The photosensitive resin composition according to any one of [2] to [4], which is 0.1 to 0.8.
[6] When the content of the component (A-1) is A1 and the content of the component (A-2) is A2, A1 / A2 is 0.2 or more and 3.5 or less. [1] -The photosensitive resin composition according to any one of [5].
[7] The photosensitive resin composition according to any one of [1] to [6], wherein the component (D) contains at least one of a biphenyl epoxy resin and a tetraphenylethane epoxy resin.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the component (B) contains silica.
[9] A photosensitive film containing the photosensitive resin composition according to any one of [1] to [8].
[10] A photosensitizer with a support comprising: a support; and a photosensitive resin composition layer including the photosensitive resin composition according to any one of [1] to [8] provided on the support. Film.
[11] A printed wiring board including an insulating layer formed of a cured product of the photosensitive resin composition according to any one of [1] to [8].
[12] The printed wiring board according to [11], wherein the insulating layer is a solder resist.
[13] A semiconductor device including the printed wiring board according to [11] or [12].

  According to the present invention, a photosensitive resin composition having excellent tackiness, flexibility, and resolution, capable of obtaining a cured product having a low average linear thermal expansion coefficient, a high glass transition temperature, and excellent crack resistance; A photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the photosensitive resin composition can be provided.

  Hereinafter, the photosensitive resin composition, photosensitive film, photosensitive film with support, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises: (A-1) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of a main chain of 150 ° C. or more; 2) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of the main chain of -20 ° C or less, and (B) an average particle size of 0.5 µm or more and 2.5 µm or less And (C) a photopolymerization initiator and (D) an epoxy resin, wherein the weight average molecular weight of the components (A-1) and (A-2) is Is 30,000 or less, and the content of the component (B) is 60% by mass or more and 85% by mass or less when the entire solid content of the photosensitive resin composition is 100% by mass.

  By containing the components (A-1) to (A-2) and the components (B) to (D), a cured product having a low average linear thermal expansion coefficient, a high glass transition temperature and excellent crack resistance can be obtained. It is excellent in tackiness, flexibility and resolution. In addition, the photosensitive resin composition may further include (A-3) a component, (E) a reactive diluent, and (F) an organic solvent, if necessary. Hereinafter, each component contained in the photosensitive resin composition will be described in detail. Here, the component (A-1), the component (A-2), and the component (A-3) may be collectively referred to as a “component (A)”.

<(A-1) (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of the main chain of 150 ° C. or more>
The photosensitive resin composition contains (A-1) an ethylenically unsaturated group and a carboxyl group, has a glass transition temperature of a main chain of 150 ° C. or more, and has a weight average molecular weight of 30,000 or less. Contains a copolymer. By containing the component (A-1), the coating properties, properties, and crack resistance of the film can be improved, the average linear thermal expansion coefficient can be reduced, and the glass transition temperature can be increased. it can. “(Meth) acrylic copolymer” refers to an acrylic copolymer and a methacrylic copolymer.

  Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propargyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadimide group, and a (meth) acryl group. In view of the above, a (meth) acryl group is preferable. The “(meth) acryl group” refers to a methacryl group and an acryl group.

  The component (A-1) is a compound having a glass transition temperature of a main chain of 150 ° C. or higher, having an ethylenically unsaturated group and a carboxyl group, and enabling photoradical polymerization and alkali development. There is no particular limitation so long as it is a (meth) acrylic copolymer having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule.

  Examples of the component (A-1) include an acid-modified unsaturated epoxy (meth) acrylic copolymer obtained by reacting (meth) acrylic acid with an epoxy group-containing copolymer and further reacting with an acid anhydride. . For details, reacting (meth) acrylic acid with an epoxy group-containing copolymer to obtain an unsaturated epoxy (meth) acrylic copolymer and reacting the unsaturated epoxy (meth) acrylic copolymer with an acid anhydride To obtain an acid-modified unsaturated epoxy (meth) acrylic copolymer. The epoxy group of the epoxy group-containing copolymer is usually substantially eliminated by the reaction with (meth) acrylic acid. "(Meth) acrylic acid" refers to acrylic acid and methacrylic acid.

  The epoxy group-containing copolymer used for obtaining the component (A-1) can be obtained by polymerizing an epoxy group-containing monomer and, if necessary, an arbitrary monomer.

  Examples of the epoxy group-containing monomer include epoxy group-containing monomers such as glycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, 2-methyl-3,4-epoxycyclohexyl (meth) acrylate, and allyl glycidyl ether. (Meth) acrylate monomers, with glycidyl (meth) acrylate being preferred. The epoxy group-containing monomers may be used alone or as a mixture of two or more.

  Examples of the optional monomer include styrene, (meth) acrylic acid, methyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl methacrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate, 2-ethylhexyl methacrylate, nonyl (meth) acrylate , Decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, cyclohexyl (meth ) Acrylate, 4-tert-butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, benzyl (meth) acrylate, acrylamide, N, N-dimethyl (meth) acrylamide, (meth) Acrylonitrile, 3- (meth) acryloylpropyltrimethoxysilane, N, N-dimethylaminoethyl (meth) acrylate, glycidyl (meth) acrylate, styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, 2- Hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxy-n-butyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-n-butyl (Meth) acrylate, 3-hydroxy-n-butyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, glycerin mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono ( (Meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl phthalate, lactone-modified (meth) acrylate having a hydroxyl group at a terminal, 1-adamantyl (meth) Acrylate and the like. The arbitrary monomers may be used alone or in combination of two or more.

  Examples of the acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid dianhydride. Anhydrides and the like may be mentioned, and these may be used alone or in combination of two or more. Among them, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the resolution of the cured product and the insulation reliability.

  In obtaining an acid-modified unsaturated epoxy (meth) acryl copolymer, an epoxy group-containing copolymer is reacted with an unsaturated carboxylic acid in the presence of a catalyst to obtain an unsaturated epoxy (meth) acryl copolymer. The unsaturated epoxy (meth) acrylic copolymer may be reacted with an acid anhydride. Moreover, you may use a solvent and a polymerization inhibitor as needed.

  The glass transition temperature of the main chain of the component (A-1) is 150 ° C. or higher, preferably 155 ° C. or higher, more preferably 160 ° C. or higher, and 165 ° C. or higher, from the viewpoint of improving heat resistance. The upper limit is preferably 300 ° C. or lower, more preferably 280 ° C. or lower, and further preferably 250 ° C. or lower, from the viewpoint of improving alkali solubility.

The glass transition temperature of the main chain of the component (A-1) is the theoretical glass transition temperature of the main chain of the component (A-1), and the theoretical glass transition temperature is obtained by the following FOX equation. Can be calculated. Since the glass transition temperature determined by the FOX equation substantially matches the glass transition temperature measured by differential scanning calorimetry (TMA, DSC, DTA), the glass of the main chain of the component (A-1) is determined by differential scanning calorimetry. The transition temperature may be measured.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) +... + (Wm / Tgm)
W1 + W2 + ... + Wm = 1
Wm represents the content (% by mass) of each monomer constituting the component (A-1), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (A-1).

  The weight average molecular weight of the component (A-1) is 30,000 or less, preferably 28,000 or less, more preferably 25,000 or less from the viewpoint of developability. The lower limit is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 15,000 or more, from the viewpoint of coatability. The weight average molecular weight can be measured in accordance with the description of (measurement of weight average molecular weight (Mw) of component (A)) described later.

The acid value of the component (A-1) is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g, from the viewpoint of improving the alkali developability of the photosensitive resin composition. More preferably, it is more preferably 1 mgKOH / g or more. On the other hand, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, from the viewpoint of suppressing the fine pattern of the cured product from being melted out by development and improving insulation reliability. More preferably, it is 100 mgKOH / g or less. Here, the acid value is the residual acid value of the carboxyl group present in the component (A-1), and the acid value can be measured by the following method. First, about 1 g of a measurement resin solution is precisely weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Then, an appropriate amount of phenolphthalein as an indicator is added to the solution, and titration is performed using a 0.1 N aqueous KOH solution. Then, the acid value is calculated by the following equation.
Formula: A = 10 × Vf × 56.1 / (Wp × I)

  In the above formula, A represents an acid value (mg KOH / g), Vf represents a titer (mL) of KOH, Wp represents a mass (g) of the measured resin solution, and I represents a nonvolatile content of the measured resin solution. (% By mass).

  In the production of the component (A-1), from the viewpoint of improving the storage stability, the number of moles of the epoxy group of the epoxy group-containing copolymer and the number of moles of the total carboxyl group of the unsaturated carboxylic acid and the acid anhydride. Is preferably in the range of 1: 0.8 to 1.3, and more preferably in the range of 1: 0.9 to 1.2.

  From the viewpoint of improving the heat resistance, the component (A-1) preferably has a content of 0.5% by mass or more when the total solid content of the photosensitive resin composition is 100% by mass, and 1% by mass or more. It is more preferably at least 1.5% by mass, more preferably at least 1.5% by mass. The upper limit is preferably 15% by mass or less, more preferably 14% by mass or less, and even more preferably 12% by mass or less, from the viewpoint of improving alkali developability.

<(A-2) (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of a main chain of −20 ° C. or less>
The photosensitive resin composition contains (A-2) an ethylenically unsaturated group and a carboxyl group, the glass transition temperature of the main chain is -20 ° C or less, and the weight average molecular weight is 30000 or less (meta ) It contains an acrylic copolymer. By containing the component (A-2), the appearance, flexibility and resolution of the photosensitive film can be improved.

  The glass transition temperature of the main chain of the component (A-2) is -20C or lower, preferably -23C or lower, more preferably -25C or lower, from the viewpoint of improving flexibility. The upper limit is preferably −300 ° C. or higher, more preferably −200 ° C. or higher, still more preferably −100 ° C. or higher, and −80 ° C. or higher, from the viewpoint of improving alkali solubility.

  The glass transition temperature of the main chain of the component (A-2) is the theoretical glass transition temperature of the main chain of the component (A-2). The theoretical glass transition temperature of the component (A-1) Can be calculated by the same method as the glass transition temperature.

  The ethylenically unsaturated group is the same as the ethylenically unsaturated group in the component (A-1), and the preferred range is also the same.

  The component (A-2) is a compound having a glass transition temperature of a main chain of −20 ° C. or less, having an ethylenically unsaturated group and a carboxyl group, and enabling photoradical polymerization and alkali development. There is no particular limitation so long as it is a (meth) acrylic copolymer having both a carboxyl group and two or more ethylenically unsaturated groups in one molecule.

  As the component (A-2), an acid-modified unsaturated epoxy (meth) acrylic copolymer obtained by reacting (meth) acrylic acid with an epoxy group-containing copolymer and further reacting with an acid anhydride is exemplified. . For details, reacting (meth) acrylic acid with an epoxy group-containing copolymer to obtain an unsaturated epoxy (meth) acrylic copolymer and reacting the unsaturated epoxy (meth) acrylic copolymer with an acid anhydride To obtain an acid-modified unsaturated epoxy (meth) acrylic copolymer. The epoxy group of the epoxy group-containing copolymer is usually substantially eliminated by the reaction with (meth) acrylic acid.

  This acid-modified unsaturated epoxy (meth) acryl copolymer can be produced in the same manner as the method for producing the acid-modified unsaturated epoxy (meth) acryl copolymer in the component (A-1).

  The epoxy group-containing copolymer used for obtaining the component (A-2) is preferably an epoxy group-containing copolymer obtained by polymerizing an epoxy group-containing monomer and an arbitrary monomer. As the epoxy group-containing monomer, the same epoxy group-containing monomer used when obtaining the component (A-1) can be used.

  Examples of the optional monomer include n-butyl methacrylate, and the same optional monomer as the optional monomer that can be used for producing the component (A-1). The arbitrary monomers may be used alone or in combination of two or more.

  As a preferred embodiment of the component (A-2), a compound obtained by reacting an epoxy group-containing copolymer obtained by polymerizing an epoxy group-containing monomer and an arbitrary monomer, (meth) acrylic acid and an acid anhydride Wherein the epoxy-containing monomer is glycidyl methacrylate, the optional monomer is butyl acrylate, and the acid anhydride is tetrahydrophthalic anhydride.

  The weight average molecular weight of the component (A-2) is 30,000 or less, preferably 28,000 or less, more preferably 25,000 or less from the viewpoint of developability. The lower limit is preferably 5,000 or more, more preferably 10,000 or more, and still more preferably 15,000 or more, from the viewpoint of coatability. The weight average molecular weight can be measured in accordance with the description of (measurement of weight average molecular weight (Mw) of component (A)) described later.

  The acid value of the component (A-2) is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g, from the viewpoint of improving the alkali developability of the photosensitive resin composition. More preferably, it is more preferably 1 mgKOH / g or more. On the other hand, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, from the viewpoint of suppressing the fine pattern of the cured product from being melted out by development and improving insulation reliability. More preferably, it is 100 mgKOH / g or less. The acid value can be calculated by the same method as the acid value in the component (A-1).

  From the viewpoint of improving flexibility, the component (A-2) preferably has a content of 0.5% by mass or more when the entire solid content of the photosensitive resin composition is 100% by mass. It is more preferably at least 0.8% by mass, and even more preferably at least 1% by mass. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of improving heat resistance.

  When the content of the component (A-1) is A1 and the content of the component (A-2) is A2, A1 / A2 is preferably 0.75 from the viewpoint of achieving both heat resistance and flexibility. It is more preferably 0.8 or more, and still more preferably 1 or more. The lower limit is preferably 3.5 or less, more preferably 3.4 or less, and still more preferably 3.3 or less.

<(A-3) Resin containing ethylenically unsaturated group and carboxyl group>
The photosensitive resin composition may contain (A-3) an ethylenically unsaturated group and a carboxyl group. By including the component (A-3), effects such as developability and adhesion can be obtained. However, the component (A-3) does not include the component (A-1) and the component (A-2).

  The ethylenically unsaturated group is the same as the ethylenically unsaturated group in the component (A-1), and the preferred range is also the same.

  The component (A-3) is not particularly limited as long as it has an ethylenically unsaturated group and a carboxyl group, and is a compound that enables photoradical polymerization and alkali development. And a resin having two or more ethylenically unsaturated groups. As the component (A-3), for example, a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of the main chain of more than −20 ° C. and less than 150 ° C., or Examples thereof include an acid-modified unsaturated epoxy ester resin described below.

  One embodiment of the acid-modified unsaturated epoxy ester resin is obtained by reacting an epoxy compound with an unsaturated carboxylic acid and further reacting an acid anhydride. Specifically, an unsaturated epoxy ester resin is obtained by reacting an unsaturated carboxylic acid with an epoxy compound, and an acid-modified unsaturated epoxy ester resin can be obtained by reacting the unsaturated epoxy ester resin with an acid anhydride. As the acid anhydride, the same acid anhydride as that used for obtaining the component (A-1) can be used.

  As the epoxy compound, any compound having an epoxy group in the molecule can be used. For example, bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin Bisphenol F epoxy resin such as modified bisphenol F epoxy resin obtained by reacting epichlorohydrin with bisphenol S epoxy resin and bisphenol F epoxy resin; biphenol epoxy resin, tetramethyl biphenol resin, etc. Novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type novolak type epoxy resin and alkylphenol novolak type epoxy resin Epoxy resins; fluorine-containing epoxy resins such as bisphenol AF epoxy resins and perfluoroalkyl epoxy resins; naphthalene epoxy resins, dihydroxynaphthalene epoxy resins, polyhydroxybinaphthalene epoxy resins, naphthol epoxy resins, and binaphthol epoxy resins Epoxy resin having a naphthalene skeleton (naphthalene skeleton-containing epoxy resin) such as a resin, a naphthylene ether type epoxy resin, a naphthol novolak type epoxy resin, a naphthalene type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes; Epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; anthracene type epoxy resin Epoxy resin containing a condensed ring skeleton such as silicone resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin having butadiene structure; alicyclic epoxy resin; Heterocyclic epoxy resin; Spiro ring-containing epoxy resin; Cyclohexane dimethanol type epoxy resin; Trimethylol type epoxy resin; Tetraphenylethane type epoxy resin; Polyglycidyl (meth) acrylate, copolymer of glycidyl methacrylate and acrylate Such as glycidyl group-containing acrylic resins; fluorene type epoxy resins; halogenated epoxy resins, and the like.

  From the viewpoint of reducing the average coefficient of linear thermal expansion, an epoxy resin containing an aromatic skeleton is preferable. Here, the aromatic skeleton is a concept including a polycyclic aromatic ring and an aromatic heterocyclic ring. Of these, a naphthalene skeleton-containing epoxy resin, a condensed ring skeleton-containing epoxy resin, a biphenyl type epoxy resin, a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, a cresol novolak type epoxy resin, and a glycidyl ester type epoxy resin are preferable. Among them, since the molecular rigidity is increased, the movement of the molecules is suppressed, and as a result, the glass transition temperature of the cured product of the resin composition becomes higher, and from the viewpoint of lowering the average linear thermal expansion coefficient of the cured product, naphthalene A skeleton-containing epoxy resin, an epoxy resin having a condensed ring skeleton, and a biphenyl-type epoxy resin are more preferable, and a naphthalene skeleton-containing epoxy resin is further more preferable. As the naphthalene skeleton-containing epoxy resin, a dihydroxynaphthalene-type epoxy resin, a polyhydroxybinaphthalene-type epoxy resin, and a naphthalene-type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes are preferable.

  Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, and 2,3-diglycol. Glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene and the like can be mentioned.

  Examples of the polyhydroxybinaphthalene type epoxy resin include 1,1′-bi- (2-glycidyloxy) naphthyl, 1- (2,7-diglycidyloxy) -1 ′-(2′-glycidyloxy) binaphthyl, 1,1′-bi- (2,7-diglycidyloxy) naphthyl and the like.

  Examples of naphthalene type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes include 1,1′-bis (2,7-diglycidyloxynaphthyl) methane and 1- (2,7-diglycidyloxynaphthyl). ) -1 ′-(2′-glycidyloxynaphthyl) methane and 1,1′-bis (2-glycidyloxynaphthyl) methane.

  Among these, a polyhydroxybinaphthalene-type epoxy resin having two or more naphthalene skeletons in one molecule and a naphthalene-type epoxy resin obtained by a condensation reaction of polyhydroxynaphthalene and aldehydes are preferable, and an epoxy resin in one molecule is particularly preferable. 1,1′-bis (2,7-diglycidyloxynaphthyl) methane having 3 or more groups, 1- (2,7-diglycidyloxynaphthyl) -1 ′-(2′-glycidyloxynaphthyl) methane, 1- (2,7-diglycidyloxy) -1 ′-(2′-glycidyloxy) binaphthyl and 1,1′-bi- (2,7-diglycidyloxy) naphthyl were added to the average linear thermal expansion coefficient. It is preferable because it has excellent heat resistance.

  Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in this specification, the epoxy ester resin which is a reaction product of the above-mentioned epoxy compound and (meth) acrylic acid may be described as “epoxy (meth) acrylate”, wherein the epoxy group of the epoxy compound is Usually, it is substantially eliminated by the reaction with (meth) acrylic acid.

  In obtaining an acid-modified unsaturated epoxy ester resin, an unsaturated carboxylic acid is reacted with an epoxy resin in the presence of a catalyst to obtain an unsaturated epoxy ester resin, and then the unsaturated epoxy ester resin is reacted with an acid anhydride. Is also good. Moreover, you may use a solvent and a polymerization inhibitor as needed.

  As the acid-modified unsaturated epoxy ester resin, an acid-modified epoxy (meth) acrylate is preferable. “Epoxy” in the acid-modified unsaturated epoxy ester resin represents a structure derived from the above-mentioned epoxy compound. For example, "acid-modified bisphenol-type epoxy (meth) acrylate" refers to an acid-modified unsaturated epoxy ester resin obtained by using a bisphenol-type epoxy resin as an epoxy compound and (meth) acrylic acid as an unsaturated carboxylic acid. Point to. The preferred range of the acid-modified epoxy (meth) acrylate is derived from the preferred range of the epoxy compound. That is, the acid-modified unsaturated epoxy ester resin is preferably an acid-modified naphthalene skeleton-containing epoxy (meth) acrylate from the viewpoint of increasing the glass transition temperature of the cured product of the resin composition and lowering the average coefficient of linear thermal expansion. The acid-modified naphthalene skeleton-containing epoxy (meth) acrylate is a compound obtained by reacting a reaction product of a naphthalene-type epoxy resin and (meth) acrylate with an acid anhydride such as succinic anhydride or tetrahydrophthalic anhydride. .

  As such an acid-modified unsaturated epoxy ester resin, a commercially available product can be used. As a specific example, “ZAR-2000” (manufactured by Nippon Kayaku Co., Ltd.) (bisphenol A type epoxy resin, acrylic acid, and succinic anhydride) Reactants), "ZFR-1491H", "ZFR-1533H" (reactant of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "PR-300CP" (Cresol novolac epoxy manufactured by Showa Denko KK) A reaction product of a resin, acrylic acid, and an acid anhydride). These may be used alone or in combination of two or more.

  As another embodiment of the resin containing an ethylenically unsaturated group and a carboxyl group, an epoxy compound containing an ethylenically unsaturated group is added to a (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid. An unsaturated modified (meth) acrylic resin into which an ethylenically unsaturated group has been introduced by reaction is exemplified. Examples of the ethylenically unsaturated group-containing epoxy compound include glycidyl methacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Further, it is also possible to react an acid anhydride with a hydroxyl group generated upon introduction of an unsaturated group. As the acid anhydride, those similar to the above-mentioned acid anhydrides can be used, and the preferable range is also the same. As the component (A-3), a (meth) acrylic copolymer having a glass transition temperature of the main chain of more than −20 ° C. and less than 150 ° C. is preferable.

  Commercially available products of such unsaturated modified (meth) acrylic resin can be used, and specific examples include “SPC-1000” and “SPC-3000” manufactured by Showa Denko KK and “Cyclomer” manufactured by Daicel Ornex. P (ACA) Z-250 "," Cyclomer P (ACA) Z-251 "," Cyclomer P (ACA) Z-254 "," Cyclomer P (ACA) Z-300 "," Cyclomer P ( ACA) Z-320 ".

  The weight average molecular weight of the component (A-3) is preferably 1,000 or more, more preferably 1500 or more, and even more preferably 2,000 or more, from the viewpoint of film-forming properties. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7500 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

  From the viewpoint of improving the alkali developability of the photosensitive resin composition, the acid value of the component (A-3) is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more. More preferably, it is more preferably 1 mgKOH / g or more. On the other hand, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, from the viewpoint of suppressing the fine pattern of the cured product from being melted out by development and improving insulation reliability. More preferably, it is 100 mgKOH / g or less. The acid value can be calculated by the same method as the acid value in the component (A-1).

  In the production of the component (A-3), from the viewpoint of improving storage stability, the ratio of the number of moles of epoxy groups of the epoxy resin to the total number of moles of carboxyl groups of the unsaturated carboxylic acid and the acid anhydride is determined. , 1: 0.8-1.3, more preferably 1: 0.9-1.2.

  When the photosensitive resin composition contains the component (A-3), the component (A-3) is used when the total solid content of the photosensitive resin composition is 100% by mass from the viewpoint of improving alkali developability. The content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and still more preferably 25% by mass or less, from the viewpoint of improving heat resistance.

  When the photosensitive resin composition contains the component (A-3), the content is A1, the content of the component (A-2) is A2, and the content of the component (A-3) is A3. , (A1 + A2) / A3 are preferably 0.1 or more, more preferably 0.15 or more, still more preferably 0.2 or more, and still more preferably, from the viewpoint of achieving both developability, heat resistance, and flexibility. 0.25 or more. The upper limit is preferably 0.8 or less, more preferably 0.7 or less, and still more preferably 0.6 or less.

<(B) Inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less>
The photosensitive resin composition contains (B) an inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less. By containing the component (B), it is possible to provide a photosensitive resin composition capable of obtaining a cured product having a low average coefficient of linear thermal expansion.

  Although the material of the inorganic filler is not particularly limited, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , Zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium tungstate phosphate. Among these, silica is particularly preferred. As the silica, spherical silica is preferable. One kind of the inorganic filler may be used alone, or two or more kinds may be used in combination.

  The average particle diameter of the inorganic filler must be large in order to obtain a cured product having a low average coefficient of linear thermal expansion, and from the viewpoint of the filling property, it is 0.5 μm or more, and preferably 0.5 μm or more. It is at least 8 μm, more preferably at least 1 μm. The upper limit of the average particle size is 2.5 μm or less, preferably 2 μm or less, more preferably 1.5 μm or less, and still more preferably 1.3 μm or less, from the viewpoint of obtaining excellent resolution. Commercially available inorganic fillers having such an average particle size include, for example, "SC4050" and "Admafine" manufactured by Admatechs, "SFP Series" manufactured by Denki Kagaku Kogyo, and "SP" manufactured by Nippon Steel & Sumitomo Metal Materials. (H) Series "," Sciqas Series "manufactured by Sakai Chemical Industry Co., Ltd.," Sea Hostar Series "manufactured by Nippon Shokubai Co., Ltd." AZ Series "," AX Series "manufactured by Nippon Steel & Sumikin Materials Co., Ltd. B series "and" BF series ".

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be measured on a volume basis by a laser diffraction / scattering type particle size distribution measuring apparatus, and the median diameter can be measured by setting the median diameter as the average particle diameter. As the measurement sample, a sample in which an inorganic filler is dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba, Ltd., "SALD-2200" manufactured by Shimadzu, etc. can be used.

  From the viewpoint of increasing the moisture resistance and dispersibility of the inorganic filler, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanates It is preferably treated with one or more surface treatment agents such as a system coupling agent. Commercially available surface treatment agents include, for example, “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu "KBE903" (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

  The content of the inorganic filler is 60% by mass or more, and preferably 61% by mass, when the nonvolatile component in the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. % Or more, more preferably 62% by mass or more. The upper limit is 85% by mass or less, preferably 83% by mass or less, more preferably 80% by mass or less from the viewpoint of suppressing light reflection.

<(C) Photopolymerization initiator>
The photosensitive resin composition contains (C) a photopolymerization initiator. By containing the component (C), the photosensitive resin composition can be efficiently photocured.

  Although the component (C) is not particularly limited, for example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl Α-aminoalkylphenones such as methyl)-[4- (4-morpholinyl) phenyl] -1-butanone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Photopolymerization initiator; Oxime ester photopolymerization initiator such as ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) Benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphene Nyl- (2,4,6-trimethylbenzoyl) phosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate, 4,4′-bis (diethylamino) benzophenone, 1-hydroxy-cyclohexyl-phenylketone , 2,2-dimethoxy-1,2-diphenylethan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like, and a sulfonium salt-based photopolymerization initiator and the like can also be used. These may be used alone or in combination of two or more.

  Further, the photosensitive resin composition may be used in combination with the component (C), as a photopolymerization initiation aid, as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-acid. It may contain tertiary amines such as dimethylaminobenzoate, triethylamine and triethanolamine, or may contain a photosensitizer such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones, etc. Good. These may be used alone or in combination of two or more.

  Specific examples of the component (C) include “Omnirad 907”, “Omnirad 369”, “Omnirad 379”, “Omnirad 819”, “Omnirad TPO” and “Irgacure OXE-01” and “Irgac02X” manufactured by BASF manufactured by IGM. "N-1919" manufactured by ADEKA Corporation and the like.

  The content of the component (C) is preferably from the viewpoint of sufficiently photocuring the photosensitive resin composition and improving the insulation reliability, when the total solid content of the photosensitive resin composition is 100% by mass. It is 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.05% by mass or more. On the other hand, the upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less, from the viewpoint of suppressing a decrease in resolution due to excessive sensitivity.

<(D) Epoxy resin>
The photosensitive resin composition contains (D) an epoxy resin. By including the component (D), insulation reliability can be improved. However, the component (D) here does not include the resin corresponding to the component (A).

  As the component (D), for example, a fluorine-containing epoxy resin such as a bisphenol AF type epoxy resin and a perfluoroalkyl type epoxy resin; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; a bisphenol S type epoxy resin; Epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolak type epoxy resin; phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; naphthol type epoxy resin; anthracene type epoxy Resin; glycidylamine type epoxy resin; glycidyl ester type epoxy resin; cresol novolak type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin An epoxy resin having a butadiene structure; an alicyclic epoxy resin, an alicyclic epoxy resin having an ester skeleton; a heterocyclic epoxy resin; a spiro ring-containing epoxy resin; a cyclohexane dimethanol type epoxy resin; a naphthylene ether type epoxy resin; Trimethylol type epoxy resin; tetraphenylethane type epoxy resin, halogenated epoxy resin, etc., from the viewpoint of improving adhesion, bisphenol F type epoxy resin and biphenyl type epoxy resin are preferable, and biphenyl type epoxy resin is more preferable. Preferred. Further, from the viewpoint of improving heat resistance, a naphthalene type epoxy resin, a naphthol type epoxy resin, an anthracene type epoxy resin, a naphthylene ether type epoxy resin, and a tetraphenylethane type epoxy resin are preferable, and a tetraphenylethane type epoxy resin is more preferable. . One epoxy resin may be used alone, or two or more epoxy resins may be used in combination. The component (E) preferably contains at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin from the viewpoint of improving adhesion and heat resistance.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. As the component (E), two or more epoxy resins may be used in combination.

  Specific examples of the epoxy resin include “HP4032”, “HP4032D”, “HP4032SS”, “HP4032H” (naphthalene type epoxy resin) manufactured by DIC, “828US” and “jER828EL” (bisphenol A type) manufactured by Mitsubishi Chemical Corporation. Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (Mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type) manufactured by Nagase ChemteX Corporation Epoxy tree ), “CELLOXIDE 2021P” (alicyclic epoxy resin having an ester skeleton), “PB-3600” (epoxy resin having a butadiene structure), “ZX1658”, “ZX1658GS”, manufactured by Nippon Steel Chemical Co., Ltd. (Liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy resin) manufactured by Daikin Industries, Ltd. "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation. , “HP-7200”, “HP-7200HH”, “HP-7200H” Lopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Japan "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin) manufactured by Kayaku Co., Ltd. "ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YSLV-80XY" (tetramethylbisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation, "YX4000H" manufactured by Mitsubishi Chemical Corporation. ”,“ YL61 21 "(biphenyl type epoxy resin)," YX4000HK "(bixylenol type epoxy resin)," YX8800 "(anthracene type epoxy resin)," PG-100 "and" CG-500 "manufactured by Osaka Gas Chemical Company, Mitsubishi Chemical Corporation "YL7800" (fluorene type epoxy resin), Mitsubishi Chemical Corporation "1010", (solid bisphenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF) Type epoxy resin).

  The content of the component (D) is preferably 1% by mass or more when the entire solid content of the photosensitive resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer having good tensile strength and insulation reliability. , More preferably 5% by mass or more, even more preferably 7% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exerted, but is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less.

  The epoxy equivalent of the epoxy resin is preferably from 50 to 5,000, more preferably from 50 to 3,000, further preferably from 80 to 2,000, and still more preferably from 110 to 1,000. When the content falls within this range, the cured product of the photosensitive resin composition has a sufficient crosslink density and can provide an insulating layer having a small surface roughness. The epoxy equivalent can be measured according to JIS K7236 and is the mass of a resin containing one equivalent of an epoxy group.

  The weight average molecular weight of the epoxy resin is preferably from 100 to 5000, more preferably from 250 to 3000, and still more preferably from 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(E) Reactive diluent>
The photosensitive resin composition may further contain (E) a reactive diluent. By containing the component (E), photoreactivity can be improved. As the component (E), for example, a liquid, solid, or semi-solid photosensitive (meth) acrylate compound having one or more (meth) acryloyl groups in one molecule at room temperature can be used. Room temperature means about 25 ° C. “(Meth) acryloyl group” refers to an acryloyl group and a methacryloyl group.

  Representative photosensitive (meth) acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono- or diacrylates, acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, aminoalkyl acrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Polyhydric alcohols or polyhydric acrylates of these adducts of ethylene oxide, propylene oxide or ε-caprolactone; Phenols such as nonoxyacrylate and phenoxyethyl acrylate, or acrylates such as ethylene oxide or propylene oxide adduct thereof, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and / or Examples include methacrylates corresponding to the above acrylates. Among these, polyhydric acrylates or polyhydric methacrylates are preferable. For example, as trivalent acrylates or methacrylates, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylol propane EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetrafurfuryl alcohol oligo (meth) acrylate, ethyl carbitol oligo (meth) acrylate, 1,4-butanediol Oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate Rate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, (meth) acrylate of N, N, N ′, N′-tetrakis (β-hydroxyethyl) ethyldiamine, and the like. Examples of tri- or higher acrylates or methacrylates include tri (2- (meth) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, and tri (3- (meth) acryloyloxypropyl). Phosphate, tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- ( Meta) Acri Yl-2-hydroxy propyl) and di (2- (meth) acryloyloxyethyl) phosphate triester (meth) acrylates such as phosphates. One of these photosensitive (meth) acrylate compounds may be used alone, or two or more thereof may be used in combination.

  The content of the component (E) when the component is blended is, from the viewpoint of promoting photocuring and suppressing stickiness when the cured product is formed, when the entire solid content of the photosensitive resin composition is 100% by mass. , Preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 5% by mass or more, and 8% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

<(F) Organic solvent>
The photosensitive resin composition may further contain (F) an organic solvent. The varnish viscosity can be adjusted by including the component (F). (F) Examples of the organic solvent include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol and propylene glycol. Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate, esters such as ethyl diglycol acetate, Examples include aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. When the organic solvent is used, the content can be appropriately adjusted from the viewpoint of applicability of the photosensitive resin composition.

<(G) Other additives>
The photosensitive resin composition may further contain (G) other additives to such an extent that the object of the present invention is not impaired. (G) Other additives include, for example, thermoplastic resins, organic fillers, fine particles such as melamine, organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, Colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, and pyrogallol; thickeners such as bentone and montmorillonite; silicone-based, fluorine-based, and vinyl resin-based defoamers; Flame retardants such as brominated epoxy compounds, acid-modified brominated epoxy compounds, antimony compounds, aromatic condensed phosphate esters, halogen-containing condensed phosphate esters, phenolic curing agents, cyanate ester curing agents, etc. May be added thermosetting resins, various additives like.

  The photosensitive resin composition is obtained by mixing the above-mentioned components (A) to (D) as essential components, appropriately mixing the above-mentioned components (E) to (G) as optional components, and, if necessary, three rolls. A resin varnish can be produced by kneading or stirring with a kneading means such as a ball mill, a bead mill, and a sand mill, or a stirring means such as a super mixer and a planetary mixer.

<Physical properties and uses of photosensitive resin composition>
Since the photosensitive resin composition of the present invention contains the component (A-1) and the component (A-2), even if the content of the component (B) is large, it exhibits excellent resolution. For this reason, there is usually no residue such as resin in the unexposed portion. Further, since the resolution is excellent, there is usually no resin filling or peeling between L / S (line / space). The minimum opening via diameter with no residue is preferably 100 μm or less, more preferably 90 μm or less, further preferably 80 μm or less, and 70 μm or less. The lower limit is not particularly limited, but may be 1 μm or more. The resolution can be evaluated according to the method described below in <Evaluation of Resolution>.

  The cured product obtained by photocuring the photosensitive resin composition of the present invention at 190 ° C. for 90 minutes after photocuring exhibits a characteristic of low average coefficient of linear thermal expansion. That is, an insulating layer and a solder resist having a low average linear thermal expansion coefficient are provided. The average coefficient of linear thermal expansion is preferably 50 ppm or less, more preferably 45 ppm or less, and even more preferably 40 ppm or less. The lower limit is not particularly limited, but may be 10 ppm or more. The average linear thermal expansion coefficient can be measured according to the method described below in <Measurement of average linear thermal expansion coefficient, glass transition temperature, and evaluation of crack resistance>.

  A cured product obtained by photocuring the photosensitive resin composition of the present invention at 190 ° C. for 90 minutes after photocuring exhibits a property of a high glass transition temperature. That is, an insulating layer and a solder resist having a high glass transition temperature are provided. The glass transition temperature is preferably 150 ° C. or higher, more preferably 160 ° C. or higher, and further preferably 170 ° C. or higher. The upper limit is not particularly limited, but may be 300 ° C. or less. The glass transition temperature can be measured according to the method described below in <Measurement of average linear thermal expansion coefficient, glass transition temperature, and evaluation of crack resistance>.

  The cured product obtained by photocuring the photosensitive resin composition of the present invention and then heat-curing at 190 ° C. for 90 minutes exhibits excellent crack resistance. That is, an insulating layer and a solder resist having excellent crack resistance are provided. Even if the temperature rise test between −65 ° C. and 150 ° C. is repeated 500 times, cracks and peeling are not observed. The crack resistance can be evaluated according to the method described below in <Measurement of average linear thermal expansion coefficient, glass transition temperature, evaluation of crack resistance>.

  The use of the photosensitive resin composition of the present invention is not particularly limited, but a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, a circuit board (laminate board use, a multilayer printed wiring board use, etc.), It can be used in a wide range of applications requiring a photosensitive resin composition such as a solder resist, an underfill material, a die bonding material, a semiconductor sealing material, a filling resin, and a filling resin for components. Among them, a photosensitive resin composition for an insulating layer of a printed wiring board (a printed wiring board using a cured product of the photosensitive resin composition as an insulating layer), a photosensitive resin composition for an interlayer insulating layer (a photosensitive resin composition). Printed wiring board using cured product as interlayer insulating layer), photosensitive resin composition for plating (printed wiring board with plating formed on cured product of photosensitive resin composition), and photosensitive resin composition for solder resist (A printed wiring board using a cured product of the photosensitive resin composition as a solder resist).

[Photosensitive film]
The photosensitive resin composition of the present invention can be coated on a support substrate in a resin varnish state, and dried by an organic solvent to form a photosensitive resin composition layer, thereby forming a photosensitive film. Alternatively, a photosensitive film formed in advance on a support may be laminated on a support substrate. The photosensitive film can be laminated on various supporting substrates. As the supporting substrate, a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate can be mainly used.

[Photosensitive film with support]
The photosensitive resin composition of the present invention can be suitably used in the form of a photosensitive film with a support in which a photosensitive resin composition layer is formed on a support. That is, the photosensitive film with a support includes a support and a photosensitive resin composition layer formed of the photosensitive resin composition of the present invention provided on the support.

  Examples of the support include a polyethylene terephthalate film, a polyethylene naphthalate film, a polypropylene film, a polyethylene film, a polyvinyl alcohol film, a triacetyl acetate film and the like, and a polyethylene terephthalate film is particularly preferred.

  Commercially available supports include, for example, product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name “PS-25” manufactured by Teijin Limited. And the like, but not limited thereto. These supports are preferably coated with a release agent such as a silicone coating agent on the surface to facilitate removal of the photosensitive resin composition layer. The thickness of the support is preferably in the range of 5 μm to 50 μm, and more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 μm or more, it is possible to prevent the support from being broken when the support is peeled off before development, and by setting the thickness to 50 μm or less, it is possible to reduce Resolution can be improved. Further, a low fisheye support is preferred. Here, fisheye means that when a film is produced by hot-melting a material, kneading, extruding, biaxial stretching, casting method, etc., foreign matter, undissolved matter, oxidized degraded matter, etc. of the material are taken into the film. It is a thing.

  Further, in order to reduce scattering of light at the time of exposure by active energy rays such as ultraviolet rays, the support is preferably one having excellent transparency. Specifically, the support preferably has a turbidity (haze standardized by JIS K6714) as an index of transparency of 0.1 to 5. Further, the photosensitive resin composition layer may be protected by a protective film.

  By protecting the photosensitive resin composition layer side of the photosensitive film with a support with a protective film, it is possible to prevent dust and the like from adhering to the surface of the photosensitive resin composition layer and from scratches. As the protective film, a film composed of the same material as the above-mentioned support can be used. The thickness of the protective film is not particularly limited, but is preferably in the range of 1 μm to 40 μm, more preferably in the range of 5 μm to 30 μm, and still more preferably in the range of 10 μm to 30 μm. When the thickness is 1 μm or more, the handleability of the protective film can be improved, and when the thickness is 40 μm or less, the cost tends to be improved. The protective film preferably has a smaller adhesive force between the photosensitive resin composition layer and the protective film than the adhesive force between the photosensitive resin composition layer and the support.

  The photosensitive film with a support of the present invention is prepared by, for example, preparing a resin varnish obtained by dissolving the photosensitive resin composition of the present invention in an organic solvent according to a method known to those skilled in the art, and coating the resin varnish on a support. Then, the organic solvent can be dried by heating or blowing with hot air to form a photosensitive resin composition layer. Specifically, first, after completely removing bubbles in the photosensitive resin composition by a vacuum defoaming method or the like, the photosensitive resin composition is applied on a support, and the solvent is removed using a hot air oven or a far-infrared oven. The photosensitive film with a support can be manufactured by removing and drying, and then laminating a protective film on the photosensitive resin composition layer obtained as required. Specific drying conditions vary depending on the curability of the photosensitive resin composition and the amount of the organic solvent in the resin varnish, but in the case of a resin varnish containing 30% by mass to 60% by mass of an organic solvent, 80 ° C to 120 ° C. For 3 to 13 minutes. The amount of the residual organic solvent in the photosensitive resin composition layer is preferably 5% by mass or less based on the total amount of the photosensitive resin composition layer, from the viewpoint of preventing diffusion of the organic solvent in a later step. More preferably, the content is 2% by mass or less. Those skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the photosensitive resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing a decrease in sensitivity and resolution inside the photosensitive resin composition layer. , More preferably in the range of 10 µm to 200 µm, still more preferably in the range of 15 µm to 150 µm, still more preferably in the range of 20 µm to 100 µm, and still more preferably in the range of 20 µm to 60 µm.

Examples of the coating method of the photosensitive resin composition include a gravure coating method, a microgravure coating method, a reverse coating method, a kiss reverse coating method, a die coating method, a slot die method, a lip coating method, a comma coating method, a blade coating method, Roll coating, knife coating, curtain coating, chamber gravure coating, slot orifice, spray coating, dip coating, and the like.
The photosensitive resin composition may be applied several times, may be applied once, or may be applied in combination of different methods. Among them, the die coating method, which is excellent in uniform coating property, is preferable. In addition, in order to prevent foreign matter from entering, it is preferable to carry out the coating step in an environment in which foreign matter is less generated, such as a clean room.

  The photosensitive resin composition layer of the photosensitive film with a support of the present invention has a property of being excellent in tackiness. Even if the surface of the photosensitive resin composition layer is strongly pressed with a finger, it is preferable that a fingerprint mark is slightly left, and it is more preferable that there is no fingerprint mark. The tackiness can be measured according to the description of <Evaluation of Film Appearance and Tackability> described below.

  The photosensitive resin composition layer of the photosensitive film with a support according to the present invention exhibits excellent flexibility. Even when the photosensitive resin composition layer is cut out with a cutter knife, it is preferable that scattering and cracks of the photosensitive resin composition are not found. Also, even if the photosensitive resin composition layer is bent 180 °, It is preferable that no scattering or crack of the object is observed. The flexibility can be measured according to the description of <Evaluation of flexibility> described later.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer formed of a cured product of the photosensitive resin composition of the present invention. The insulating layer is preferably used as a solder resist.

  Specifically, the printed wiring board of the present invention can be manufactured using the above-described photosensitive film or the photosensitive film with a support. Hereinafter, a case where the insulating layer is a solder resist will be described.

<Coating and drying process>
The photosensitive resin composition is directly applied on a circuit board in a resin varnish state, and the organic solvent is dried to form a photosensitive film on the circuit board.

  Examples of the circuit board include a glass epoxy board, a metal board, a polyester board, a polyimide board, a BT resin board, and a thermosetting polyphenylene ether board. Here, the circuit substrate refers to a substrate on which a patterned conductor layer (circuit) is formed on one surface or both surfaces of the substrate as described above. In a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which one or both surfaces of the outermost layer of the multilayer printed wiring board are a patterned conductor layer (circuit) is also used. Included in the circuit board. The surface of the conductor layer may be previously subjected to a roughening treatment by a blackening treatment, a copper etching or the like.

  As the coating method, full-screen printing by a screen printing method is generally widely used, but any other coating method may be used as long as the coating method enables uniform coating. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method , Brushing and other usual coating methods can all be used. After the application, drying is performed in a hot air oven or a far-infrared oven, if necessary. The drying conditions are preferably 80 ° C. to 120 ° C. for 3 minutes to 13 minutes. Thus, a photosensitive film is formed on the circuit board.

<Lamination process>
When a photosensitive film with a support is used, the photosensitive resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the laminating step, if the photosensitive film with the support has a protective film, after removing the protective film, the photosensitive film with the support and the circuit board are preheated as necessary, and the photosensitive resin composition The object layer is pressed against the circuit board while applying pressure and heating. In the case of a photosensitive film with a support, a method of laminating a circuit board under reduced pressure by a vacuum lamination method is suitably used.

Although the conditions of the laminating step are not particularly limited, for example, the pressing temperature (laminating temperature) is preferably 70 ° C. to 140 ° C., and the pressing pressure is preferably 1 kgf / cm ^{2 to} 11 kgf / cm ² (9. 8 × 10 ⁴ N / m ² -107.9 × 10 ⁴ N / m ² ), preferably in a pressure bonding time of 5 seconds to 300 seconds, and under a reduced pressure of an air pressure of 20 mmHg (26.7 hPa) or less. Is preferred. The laminating step may be a batch type or a continuous type using a roll. The vacuum lamination method can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum press laminator manufactured by Meiki Seisakusho, a roll dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. Thus, a photosensitive film is formed on the circuit board.

<Exposure process>
After a photosensitive film is provided on a circuit board by a coating and drying process, or a laminating process, then, through a mask pattern, a predetermined portion of the photosensitive resin composition layer is irradiated with actinic rays, and the photosensitive portion of the irradiated portion is exposed. An exposure step of photo-curing the resin composition layer is performed. Examples of the actinic ray include an ultraviolet ray, a visible ray, an electron beam, an X-ray, and the like, and an ultraviolet ray is particularly preferable. Dose of ultraviolet light is approximately ^{10mJ / cm 2 ~1000mJ / cm 2} . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board and a non-contact exposure method in which exposure is carried out using a parallel light beam without bringing the mask pattern into contact with each other, and either method may be used. When a support is present on the photosensitive resin composition layer, exposure may be performed from above the support, or exposure may be performed after removing the support.

  Since the solder resist uses the photosensitive resin composition of the present invention, it has excellent resolution. For this reason, as the exposure pattern in the mask pattern, for example, the ratio (L / S) of the circuit width (line; L) and the width between circuits (space; S) is 100 μm / 100 μm or less (ie, the wiring pitch is 200 μm or less). , L / S = 80μm / 80μm or less (wiring pitch 160μm or less), L / S = 70μm / 70μm or less (wiring pitch 140μm or less), L / S = 60μm / 60μm or less (wiring pitch 120μm or less) It is. Note that the pitch need not be the same over the entire circuit board.

<Development process>
After the exposure step, if a support is present on the photosensitive resin composition layer, the support is removed, and then a portion that has not been photocured (unexposed portion) is removed by wet development or dry development. Then, the pattern can be formed.

  In the case of the above wet development, a safe and stable developer having good operability, such as an alkaline aqueous solution, an aqueous developer, and an organic solvent, is used as the developer, and a developing step using an alkaline aqueous solution is preferable. In addition, as a developing method, a known method such as spraying, rocking immersion, brushing, and scraping is appropriately employed.

Examples of the alkaline aqueous solution used as a developer include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; and sodium phosphate. An alkali metal phosphate such as potassium phosphate, sodium pyrophosphate, an aqueous solution of an alkali metal pyrophosphate such as potassium pyrophosphate, and an aqueous solution of an organic base containing no metal ion such as tetraalkylammonium hydroxide, An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred because it does not contain metal ions and does not affect the semiconductor chip.
To these alkaline aqueous solutions, a surfactant, an antifoaming agent or the like can be added to the developer for improving the developing effect. The pH of the alkaline aqueous solution is, for example, preferably in the range of 8 to 12, and more preferably in the range of 9 to 11. Further, the base concentration of the alkaline aqueous solution is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline aqueous solution can be appropriately selected according to the developability of the photosensitive resin composition layer, but is preferably from 20 ° C to 50 ° C.

  Organic solvents used as a developer include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Monobutyl ether.

  The concentration of such an organic solvent is preferably 2% by mass to 90% by mass based on the total amount of the developer. Further, the temperature of such an organic solvent can be adjusted according to the developing property. Further, such organic solvents can be used alone or in combination of two or more. Examples of the organic solvent-based developer used alone include 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

  In pattern formation, two or more of the above-described developing methods may be used in combination, if necessary. Development methods include a dip method, a battle method, a spray method, a high-pressure spray method, brushing, and slapping, and a high-pressure spray method is suitable for improving resolution. When the spray method is adopted, the spray pressure is preferably 0.05 MPa to 0.3 MPa.

<Heat curing (post bake) process>
After the development step, a heat curing (post bake) step is performed to form a solder resist. Examples of the post-baking step include an ultraviolet irradiation step using a high-pressure mercury lamp and a heating step using a clean oven. When irradiating with ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed at an irradiation amount of about 0.05 J / cm ^{2 to} 10 J / cm ² . The heating conditions may be appropriately selected according to the type and content of the resin component in the photosensitive resin composition, but are preferably in the range of 150 ° C. to 220 ° C. for 20 minutes to 180 minutes, more preferably The temperature is selected in the range of 160 ° C to 200 ° C for 30 minutes to 120 minutes.

<Other steps>
The printed wiring board may further include a drilling step and a desmearing step after forming the solder resist. These steps may be performed according to various methods used in the manufacture of printed wiring boards and known to those skilled in the art.

  After the formation of the solder resist, a via hole and a through hole are formed by performing a drilling step on the solder resist formed on the circuit board, if desired. The drilling step can be performed, for example, by a known method such as a drill, a laser, or plasma, or a combination of these methods as necessary. A drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferable.

  The desmear process is a process of performing a desmear process. Generally, resin residue (smear) adheres to the inside of the opening formed in the drilling step. Since such smear causes electrical connection failure, a process of removing smear (desmear process) is performed in this step.

  The desmear treatment may be performed by a dry desmear treatment, a wet desmear treatment, or a combination thereof.

  Examples of the dry desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be performed using a commercially available plasma desmear treatment device. Among commercially available plasma desmear treatment apparatuses, examples suitable for use in the production of printed wiring boards include a microwave plasma apparatus manufactured by Nissin Corporation and a normal pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd.

  Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When performing desmear treatment using an oxidizing agent solution, it is preferable to perform swelling treatment with a swelling solution, oxidation treatment with an oxidizing agent solution, and neutralization treatment with a neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing the substrate having via holes or the like formed therein in a swelling liquid heated to 60 ° C to 80 ° C for 5 minutes to 10 minutes. As the oxidizing agent solution, an aqueous solution of alkaline permanganate is preferable. For example, a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be given. The oxidation treatment with the oxidant solution is preferably performed by immersing the substrate after the swelling treatment in the oxidant solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably performed by immersing the substrate after the oxidation treatment in the neutralizing solution at 30 ° C. to 50 ° C. for 3 minutes to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and examples of commercially available products include “Reduction Solution Securiganto P” manufactured by Atotech Japan.

  When the dry desmear treatment and the wet desmear treatment are performed in combination, the dry desmear treatment may be performed first, or the wet desmear treatment may be performed first.

  The case where the insulating layer is used as an interlayer insulating layer can be performed in the same manner as in the case of the solder resist. After the thermosetting step, a drilling step, a desmear step, and a plating step may be performed.

  The plating step is a step of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method for forming the pattern thereafter, for example, a subtractive method, a semi-additive method, or the like known to those skilled in the art can be used.

[Semiconductor device]
The semiconductor device of the present invention includes a printed wiring board. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electric appliances (for example, computers, mobile phones, digital cameras, televisions, and the like) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction point” is a “point where an electric signal is transmitted on the printed wiring board”, and the point may be a surface or an embedded point. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The method of mounting a semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Specifically, a wire bonding mounting method, a flip chip mounting method, and no bump There are a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), and the like. Here, the “mounting method using the bump-less build-up layer (BBUL)” refers to a “mounting method for directly embedding a semiconductor chip in a recess of a printed wiring board and connecting the semiconductor chip to wiring on the printed wiring board”. It is.

  Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited to these Examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

(Measurement of glass transition temperature of main chain of component (A))
The glass transition temperature of the main chain of each component (A) was calculated by the FOX equation shown below.
1 / Tg = (W1 / Tg1) + (W2 / Tg2) +... + (Wm / Tgm)
W1 + W2 + ... + Wm = 1
Wm represents the content (% by mass) of each monomer constituting the component (A), and Tgm represents the glass transition temperature (K) of each monomer constituting the component (A).

(Measurement of weight average molecular weight (Mw) of component (A))
The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) was defined as the weight average molecular weight of the component (A).

(Synthesis Example 1: Synthesis of Component (A-1))
350 g of methyl isobutyl ketone, 71 g of glycidyl methacrylate, 188 g of 1-adamantyl methacrylate and 16 g of azobisisobutyronitrile are added to a 5-neck reaction vessel having a content of 2 liters, and heated at 80 ° C. for 6 hours while blowing nitrogen gas. did. Next, 36 g of acrylic acid, 4 mg of methquinone and 4 mg of triphenylphosphine were added to the obtained reaction solution, and heated at 100 ° C. for 24 hours while blowing air. To the obtained reaction mixture, 48 g of tetrahydrophthalic anhydride was added, heated at 70 ° C. for 10 hours, and a solvent was added to obtain a polymer solution (theoretical Tg value of the polymer main chain was 172 ° C., solid content: 25% by mass, Mw: 20,000, acid value: 52 mgKOH / g).

(Synthesis Example 2: Synthesis of Component (A-2))
In Synthesis Example 1, 188 g of 1-adamantyl methacrylate was changed to 136 g of butyl acrylate. Except for the above, a polymer solution was obtained in the same manner as in Synthesis Example 1 (theoretical Tg value of the polymer main chain was −28 ° C., solid content: 45% by mass, Mw: 18,000, acid value: 52 mg KOH / g). .

(Synthesis example 3)
In Synthesis Example 1, the amount of azobisisobutyronitrile was changed from 16 g to 42 g. Except for the above, a polymer solution was obtained in the same manner as in Synthesis Example 2 (theoretical Tg value of the main skeleton of the polymer was 172 ° C., solid content: 25% by mass, Mw: 40000, acid value: 52 mg KOH / g).

(Synthesis example 4)
In Synthesis Example 1, 188 g of 1-adamantyl methacrylate was changed to 55 g of 1-adamantyl methacrylate and 25 g of methyl methacrylate, and the amount of azobisisobutyronitrile was changed from 16 g to 8 g. Except for the above, a polymer solution was obtained in the same manner as in Synthesis Example 2 (theoretical Tg value of the main skeleton of the polymer was 111 ° C., solid content: 25% by mass, Mw: 25000, acid value: 75 mg KOH / g).

(Synthesis Example 5: Synthesis of Component (A-3))
162 parts of 1,1′-bis (2,7-diglycidyloxynaphthyl) methane having an epoxy equivalent of 162 (“EXA-4700”, manufactured by Dainippon Ink and Chemicals, Inc.) is introduced into a gas introduction pipe, a stirrer, and a cooling pipe. And 340 parts of carbitol acetate were added thereto, dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. The mixture was heated to 95 to 105 ° C., and 72 parts of acrylic acid was gradually added dropwise and reacted for 16 hours. The reaction product was cooled to 80 to 90 ° C., and 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. In this way, a resin solution having a solid matter having an acid value of 90 mgKOH / g (nonvolatile content: 70%) was obtained.

<Examples 1 to 7, Comparative Examples 1 to 5>
Each component was blended at the blending ratio shown in the following table, and a resin varnish was prepared using a high-speed rotation mixer. Next, a PET film ("Lumirror T6AM" manufactured by Toray Industries, Inc., having a thickness of 38 µm, a softening point of 130 ° C, a release temperature of alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) as a support. PET ") was prepared. The adjusted resin varnish is uniformly applied to the release PET by a die coater so that the thickness of the photosensitive resin composition layer after drying becomes 40 μm, and dried at 80 ° C. to 110 ° C. for 5 minutes to release. A photosensitive film with a support having a photosensitive resin composition layer on a mold PET was obtained.

  The measurement method and the evaluation method in the physical property evaluation will be described.

<Evaluation of film appearance and tackiness>
The appearance of the photosensitive resin composition layer of the photosensitive film with a support produced in each of Examples and Comparative Examples was visually evaluated. Further, the tackiness of the photosensitive film with the support was evaluated in a constant temperature room at 25 ° C. using a probe tack tester (TE-6002). The measurement conditions were a probe having a diameter of 5 mm, a load of 1 kgf / cm ² , a contact time of 10 seconds, and a peeling rate of 0.1 mm / sec.
：: The appearance of the film is good and no trace is left on the probe.
Δ: The appearance of the film is good, but a slight mark remains on the probe.
×: The film has cissing or unevenness, or resin remains on the probe, and the film is broken.

<Evaluation of flexibility>
When the photosensitive resin composition layer of the photosensitive film with a support produced in each of the examples and the comparative examples was cut out at three places by a cutter knife, scattering of the resin and occurrence of cracks were visually evaluated. Furthermore, the state of occurrence of cracks when bent at 180 ° at three places was visually checked.
〇: No scattering or cracking of the photosensitive resin composition is observed at three places.
Δ: Either scattering or cracking of the photosensitive resin composition is observed at any of the three locations.
×: Scattering or cracking of the photosensitive resin composition is observed in any of the three places.

<Evaluation of resolution>
(Formation of laminate for evaluation)
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit in which a copper layer having a thickness of 18 μm is patterned is roughened by a treatment with a surface treating agent containing organic acid (CZ8100, manufactured by MEC Corporation). Was given. Next, the photosensitive resin composition layer of the photosensitive film with a support obtained in each of Examples and Comparative Examples was disposed so as to be in contact with the copper circuit surface, and a vacuum laminator (Nikko Materials VP160) was used. Lamination was performed to form a laminate in which the copper-clad laminate, the photosensitive resin composition layer, and the support were laminated in this order. The pressure bonding conditions were a vacuum evacuation time of 30 seconds, a pressure bonding temperature of 80 ° C., a pressure bonding pressure of 0.7 MPa, and a pressure pressing time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and exposed to ultraviolet light from above the support of the laminate using a pattern forming apparatus using a round hole pattern. Opening pattern: 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm round hole, L / S (line / space): 50 μm / 50 μm, 60 μm / 60 μm, 70 μm / 70 μm, 80 μm / 80 μm, 90 μm / 90 μm, 100 μm A / 100 μm line and space, a quartz glass mask for drawing a 1 cm × 2 cm square was used. After allowing to stand at room temperature for 30 minutes, the support was peeled off from the laminate. A 1% by mass aqueous solution of sodium carbonate at 30 ° C. as a developing solution was spray-developed at a spray pressure of 0.2 MPa for 2 minutes on the entire surface of the photosensitive resin composition layer on the laminate. After the spray development, ultraviolet ray irradiation of 1 J / cm ² was performed, and heat treatment was further performed at 180 ° C. for 30 minutes to form an insulating layer having an opening on the laminate. This was used as a laminate for evaluation.

(Evaluation of resolution)
An unexposed portion of a 1 cm × 2 cm portion of the evaluation laminate was visually observed. When no resin was left in the unexposed area, the evaluation was evaluated as Δ, and when the resin was visually confirmed, the evaluation was evaluated as X. Next, the formed via and L / S were observed by SEM (magnification: 1000 times), and the minimum opening via diameter without residue was measured. The L / S shapes at three arbitrary points were evaluated according to the following criteria.
：: There is no resin burial or peeling between the three L / S points.
×: Resin filling or peeling is observed between L / S at three points.

<Measurement of average linear thermal expansion coefficient, glass transition temperature, evaluation of crack resistance>
(Formation of cured product for evaluation)
The resin composition layers of the photosensitive films with a support obtained in Examples and Comparative Examples were exposed to ultraviolet light of 100 mJ / cm ² and light-cured. Thereafter, a 1% by mass aqueous solution of sodium carbonate at 30 ° C. as a developing solution was spray-developed on the entire surface of the photosensitive resin composition layer at a spray pressure of 0.2 MPa for 2 minutes. After spray development, 1 J / cm ² ultraviolet irradiation was performed, and further, heat treatment was performed at 190 ° C. for 90 minutes to form a cured product. Thereafter, the support was peeled off to obtain a cured product for evaluation.

(Measurement of average linear thermal expansion coefficient)
The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, and subjected to thermomechanical analysis by a tensile loading method using a thermomechanical analyzer (manufactured by Rigaku Corporation, Thermo Plus TMA8310). After attaching the test piece to the above-mentioned apparatus, measurement was continuously performed twice under a measurement condition of 1 g of load and a heating rate of 5 ° C./min. The average linear thermal expansion coefficient (ppm) from 25 ° C. to 150 ° C. in the second measurement was calculated.

(Measurement of glass transition temperature)
The cured product for evaluation was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and subjected to thermomechanical analysis by a tensile load method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology). . After the test piece was mounted on the above-mentioned apparatus, the measurement was performed under a load of 200 mN and a measurement rate of 2 ° C./min. The obtained peak top of tan δ was calculated as a glass transition temperature (° C.).

(Evaluation of crack resistance)
The obtained laminate for evaluation was exposed to the air at −65 ° C. for 15 minutes, and then heated at a rate of 180 ° C./min, and then exposed to the air at 150 ° C. for 15 minutes. A test was conducted in which the treatment by a heat cycle of lowering the temperature at a rate of ° C./min was repeated 500 times. After the test, the degree of cracking and peeling of the evaluation substrate was observed with an optical microscope (manufactured by Nikon Corporation, "ECLIPSE LV100ND"), and evaluated according to the following criteria.
：: No crack or peeling was observed.
X: Cracks and peeling are observed.

Abbreviations in the table are as follows.
(A) Component / Synthesis example 1: (A-1) component synthesized in Synthesis example 1 / Synthesis example 2: Component (A-2) synthesized in Synthesis example 2 / Synthesis example 3: Component synthesized in Synthesis example 3 -Synthesis Example 4: Component synthesized in Synthesis Example 4-Synthesis Example 5: (A-3) component synthesized in Synthesis Example 5-ZFR-1491H: bisphenol F type epoxy acrylate (Nippon Kayaku Co., Ltd., acid value 99mgKOH / g, solid content concentration about 70%)
-ZAR-2000: bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, solid content concentration about 70%)
Component (B) SC2050: 100 parts by mass of fused silica (manufactured by Admatechs, average particle size: 0.5 μm) and surface-treated with 0.5 parts by mass of aminosilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) (C) Component IrgacureOXE-02: 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (manufactured by BASF)
(D) Component: NC3000H: biphenyl type epoxy resin (Nippon Kayaku Co., Ltd., epoxy equivalent: about 272)
1031S: tetrakishydroxyphenylethane-type epoxy resin (Mitsubishi Chemical Corporation, epoxy equivalent: about 200)
(E) Component DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., acrylic equivalent: about 96)
(F) Component-EDGAc: Ethyl diglycol acetate-MEK: Methyl ethyl ketone (A1): Content (% by mass) of component (A-1) when the nonvolatile component in the resin composition is 100% by mass.
(A2): Content of the component (A-2) when the nonvolatile component in the resin composition is 100% by mass (A3): (A-) when the nonvolatile component in the resin composition is 100% by mass. 3) Content of component (B) Content of component: Content of component (B) when the total solid content of the photosensitive resin composition is 100% by mass.

  From the results in the above table, in Examples using the photosensitive resin composition of the present invention, the appearance, flexibility, resolution, and crack resistance of the film, the average linear thermal expansion coefficient is low, the glass transition temperature is It turned out to be high.

  On the other hand, Comparative Example 1 and Comparative Example 2, which do not contain the component (A-1), have poor flexibility, resolution, or crack resistance, have a high average linear thermal expansion coefficient, and have a low glass transition temperature. However, it could not be used as a photosensitive resin composition. Comparative Example 3 containing no (A-2) component had poor tackiness and resolution, and could not be used as a photosensitive resin composition. Further, Comparative Examples 4 and 5, which do not contain the component (A-1) and the component (A-2), are poor in any of film appearance, resolution and crack resistance, and are used as a photosensitive resin composition. I couldn't do it. In Comparative Example 1, Comparative Example 3, and Comparative Example 5, the residue in the unexposed portion was large, and the minimum via diameter and the separation of L / S could not be measured.

  In each of the examples, it was confirmed that even when the components (E) to (F) were not contained, the results were similar to those in the above examples, although the degree was different.

Claims (13)

(A-1) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of a main chain of 150 ° C. or more,
(A-2) a (meth) acrylic copolymer containing an ethylenically unsaturated group and a carboxyl group and having a glass transition temperature of a main chain of −20 ° C. or less;
(B) an inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less,
A photosensitive resin composition containing (C) a photopolymerization initiator, and (D) an epoxy resin,
The weight average molecular weight of each of the component (A-1) and the component (A-2) is 30,000 or less,
(B) The photosensitive resin composition, wherein the content of the component is 60% by mass or more and 85% by mass or less when the total solid content of the photosensitive resin composition is 100% by mass.   The photosensitive resin composition according to claim 1, further comprising (A-3) a resin containing an ethylenically unsaturated group and a carboxyl group.   The photosensitive resin composition according to claim 2, wherein the component (A-3) has a naphthalene skeleton.   The photosensitive resin composition according to claim 2 or 3, wherein the component (A-3) is an acid-modified naphthalene skeleton-containing epoxy (meth) acrylate.   When the content of the component (A-1) is A1, the content of the component (A-2) is A2, and the content of the component (A-3) is A3, (A1 + A2) / A3 is equal to 0. The photosensitive resin composition according to any one of claims 2 to 4, wherein the content is 1 or more and 0.8 or less.   A1 / A2 is 0.2 or more and 3.5 or less when the content mass of the (A-1) component is A1 and the content mass of the (A-2) component is A2. The photosensitive resin composition according to claim 1.   The photosensitive resin composition according to any one of claims 1 to 6, wherein the component (D) contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin.   The photosensitive resin composition according to any one of claims 1 to 7, wherein the component (B) contains silica.   A photosensitive film containing the photosensitive resin composition according to claim 1.   A photosensitive film with a support, comprising: a support; and a photosensitive resin composition layer containing the photosensitive resin composition according to claim 1 provided on the support.   A printed wiring board comprising an insulating layer formed of a cured product of the photosensitive resin composition according to claim 1.   The printed wiring board according to claim 11, wherein the insulating layer is a solder resist.   A semiconductor device comprising the printed wiring board according to claim 11.