KR20200035886A - Resin composition, photosensitive film, photosensitive film with support, printed wiring board and semiconductor device - Google Patents

Abstract

The present invention relates to a photosensitive resin composition capable of obtaining a cured product excellent in undercut resistance and, more specifically, to a resin composition comprising: (A) a resin containing an ethylenically unsaturated group and a carboxyl group; (B) an inorganic filler having an average particle diameter of 0.5 μm or more; (C) an epoxy resin; and (D) a photopolymerization initiator, wherein the (A) component contains (A-1) a naphthalene skeleton-containing resin.

Description

Resin composition, photosensitive film, photosensitive film with support, printed wiring board and semiconductor device {RESIN COMPOSITION, PHOTOSENSITIVE FILM, PHOTOSENSITIVE FILM WITH SUPPORT, PRINTED WIRING BOARD AND SEMICONDUCTOR DEVICE}

The present invention relates to a resin composition. Moreover, it is related with the photosensitive film obtained by using the said resin composition, the photosensitive film with a support body, a printed wiring board, and a semiconductor device.

In a printed wiring board, a solder resist may be formed as a permanent protective film for suppressing the adhesion of solder to portions where solder is unnecessary and to suppress corrosion of the circuit board. As a solder resist, it is common to use the photosensitive resin composition as described in patent document 1, for example.

Patent Document 1: Japanese Patent Application Publication No. 2014-115672

Since the solder resist is connected by soldering between the substrates, it is desired to have a fine opening pattern in which a part of the conductor layer having a wiring pattern is exposed. In addition, from the viewpoint of adhesiveness of the solder, it is required that the cross-sectional shape of the opening does not have an inverted taper shape, and in particular, it is required that the side surface of the opening is close to perpendicular to the layer plane. Here, the cross-sectional shape of the inverted taper shape means a wider shape as the diameter of the opening is inside, and specifically, a shape having a wider opening bottom than the front of the opening. In this specification, it is sometimes said that the property in which the cross-sectional shape is hard to be an inverse taper shape is excellent in "undercut resistance". On the other hand, the above-mentioned problem is a problem that arises even when the solder resist is formed using the resin composition.

The subject of this invention is the resin composition which can obtain the hardened | cured material excellent in undercut resistance; It is to provide the photosensitive film obtained by using the said resin composition, the photosensitive film with a support body, a printed wiring board, and a semiconductor device.

The present inventor, as a result of careful examination to solve the above problems, (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle diameter of 0.5 μm or more, (C) an epoxy resin, and , (D) As a resin composition containing a photopolymerization initiator, it was found that the above problems can be solved by using a resin composition in which the component (A) contains a (A-1) naphthalene skeleton-containing resin. The invention was completed.

In addition, the present inventor, as a result of diligent investigation to solve the above problems, (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle diameter of 0.5 μm or more, (C) an epoxy resin , And (D) as a resin composition containing a photopolymerization initiator, the weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in an alkali solution is as follows: (I):

Equation (I)

5≤S _(A) ≤110

By using the resin composition satisfying the above, it was found that the above problems can be solved and the present invention was completed.

That is, the present invention includes the following contents.

[1] (A) A resin containing an ethylenically unsaturated group and a carboxyl group,

(B) an inorganic filler having an average particle diameter of 0.5 µm or more,

(C) epoxy resin, and,

(D) Photopolymerization initiator

As a resin composition containing,

The resin composition in which (A) component contains (A-1) naphthalene skeleton containing resin.

[2] The resin composition according to [1], wherein the component (A-1) is a naphthol aralkyl-type resin.

[3] The resin composition according to [1] or [2], wherein the content of the component (A-1) is 5% by mass or more when the nonvolatile component in the component (A) is 100% by mass.

[4] The resin composition according to any one of [1] to [3], wherein the content of the component (A) is 10 mass% or more and 30 mass% or less when the nonvolatile component in the resin composition is 100 mass%.

[5] The resin composition according to any one of [1] to [4], wherein the content of the component (B) is 60% by mass or more when the nonvolatile component in the resin composition is 100% by mass.

[6] The resin composition according to any one of [1] to [5], wherein the component (A) contains an acid-modified epoxy (meth) acrylate resin other than the component (A-2) (A-1).

[7] The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in an alkali solution is represented by the following equation (I):

Equation (I)

5≤S _(A) ≤110

The resin composition according to any one of [1] to [6], which satisfies

[8] (A) A resin containing an ethylenically unsaturated group and a carboxyl group,

(B) an inorganic filler having an average particle diameter of 0.5 μm or more,

(C) epoxy resin, and,

(D) Photopolymerization initiator

As a resin composition containing,

(A) The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component in an alkali solution is represented by the following equation (I):

Equation (I)

5≤S _(A) ≤110

To satisfy the resin composition.

[9] The resin composition according to any one of [1] to [8], which is a resin composition for forming a solder resist of a printed wiring board.

[10] A photosensitive film containing the resin composition according to any one of [1] to [9].

[11] A photosensitive film with a support having a support and a resin composition layer comprising the resin composition according to any one of [1] to [9], formed on the support.

[12] A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].

[13] A semiconductor device comprising the printed wiring board according to [12].

According to the present invention, a resin composition capable of obtaining a cured product excellent in undercut resistance; The photosensitive film obtained by using the said resin composition, the photosensitive film with a support body, a printed wiring board, and a semiconductor device can be provided.

1 is a cross-sectional view of the laminate for evaluation used in Examples of the present invention, and is a cross-sectional view schematically showing a state when cut in a plane passing through a central axis of a circular via hole formed in an insulating layer.

[One. Resin composition according to the first embodiment of the present invention]

Hereinafter, the resin composition according to the first embodiment of the present invention will be described in detail.

The resin composition according to the first embodiment of the present invention includes (A) a resin comprising an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle diameter of 0.5 μm or more, (C) an epoxy resin, and (D) ) It is a resin composition containing a photopolymerization initiator. The component (A) of the resin composition according to the first embodiment contains (A-1) a naphthalene skeleton-containing resin. By using the resin composition according to the first embodiment of the present invention, a cured product excellent in undercut resistance can be obtained.

The resin composition may further contain (E) a reactive diluent, (F) an organic solvent, and (G) other additives as necessary. Hereinafter, each component contained in the resin composition will be described in detail.

<(A) Resin containing ethylenically unsaturated groups and carboxyl groups>

The resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group.

Examples of the ethylenically unsaturated group include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group and (meth) acryloyl group. From the viewpoint of the reactivity of photo-radical polymerization, a (meth) acryloyl group is preferred. The "(meth) acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. (A) Since component contains ethylenically unsaturated group, photo-radical polymerization is possible. The number of ethylenically unsaturated groups per molecule of the component (A) may be one, or two or more. Moreover, when (A) component contains 2 or more ethylenically unsaturated groups per molecule, these ethylenically unsaturated groups may be same or different.

In addition, since the component (A) contains a carboxyl group, the resin composition containing the component (A) exhibits solubility in an alkali solution (for example, 1% by mass aqueous sodium carbonate solution as an alkaline developer). (A) The number of carboxyl groups per molecule of the component may be one, or two or more.

In this embodiment, (A) component contains (A-1) naphthalene skeleton containing resin. (A) A component may further contain (A-2) acid-modified epoxy (meth) acrylate resin as needed. This (A-2) component is an example of (A) component other than (A-1) component.

<(A-1) Naphthalene skeleton-containing resin>

The component (A-1) is a resin belonging to the component (A), and therefore is a resin containing an ethylenically unsaturated group and a carboxyl group. For this reason, the (A-1) component is capable of photo-radical polymerization, and the resin composition containing the (A-1) component all exhibits solubility in an alkali solution.

It is preferable that (A-1) component has several ethylenically unsaturated groups in 1 molecule. Thereby, the mechanical strength and solvent resistance of the hardened | cured material of a resin composition can be improved. Moreover, it is preferable that (A-1) component has 2 or less ethylenically unsaturated groups with respect to one naphthalene skeleton. Thereby, since the crosslinking position (crosslinking point) can be adjusted, the mechanical strength and solvent resistance of the cured product of the resin composition can be controlled. More preferably, the ethylenically unsaturated group is contained in the substituent group of the naphthalene skeleton. In order to include an ethylenically unsaturated group in the substituent of the naphthalene skeleton, as the first precursor, for example, the H atom of the OH group of naphthol is substituted with a substituent containing an epoxy group (for example, an epoxy group, a glycidyl group) Can be obtained by adding a compound having an ethylenically unsaturated bond (for example, an unsaturated carboxylic acid, preferably (meth) acrylic acid) to the first precursor. Thereby, an ethylenically unsaturated group can be introduce | transduced into the substituent which a naphthalene skeleton has.

It is preferable that (A-1) component has a some carboxyl group in 1 molecule. Thereby, the solubility of the resin composition in an alkali solution (for example, an alkaline developer) can be enhanced. It is preferable that (A-1) component has 2 or less carboxyl groups with respect to 1 naphthalene skeleton. Thereby, solubility can be controlled. More preferably, the carboxyl group is contained in the substituent group of the naphthalene skeleton. In order to include a carboxyl group in the substituent of the naphthalene skeleton, as a first precursor, for example, a compound in which the H atom of the OH group of naphthol is substituted with a substituent containing an epoxy group is prepared, and for the first precursor, ethylenically unsaturated A compound having a bond (for example, unsaturated carboxylic acid, preferably (meth) acrylic acid) is added, thereby obtaining a second precursor having a secondary hydroxyl group, and for the second precursor, a carboxylic acid anhydride (for example tetrahydrophthalic acid) ). Thereby, both the ethylenically unsaturated group and the carboxyl group can be introduced into the substituent of the naphthalene skeleton.

Moreover, (A-1) component is a naphthalene skeleton containing resin. The naphthalene skeleton-containing resin refers to a compound containing one or more naphthalene skeletons in one molecule. The component (A-1) can be favorably mixed even if the resin composition contains the components (C) to (E), and thus the bias of the composition in the resin composition can be suppressed. Further, the component (A-1) can be dissolved in an alkali solution (for example, an alkaline developer) at an appropriate range of dissolution rate. In addition, when the resin composition containing the component (A-1) is developed with an alkaline developer, it is possible to suppress the occurrence of a portion that is too melted against the intention and a portion that does not melt against the intention, locally occurring in the resin composition. Therefore, the undercut resistance of the resin composition can be improved, and preferably, the side surface of the opening pattern can be made perpendicular to the plane of the layer.

In addition, when a naphthalene skeleton-containing resin is used as the component (A-1), the molecular stiffness is usually increased, so that the movement of the molecules in the resin composition is suppressed, and as a result, the glass transition temperature of the cured product of the resin composition is more It becomes high, and the average linear thermal expansion rate of hardened | cured material falls more. In addition, by the action of the component (A-1), the resistance of the cured product to internal stress caused by thermal expansion or thermal contraction is usually improved, so that damage to the cured product due to temperature change can be suppressed.

(A-1) A component may contain one naphthalene skeleton in one molecule, and may contain two or more naphthalene skeletons.

(A-1) A component is a resin containing the structure shown in following formula (1), for example. The component (A-1) may have a plurality of structures (for example, 1 to 10, preferably 1 to 6) represented by the following formula (1), or a plurality of structures represented by the following formula (1). In this case, the component (A-1) may contain a plurality of structures represented by the following formula (1) as structural units (repeating units). In addition, in the following general formula (1), the bonding hand bonded to R ¹ may be bonded to any of the carbon atoms capable of bonding among the carbon atoms of the naphthalene skeleton. Therefore, the bonding group to which R ¹ is bonded is bonded to a carbon atom of the same benzene ring as the bonding group (hereinafter sometimes referred to as “terminal bonding group”) in Formula (1) bonded to R ¹ and OR '. It may be present, or may be bonded to another benzene ring carbon atom. For example, the combination of the position of the terminal bond in the naphthalene skeleton and the bond attached to R ¹ is 1, 2 position, 1, 3 position, 1, 4 position, 1, 5 position, 1, of the naphthalene ring. 6 position, 1, 7 position, 1, 8 position, 2, 3 position, 2, 6 position, 2, 7 position may be sufficient.

Formula (1)

In the formula (1), R ¹ and R ² each independently represent an alkylene group which may have a substituent. The number of carbon atoms in R ¹ is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Moreover, the alkylene group may be linear or branched. As an alkylene group, a methylene group, ethylene group, propylene group, butylene group, etc. are mentioned, for example.

The substituents which R ¹ and R ² may have are each independently, for example, a halogen atom, an alkyl group, an alkoxy group, an aryl group, an arylalkyl group, a silyl group, an acyl group, an acyloxy group, a carboxy group, a sulfo group, and a cyano group. And an ogee group, a nitro group, a hydroxyl group, a mercapto group, and an oxo group.

In the formula (1), X represents an arylene group which may have a substituent. The number of carbon atoms in X is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 10. The arylene group is, for example, a phenylene group, anthracenyl group, phenanthrenylene group, or biphenylene group.

Substituents which X may have include, for example, the same substituents as R ¹ and R ² may have.

In the formula (1), a represents 0 or 1. Here, a is the number of groups X.

In the formula (1), s represents 0 or 1. Here, s and t are the number of groups R ¹ and R ² , respectively. In addition, in said Formula (1), t represents 0 or 1. However, s + t does not become 0 in s and t. Especially, when a = 1, it is preferable that both s and t are 1. When a = 0, it is preferable that one of s and t is 0.

In the formula (1), OR 'is a substituent on the naphthalene skeleton. In the formula (1), R 'each independently represents an organic group containing an ethylenically unsaturated group and a carboxyl group.

R 'preferably represents a group represented by the following formula (2).

Formula (2)

In the formula (2), R ³ represents a trivalent group, preferably a trivalent hydrocarbon group which may have a substituent (however, a hetero atom may be interposed between the carbon-carbon bonds (CC bonds)) In particular, a trivalent aliphatic hydrocarbon group which may have a substituent is particularly preferable.

This R ³ may be a trivalent residue of an epoxy group-containing substituent which may have a substituent. R ³ teeth Substituents which can have, for example, the same as the substituents that R ¹ and R ² may have include.

In the formula (2), R ⁴ represents an organic group containing an ethylenically unsaturated group. As a preferable example of the organic group containing an ethylenically unsaturated group, a (meth) acryloyloxy group is mentioned. The "(meth) acryloyloxy group" includes acryloyloxy group, methacryloyloxy group, and combinations thereof.

In the formula (2), R ⁵ is an organic group containing a carboxyl group. An example of an organic group containing a carboxyl group is -OCO-R ⁶ -COOH. Here, R ⁶ represents a divalent group. As R ⁶ , a divalent hydrocarbon group which may have a substituent is preferable. The number of carbon atoms in R ⁶ is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 6. Examples of the divalent hydrocarbon group include, for example, a linear or branched acyclic alkylene group such as a methylene group, an ethylene group, a propylene group, and a butylene group; A saturated or unsaturated divalent alicyclic hydrocarbon group; And arylene groups such as phenylene groups and naphthylene groups. Especially, a divalent alicyclic hydrocarbon group and an arylene group are preferable, and a 4-cyclohexylene group and a phenylene group are particularly preferable. In addition, the substituents which R ⁶ may have include, for example, the same examples as the substituents that R ¹ and R ² may have. -OCO-R ⁶ -COOH in -CO-R ⁶ -COOH is typically the residue of a carboxylic anhydride. Examples of the carboxylic anhydride are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride.

In the formula (1), c usually represents an integer of 1 to 6, preferably 1 to 3, and more preferably 1 to 2. Here, c is the number of groups OR '.

<First example of component (A-1) (a = 1)>

A preferable example of the component (A-1) is a naphthol aralkyl-type resin. The "naphthol aralkyl type resin" is a resin containing a group having a structure excluding the H atom of the OH group from the naphthol aralkylene group.

A preferable naphthol aralkyl-type resin is a resin containing the structure of a = 1 in the said general formula (1), For example, it is a resin containing the structure shown in the following general formula (3).

Formula (3)

In the formula (3), R ¹ , R ² , X, s, t, R 'and c are as described above. It is preferable that both s and t are 1.

More preferable resin of the naphthol aralkyl type resin is a resin containing the structure of c = 1, s = 1, and t = 1 in the formula (3), for example, the following formula (4) or It is a naphthol aralkyl-type resin containing the bivalent group of the structure shown in (5).

Formula (4)

Formula (5)

In the above formula (4) or (5), R ¹ , R ² , X, R 'and c are as described above. The naphthol aralkyl-type resin represented by the said Formula (4) or (5) is a resin which can synthesize | combine the naphthol aralkyl-type epoxy resin B used in the synthesis example 2 mentioned later as a material. The naphthol aralkyl-type epoxy resin B can be obtained, for example, as "ESN-475V" (Epoxy equivalent 325) manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd.

<Second example of (A-1) component (a = 0)>

Preferred examples of the component (A-1) other than the naphthol aralkyl-type resin (a = 0) include the structures of c = 2, s = 1, and t = 0 in the formula (1). It is a resin, for example, a naphthalene skeleton-containing resin containing a divalent group having a structure represented by the following formula (6).

Formula (6)

In the formula (6), R ¹ , R and R 'are as described above. The naphthalene skeleton-containing resin represented by the formula (6) can be synthesized using a naphthalene skeleton-containing epoxy resin A (1,1'-bis (2,7-diglycidyloxynaphthyl) methane, epoxy equivalent 162) as a material. Resin (see Synthesis Example 1 to be described later). The naphthalene skeleton-containing epoxy resin A can be obtained, for example, as “EXA-4700” manufactured by Dainippon Inki Chemical Industries, Ltd.

(A-1) As a weight average molecular weight of a component, from a viewpoint of film-forming property, it is preferable that it is 500 or more, it is more preferable that it is 1000 or more, it is more preferable that it is 1500 or more, and it is still more preferable that it is 2000 or more. As an upper limit, from a viewpoint of developability, it is preferable that it is 10000 or less, it is more preferable that it is 8000 or less, and it is still more preferable that it is 7500 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The acid value of the component (A-1) is preferably 0.1 mgKOH / g, 0.5 mgKOH / g or more, or 1 mgKOH / g or more from the viewpoint of improving the solubility of the resin composition in an alkali solution. On the other hand, it is preferable that the acid value is 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and more preferably 100 mgKOH / g or less from the viewpoint of suppressing the elution of the fine pattern of the cured product into an alkali solution and improving undercut resistance. It is more preferable. Here, the acid value means 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 the measured resin solution is precisely weighed, then 30 g of acetone is added to the resin solution, and the resin solution is uniformly dissolved. Then, an appropriate amount of phenolphthalein, 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 (7).

Equation (7)

A = 10 × Vf × 56.1 / (Wp × I)

On the other hand, in the equation (7), A represents the acid value [mgKOH / g], Vf represents the appropriate amount of KOH [mL], Wp represents the measured resin solution mass [g], and I represents the measured resin solution. It shows the ratio [mass%] of non-volatile components.

The weighted average value S _(A-1) based on the mass ratio of the dissolution rate [nm / sec] of the component (A-1) in an alkali solution is represented by the following equation (II):

Equation (II)

5≤S _(A-1) ≤110

It is preferable to satisfy. The dissolution rate in an alkali solution can be measured, for example, by the method described in Examples. More specifically, the weighted average value S _(A-1) of the dissolution rate of the component _(A-1) is more preferably 6 nm / sec or more, more preferably 10 nm / sec or more, particularly preferably 15 nm / sec It is the above, Preferably it is 100 nm / sec or less, More preferably, it is 90 nm / sec or less, More preferably, it is 80 nm / sec or less. When the weighted average value S _(A-1) of the dissolution rate of the component _(A-1) is in the above range, it is possible to suppress that the dissolution rate that the resin composition dissolves in the alkali developer is excessively slowed or accelerated. Therefore, it is possible to suppress the occurrence of a portion that is too melted against the intention and a portion that does not melt against the intention. Therefore, the undercut resistance can be improved, and preferably, the side surface of the opening pattern can be made perpendicular to the layer plane.

More preferably, when multiple types of naphthalene skeleton-containing resins are used as the component (A-1), the respective dissolution rates [nm / sec] of the naphthalene skeleton-containing resins are in the above range. Thereby, the said weighted average value S _(A-1) can reliably satisfy the said range.

From the viewpoint of adjusting the solubility of the resin composition to the alkali solution of the component (A-1), when the nonvolatile component in the component (A) is 100% by mass, the content is preferably 5% by mass or more. , It is more preferably 10% by mass or more, and even more preferably 20% by mass or more. The upper limit is usually 100% by mass or less, from the viewpoint of improving undercut resistance, preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.

(A-1) From the viewpoint of adjusting the solubility of the resin composition in an alkali solution, the component (A-1) is preferably set to 5% by mass or more when the nonvolatile component in the resin composition is 100% by mass. It is more preferable to be mass% or more, and even more preferably to be 15 mass% or more. From the viewpoint of improving the undercut resistance, the upper limit is preferably 30% by mass or less, more preferably 29% by mass or less, and even more preferably 28% by mass or less.

<Method for producing (A-1) component>

(A-1) The component is not limited to the above-described example, and is not particularly limited as long as it is a compound having a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group. And acid-modified unsaturated naphthalene skeleton-containing epoxy ester resins in which an unsaturated carboxylic acid is reacted with a naphthalene-type epoxy compound (naphthalene skeleton-containing epoxy compound), and a carboxylic anhydride is further reacted. A method for producing an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin will be described. First, an unsaturated carboxylic acid is reacted with a naphthalene skeleton-containing epoxy compound to obtain an unsaturated naphthalene skeleton-containing epoxy ester resin, and then, an unsaturated naphthalene skeleton-containing epoxy ester resin is reacted with a carboxylic acid anhydride. In this way, an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin can be obtained.

As the naphthalene skeleton-containing epoxy compound, any compound having one or more epoxy groups in the molecule can be used. For example, monohydroxynaphthalene type epoxy resin, dihydroxynaphthalene type epoxy resin, polyhydroxybinaphthalene type epoxy resin, And naphthalene-type epoxy resins having a naphthalene skeleton in the molecule, such as naphthalene-type epoxy resins and binaphthol-type epoxy resins obtained by condensation reaction between polyhydroxynaphthalene and aldehydes. Any of these may be used alone, or two or more of them may be used in combination.

As a monohydroxy naphthalene type epoxy resin, 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene are mentioned, for example. Examples of the dihydroxynaphthalene-type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, and 1,6-di And glycidyloxynaphthalene, 2,3-diglycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, and 2,7-diglycidyloxynaphthalene.

As a polyhydroxybinaphthalene type epoxy resin, for example, 1,1'-bi- (2-glycidyloxy) naphthyl, 1- (2,7-diglycidyloxy) -1 '-(2 '-Glycidyloxy) binaphthyl, 1,1'-bi- (2,7-diglycidyloxy) naphthyl, and the like.

As a naphthalene type epoxy resin obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, for example, 1,1'-bis (2,7-diglycidyloxynaphthyl) methane, 1- (2,7 -Diglycidyloxynaphthyl) -1 '-(2'-glycidyloxynaphthyl) methane, 1,1'-bis (2-glycidyloxynaphthyl) methane.

Among these, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule, and naphthalene-type epoxy resins obtained by condensation reaction between polyhydroxynaphthalene and aldehydes are preferred. 1,1'-bis (2,7-diglycidyloxynaphthyl) methane having 3 or more, 1- (2,7-diglycidyloxynaphthyl) -1 '-(2'-glycine Dioxynaphthyl) methane, 1- (2,7-diglycidyloxy) -1 '-(2'-glycidyloxy) binaphthyl, 1,1'-bi- (2,7-di Glycidyloxy) naphthyl is preferable in addition to the average linear thermal expansion coefficient and excellent heat resistance.

As an unsaturated carboxylic acid, acrylic acid, methacrylic acid, cinnamic acid, crotonic acid etc. are mentioned, for example, These may be used individually by 1 type or in combination of 2 or more types. Especially, acrylic acid and methacrylic acid are preferable from a viewpoint of improving the photocurability of the photosensitive resin composition. In addition, in the present specification, the naphthalene-type epoxy compound ester resin, which is a reactant of the above-mentioned naphthalene-type epoxy compound and (meth) acrylic acid, may be described as "naphthalene-type epoxy compound (meth) acrylate", and here, naphthalene The epoxy group of the type epoxy compound is generally extinguished substantially by reaction with (meth) acrylic acid. "(Meth) acrylate" includes methacrylate, acrylate, and combinations thereof. In some cases, acrylic acid and methacrylic acid are combined and referred to as "(meth) acrylic acid".

Examples of the carboxylic anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, and the like. These may be used, 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 developability and insulation reliability of the cured product.

In obtaining an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, in the presence of a catalyst, an unsaturated carboxylic acid and a naphthalene skeleton-containing epoxy compound are reacted to obtain an unsaturated naphthalene skeleton-containing epoxy ester resin, and then an unsaturated naphthalene skeleton-containing epoxy ester resin and carboxylic acid anhydride. You may react.

The amount of the catalyst used at this time is preferably 2% by mass or less, more preferably 0.0005% by mass to 1% by mass, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound, and the carboxylic acid anhydride, further It is preferably in the range of 0.001% by mass to 0.5% by mass. As the catalyst, for example, N-methylmorpholine, pyridine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU), 1,5-diazabicyclo [4.3.0] nonen-5 (DBN), 1,4-diazabicyclo [2.2.2] octane (DABCO), tri-n-butylamine or dimethylbenzylamine, butylamine, octylamine, monoethanolamine, diethanolamine, triethanolamine, already Dazole, 1-methylimidazole, 2,4-dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N Various amines such as -phenyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, and tetramethylammonium hydroxide Compounds; Phosphines such as trimethylphosphine, tributylphosphine, and triphenylphosphine; tetramethylphosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxylpropyl) Phosphonium salts such as phosphonium salts, triphenylphosphonium salts, and benzylphosphonium salts; as representative counter anions, phosphonium salts having chloride, bromide, carboxylate, hydrooxide, etc .; Sulfonium salts such as trimethylsulfonium salt, benzyltetramethylenesulfonium salt, phenylbenzylmethylsulfonium salt, or phenyldimethylsulfonium salt, as representative counter anions, sulfonium salts having carboxylate, hydrooxide, etc .; And acidic compounds such as phosphoric acid, p-toluenesulfonic acid, and sulfuric acid. The reaction can be performed, for example, in the range of 50 ° C to 150 ° C, and preferably in the range of 80 ° C to 120 ° C.

In obtaining an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, an organic solvent may be used, and as the organic solvent, an organic solvent similar to the organic solvent (F) described later can be used.

In obtaining an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, a polymerization inhibitor such as hydroquinone may be used. The amount of the polymerization inhibitor used at this time is preferably 2% by mass or less, more preferably 0.0005% by mass to 1% by mass, based on the total mass of the unsaturated carboxylic acid and the naphthalene skeleton-containing epoxy compound and the carboxylic acid anhydride. , More preferably, it is in the range of 0.001 mass% to 0.5 mass%.

As the acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, an acid-modified naphthalene skeleton-containing epoxy (meth) acrylate is preferable. The acid-modified naphthalene skeleton-containing epoxy (meth) acrylate refers to an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin obtained by using a (meth) acrylic acid as an unsaturated carboxylic acid using a naphthalene skeleton-containing epoxy compound.

(A-1) As another form of a component, the unsaturated which introduce | transduced the ethylenically unsaturated group and the naphthalene skeleton containing epoxy compound to the (meth) acrylic resin which has in the structural unit obtained by superposing | polymerizing (meth) acrylic acid, and introduce | transducing the ethylenically unsaturated group is unsaturated. And modified naphthalene skeleton-containing (meth) acrylic resins. It is also possible to react a carboxylic anhydride with a hydroxyl group formed upon introduction of an unsaturated group. As the carboxylic anhydride, the same one as the acid anhydride described above can be used, and the preferred range is also the same.

<(A-2) Acid-modified epoxy (meth) acrylate resin>

The acid-modified epoxy (meth) acrylate resin as the component (A-2) is a compound having a structure in which a carboxyl group is introduced into the (meth) acrylate of the epoxy compound. However, the component (A-1) is not included in the component (A-2).

(A-2) As an embodiment of the component, an acid-modified bisphenol-type epoxy in which (meth) acrylic acid is reacted with a bisphenol-type epoxy compound such as a bisphenol A-type epoxy compound or a bisphenol F-type epoxy compound, and a carboxylic acid anhydride is further reacted. (Meth) acrylate and the like. Specifically, an acid-modified bisphenol-type epoxy (meth) acrylic is obtained by reacting (meth) acrylic acid with a bisphenol-type epoxy compound to obtain a bisphenol-type epoxy (meth) acrylate, and reacting a bisphenol-type epoxy (meth) acrylate with a carboxylic acid anhydride. Rate.

(A-2) As another form of a component, acid-modified biphenyl-type epoxy (meth) acrylate etc. which made (meth) acrylic acid react with a biphenyl type epoxy compound, and further reacted with carboxylic anhydride are mentioned. Specifically, an acid-modified biphenyl-type epoxy is obtained by reacting (meth) acrylic acid with a biphenyl-type epoxy compound to obtain a biphenyl-type epoxy (meth) acrylate, and reacting the biphenyl-type epoxy (meth) acrylate with a carboxylic acid anhydride. (Meth) acrylate can be obtained.

(A-2) As another aspect of a component, the acid-modified epoxy (meth) acrylate which made (meth) acrylic acid react with the epoxy compound other than the above-mentioned epoxy compound, and further reacted with carboxylic anhydride is mentioned. As such an epoxy compound, For example, novolak-type epoxy resins, such as a phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, bisphenol A-type novolak-type epoxy resin, and alkylphenol novolak-type epoxy resin; Fluorine-containing epoxy resins such as perfluoroalkyl-type epoxy resins, and bixylenol-type epoxy resins; Dicyclopentadiene type epoxy resin; Trisphenol-type epoxy resins; tert-butyl-catechol type epoxy resin; Epoxy resins containing condensed ring skeletons such as anthracene type epoxy resins; Glycidylamine type epoxy resins; Glycidyl ester type epoxy resins; Linear aliphatic epoxy resins; Epoxy resin having a butadiene structure; Alicyclic epoxy resins; Heterocyclic epoxy resins; Spiro ring-containing epoxy resin; Cyclohexane dimethanol type epoxy resin; Trimethylol type epoxy resins; Tetraphenylethane type epoxy resin; Glycidyl group-containing acrylic resins such as polyglycidyl (meth) acrylate and copolymers of glycidyl methacrylate and acrylic acid esters; Fluorene-type epoxy resins; And halogenated epoxy resins.

Commercially available products can be used for such acid-modified epoxy (meth) acrylates, and specific examples include "ZAR-2000" manufactured by Nippon Kayaku Co., Ltd. (acid-modified bisphenol-type epoxy acrylate: bisphenol A-type epoxy resin, acrylic acid, and succinic anhydride. Of reactants), `` ZFR-1491H '' (acid-modified bisphenol-type epoxy acrylate: bisphenol F-type epoxy resin, acrylic acid, and acid anhydride reactant), `` ZFR-1533H '' (acid-modified bisphenol-type epoxy acrylate: bisphenol F type Epoxy resin, acrylic acid, and reactant of tetrahydrophthalic anhydride), `` ZCR-1569H '' (acid-modified biphenyl-type epoxy acrylate: reactant of biphenyl-type epoxy resin, acrylic acid, and acid anhydride), manufactured by Showa Denko And "PR-300CP" (reactants of cresol novolac-type epoxy resin, acrylic acid, and acid anhydride). These may be used individually by 1 type, or may be used in combination of 2 or more type.

(A-2) As another form of a component, the unsaturated modification which introduce | transduced (meth) acrylate of the epoxy compound to (meth) acrylic resin which has in the structural unit obtained by superposing | polymerizing (meth) acrylic acid, and introduce | transducing ethylenically unsaturated groups ( And meta) acrylic resins. The (meth) acrylate of the epoxy compound is, for example, glycidyl methacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth) acrylate, etc. Can be mentioned. It is also possible to react a carboxylic anhydride with a hydroxyl group formed upon introduction of an unsaturated group. As the carboxylic anhydride, the same ones as the carboxylic anhydride described above can be used, and the preferred range is also the same.

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

(A-2) As a weight average molecular weight of a component, from a viewpoint of film-forming property, it is preferable that it is 1000 or more, it is more preferable that it is 1500 or more, and it is still more preferable that it is 2000 or more. As an upper limit, from a viewpoint of developability, it is preferable that it is 20000 or less, it is more preferable that it is 15000 or less, and it is still more preferable that it is 14000 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

(A-2) As the acid value of the component, from the viewpoint of improving the solubility of the resin composition in an alkali solution, the acid value is preferably 0.1 mgKOH / g or more, more preferably 0.5 mgKOH / g or more, and more preferably 1 mgKOH / g or more It is more preferable. On the other hand, from the viewpoint of suppressing the elution of the alkali solution from the fine pattern of the cured product and improving the undercut resistance, the acid value is preferably 150 mgKOH / g or less, more preferably 120 mgKOH / g or less, and more preferably 100 mgKOH / g or less It is more preferable. Here, the acid value means the residual acid value of the carboxyl group present in the component (A-2), and the acid value can be measured by the aforementioned method.

The weighted average value S _(A-2) based on the mass ratio of the dissolution rate [nm / sec] of the component (A-2) in an alkali solution is represented by the following equation (III):

Equation (III)

1≤S _(A-2) ≤150

It is preferable to satisfy, more preferably, the following equation (IIIa):

Equation (IIIa)

1≤S _(A-2) ≤131

Satisfy. Thereby, the solubility of the resin composition in the alkali solution can be adjusted in consideration of the content of the component (A-1), and the undercut resistance can be controlled. The dissolution rate can be measured, for example, by the method described in Examples.

More preferably, when a plurality of types of acid-modified epoxy (meth) acrylate resins are used as the component (A-2), the respective dissolution rates [nm / sec] of the acid-modified epoxy (meth) acrylate resins are as described above. It is more preferably in the range of. Thereby, the said weighted average value S _(A-2) can reliably satisfy the said range.

(A-2) A component is 100 mass% of the nonvolatile component of (A) component from a viewpoint of adjustment of solubility to an alkali solution, and its content is the same as that of (A-1) component, or Less than that is preferable, and more preferably, when the content of the (A-2) component is 100 mass% of the nonvolatile component of the (A) component, 50 mass% of the content of the (A-1) component It is the following, More preferably, it is 45 mass% or less. (A-2) When content of a component is 100 mass% of the nonvolatile component of a resin composition, it is preferable to set it as 30 mass% or less from a viewpoint of adjusting the solubility of a resin composition with respect to an alkali solution, and 20 mass It is more preferable to use% or less, more preferably 15% by mass or less, and the lower limit is usually 0% by mass, but when used in combination with the component (A-1), the lower limit is 0.1% by mass or 0.2 It is good also as mass%.

The component (A-2) is preferably used in combination with the component (A-1) from the viewpoint of adjusting the heat resistance and mechanical strength, for example, the average linear thermal expansion coefficient and the glass transition temperature.

<(A-3) Any resin containing an ethylenically unsaturated group and a carboxyl group>

The component (A) may further contain (A-3) an arbitrary resin containing an ethylenically unsaturated group and a carboxyl group in combination with the above-mentioned (A-1) component and (A-2) component. (A-1) component and (A-2) component are not included in this (A-3) component.

Although the weight average molecular weight and acid value of (A-3) component are arbitrary, it is preferable that it exists in the same range as the weight average molecular weight and acid value of (A-2) component mentioned above. Thereby, the advantage as demonstrated in the term of the component (A-2) can be obtained.

<(A) Overall properties of component>

As the lower limit, the weight average molecular weight of the component (A) is preferably 500 or more or 1000 or more, more preferably 1500 or more, and even more preferably 2000 or more from the viewpoint of film-forming properties. As an upper limit, from a viewpoint of developability, it is preferable that it is 20000 or less, it is more preferable that it is 15000 or less, and it is still more preferable that it is 14500 or less. The weight average molecular weight is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in the alkali solution is the following equation (I):

Equation (I)

5≤S _(A) ≤110

It is preferable to satisfy. The dissolution rate in an alkali solution can be measured, for example, by the method described in Examples. More specifically, the weighted average value S _(A) of the dissolution rate of the component _(A) is usually 5 nm / sec or more, more preferably 10 nm / sec or more, still more preferably 15 nm / sec or more, and usually 110 nm / sec Hereinafter, it is preferably 100 nm / sec or less, more preferably 90 nm / sec or less, still more preferably 80 nm / sec or less. When the weighted average value S _(A) of the dissolution rate of the component _(A) is in the above range, it is possible to suppress that the dissolution rate in which the resin composition is dissolved in the alkali developer is excessively slowed or accelerated. Therefore, it is possible to suppress the occurrence of a portion that is too melted against the intention and a portion that does not melt against the intention. Therefore, the undercut resistance can be improved, and preferably, the side surface of the opening pattern can be made perpendicular to the layer plane.

More preferably, when a resin containing plural kinds of ethylenically unsaturated groups and carboxyl groups is used as the component (A), the dissolution rate [nm / sec] of each of the resins containing ethylenically unsaturated groups and carboxyl groups is the above. It is more preferably in the range of. Thereby, the said weighted average value S _(A) can reliably satisfy the said range.

(A) From the viewpoint of adjusting the solubility of the resin composition in an alkali solution, the component (A), when the non-volatile component in the resin composition is 100% by mass, is preferably 10% by mass or more, and 15% by mass It is more preferable to set it as above, and it is still more preferable to set it as 20 mass% or more. From the viewpoint of improving the undercut resistance, the upper limit is preferably 30% by mass or less, more preferably 29.5% by mass or less, and even more preferably 29% by mass or less.

<(B) Inorganic filler having an average particle diameter of 0.5 µm or more>

The resin composition contains (B) an inorganic filler having an average particle diameter of 0.5 µm or more. Even if the resin composition contains the component (B) (that is, even if the average particle diameter of the inorganic filler is large), it is possible to provide a resin composition capable of obtaining a cured product excellent in undercut resistance. In addition, by using the component (B), it is usually possible to lower the average linear thermal expansion coefficient of the cured product.

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, Aluminum hydroxide, 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 titanate, barium titanate , Barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly suitable. Moreover, as silica, spherical silica is preferable. The inorganic filler may be used singly or in combination of two or more kinds.

The average particle diameter of the inorganic filler is 0.5 µm or more, preferably 0.8 µm or more, and more preferably 1 µm or more from the viewpoint of obtaining a cured product excellent in undercut resistance. The upper limit of the average particle diameter is preferably 2.5 µm or less, more preferably 2 µm or less, still more preferably 1.5 µm or less, and even more preferably from the viewpoint of suppressing light reflection during exposure and obtaining excellent developability. It is 1.3 µm or less. Commercially available products of the inorganic filler having such an average particle diameter include, for example, "SC4050" manufactured by Adomatex, "Adoma Fine", "SFP series" manufactured by Denki Kagaku Kogyo, and manufactured by Shinnitetsu Sumikin Materials " SP (H) series '', `` Sciqas series '' manufactured by Sakai Kagaku Kogyo, `` Shihostar series '' manufactured by Nippon Shokubai Co., Ltd., `` AZ series '' manufactured by Shinnitetsu Sumikin Materials, `` AX series '', Sakai Kagaku And "B series" and "BF series" manufactured by Kogyo Co., Ltd. and the like.

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

The specific surface area of the inorganic filler is preferably 1 m 2 / g or more, more preferably 3 m 2 / g or more, particularly preferably 5 m 2 / g or more, from the viewpoint of obtaining a cured product excellent in undercut resistance. The upper limit is not particularly limited, but is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area can be obtained by adsorbing nitrogen gas on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, or a titanate-based compound from the viewpoint of increasing moisture resistance and dispersibility. It is preferably treated with at least one surface treatment agent such as a coupling agent. As a commercial item of a surface treatment agent, for example, "KBM403" manufactured by Shin-Etsu Chemical Co., Ltd. (3-glycidoxypropyl trimethoxysilane), "KBM803" manufactured by Shin-Etsu Chemical Co., Ltd. (3-mercaptopropyl trimethoxy Silane), `` KBE903 '' (3-aminopropyl triethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., `` KBM573 '' (N-phenyl-3-aminopropyl trimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. `` SZ-31 '' manufactured by Kogyo Co., Ltd. (hexamethyldisilazane), `` KBM103 '' manufactured by Shin-Etsu Chemical Co., Ltd. (phenyltrimethoxysilane), `` KBM-4803 '' manufactured by Shin-Etsu Chemical Co., Ltd. (long-chain epoxy type silane couple Ring agent) and the like.

(B) From the viewpoint of obtaining a cured product having a low average linear thermal expansion rate, the content of the component (B) is preferably 60% by mass or more, more preferably 60.5% by mass or more, when the nonvolatile component in the resin composition is 100% by mass. , More preferably 61% by mass or more. The upper limit is, for example, 90 mass% or less, 85 mass% or less, 82 mass% or less, or 80 mass% or less from the viewpoint of suppressing light reflection during exposure and obtaining excellent developability.

<(C) Epoxy resin>

The resin composition contains (C) an epoxy resin. By containing (C) component, reaction of (C) component or reaction of (C) component and (A) component becomes possible, and the mechanical strength and solvent resistance of hardened | cured material of a resin composition can be raised. However, (C) component mentioned here does not include the epoxy resin which belongs to (A) component.

Examples of the component (C) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins and bisphenol S type epoxy resins; Silenol type 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 novolac type epoxy resin; biphenyl type epoxy resin; linear aliphatic epoxy resin; epoxy resin having a butadiene structure; alicyclic Epoxy resin, alicyclic epoxy resin having an ester skeleton; heterocyclic epoxy resin; spiro ring-containing epoxy number ; Cyclohexane dimethanol type epoxy resins; naphthylene ether type epoxy resins; trimethylol type epoxy resins; tetraphenylethane type epoxy resins, halogenated epoxy resins, etc., from the viewpoint of improving adhesion, bisphenol F type epoxy resins, Biphenyl-type epoxy resins are preferred, and biphenyl-type epoxy resins are more preferred, and from the viewpoint of improving heat resistance, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, naphthylene-ether-type epoxy resins, tetra Phenylethane-type epoxy resins are preferred, and tetraphenylethane-type epoxy resins are more preferred Epoxy resins may be used alone or in combination of two or more. (C) The component has adhesion and heat resistance. From the viewpoint of improving the, biphenyl-type epoxy resin, and tetraphenylethane-type epoxy Preferably containing at least one of a support, and more preferably containing both.

It is preferable that an epoxy resin contains the epoxy resin which has 2 or more epoxy groups in 1 molecule. When the nonvolatile component of the epoxy resin is 100 mass%, it is preferable that at least 50 mass% or more is an epoxy resin having two or more epoxy groups in one molecule. As the component (C), two or more epoxy resins may be used in combination.

As a specific example of an epoxy resin, "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL" (bisphenol A type epoxy resin manufactured by Mitsubishi Chemical Corporation) ), "JER807" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), manufactured by Shinnitetsu Sumkin Chemical Co., Ltd. `` ZX1059 '' (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Shinnitetsu Sumikin Kagaku Corporation `` YD-8125G '' (bisphenol A type epoxy resin), `` EX-721 '' manufactured by Nagase Chemtex ((Glycidyl ester-type epoxy resin), "Celloxide 2021P" (dicyclic epoxy resin having an ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin having a butadiene structure), manufactured by Shinnitetsu Kagaku Co., Ltd. `` ZX1658 '', `` ZX1658GS '' (liquid 1,4- writing Risidylcyclohexane), Mitsubishi Chemical Corporation's "630LSD" (glycidylamine type epoxy resin), Daikin Kogyo's "E-7432", and "E-7632" (perfluoroalkyl type epoxy resin) , DIC Corporation's "HP-4700", "HP-4710" (naphthalene type 4-functional epoxy resin), "N-690" (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy Resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4 , "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., "NC7000L" (naphthol novolak type epoxy resin) ), `` NC3000H '', `` NC3000 '', `` NC3000L '', `` NC3100 '' (biphenyl type epoxy resin), `` ESN475V '' (naphthol aralkyl type epoxy resin), `` ESN485 '' (naphthol) by Shinnitetsu Sumikin Kagaku Co., Ltd. Bolac type epoxy resin), "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), Mitsubishi Chemical Corporation "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bicylenol type epoxy resin) ), `` YX8800 '' (Anthracene type epoxy resin), `` PG-100 '', `` CG-500 '' manufactured by Osaka Gas Chemical, `` YL7800 '' (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and Mitsubishi Chemical Corporation "1010" (solid bisphenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and the like.

The content of the component (C) is preferably 1 mass% or more, more preferably 5, when the nonvolatile component of the resin composition is 100 mass% from the viewpoint of improving the mechanical strength and solvent resistance of the cured product of the resin composition. It is at least 8% by mass, more preferably at least 8% by mass. The upper limit of the content of the epoxy resin is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50 g / eq. To 5000 g / eq., More preferably 50 g / eq. To 3000 g / eq., More preferably 80 g / eq. To 2000 g / eq., Even more preferably 110 g / eq. To 1000 g / eq. By becoming in this range, the crosslinking density of hardened | cured material of a resin composition becomes sufficient, and the insulating layer with a small surface roughness can be formed. In addition, epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing one equivalent of epoxy groups.

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

<(D) Photopolymerization initiator>

The resin composition contains (D) a photopolymerization initiator. (D) By containing a component, a resin composition can be photocured efficiently.

(D) Although component is not specifically limited, For example, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2- (dimethylamino) -2- [ (4-methylphenyl) methyl]-[4- (4-morpholinyl) phenyl] -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1 Α-aminoalkylphenone-based photopolymerization initiators such as -one; Oxime ester-based photopolymerization initiators such as ethanone and 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, diphenyl- (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 sulfonium salt-based photopolymerization initiators and the like can also be used. These may be used alone or in combination of two or more.

(D) As a specific example of a component, "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", "OmniradTPO", "IrgacureTPO", "IrgacureOXE-01", "IrgacureOXE-01", "IrgacureOXE-02" manufactured by IGM Corporation , &Quot; N-1919 &quot; manufactured by ADEKA Corporation.

(D) The content of the component is preferably 0.01 when the non-volatile component of the resin composition is 100% by mass from the viewpoint of sufficiently photocuring the resin composition and increasing the mechanical strength and solvent resistance of the cured product of the resin composition. It is mass% or more, more preferably 0.03 mass% or more, still more preferably 0.05 mass% or more. On the other hand, from the viewpoint of suppressing the decrease in developability due to excessive sensitivity, the upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

In addition, the resin composition, in combination with the component (D), as a photopolymerization initiator, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylaminobenzoate, tri Tertiary amines such as ethylamine and triethanolamine may be included, and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones may be included. These may be used alone or in combination of two or more.

<(E) reactive diluent>

The resin composition may further contain (E) a reactive diluent. (E) By containing a component, photoreactivity can be improved. As the component (E), for example, a liquid, solid or semi-solid photosensitive (meth) acrylate compound at 25 ° C having one or more (meth) acryloyl groups in one molecule can be used. The "(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, ethylene glycol, methoxytetraethylene glycol, and polyethylene glycol, Mono or diacrylates of glycols such as propylene glycol, acrylamides such as N, N-dimethylacrylamide and N-methylolacrylamide, and aminoalkylacrylates such as N, N-dimethylaminoethylacrylate, Polyhydric alcohols such as trimethylolpropane, pentaerythritol and dipentaerythritol or polyvalent acrylates of ethylene oxide, propylene oxide or ε-caprolactone (e.g. DPHA: dipentaerythritol hexaacrylate), phenoxyacrylic Phenols such as lactates and ethoxyethyl acrylate, or ethylene oxide or propylene thereof Acrylates such as side adducts, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and / or methacrylates corresponding to the acrylates, etc. Can be mentioned. Among these, polyvalent acrylates or polyvalent methacrylates are preferable, and, for example, as trivalent acrylates or methacrylates, trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylic Rate, trimethylolpropane 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, tetramethyl All methane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, N, N, N ', N'-tetrakis (β-hydro And (meth) acrylic acid esters of hydroxyethyl) ethyldiamine. Examples of trivalent or higher acrylates or methacrylates include tri (2- (meth) acryloyloxyethyl) phosphate and tri (2- ( Meta) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyl-2-hydroxyloxypropyl) phosphate, di (3- ( Meta) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) acryloyl-2-hydroxyloxypropyl) di (2- (metha) ) Phosphoric acid triester (meth) acrylates, such as acryloyloxyethyl) phosphate. These photosensitive (meth) acrylate compounds may be used alone or in combination of two or more.

(E) The content in the case of blending components is 1 mass% to 1 mass% when the nonvolatile component of the resin composition is 100 mass% from the viewpoint of promoting photocuring and suppressing stickiness when used as a cured product. 10 mass% is preferable, and 3 mass% to 8 mass% is more preferable.

<(F) Organic solvent>

The resin composition may further contain (F) an organic solvent. The viscosity of the resin varnish can be adjusted by containing 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, and butyl. Glycol ethers such as carbitol, propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, and carbitol acetate (EDGAc: diethylene glycol monoethyl ether acetate), esters such as ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers, petroleum naphtha, hydrogenated petroleum naphtha, and solvent petroleum solvents such as naphtha. You can. These are used individually by 1 type or in combination of 2 or more types. Content when using an organic solvent can be adjusted suitably from a viewpoint of the coatability of a resin composition.

<(G) Other additives>

The resin composition may further contain (G) other additives so as not to impair the object of the present invention. (G) Other additives include, for example, thermoplastic resins, organic fillers, melamine, and fine particles such as organic bentonite, phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, naphthalene black Coloring agents such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, polymerization inhibitors such as bentons, montmorillonite, thickeners, silicone-based, fluorine-based, vinyl resin-based antifoaming agents, brominated epoxy Various additives such as flame retardants such as compounds, acid-modified brominated epoxy compounds, antimony compounds, phosphorus compounds, aromatic condensed phosphoric acid esters, halogen condensed phosphoric acid esters, thermosetting resins such as phenolic curing agents and cyanate ester based curing agents, etc. can be added. You can.

<Manufacturing method>

The resin composition can be produced by mixing the above-mentioned components. When mixing, if necessary, kneading or stirring may be performed by means of kneading such as three rolls, a ball mill, a bead mill, or a sand mill, or a stirring means such as a super mixer or planetary mixer. The resin composition can be obtained as a resin varnish, for example, by including (F) an organic solvent.

[2. Resin composition according to the second embodiment of the present invention]

Hereinafter, the resin composition according to the second embodiment of the present invention will be described in detail.

The resin composition according to the second embodiment of the present invention includes (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle diameter of 0.5 μm or more, (C) an epoxy resin, and (D) ) It is a resin composition containing a photopolymerization initiator. In the resin composition according to the second embodiment, the weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in an alkali solution is represented by the following equation (I):

Equation (I)

5≤S _(A) ≤110

Satisfies The dissolution rate in an alkali solution can be measured, for example, by the method described in Examples. As an alkali solution, the developing solution used for image development is mentioned normally. In order to make the dissolution rate possible, it is preferable to use an aqueous sodium carbonate solution having a constant pH (pH: 11.7) at 23 ° C as an alkaline solution. The temperature and pH of the alkali solution may be appropriately changed as long as the dissolution rate is not significantly affected.

By using the resin composition according to the second embodiment of the present invention, a cured product excellent in undercut resistance can be obtained.

<(A) component, (B) component, (C) component, and (D) component>

About (A) component, (B) component, (C) component, and (D) component which the resin composition which concerns on 2nd Embodiment contains, (A) component does not need to contain (A-1) component , (A) component (A), (B) component included in the resin composition according to the first embodiment, except that the weighted average value S _(A) of the dissolution rate of the component satisfies the formula (I) It is the same as (C) component and (D) component. Thereby, the same advantages as the resin composition according to the first embodiment can be obtained.

The content of the component (A), the weight average molecular weight, and the acid value are arbitrary, but preferably in the same range as the content of the component (A), the weight average molecular weight, and the acid value described in the first embodiment. Thereby, the advantage similar to what was described in the term of the component (A) in 1st Embodiment can be obtained. Although the content of the component (B), the average particle diameter and the specific surface area are arbitrary, it is preferable that the content of the component (B), the average particle diameter and the specific surface area described above in the first embodiment are in the same range. Thereby, the advantage similar to that described in the term of the component (B) in the first embodiment can be obtained. Although the content of the component (C), the epoxy equivalent and the weight average molecular weight are arbitrary, it is preferable that the content of the component (C), the epoxy equivalent and the weight average molecular weight described in the first embodiment are in the same range. Thereby, the advantage similar to what was described in the term of the component (C) in the first embodiment can be obtained. The content of the component (D) is arbitrary, but is preferably in the same range as the content of the component (D) described in the first embodiment. Thereby, the advantage similar to what was described in the term of the component (D) in the first embodiment can be obtained.

The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] in the alkali solution of the component (A) contained in the resin composition according to the present embodiment satisfies the above formula (I). . More specifically, the weighted average value S _(A) of the dissolution rate of the component _(A) is usually 5 nm / sec or more, more preferably 6 nm / sec or more, still more preferably 10 nm / sec or more, particularly preferably 15 nm / sec or more, and usually 110 nm / sec or less, preferably 100 nm / sec or less, more preferably 90 nm / sec or less, still more preferably 80 nm / sec or less. When the weighted average value S _(A) of the dissolution rate of the component _(A) is in the above range, it is possible to suppress that the dissolution rate in which the resin composition is dissolved in the alkali developer is excessively slowed or accelerated. Therefore, it is possible to suppress the occurrence of a portion that is too melted against the intention and a portion that does not melt against the intention. Therefore, the undercut resistance can be improved, and preferably, the side surface of the opening pattern can be made perpendicular to the layer plane.

(A) As a method to enter the weighted average value S _(A) of the dissolution rate of a component into the above-mentioned range, the method of employing the (A) component containing the (A-1) component is mentioned, for example. However, for example, the type and amount of the component (A) other than the component (A-1) may be appropriately adjusted, and the weighted average value S _(A) of the dissolution rate of the component _(A) may fall within the above-described range.

(A) When a resin containing a plurality of types of ethylenically unsaturated groups and carboxyl groups is used as the component, the dissolution rate [nm / sec] of each of the resins containing ethylenically unsaturated groups and carboxyl groups is within the above range. It is more preferable. As the component (A) having a dissolution rate [nm / sec] in the range of 5 to 110, more preferably in the range of 5 to 100, the resin solution (A-1a) obtained by Synthesis Example 1 described later, the synthesis example The resin solution (A-1b) obtained by 2 and "ZAR-2000" by Nippon Kayaku Co., Ltd. (acid-modified bisphenol-type epoxy acrylate: reactant of bisphenol A-type epoxy resin, acrylic acid, and succinic anhydride) are mentioned. .

<(E) component, (F) component, and (G) component>

The resin composition according to the present embodiment may further include (E) a reactive diluent, (F) an organic solvent, and (G) other additives, if necessary. About (E) component, (F) component, and (G) component which the resin composition which concerns on 2nd embodiment can contain, (E) component which can contain the resin composition which concerns on 1st embodiment, (F ) Component and (G) component. Thereby, the same advantages as the resin composition according to the first embodiment can be obtained.

<Manufacturing method>

The resin composition can be produced by mixing the above-mentioned components. When mixing, if necessary, kneading or stirring may be carried out by means of kneading such as three rolls, a ball mill, a bead mill, or a sand mill, or by a stirring means such as a super mixer or a planetary mixer. The resin composition can be obtained as a resin varnish, for example, by including (F) an organic solvent.

<Physical properties and uses of the resin composition>

The photocured resin composition according to the first embodiment of the present invention or the resin composition according to the second embodiment, and the cured product thermally cured at 190 ° C. for 90 minutes exhibits excellent undercut resistance. That is, an insulating layer and solder resist having excellent undercut resistance are formed. The value of the undercut is preferably +10 µm or less, more preferably +5 µm or less, more preferably +4 µm or less, even more preferably +3 µm or less from the viewpoint of suppressing the net taper shape. . Here, the cross-sectional shape of the net taper shape means a narrower shape as the diameter of the opening is inside, and specifically, a shape having a narrower opening bottom than the front of the opening. The lower limit is preferably -5 µm or less, more preferably -4 µm or less, still more preferably -3 µm or less, from the viewpoint of suppressing the reverse taper shape. The value of the undercut can be measured according to the method described in <Evaluation of Developability, Crack Resistance, and Undercut Resistance> described later.

Moreover, after photocuring the resin composition which concerns on 1st Embodiment or 2nd Embodiment of this invention, the hardened | cured material heat-cured at 190 degreeC for 90 minutes tends to exhibit the property of being excellent in developability. For this reason, normally, residues such as resin do not exist in the unexposed portion. The minimum via hole diameter without residue is preferably 100 µm or less, more preferably 90 µm or less, and even more preferably 80 µm or less. The lower limit is not particularly limited, but may be 1 µm or more. The evaluation of developability can be evaluated according to the method described in <Evaluation of Developability, Crack Resistance, and Undercut Resistance> described later.

The cured product heat-cured at 190 ° C for 90 minutes after photocuring the resin composition according to the first or second embodiment of the present invention tends to exhibit properties of low average linear thermal expansion. That is, an insulating layer and a solder resist having a low average linear thermal expansion rate are formed. The average linear thermal expansion rate is preferably 45 ppm / ° C or less, more preferably 40 ppm / ° C or less, further preferably 36 ppm / ° C or less, 35 ppm / ° C or less. The lower limit is not particularly limited, but may be 10 ppm / ° C or higher. The average linear thermal expansion coefficient can be measured according to the method described in <Measurement of average linear thermal expansion coefficient and glass transition temperature> which will be described later.

After photocuring the resin composition according to the first or second embodiment of the present invention, the cured product heat-cured at 190 ° C for 90 minutes tends to exhibit properties of high glass transition temperature. That is, an insulating layer and a solder resist having a high glass transition temperature are formed. The glass transition temperature is preferably more than 135 ° C, more preferably 170 ° C or more, and even more preferably 180 ° C or more. The upper limit is not particularly limited, but may be 300 ° C or lower. The glass transition temperature can be measured according to the method described in <Measurement of average linear thermal expansion coefficient and glass transition temperature> described later.

After photocuring the resin composition according to the first or second embodiment of the present invention, the cured product heat-cured at 190 ° C for 90 minutes exhibits excellent crack resistance. That is, an insulating layer having excellent crack resistance and a solder resist are formed. Even if 500 cycles of heat cycle and temperature rise between -65 ° C and 150 ° C were repeated, no cracks and peeling were observed. Evaluation of crack resistance can be evaluated in accordance with a method described in <Evaluation of Developability, Crack Resistance, and Undercut Resistance> described later.

Although the use of the resin composition according to the first or second embodiment of the present invention is not particularly limited, insulating resin sheets such as photosensitive films, photosensitive films with supports, and prepregs, circuit boards (laminated board applications, multilayer printed wiring boards) Applications, etc.), solder resist, underfill material, die bonding material, semiconductor sealing material, hole filling resin, component embedded resin, and the like, can be widely used in applications requiring a resin composition. Among them, the resin composition for the insulating layer of the printed wiring board (printed wiring board using the cured product of the resin composition as an insulating layer), the resin composition for the interlayer insulating layer (printed wiring board using the cured product of the resin composition as the interlayer insulating layer), the resin for plating formation It can be suitably used as a composition (printed wiring board in which plating is formed on a cured product of a resin composition) and a resin composition for a solder resist (printed wiring board using a cured product of a resin composition as a solder resist).

[Photosensitive film]

The photosensitive film containing the said resin composition can be obtained by using the resin composition which concerns on 1st embodiment or 2nd embodiment of this invention. For example, a resin composition layer can be formed by applying a resin composition on a support substrate in a resin varnish state and drying the organic solvent to form a photosensitive film. In addition, a photosensitive film previously formed on a support may be used by laminating it on a supporting substrate. The photosensitive film can be laminated to various supporting substrates. Examples of the supporting substrate include substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.

[Photosensitive film with support]

The resin composition according to the first or second embodiment of the present invention can be suitably used in the form of a photosensitive film with a support having a resin composition layer layered on the support. That is, the photosensitive film with a support includes a support and a resin composition layer formed of the resin composition of the present invention formed on the support.

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

As a commercially available support, for example, Oji Seshi Co., Ltd. product names "Alpan MA-410", "E-200C", polypropylene film such as Shin-Etsu Film Co., Ltd. product name "PS-25" manufactured by Tejin Corporation, etc. Polyethylene terephthalate films, such as PS series, etc. are mentioned, but it is not limited to these. In order to facilitate removal of the resin composition layer, such a support is preferably coated with a release agent such as a silicone coating agent on the surface. The thickness of the support is preferably in the range of 5 μm to 50 μm, more preferably in the range of 10 μm to 25 μm. By setting the thickness to 5 µm or more, it is possible to suppress cracking of the support at the time of peeling the support performed before development, and by setting the thickness to 50 µm or less, the resolution when exposing on the support can be improved. Also, a low fish eye support is preferred. Here, the fish eye is a material that thermally melts, and when a film is produced by kneading, extrusion, biaxial stretching, casting, or the like, foreign matter, coarse lysate, and oxidized deterioration of the material are contained in the film.

Moreover, in order to reduce the scattering of light during exposure by active energy rays such as ultraviolet rays, it is preferable that the support is excellent in transparency. Specifically, the support preferably has a turbidity (haze standardized in JIS K6714) as an index of transparency of 0.1 to 5. Moreover, the resin composition layer may be protected with a protective film.

By protecting the resin composition layer side of the photosensitive film with a support with a protective film, adhesion or scratches to the surface of the resin composition layer can be prevented. As the protective film, a film made of the same material as the above 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 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 it is 40 µm or less, the inexpensiveness tends to be improved. Moreover, it is preferable that the adhesive force between a resin composition layer and a protective film is small with respect to the adhesive force between a resin composition layer and a support body.

The photosensitive film with a support of the present invention is prepared by, for example, a resin varnish in which the resin composition of the present invention is dissolved in an organic solvent according to a method known to those skilled in the art, and the resin varnish is applied onto the support, followed by heating or hot air spraying. It can be manufactured by drying an organic solvent with or the like to form a resin composition layer. Specifically, first, after the bubbles in the resin composition are completely removed by a vacuum degassing method or the like, the resin composition is applied onto a support, the solvent is removed by a hot air furnace or a far infrared ray, dried, and then the resin composition obtained as necessary. A photosensitive film with a support can be produced by laminating a protective film on a layer. The specific drying conditions vary depending on the curability of the resin composition and the amount of the organic solvent in the resin varnish, but in the resin varnish containing 30% by mass to 60% by mass of the organic solvent, from 80 ° C to 120 ° C for 3 to 13 minutes. It can be dried. The amount of the remaining organic solvent in the resin composition layer is preferably 5% by mass or less, and more preferably 2% by mass or less, with respect to the total amount of the resin composition layer, in order to prevent diffusion of the organic solvent in the subsequent step. desirable. Those skilled in the art can set appropriate and suitable drying conditions by simple experiments. The thickness of the resin composition layer is preferably in the range of 5 µm to 500 µm, from 10 µm to 200 µm, from the viewpoint of improving handleability and suppressing deterioration of sensitivity and resolution inside the resin composition layer. It is more preferably in the range, more preferably in the range of 15 μm to 150 μm, even more preferably in the range of 20 μm to 100 μm, particularly preferably in the range of 20 μm to 60 μm. .

As the coating method of the resin composition, for example, gravure coat method, microgravure coat method, reverse coat method, kiss reverse coat method, die coat method, slot die method, lip coat method, comma coat method, blade coat method, roll And a coat method, a knife coat method, a curtain coat method, a chamber gravure coat method, a slot orifice method, a spray coat method, and a dip coat method.

The resin composition may be applied several times, or may be applied once, or may be applied in combination of a plurality of different methods. Especially, the die-coating system excellent in uniform coatability is preferable. In addition, in order to avoid foreign matter mixing and the like, it is preferable to perform the coating process in an environment where there is little foreign matter generation, such as a clean room.

[Printed wiring board]

The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition according to the first or second embodiment of the present invention. It is preferable to use the said insulating layer as a solder resist.

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

<Coating and drying process>

The photosensitive film is formed on the circuit board by applying the resin composition directly onto the circuit board in the resin varnish state and drying the organic solvent.

Examples of the circuit board include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. In addition, a circuit board here means the board | substrate in which the conductor layer (circuit) by which the pattern process was carried out is formed in one side or both surfaces of the said board | substrate. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate made of a conductor layer (circuit) on which one or both sides of the outermost layer of the multilayer printed wiring board is patterned is also applied to the circuit board referred to herein. Is included. Moreover, roughening treatment may be previously performed on the surface of the conductor layer by blackening treatment, copper etching, or the like.

As the coating method, the front printing by the screen printing method is generally used, but any other means may be used as long as it is a coating method that can be applied uniformly. For example, spray coat method, hot melt coat method, bar coat method, applicator method, blade coat method, knife coat method, air knife coat method, curtain flow coat method, roll coat method, gravure coat method, offset printing method, dip Any coating method, brushing, or other conventional coating methods can be used. After application, drying is performed with a hot air furnace or a far infrared ray, if necessary. The drying conditions are preferably from 3 to 13 minutes at 80 ° C to 120 ° C. In this way, a photosensitive film is formed on the circuit board.

<Laminate process>

Moreover, when using the photosensitive film with a support body, the resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film and the circuit board with a support are preheated as necessary, and the circuit is pressed and heated while pressing and heating the resin composition layer. The substrate is pressed. In the photosensitive film with a support body, the method of laminating to a circuit board under reduced pressure by a vacuum lamination method is suitably used.

The conditions of the lamination process are not particularly limited, but, for example, the compression temperature (laminate temperature) is preferably 70 ° C to 140 ° C, and the compression pressure is preferably 1kgf / cm2 to 11kgf / cm2 (SI unit) 9.8 × 10 ⁴ N / m 2 to 107.9 × 10 ⁴ N / m 2), and the compression time is preferably 5 seconds to 300 seconds, and it is laminated under reduced pressure with an air pressure of 20 mmHg (26.7 hPa in SI units) or less. desirable. In addition, the lamination process 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. Commercial vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meki Sesakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. In this way, a photosensitive film is formed on the circuit board.

<Exposure process>

After a photosensitive film is formed on a circuit board by a coating and drying process or a lamination process, an exposure process of irradiating an active light to a predetermined portion of the resin composition layer through a mask pattern and then photocuring the resin composition layer of the irradiation part through a mask pattern To perform. Examples of the active light include ultraviolet light, visible light, electron beam, and X-ray, and ultraviolet light is particularly preferable. The irradiation amount of ultraviolet rays is approximately 10 mJ / cm 2 to 1000 mJ / cm 2. The exposure method includes a contact exposure method performed by adhering a mask pattern to a printed wiring board, and a non-contact exposure method of exposing using parallel rays without adhering, but either may be used. Moreover, when a support body exists on a resin composition layer, you may expose on a support body, or you may expose a support body after peeling.

Since the solder resist uses the resin composition of the present invention, it has excellent developability. 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 (space: S) between the circuits is 100 µm / 100 µm or less (ie, wiring pitch) 200 μm or less), L / S = 80 μm / 80 μm or less (wiring pitch 160 μm or less), L / S = 70 μm / 70 μm or less (wiring pitch 140 μm or less), L / S = 60 μm / 60 μm The following pattern (wiring pitch of 120 µm or less) can be used. In addition, the pitch need not be the same across the entire circuit board.

<Development process>

After the exposure step, when the support is present on the resin composition layer, the support can be removed and then developed by wet development to remove the uncured portion (unexposed portion) to develop a pattern.

In the case of the above-mentioned wet development, an alkali solution is usually used as the developer, and among them, a development step with an aqueous alkali solution is preferable. Moreover, as a developing method, well-known methods, such as spraying, rocking immersion, brushing, and scraping, are employ | adopted suitably.

Examples of the alkali solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, and alkali metal phosphates such as bicarbonate, sodium phosphate and potassium phosphate, and sodium pyrophosphate , An aqueous solution of an alkali metal pyrophosphate such as potassium pyrophosphate, or an aqueous solution of an organic base containing no metal ions such as tetraalkylammonium hydroxide, and does not contain metal ions and does not affect semiconductor chips. In the aqueous solution of tetramethylammonium hydroxide (TMAH) is preferred.

The alkaline developer may include a developer such as a surfactant or an antifoaming agent in order to improve the development effect. The pH of the alkali solution is, for example, preferably in the range of 8 to 13, more preferably in the range of 9 to 12, and more preferably in the range of 10 to 12. Moreover, it is preferable that the base concentration of the said alkaline developer is 0.1 mass%-10 mass%. Although the temperature of the alkaline developer can be appropriately selected in accordance with the developability of the resin composition layer, it is usually room temperature, and is preferably 20 ° C to 50 ° C.

The organic solvent used as the developer is, 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 and diethylene glycol monobutyl ether.

The concentration of the organic solvent is preferably 2% by mass to 90% by mass relative to the total amount of the developer. Moreover, the temperature of such an organic solvent can be adjusted according to developability. Moreover, these organic solvents can be used alone or in combination of two or more. As an organic solvent-based developer used alone, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N, N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, γ- And butyrolactone.

In forming a pattern, if necessary, you may use together the above 2 or more types of developing methods. The development method includes a dip method, a paddle method, a spray method, a high pressure spray method, brushing, and slapping, and a high pressure spray method is suitable for improving resolution. As a spray pressure when employing the spray method, 0.05 MPa to 0.3 MPa is preferable.

According to the resin composition according to the first embodiment or the second embodiment described above, it is possible to effectively suppress the occurrence of undercut in the above-described developing step.

<The heat curing (post baking) process>

After the development process, a thermosetting (post-baking) process is performed to form a solder resist. As a post-baking process, the ultraviolet irradiation process by a high pressure mercury lamp, the heating process using a clean oven, etc. are mentioned. When irradiating ultraviolet rays, the irradiation amount can be adjusted as necessary, and for example, irradiation can be performed with an irradiation amount of about 0.05 J / cm 2 to about 10 J / cm 2. Further, the conditions for heating may be appropriately selected depending on the type, content, etc. of the resin component in the resin composition, but preferably in the range of 150 to 220 ° C for 20 to 180 minutes, more preferably 160 to 200 ° C 30 Minutes to 120 minutes.

<Other processes>

After forming the solder resist, the printed wiring board may further include a drilling process and a desmear process. These steps may be performed in accordance with various methods known to those skilled in the art, which are used in the production of printed wiring boards.

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

The desmear process is a desmear process. In general, a resin residue (smear) is attached inside the opening formed in the drilling step. Since such smear is a cause of defective electrical connection, a process for removing smear (desmear processing) 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 a desmear treatment using plasma, and the like. The desmear process using plasma can be performed using a commercially available plasma desmear processing apparatus. Among commercially available plasma desmear processing apparatuses, examples of suitable for the production use of the printed wiring board include a microwave plasma apparatus manufactured by Nisshin Corporation, an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Industries, Ltd., and the like.

Examples of the wet desmear treatment include a desmear treatment using an oxidizing agent solution and the like. When desmearing 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 liquid in this order. Examples of the swelling liquid include "Swelling Deep Securigans P" manufactured by Atotech Japan, "Swelling Deep Securigans SBU" and the like. The swelling treatment is preferably performed by immersing a substrate in which via holes or the like are formed in a swelling solution heated to 60 ° C to 80 ° C for 5 to 10 minutes. As the oxidizing agent solution, an alkaline aqueous permanganic acid solution is preferable, and examples thereof include a solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. As a commercial item of the alkaline permanganic acid aqueous solution, "Concentrate Compact CP" by Atotech Japan, "Dosing Solution Securigans P" etc. are mentioned, for example. The neutralization treatment with the neutralization liquid is preferably performed by immersing the substrate after the oxidation treatment in a neutralization liquid at 30 ° C to 50 ° C for 3 to 10 minutes. As the neutralizing solution, an acidic aqueous solution is preferable, and examples of commercial products include "reduction solution securigant P" manufactured by Atotech Japan.

When the dry desmear process and the wet desmear process are combined, the dry desmear process may be performed first, or the wet desmear process may be performed first.

Even when an insulating layer is used as an interlayer insulating layer, it can be performed in the same manner as in the case of a solder resist, and a perforation process, a desmear process, and a plating process may be performed after the thermal curing process.

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. Alternatively, the conductor layer may be formed of a plating resist having an inverse pattern, and the conductor layer may be formed only by electroless plating. As a method for forming a pattern thereafter, for example, a subtractive method, a semiadditive 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 semiconductor devices include various types of semiconductor devices provided for electric products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, streetcars, ships, and aircraft). You can.

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conduction point of a printed wiring board. The "conduction point" is "a place for transmitting an electrical signal from a printed wiring board", and the place may be either a surface or a buried place. Note that the semiconductor chip is not particularly limited as long as it is an electrical circuit element using a semiconductor as a material.

The method for 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, but specifically, the wire bonding mounting method, flip chip mounting method, bumpless (bumpless) ) The mounting method by a build-up layer (BBUL), the mounting method by an anisotropic conductive film (ACF), the mounting method by a non-conductive film (NCF), etc. are mentioned. Here, the "mounting method using the bumpless build-up layer (BBUL)" is a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board to connect a semiconductor chip and wiring on the printed wiring board."

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, in the following description, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

(Synthesis Example 1: Synthesis of resin solution (A-1a))

Epoxy resin A (1,1'-bis (2,7-diglycidyloxynaphthyl) methane containing naphthalene skeleton represented by the following formula (8) methane, epoxy equivalent 162, manufactured by Dai Nippon Inki Chemical Co., Ltd. "EXA -4700 ") 162 parts were placed in a flask equipped with a gas introduction tube, a stirring device, a cooling tube, and a thermometer, and 340 parts of carbitol acetate was added to dissolve and heated, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. Did. The mixture was heated to 95 to 105 ° C, and 72 parts of acrylic acid was slowly added dropwise to react for 16 hours. The reaction product was cooled to 80 to 90 ° C, 80 parts of tetrahydrophthalic anhydride was added, reacted for 8 hours, and cooled. Thus, a resin solution having a solid acid value of 90 mgKOH / g (70% non-volatile content, hereinafter abbreviated as "resin solution (A-1a)") was obtained.

Formula (8)

It was confirmed that the resin solution (A-1a) contained at least a resin represented by the following formula (9).

Formula (9)

(Synthesis Example 2: Synthesis of resin solution (A-1b))

In Synthesis Example 1, the naphthalene skeleton-containing epoxy resin A is a naphthol aralkyl-type epoxy resin B represented by the following formula (10) (Epoxy equivalent 325, manufactured by Shinnitetsu Sumikin Kagaku Co., Ltd. "ESN-475V") Changed to 325 copies. The same operation as in Synthesis Example 1 was performed except for the above. Thus, a resin solution having a solid acid value of 60 mgKOH / g (70% non-volatile content, hereinafter abbreviated as "resin solution (A-1b)") was obtained.

Formula (10)

(However, Z is a glycidyl group (G) or a hydrocarbon group having 1 to 8 carbon atoms (R ⁷ ), and the ratio of R ⁷ / G is 0.05 to 2.0. In addition, n is an average value of 1 to 6 Indicates.)

It was confirmed that the resin solution (A-1b) contained at least a resin containing a structure represented by the following formula (11).

Formula (11)

<Examples 1 to 7, Comparative Examples 1 to 2>

Each component was blended at a blending ratio shown in Table 1 below, and a resin varnish was prepared using a high-speed rotary mixer. Next, as a support, a PET film molded with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Co., Ltd.) ("Lumira T6AM" manufactured by Torre, thickness 38 mu m, softening point 130 DEG C, "release PET") was prepared. Did. The prepared resin varnish was uniformly coated with a die coater so that the thickness of the resin composition layer after drying on the surface treated with the alkyd resin-based release agent of the release PET was 40 µm, and dried at 80 ° C. to 110 ° C. for 6.5 minutes to release the PET. A photosensitive film with a support having a resin composition layer was obtained.

The measurement method and evaluation method in physical property evaluation are demonstrated.

<Evaluation of the dissolution rate of the resin composition>

Resin solution (A-1a), resin solution (A-1b) and resins ZFR-1491H, ZAR-2000 and ZCR-1569H described below were added to propylene glycol monomethyl ether acetate (PGMEAc), respectively, and 35 weight of nonvolatile component % Solution was prepared. The solution was applied onto a silicon wafer, and spin coating was performed to obtain a coating film. Thereafter, the coating film was dried at 120 ° C. for 3 minutes to form a resin film having a thickness of about 2 μm. The film thickness of the resin film was measured with a stylus type film thickness meter ("SURFCOM 130A" manufactured by Tokyo Semitsu Co., Ltd.). Thereafter, the resin film was immersed in a 1% by mass aqueous sodium carbonate solution (pH: 11.7) as an alkaline solution at 23 ° C for each silicon wafer. Then, the disappearance time until the resin film disappeared was measured. The disappearance of the resin film was confirmed by visually confirming that the interference streaks due to reflected light on the surface of the resin film disappeared. Therefore, the disappearance time is a time from the time when the resin film is immersed in the alkali solution to the time when the disappearance is confirmed. Then, for each resin film, the dissolution rate [nm / sec] indicating the amount of reduction in the thickness [nm] of the resin film per second was calculated. For the resin film that did not show dissolution even after immersing for 30 minutes, the dissolution rate was 1 nm / sec. The results were as follows.

(A-1) Ingredients:

A-1a: 100 nm / sec

A-1b: 6 nm / sec

(A-2) Ingredients:

ZFR-1491H: 131nm / sec

ZAR-2000: 39nm / sec

ZCR-1569H: 1nm / sec

In each of Examples and Comparative Examples, the weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in the following formula (IV) to the alkali solution was calculated.

Equation (IV)

S _(A) = Σ {s (A) × R _(A) }

Here, in the above formula (IV), s (A) is the dissolution rate of the individual (A) component in the alkali solution. In the formula (IV), R _(A) is the mass ratio of each resin (A) when the nonvolatile component in the component (A) is 100% by mass.

<Evaluation of developability, crack resistance, and undercut resistance>

(Formation of laminate for evaluation)

The copper layer of the glass epoxy substrate (copper-clad laminate) on which a circuit patterning a copper layer having a thickness of 18 µm was formed was harmonized by treatment with a surface treatment agent containing organic acid (CZ8100, manufactured by Mack). Next, the resin composition layer of the photosensitive film with a support obtained in Examples 1 to 7 and Comparative Examples 1 to 2 was placed in contact with the copper circuit surface, and pressed using a vacuum laminator (manufactured by Nikko Materials, VP160), The copper-clad laminate, the resin composition layer, and the support were formed in a stack in this order. The crimping conditions were a vacuum treatment time of 30 seconds, a pressing temperature of 80 ° C, a pressing pressure of 0.7 MPa, and a pressing time of 30 seconds. The laminate was left at room temperature for 30 minutes or more, and exposure was performed with ultraviolet rays from the support side of the laminate, using a quartz glass mask and a pattern forming apparatus in which an exposure pattern for forming a round hole was formed. On the quartz glass mask used, a pattern capable of drawing all six round holes having a diameter of 50 µm / 60 µm / 70 µm / 80 µm / 90 µm / 100 µm was formed. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. On the entire surface of the resin composition layer on the laminated board, a spray development was performed for 2 minutes at a spray pressure of 0.2 MPa with a 1% by mass aqueous sodium carbonate solution at 30 ° C as an alkaline developer. As a result, in Examples 1 to 7 and Comparative Example 2, the round hole portion eluted, a via hole was formed in the resin composition layer, and on the other hand, in Comparative Example 1, no via hole was formed. After the spray development, 1J / cm 2 of ultraviolet irradiation was performed, and further heat treatment was performed at 180 ° C. for 30 minutes. As a result, the resin composition layer was cured, and in Examples 1 to 7 and Comparative Example 2, an evaluation laminate having an insulating layer having an opening (via hole) on a copper-clad laminate was obtained. In addition, in Comparative Example 1, an evaluation laminate having an insulating layer without via holes formed thereon was obtained.

(Evaluation of developability)

The via holes formed in the evaluation laminate were observed by SEM (magnification 1000 times), and among the six via holes, the minimum via hole diameter without residue was specified. When the opening (via hole) could not be confirmed in the evaluation laminate, it was judged that it was impossible to specify the minimum via hole diameter, and it was evaluated as "x".

(Evaluation of crack resistance)

The laminate for evaluation was exposed to an atmosphere of -65 ° C for 15 minutes, then heated at a temperature increase rate of 180 ° C / min, and then exposed to air at 175 ° C for 15 minutes, and then at a temperature drop rate of 180 ° C / min. A test in which the treatment by the thermal cycle of cooling down was repeated 500 times was performed. After the test, the degree of cracking and peeling of the laminate for evaluation was observed with an optical microscope ("ECLIPSE LV100ND" manufactured by Nikon Corporation) and evaluated according to the following criteria.

○: neither crack nor peeling was observed.

X: One or both of cracks and peeling are seen.

(Evaluation of undercut resistance)

1 is a cross-sectional view of a laminate for evaluation used in Examples. As shown in FIG. 1, the laminate 100 for evaluation had a via hole 130 having a diameter of 100 μm as an opening in the insulating layer 120 made of a cured product of the resin composition formed on the copper clad laminate 110. . The insulating layer 120 of the evaluation laminate 100 is cut into a plane passing through the central axis of the via hole 130, the cross section is observed by SEM, and the opening front 140 shown in FIG. By measuring the radius (x [µm]) and the radius (y [µm]) of the opening bottom surface 150, and obtaining the difference x-y [µm], the undercut value [µm] was calculated. When the opening (via hole) could not be confirmed in the evaluation laminate, it was judged that calculation of the undercut value was impossible, and evaluated as "x".

<Measurement of average linear thermal expansion rate and glass transition temperature>

(Formation of cured product for evaluation)

The resin composition layer of the photosensitive film with a support obtained in Examples and Comparative Examples was exposed to UV light at 100 mJ / cm 2 for photocuring. Thereafter, on the entire surface of the resin composition layer, a 1% by mass aqueous sodium carbonate solution at 30 ° C as an alkaline developer was sprayed for 2 minutes at a spray pressure of 0.2 MPa. After the spray development, 1J / cm 2 of ultraviolet irradiation was performed, and further heat treatment at 190 ° C. for 90 minutes was performed to form a cured product. Thereafter, the support was peeled off to obtain a cured product for evaluation.

(Measurement of average linear thermal expansion rate)

The cured product for evaluation was cut into a test piece having a width of 5 mm and a length of 15 mm, a thermomechanical analysis device (Thermo Plus TMA8310, manufactured by Rigaku Corporation) was used, and thermomechanical analysis was performed by a tensile weighting method. After attaching the test piece to the above apparatus, it was continuously measured twice under the measurement conditions of a load of 1 g and a heating rate of 5 ° C / min. The average linear thermal expansion coefficient (ppm / ° C) 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 thermomechanical analysis was performed by a tensile weighting method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology). After attaching the test piece to the device, the load was measured under measurement conditions of 200 mN and a heating rate of 2 ° C / min. The peak top of the obtained tanδ was calculated as the glass transition temperature (° C).

The components used are as follows.

(A) Ingredients:

(A-1) Ingredient

A-1a: Resin solution synthesized in Synthesis Example 1 (A-1a)

A-1b: Resin solution synthesized in Synthesis Example 2 (A-1b)

(A-2) Ingredient

ZFR-1491H: Bisphenol F-type epoxy acrylate (made by Nippon Kayaku Co., Ltd., acid value 99mgKOH / g, non-volatile component concentration 70%)

ZAR-2000: Bisphenol A type epoxy acrylate (made by Nippon Kayaku Co., Ltd., acid value 99mgKOH / g, non-volatile component concentration 70%)

ZCR-1569H: Biphenyl-type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 98 mgKOH / g, nonvolatile component concentration 70%)

(B) Ingredient:

SC2050: Surface treated with 0.5 parts by mass of aminosilane (Shin-Etsu Chemical Co., Ltd., KBM573) with respect to 100 parts by mass of fused silica (manufactured by Adomatex, average particle diameter 0.5 µm, specific surface area 5.9 m2 / g)

(C) Ingredient:

NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent approximately 272)

1031S: Tetrakishydroxyphenylethane type epoxy resin (Mitsubishi Chemical Corporation, epoxy equivalent about 200)

(D) Ingredients:

IrgacureTPO: bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide) (manufactured by BASF)

(E) Ingredients:

DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent approximately 96)

(F) Ingredients:

EDGAc: Diethylene glycol monoethyl ether acetate

MEK: methyl ethyl ketone

Content of component (B): Content of component (B) [mass%] when the nonvolatile component of the resin composition is 100 mass%

Weighted average value of dissolution rate S _(A) : Weighted average value based on mass ratio of dissolution rate [nm / sec] of the (A) component to the alkaline solution

· Value of undercut: The value of the undercut in a via hole having a diameter of 100 μm [㎛]

<Review>

From the results of Table 1 above, it was found that Examples 1 to 7 using the resin composition of the present invention had excellent undercut resistance. This allows the component (A-1) itself to dissolve in an alkali solution (e.g., alkaline developer) at an appropriate range of dissolution rate, and further develops the resin composition containing the component (A-1) with an alkaline developer. In some cases, it is considered that the portion that is too insoluble against the intention and the portion that does not melt against the intention can be suppressed from occurring locally in the resin composition. As one cause, it is presumed that the component (A-1) was mixed well even if the resin composition contained the components (C) to (E), so that the bias of the composition in the resin composition could be suppressed.

In addition, it was found that Examples 1 to 7 had better developability, heat resistance, mechanical strength, and crack resistance than Comparative Examples 1 and 2. Specifically, in Examples 1 to 7, it was found that the average linear thermal expansion coefficient was low and the glass transition temperature was high. This means that when the (A-1) component uses a naphthalene skeleton-containing resin, the molecular stiffness is usually increased, so that the movement of the molecules in the resin composition is suppressed, and as a result, the glass transition temperature of the cured product of the resin composition is higher. It is thought that it is because it is high and the average linear thermal expansion rate of hardened | cured material falls more. In addition, it is considered that, due to the action of the component (A-1), the resistance of the cured product to internal stress caused by thermal expansion or thermal contraction is usually improved, so that damage to the cured product due to temperature change can be suppressed.

Further, according to Examples 4 to 6, by using the components (A-1) and (A-2) in combination, the weighted average value S _(A) of the dissolution rates of Examples 1 to 4 and 7, the average linear thermal expansion rate And it can be seen that the value of the glass transition temperature can be adjusted. Further, according to the contrast between Examples 1 to 5 and Examples 6 and 7, by using the resin solution (A-1a), the minimum via hole diameter can be suppressed to be small, and the value of the undercut is +10 µm to- It tends to be limited to a positive value even within the range of 5 µm. On the other hand, by using the resin solution (A-1b), the load average value S of the dissolution rate is higher than when the resin solution (A-1a) is used alone. _It can be seen that _(A) can be increased, whereby the side surface of the opening pattern can be made perpendicular to the layer plane.

On the other hand, in Comparative Examples 1 and 2, since the component (A-1) was not used, undercut resistance was poor. (A) It is thought that the dissolution rate of the component is too low or the dissolution rate is too high.

In each Example, even if it does not contain the component (E) or the like, it was confirmed that although it differs in degree, it results in the same results as in the above Example.

100 laminate for evaluation
110 copper clad laminate
120 insulation layer
130 Via Hall
140 opening front
150 opening bottom

Claims (13)

(A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) an inorganic filler having an average particle diameter of 0.5 µm or more,
(C) epoxy resin, and,
(D) Photopolymerization initiator
As a resin composition containing,
(A) component,
(A-1) A resin composition containing a naphthalene skeleton-containing resin. The resin composition according to claim 1, wherein the component (A-1) is a naphthol aralkyl-type resin. The resin composition according to claim 1, wherein the content of the component (A-1) is 5% by mass or more when the nonvolatile component in the component (A) is 100% by mass. The resin composition according to claim 1, wherein the content of the component (A) is 10 mass% or more and 30 mass% or less when the nonvolatile component in the resin composition is 100 mass%. The resin composition according to claim 1, wherein the content of the component (B) is 60 mass% or more when the nonvolatile component in the resin composition is 100 mass%. According to claim 1, (A) component,
(A-2) A resin composition containing an acid-modified epoxy (meth) acrylate resin other than the component (A-1). The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in an alkali solution according to claim 1, is represented by the following equation (I):
Equation (I)
5≤S _(A) ≤110
To satisfy the resin composition. (A) a resin containing an ethylenically unsaturated group and a carboxyl group,
(B) an inorganic filler having an average particle diameter of 0.5 µm or more,
(C) epoxy resin, and,
(D) Photopolymerization initiator
As a resin composition containing,
The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) in an alkali solution is represented by the following equation (I):
Equation (I)
5≤S _(A) ≤110
To satisfy the resin composition. The resin composition according to claim 1 or 8, which is a resin composition for forming a solder resist of a printed wiring board. A photosensitive film containing the resin composition according to claim 1 or 8. A photosensitive film with a support having a support and a resin composition layer comprising the resin composition according to claim 1 formed on the support. A printed wiring board comprising an insulating layer formed of a cured product of the resin composition according to claim 1 or 8. A semiconductor device comprising the printed wiring board according to claim 12.

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