JP2022060252A - Resin composition, photosensitive film, photosensitive film with support, printed wiring board and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition or the like that makes it possible to obtain a cured product having excellent undercut resistance.

SOLUTION: A resin composition contains (A) a resin containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler with an average particle size of 0.5 μm or more, (C) an epoxy resin, and (D) a photopolymerization initiator, the (A) component containing (A-1) a naphthalene skeleton-containing resin.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

In the printed wiring board, a solder resist may be provided as a permanent protective film for suppressing the adhesion of solder to the portion where the solder is unnecessary and for suppressing the corrosion of the circuit board. As the solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

Japanese Unexamined Patent Publication No. 2014-115672

Since the solder resist is connected by soldering between the substrates, it is required to have a fine opening pattern such that a part of the conductor layer having the wiring pattern is exposed. Further, from the viewpoint of solder adhesion, the cross-sectional shape of the opening is required not to be reversely tapered, and in particular, the side surface of the opening is required to be close to perpendicular to the layer plane. There is. Here, the inverted tapered cross-sectional shape means a shape in which the diameter of the opening is wider toward the back, and specifically, a shape in which the bottom surface of the opening is wider than the top surface of the opening. In the present specification, the property that the cross-sectional shape is less likely to be reverse-tapered is said to be excellent in "undercut resistance". It should be noted that the above-mentioned problems also occur in cases other than the case of forming a solder resist using the resin composition.

The subject of the present invention is a resin composition capable of obtaining a cured product having excellent undercut resistance; a photosensitive film, a photosensitive film with a support, a printed wiring board, and a semiconductor device obtained by using the resin composition. Is to provide.

As a result of diligent studies to solve the above problems, the present inventor has found that (A) a resin containing an ethylenically unsaturated group and a carboxyl group, and (B) an inorganic filler having an average particle size of 0.5 μm or more. By using a resin composition containing C) an epoxy resin and (D) a photopolymerization initiator, wherein the component (A) contains (A-1) a naphthalene skeleton-containing resin. , The present invention was completed by finding that the above-mentioned problems can be solved.

Further, as a result of diligent studies to solve the above problems, the present inventor (A) a resin containing an ethylenically unsaturated group and a carboxyl group, and (B) an inorganic filler having an average particle size of 0.5 μm or more. , (C) Epoxy resin and (D) A resin composition containing a photopolymerization initiator, the weighted average value of the component (A) based on the mass ratio of the dissolution rate [nm / sec] to the alkaline solution. S _(A) is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
The present invention has been completed by finding that the above-mentioned problems can be solved by using a resin composition satisfying the above conditions.

That is, the present invention includes the following contents.
[1] (A) A resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) A resin composition containing a photopolymerization initiator.
A resin composition in which the component (A) contains (A-1) a resin containing a naphthalene skeleton.
[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 non-volatile component in the component (A) is 100% by mass. ..
[4] The content of the component (A) is 10% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass, according to any one of [1] to [3]. Resin composition.
[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 non-volatile 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 components (A-2) and (A-1). ..
[7] The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) to the alkaline solution is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
The resin composition according to any one of [1] to [6], which satisfies the above conditions.
[8] (A) A resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) 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) to the alkaline solution is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
A resin composition that meets the requirements.
[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 provided on the support and containing the resin composition according to any one of [1] to [9].
[12] A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of [1] to [9].
[13] A semiconductor device including the printed wiring board according to [12].

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

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

[1. 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 containing an ethylenically unsaturated group and a carboxyl group, (B) an inorganic filler having an average particle size of 0.5 μm or more, and (C) an epoxy. It is a resin composition containing a resin and (D) 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 having excellent undercut resistance can be obtained.

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

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

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, a propagyl group, a butenyl group, an ethynyl group, a phenylethynyl group, a maleimide group, a nadiimide group and a (meth) acryloyl group, and examples thereof include reactivity of photoradical polymerization. From this point of view, a (meth) acryloyl group is preferable. The "(meth) acryloyl group" includes a methacryloyl group, an acryloyl group, and a combination thereof. Since the component (A) contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of the component (A) may be one or two or more. Further, when the component (A) contains two or more ethylenically unsaturated groups per molecule, the ethylenically unsaturated groups may be the same or different.

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

In the present embodiment, the component (A) contains (A-1) a naphthalene skeleton-containing resin. The component (A) may further contain (A-2) acid-modified epoxy (meth) acrylate resin, if necessary. This component (A-2) is an example of the component (A) other than the component (A-1).

<(A-1) Naphthalene skeleton-containing resin>
Since the component (A-1) is a resin belonging to the component (A), it is a resin containing an ethylenically unsaturated group and a carboxyl group. Therefore, the component (A-1) is capable of photoradical polymerization, and all the resin compositions containing the component (A-1) are soluble in an alkaline solution.

The component (A-1) preferably has a plurality of ethylenically unsaturated groups in one molecule. This makes it possible to increase the mechanical strength and solubility resistance of the cured product of the resin composition. Further, the component (A-1) preferably has two or less ethylenically unsaturated groups per naphthalene skeleton. As a result, the cross-linking position (cross-linking point) can be adjusted, so that the mechanical strength and solubility resistance of the cured product of the resin composition can be controlled. More preferably, the ethylenically unsaturated group is contained in the substituent contained in the naphthalene skeleton. In order to include an ethylenically unsaturated group in the substituent of the naphthalene skeleton, as a first precursor, for example, the H atom of the OH group of naphthol is a substituent containing an epoxy group (for example, an epoxy group or glycidyl). It is obtained by preparing a compound substituted with a group) and adding a compound having an ethylenically unsaturated bond (for example, an unsaturated carboxylic acid, preferably (meth) acrylic acid) to the first precursor. Can be done. This makes it possible to introduce an ethylenically unsaturated group into the substituent of the naphthalene skeleton.

The component (A-1) preferably has a plurality of carboxyl groups in one molecule. This makes it possible to increase the solubility of the resin composition in an alkaline solution (for example, an alkaline developer). The component (A-1) preferably has two or less carboxyl groups per naphthalene skeleton. This makes it possible to control the solubility. More preferably, the carboxyl group is contained in the substituent contained in the naphthalene skeleton. In order to include the carboxyl group in the substituent of the naphthalene skeleton, for example, a compound in which the H atom of the OH group of naphthol is substituted with the substituent containing the epoxy group is prepared as the first precursor. A compound having an ethylenically unsaturated bond (for example, unsaturated carboxylic acid, preferably (meth) acrylic acid) is added to the precursor of No. 1 to obtain a second precursor having a secondary hydroxyl group. , Can be obtained by adding a carboxylic acid anhydride (eg, tetrahydrophthalic acid) to the second precursor. As a result, both an ethylenically unsaturated group and a carboxyl group can be introduced into the substituent of the naphthalene skeleton.

The component (A-1) is a naphthalene skeleton-containing resin. The naphthalene skeleton-containing resin refers to a compound containing one or more naphthalene skeletons in one molecule. Since the component (A-1) can be mixed well with the components (C) to (E), it is possible to suppress the bias of the composition in the resin composition. Further, the component (A-1) can be dissolved in an alkaline solution (for example, an alkaline developer) at a dissolution rate in an appropriate range. Further, when the resin composition containing the component (A-1) is developed with an alkaline developer, a portion that unintentionally dissolves too much and a portion that does not unintentionally dissolve are locally generated in the resin composition. Can be suppressed. Therefore, the undercut resistance of the resin composition can be improved, and preferably the side surface of the opening pattern can be brought close to perpendicular to the layer plane.

Further, when a naphthalene skeleton-containing resin is used as the component (A-1), the rigidity of the molecules is usually increased, so that the movement of the molecules in the resin composition is suppressed, and as a result, the cured product of the resin composition is suppressed. The glass transition temperature is higher and the average linear thermal expansion coefficient of the cured product is lower. Furthermore, the action of the component (A-1) usually improves the resistance of the cured product to internal stresses caused by thermal expansion or contraction, so that damage to the cured product due to temperature changes can be suppressed.

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

The component (A-1) is, for example, a resin containing a structure represented by the following formula (1). The component (A-1) may have a plurality of structures represented by the following formula (1) (for example, 1 to 10, preferably 1 to 6), and may have a plurality of structures represented by the following formula (1). When having the individual components (A-1), the component (A-1) may contain a plurality of the structures represented by the following formula (1) as structural units (repeating units). Further, in the following formula (1), the bond bonded to R ¹ may be bonded to any of the carbon atoms of the naphthalene skeleton that can be bonded. Therefore, the bond to which R ¹ is bonded is the carbon atom of the same benzene ring as the bond in formula (1) bonded to other than R ¹ and OR'(hereinafter, may be referred to as "terminal bond"). It may be bonded to a carbon atom of a different benzene ring. For example, the combination of the positions of the terminal bond in the naphthalene skeleton and the bond bound to R ¹ is 1, 2, 1, 3, 1, 4, 1, 5, 1, 6, and 1. , 7th, 1, 8th, 2nd, 3rd, 2nd, 6th, 2nd and 7th.

In the above formula (1), R ¹ and R ² each independently represent an alkylene group which may have a substituent. The number of carbon atoms of R ¹ is usually 1 to 20, preferably 1 to 10, and more preferably 1 to 6. Further, the alkylene group may be linear or branched. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group and the like.

The substituents that R ¹ and R ² can have are 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, and a sulfo group. , Cyano group, nitro group, hydroxy group, mercapto group, oxo group and the like.

In the above formula (1), X represents an arylene group which may have a substituent. The number of carbon atoms of 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, an anthrasenylene group, a phenanthrenylene group, or a biphenylene group.

Examples of the substituents that X can have include the same examples as the substituents that ^R1 and ^R2 can have.

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

In the above formula (1), s represents 0 or 1. Here, s and t are the numbers of the groups ^R1 and the groups ^R2 , respectively. Further, in the above formula (1), t represents 0 or 1. However, for s and t, s + t does not become 0. Above all, 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 above formula (1), OR'is a substituent on the naphthalene skeleton. In the above formula (1), R'independently represents an organic group containing an ethylenically unsaturated group and a carboxyl group, respectively.

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

In the above formula (2), R ³ represents a trivalent group, preferably a trivalent hydrocarbon group which may have a substituent (however, a carbon-carbon bond (CC bond)). A heteroatom may be interposed between them), and among them, a trivalent aliphatic hydrocarbon group which may have a substituent is preferable. The R ³ may be a trivalent residue of an epoxy group-containing substituent which may have a substituent. Examples of the substituents that R ³ can have include the same examples as the substituents that R ¹ and R ² can have.

In the above formula (2), ^R4 represents an organic group containing an ethylenically unsaturated group. Preferred examples of organic groups containing ethylenically unsaturated groups include (meth) methylenedioxy groups. The "(meth) methylenedioxy group" includes an acryloyloxy group, a methacryloyloxy group, and a combination thereof.

In the above formula ( ² ), R5 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 ^R6 , a divalent hydrocarbon group which may have a substituent is preferable. The number of carbon atoms of R ⁶ is usually 1 to 30, preferably 1 to 20, and more preferably 1 to 6. Examples of the divalent hydrocarbon group include 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. Hydrogen group; arylene group such as phenylene group and naphthylene group can be mentioned. Of these, a divalent alicyclic hydrocarbon group and an arylene group are preferable, and a 4-cyclohexenylene group and a phenylene group are particularly preferable. Further, as the substituent that R ⁶ can have, for example, the same example as the substituent that R ¹ and R ² can have can be mentioned. -CO-R ⁶ -COOH in -OCO-R ⁶ -COOH is usually a residue of carboxylic acid anhydride. Examples of carboxylic acid anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid di. It is anhydrous.

In the above 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 the base OR'.

<First example of (A-1) component (a = 1)>
A preferred 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 in which the H atom of the OH group is removed from the naphthol aralkylene group.

A preferable naphthol aralkyl type resin is a resin having a structure of a = 1 in the above formula (1), and is, for example, a resin having a structure represented by the following formula (3).

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

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

In the above formula (4) or (5), ^R1 , ^R2 , X, R'and c are the same as described above. The naphthol aralkyl type resin represented by the above formula (4) or (5) is a resin that can be synthesized using the naphthol aralkyl type epoxy resin B used in Synthesis Example 2 described later as a material. The naphthol aralkyl type epoxy resin B is available as, for example, "ESN-475V" (epoxy equivalent 325) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

<Second example of (A-1) component (a = 0)>
Among the components (A-1), a preferable example other than the naphthol aralkyl type resin (a = 0) is a resin having a structure of c = 2, s = 1 and t = 0 in the above formula (1). For example, it is a naphthalene skeleton-containing resin containing a divalent group having a structure represented by the following formula (6).

In the above formula (6), ^R1 , R and R'are the same as described above. The naphthalene skeleton-containing resin represented by the above formula (6) is a resin that can be synthesized from the naphthalene skeleton-containing epoxy resin A (1,1'-bis (2,7-diglycidyloxynaphthyl) methane, epoxy equivalent 162). (See Synthesis Example 1 below). The naphthalene skeleton-containing epoxy resin A is available, for example, as "EXA-4700" manufactured by Dainippon Ink and Chemicals.

The weight average molecular weight of the component (A-1) is preferably 500 or more, more preferably 1000 or more, still more preferably 1500 or more, and more preferably 2000 or more, from the viewpoint of film forming property. Is even more preferable. From the viewpoint of developability, the upper limit is preferably 10,000 or less, more preferably 8,000 or less, and even more preferably 7,500 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

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 alkaline solution. .. On the other hand, from the viewpoint of suppressing the fine pattern of the cured product from dissolving in the alkaline solution and improving the undercut resistance, the acid value is preferably 150 mgKOH / g or less, and 120 mgKOH / g or less. It is more preferably 100 mgKOH / g or less, and even more preferably 100 mgKOH / g or less. Here, the acid value is the residual acid value of the carboxyl group present in the component (A-1), and the acid value can be measured by the following method. First, about 1 g of the measurement resin solution is precisely weighed, and then 30 g of acetone is added to the resin solution to uniformly dissolve the resin solution. Next, an appropriate amount of phenolphthalein, which is an indicator, is added to the solution, and titration is performed using a 0.1 N KOH aqueous solution. Then, the acid value is calculated by the following formula (7).
Formula: A = 10 × Vf × 56.1 / (Wp × I) ・ ・ ・ (7)

In the above formula (7), A represents an acid value [mgKOH / g], Vf represents a titration amount of KOH [mL], Wp represents a measurement resin solution mass [g], and I represents a measurement resin solution. Represents the proportion [mass%] of the non-volatile component of.

The weighted average value S _(A-1) based on the mass ratio of the dissolution rate [nm / sec] of the component (A-1) to the alkaline solution is the following formula (II) :.
5 ≤ S _(A-1) ≤ 110 ... (II)
It is preferable to satisfy. The dissolution rate in an alkaline 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, further preferably 10 nm / sec or more, and particularly preferably 15 nm / sec or more. It is preferably 100 nm / sec or less, more preferably 90 nm / sec or less, and further preferably 80 nm / sec or less. (A-1) When the weighted average value S _(A-1) of the dissolution rate of the component is in the above range, the dissolution rate of the resin composition in the alkaline developer becomes excessively slow or fast. Can be suppressed. Therefore, it is possible to suppress the local occurrence of a portion that melts too much unintentionally and a portion that does not melt unintentionally. Therefore, the undercut resistance can be improved, and preferably the side surface of the opening pattern can be brought closer to perpendicular to the layer plane.

More preferably, when a plurality of types of naphthalene skeleton-containing resins are used as the component (A-1), the dissolution rate [nm / sec] of each of the naphthalene skeleton-containing resins is in the above range. Thereby, the weighted average value S _(A-1) can surely satisfy the above range.

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

From the viewpoint of adjusting the solubility of the resin composition in an alkaline solution, the content of the component (A-1) shall be 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. Is more preferable, and it is more preferably 10% by mass or more, and further preferably 15% by 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 further preferably 28% by mass or less.

<Manufacturing method of (A-1) component>
The component (A-1) is not limited to the above-mentioned example as long as it is a compound having a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group, and is not particularly limited, but one embodiment thereof. Examples thereof include an acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin obtained by reacting a naphthalene-type epoxy compound having a naphthalene skeleton (naphthalene skeleton-containing epoxy compound) with an unsaturated carboxylic acid and further reacting with a carboxylic acid anhydride. Be done. 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, a monohydroxynaphthalene type epoxy resin, a dihydrooxynaphthalene type epoxy resin, and a polyhydroxybinaphthalene type epoxy resin can be used. Examples thereof include naphthalene-type epoxy resins having a naphthalene skeleton in the molecule, such as naphthalene-type epoxy resins and binaphthol-type epoxy resins obtained by a condensation reaction between polyhydroxynaphthalene and aldehydes. Any one of these may be used alone, or two or more thereof may be used in combination.

Examples of the monohydroxynaphthalene type epoxy resin include 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene. Examples of the dihydroxynaphthalene type epoxy resin include 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, and 2,3-di. Examples thereof include glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene and 2,7-diglycidyloxynaphthalene.

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

Examples of the naphthalene-type epoxy resin obtained by the condensation reaction between polyhydroxynaphthalene and aldehydes include 1,1'-bis (2,7-diglycidyloxynaphthyl) methane and 1- (2,7-diglycidyloxynaphthyl). ) -1'-(2'-Glysidyloxynaphthyl) methane and 1,1'-bis (2-glycidyloxynaphthyl) methane can be mentioned.

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

Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid and the like, and these may be used alone or in combination of two or more. Of these, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In the present specification, the naphthalene-type epoxy compound ester resin, which is a reaction product of the above-mentioned naphthalene-type epoxy compound and (meth) acrylic acid, may be referred to as "naphthalene-type epoxy compound (meth) acrylate". The epoxy group of the naphthalene-type epoxy compound is usually substantially eliminated by the reaction with (meth) acrylic acid. "(Meth) acrylate" includes methacrylates, acrylates and combinations thereof. Acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic acid".

Examples of the carboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone tetracarboxylic acid. Examples thereof include dianhydrides and the like, and any one of them may be used alone or two or more thereof may be used in combination. Of these, succinic anhydride and tetrahydrophthalic anhydride are preferable from the viewpoint of improving the developability and insulation reliability of the cured product.

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

The amount of the catalyst used in this case is preferably 2% by mass or less, more preferably 0.0005% by mass or more, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound and the carboxylic acid anhydride. It is in the range of 1% by mass, more preferably 0.001% by mass to 0.5% by mass. Examples of the catalyst include N-methylmorpholin, 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, imidazole, 1-methylimidazole , 2,4-Dimethylimidazole, 1,4-diethylimidazole, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (N-phenyl) aminopropyltrimethoxysilane, 3- (2-amino Various amine compounds such as ethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, tetramethylammonium hydroxide; phosphines such as trimethylphosphine, tributylphosphine, triphenylphosphine; tetramethyl Phosphonium salts such as phosphonium salt, tetraethylphosphonium salt, tetrapropylphosphonium salt, tetrabutylphosphonium salt, trimethyl (2-hydroxylpropyl) phosphonium salt, triphenylphosphonium salt, benzylphosphonium salt, etc. Phosphonium salts having chloride, bromide, carboxylate, hydroxyoxide, etc .; sulfonium salts such as trimethylsulfonium salt, benzyltetramethylenesulfonium salt, phenylbenzylmethylsulfonium salt or phenyldimethylsulfonium salt, as typical counter anions. Sulfonium salts having carboxylates, hydroxyoxides and the like; examples thereof include acidic compounds such as phosphoric acid, p-toluenesulfonic acid and sulfuric acid. The reaction can be carried out in the range of 50 ° C to 150 ° C, preferably in the range of 80 ° C to 120 ° C.

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

In obtaining the 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 in this case is preferably 2% by mass or less, more preferably 0.0005% by mass, based on the total mass of the unsaturated carboxylic acid, the naphthalene skeleton-containing epoxy compound and the carboxylic acid anhydride. It is in the range of% to 1% by mass, more preferably 0.001% by mass to 0.5% by mass.

As the acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, 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 naphthalene skeleton-containing epoxy compound and using (meth) acrylic acid as the unsaturated carboxylic acid. ..

As another embodiment of the component (A-1), an ethylenically unsaturated group and a naphthalene skeleton-containing epoxy compound are reacted with a (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid. Examples thereof include unsaturated modified naphthalene skeleton-containing (meth) acrylic resins having an ethylenically unsaturated group introduced therein. Further, it is also possible to react the carboxylic acid anhydride with the hydroxyl group generated during the introduction of the unsaturated group. As the carboxylic acid anhydride, the same as the above-mentioned acid anhydride 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-2) does not include the component (A-1).

As one aspect of the component (A-2), an acid obtained by reacting a bisphenol type epoxy compound such as a bisphenol A type epoxy compound or a bisphenol F type epoxy compound with (meth) acrylic acid and further reacting with a carboxylic acid anhydride. Examples thereof include modified bisphenol type epoxy (meth) acrylate. For details, the bisphenol type epoxy compound is reacted with (meth) acrylic acid to obtain a bisphenol type epoxy (meth) acrylate, and the bisphenol type epoxy (meth) acrylate is reacted with a carboxylic acid anhydride to obtain an acid-modified bisphenol type epoxy (meth). Meta) Acrylate can be obtained.

Another embodiment of the component (A-2) includes an acid-modified biphenyl-type epoxy (meth) acrylate obtained by reacting a biphenyl-type epoxy compound with (meth) acrylic acid and further reacting with a carboxylic acid anhydride. For details, the biphenyl-type epoxy compound is reacted with (meth) acrylic acid to obtain a biphenyl-type epoxy (meth) acrylate, and the biphenyl-type epoxy (meth) acrylate is reacted with a carboxylic acid anhydride to obtain an acid-modified biphenyl-type epoxy (meth). Meta) Acrylate can be obtained.

As yet another embodiment of the component (A-2), an acid-modified epoxy (meth) acrylate obtained by reacting an epoxy compound other than the above-mentioned epoxy compound with (meth) acrylic acid and further reacting with a carboxylic acid anhydride can be mentioned. .. Examples of such epoxy compounds include novolak type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A type novolak type epoxy resin, and alkylphenol novolak type epoxy resin; and perfluoroalkyl type epoxy resin. Fluorine-containing epoxy resin, bixirenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; epoxy resin containing a fused ring skeleton such as anthracene type epoxy resin; glycidylamine Type epoxy resin; glycidyl ester type epoxy resin; linear aliphatic epoxy resin; epoxy resin having a butadiene structure; alicyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; Methylol type epoxy resin; tetraphenylethane type epoxy resin; polyglycidyl (meth) acrylate, glycidyl group-containing acrylic resin such as a copolymer of glycidyl methacrylate and acrylic acid ester; fluorene type epoxy resin; halogenated epoxy resin, etc. Be done.

Commercially available products can be used as such acid-modified epoxy (meth) acrylates, and specific examples thereof include "ZAR-2000" (acid-modified bisphenol type epoxy acrylate: bisphenol A type epoxy resin, acrylic) manufactured by Nippon Kayaku Co., Ltd. Acid and succinic anhydride reaction product), "ZFR-1491H" (acid-modified bisphenol type epoxy acrylate: bisphenol F type epoxy resin, acrylic acid, and acid anhydride reaction product), "ZFR-1533H" (acid modification) Bisphenol type epoxy acrylate: reaction product of bisphenol F type epoxy resin, acrylic acid, and tetrahydrophthalic anhydride), "ZCR-1569H" (acid-modified biphenyl type epoxy acrylate: biphenyl type epoxy resin, acrylic acid, and acid anhydride (Reactant), "PR-300CP" manufactured by Showa Denko Co., Ltd. (reactant of cresol novolac type epoxy resin, acrylic acid, and acid anhydride) and the like. These may be used alone or in combination of two or more.

As another embodiment of the component (A-2), the (meth) acrylic resin having a structural unit obtained by polymerizing (meth) acrylic acid is reacted with the (meth) acrylate of the epoxy compound to cause ethylenically unsaturated. Examples thereof include unsaturated modified (meth) acrylic resins into which a group has been introduced. Examples of the (meth) acrylate of the epoxy compound include glycidyl methacrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexylmethyl (meth) acrylate. Further, it is also possible to react the carboxylic acid anhydride with the hydroxyl group generated during the introduction of the unsaturated group. As the carboxylic acid anhydride, the same carboxylic acid anhydride as described above can be used, and the preferred range is also the same.

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

The weight average molecular weight of the component (A-2) is preferably 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, from the viewpoint of film forming property. From the viewpoint of developability, the upper limit is preferably 20000 or less, more preferably 15000 or less, and further preferably 14000 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

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

The weighted average value S _(A-2) based on the mass ratio of the dissolution rate [nm / sec] of the component (A-2) to the alkaline solution is the following formula (III) :.
1 ≤ S _(A-2) ≤ 150 ... (III)
It is preferable to satisfy, and more preferably, the following formula (IIIa):
1 ≤ S _(A-2) ≤ 131 ... (IIIa)
Meet. Thereby, the solubility of the resin composition in the alkaline 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 dissolution rate [nm / sec] of each of the acid-modified epoxy (meth) acrylate resins is within the above range. It is more preferable to have. Thereby, the weighted average value S _(A-2) can surely satisfy the above range.

From the viewpoint of adjusting the solubility of the component (A-2) in an alkaline solution, is the content of the component (A-1) the same as the content of the component (A-1) when the non-volatile component of the component (A) is 100% by mass? Or less than that, and more preferably, the content of the component (A-2) is 50% of the content of the component (A-1) when the non-volatile component of the component (A) is 100% by mass. It is mass% or less, more preferably 45 mass% or less. The content of the component (A-2) is preferably 30% by mass or less from the viewpoint of adjusting the solubility of the resin composition in an alkaline solution when the non-volatile component of the resin composition is 100% by mass. , 20% by mass 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 mass% or 0.2 mass% may be used.

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

<(A-3) Any resin containing ethylenically unsaturated group and carboxyl group>
The component (A) may contain any resin containing (A-3) an ethylenically unsaturated group and a carboxyl group in combination with the above-mentioned components (A-1) and (A-2). .. This component (A-3) does not include the component (A-1) and the component (A-2).

The weight average molecular weight and acid value of the component (A-3) are arbitrary, but are preferably in the same range as the weight average molecular weight and acid value of the component (A-2) described above. Thereby, the same advantages as described in the section of (A-2) component can be obtained.

<Overall characteristics of (A) component>
The lower limit of the weight average molecular weight of the component (A) is preferably 500 or more or 1000 or more, more preferably 1500 or more, and further preferably 2000 or more, from the viewpoint of film forming property. From the viewpoint of developability, the upper limit is preferably 20000 or less, more preferably 15000 or less, and further preferably 14500 or less. The weight average molecular weight is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm / sec] of the component (A) to the alkaline solution is the following formula (I) :.
5 ≤ S _(A) ≤ 110 ... (I)
It is preferable to satisfy. The dissolution rate in an alkaline 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, and further 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 prevent the dissolution rate of the resin composition from being dissolved in the alkaline developer from becoming excessively slow or fast. Therefore, it is possible to suppress the local occurrence of a portion that melts too much unintentionally and a portion that does not melt unintentionally. Therefore, the undercut resistance can be improved, and preferably the side surface of the opening pattern can be brought closer to perpendicular to the layer plane.

More preferably, when a resin containing a plurality of types of ethylenically unsaturated groups and carboxyl groups is used as the component (A), the dissolution rate [nm / sec] of each of the ethylenically unsaturated groups and the resin containing a carboxyl group is determined. It is more preferable to be in the above range. Thereby, the weighted average value S _(A) can surely satisfy the above range.

From the viewpoint of adjusting the solubility of the resin composition in an alkaline solution, the content of the component (A) is preferably 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. , 15% by mass or more, more preferably 20% by 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 further preferably 29% by mass or less.

<(B) Inorganic filler having an average particle size of 0.5 μm or more>
The resin composition contains (B) an inorganic filler having an average particle size of 0.5 μm or more. Even if the resin composition contains the component (B) (that is, even when the average particle size of the inorganic filler is large), it is possible to provide a resin composition capable of obtaining a cured product having excellent undercut resistance. It becomes. Further, by using the component (B), the average coefficient of linear thermal expansion of the cured product can usually be lowered.

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

The average particle size 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 having excellent undercut resistance. The upper limit of the average particle size is preferably 2.5 μm or less, more preferably 2 μm or less, still more preferably 1.5 μm or less, still more preferably, from the viewpoint of suppressing light reflection during exposure and obtaining excellent developability. Is 1.3 μm or less. Commercially available products of inorganic fillers having such an average particle size include, for example, "SC4050" and "Admafine" manufactured by Admatex, "SFP series" manufactured by Denki Kagaku Kogyo Co., Ltd., and "SP" manufactured by Nippon Steel & Sumikin Materials Co., Ltd. (H) Series ”, Sakai Chemical Industry Co., Ltd.“ Sciqas Series ”, Nippon Shokubai Co., Ltd.“ Sea Hoster Series ”, Nippon Steel & Sumikin Materials Co., Ltd.“ AZ Series ”,“ AX Series ”, Sakai Chemical Industry Co., Ltd.“ "B series", "BF series" and the like can be mentioned.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis using a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd., "SALD-2200" manufactured by Shimadzu Corporation, or the like 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, and particularly preferably 5 m ² / g or more, from the viewpoint of obtaining a cured product having excellent 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 is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method and calculating the specific surface area using the BET multipoint method. ..

From the viewpoint of enhancing moisture resistance and dispersibility, 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, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

The content of the component (B) is preferably 60% by mass or more, more preferably 60% by mass, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient. It is 5% by mass or more, more preferably 61% by mass or more. The upper limit is, for example, 90% by mass or less, 85% by mass or less, 82% by mass or less, or 80% by 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 the component (C), the reaction between the components (C) or the reaction between the component (C) and the component (A) becomes possible, and the mechanical strength and solubility resistance of the cured product of the resin composition become possible. Can be enhanced. However, the component (C) referred to here does not include the epoxy resin belonging to the component (A).

The component (C) includes, for example, a fluorine-containing epoxy resin such as a bisphenol AF type epoxy resin and a perfluoroalkyl type epoxy resin; a bisphenol A type epoxy resin; a bisphenol F type epoxy resin; a bisphenol S type epoxy resin; a bixirenol type. Epoxy resin; Dicyclopentadiene type epoxy resin; Trisphenol type epoxy resin; Naftor novolac type epoxy resin; Phenol novolak type epoxy resin; tert-butyl-catechol type epoxy resin; Naphthalene type epoxy resin; Naftor 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, fat having an ester skeleton Cyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexanedimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; tetraphenylethane type epoxy resin, halogenated epoxy resin, etc. From the viewpoint of improving adhesion, bisphenol F type epoxy resin and biphenyl type epoxy resin are preferable, and biphenyl type epoxy resin is more preferable. Further, from the viewpoint of improving heat resistance, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, naphthylene ether type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and tetraphenylethane type epoxy resin is more preferable. .. The epoxy resin may be used alone or in combination of two or more. The component (C) preferably contains at least one of a biphenyl type epoxy resin and a tetraphenylethane type epoxy resin, and more preferably both of them, from the viewpoint of improving adhesion and heat resistance.

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

Specific examples of the epoxy resin include "HP4032", "HP4032D", "HP4032SS", "HP4032H" (naphthalene type epoxy resin) manufactured by DIC, and "828US" and "jER828EL" (bisphenol A type) manufactured by Mitsubishi Chemical Corporation. Epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Corporation (Mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" manufactured by Nippon Steel & Sumitomo Metal Corporation (bisphenol A type epoxy resin), "EX-721" manufactured by Nagase Chemtex Co., Ltd. (glycidyl ester type) Epoxy resin), "Selokiside 2021P" manufactured by Daisel (epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), "ZX1658" manufactured by Nippon Steel Chemical Co., Ltd., " "ZX1658GS" (liquid 1,4-glycidylcyclohexane), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "E-7432", "E-7632" (perfluoroalkyl type epoxy) manufactured by Daikin Industries, Ltd. Resin), DIC's "HP-4700", "HP-4710" (naphthalen type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac 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), "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. , "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol aralkyl type epoxy resin), "ESN485" (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Corporation. , "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixirenol type epoxy resin), "YX8800" (anthracen type epoxy resin), "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., Mitsubishi "YL7800" (fluorene type epoxy resin) manufactured by Kagaku Co., Ltd., "1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Kagaku Co., Ltd., "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF) Type epoxy resin) and the like.

The content of the component (C) is preferably 1% by mass or more when the non-volatile component of the resin composition is 100% by mass, from the viewpoint of enhancing the mechanical strength and solubility resistance of the cured product of the resin composition. It is preferably 5% by mass or more, more preferably 8% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less.

The epoxy equivalent of the epoxy resin is preferably 50 g / eq. ~ 5000g / eq. , More preferably 50 g / eq. ~ 3000 g / eq. , More preferably 80 g / eq. ~ 2000g / eq. , Even more preferably 110 g / eq. ~ 1000 g / eq. Is. Within this range, the crosslink density of the cured product of the resin composition becomes sufficient, and an insulating layer having a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

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 the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

<(D) Photopolymerization Initiator>
The resin composition contains (D) a photopolymerization initiator. By containing the component (D), the resin composition can be efficiently photo-cured.

The component (D) is not particularly limited, but is, 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-one, etc. Photopolymerization initiator; Oxyme ester-based photopolymerization initiator such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) Benzofenone, 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-diphenylethane-1-one, 1, -[4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxand and the like. , A sulfonium salt-based photopolymerization initiator and the like can also be used. Any one of these may be used alone or two or more thereof may be used in combination.

Specific examples of the component (D) include "Omnirad 907", "Omnirad 369", "Omnirad 379", "Omnirad 819", "Omnirad TPO" manufactured by IGM, "IrgacureTPO", "IrgacureTPO", "IrgureOX" manufactured by BASF. -02 "," N-1919 "manufactured by ADEKA, and the like.

The content of the component (D) is 100% by mass of the non-volatile component of the resin composition from the viewpoint of sufficiently photocuring the resin composition and enhancing the mechanical strength and solubility resistance of the cured product of the resin composition. If so, it is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.05% by mass or more. On the other hand, from the viewpoint of suppressing the deterioration of developability due to excessive sensitivity, the upper limit is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.5% by mass or less.

Further, the resin composition is combined with the component (D) as a photopolymerization initiation aid, such as N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, and pentyl-4-dimethylamino. It may contain tertiary amines such as benzoate, triethylamine and triethanolamine, and may contain photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones and thioxanthones. Any one of these may be used alone or two or more thereof may be used in combination.

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

Typical photosensitive (meth) acrylate compounds include hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono or diacrylates, acrylamides such as N, N-dimethylacrylamide, N-methylolacrylamide, aminoalkylacrylates such as N, N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol, dipentaerythritol, etc. Polyvalent acrylates of valent alcohols or additives of these ethylene oxides, propylene oxides or ε-caprolactones (eg DPHA: dipentaerythritol hexaacrylates), phenols such as phenoxyacrylates and phenoxyethyl acrylates, or ethylene oxides or propylenes thereof. Examples thereof include acrylates such as oxide adducts, epoxy acrylates derived from glycidyl ethers such as trimethylolpropane triglycidyl ether, melamine acrylates, and / or methacrylates corresponding to the above acrylates. Among these, polyvalent acrylates or polyvalent methacrylates are preferable, and for example, trivalent acrylates or methacrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and trimethylolpropane. EO-added tri (meth) acrylate, glycerin PO-added tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tetraflufuryl alcohol oligo (meth) acrylate, ethylcarbitol oligo (meth) acrylate, 1,4-butanediol Oligo (meth) acrylate, 1,6-hexanediol oligo (meth) acrylate, trimethylolpropane oligo (meth) acrylate, pentaerythritol oligo (meth) acrylate, tetramethylolmethanetetra (meth) acrylate, dipentaerythritol hexa (meth) ) Acryloyl, N, N, N', N'-tetrax (β-hydroxyethyl) ethyldiamine (meth) acrylic acid ester and the like, and examples of trivalent or higher acrylates or methacrylates include tri (2-). (Meta) acryloyloxyethyl) phosphate, tri (2- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyloxypropyl) phosphate, tri (3- (meth) acryloyl-2-hydroxyloxypropyl) Phosphate, di (3- (meth) acryloyl-2-hydroxyloxypropyl) (2- (meth) acryloyloxyethyl) phosphate, (3- (meth) acryloyl-2-hydroxyloxypropyl) di (2- (meth) Acryloyloxyethyl) Phosphate and other phosphate triester (meth) acrylates can be mentioned. Any one of these photosensitive (meth) acrylate compounds may be used alone or two or more thereof may be used in combination.

The content of the component (E) when blended is 1 mass when the non-volatile component of the resin composition is 100% by mass from the viewpoint of promoting photocuring and suppressing stickiness when made into a cured product. % To 10% by mass is preferable, and 3% by mass to 8% by 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 ethylmethylketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methylcellosolve, butylcellosolve, methylcarbitol, butylcarbitol and propylene glycol. Glycol ethers such as monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate (EDGAc: diethylene glycol monoethyl ether acetate), Examples thereof include esters such as ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, petroleum ethers, petroleum naphtha, hydrogenated petroleum naphtha, and petroleum-based solvents such as solvent naphtha. These may be used alone or in combination of two or more. When an organic solvent is used, the content can be appropriately adjusted from the viewpoint of coatability of the resin composition.

<(G) Other additives>
The resin composition may further contain (G) and other additives to the extent that the object of the present invention is not impaired. (G) Other additives include, for example, thermoplastic resin, organic filler, melamine, fine particles such as organic bentonite, phthalocyanine blue, phthalocyanine green, iodin green, diazo yellow, crystal violet, titanium oxide, carbon black, and the like. Colorants such as naphthalene black, polymerization inhibitors such as hydroquinone, phenothiazine, methylhydroquinone, hydroquinone monomethyl ether, catechol, pyrogallol, thickeners such as Benton and montmorillonite, silicone-based, fluorine-based, and vinyl resin-based defoaming agents. Heat of flame retardant such as brominated epoxy compound, acid-modified brominated epoxy compound, antimony compound, phosphorus compound, aromatic condensed phosphoric acid ester, halogen-containing condensed phosphoric acid ester, phenol-based curing agent, cyanate ester-based curing agent, etc. Various additives such as cured resin can be added.

<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 a kneading means such as a three-roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. The resin composition can be obtained as a resin varnish by containing, for example, (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 size of 0.5 μm or more, and (C) an epoxy. It is a resin composition containing a resin and (D) 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) to the alkaline solution is the following formula (I) :.
5 ≤ S _(A) ≤ 110 ... (I)
Meet. The dissolution rate in an alkaline solution can be measured, for example, by the method described in Examples. As the alkaline solution, a developer usually used for development can be mentioned. In order to make the dissolution rate comparable, it is preferable to use a 1% by mass sodium carbonate aqueous solution having a constant pH (pH: 11.7) at 23 ° C. as the alkaline solution. The temperature and pH of the alkaline solution may be changed as appropriate as long as they do not significantly affect the dissolution rate.

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

<Component (A), component (B), component (C) and component (D)>
Regarding the component (A), the component (B), the component (C) and the component (D) contained in the resin composition according to the second embodiment, even if the component (A) does not contain the component (A-1). The component (A), (B) contained in the resin composition according to the first embodiment, except that the good thing and the weighted average value S _(A) of the dissolution rate of the component (A) satisfy the formula (I). ), The component (C) and the component (D). Thereby, the same advantages as those of the resin composition according to the first embodiment can be obtained.

The content, weight average molecular weight and acid value of the component (A) are arbitrary, but are preferably in the same range as the content, weight average molecular weight and acid value of the component (A) described above in the first embodiment. .. Thereby, the same advantages as described in the section of the component (A) can be obtained in the first embodiment. The content, average particle size and specific surface area of the component (B) are arbitrary, but are preferably in the same range as the content, average particle size and specific surface area of the component (B) described above in the first embodiment. .. Thereby, the same advantages as described in the section of the component (B) in the first embodiment can be obtained. The content, epoxy equivalent, and weight average molecular weight of the component (C) are arbitrary, but are preferably in the same range as the content, epoxy equivalent, and weight average molecular weight of the component (C) described above in the first embodiment. .. Thereby, the same advantages as described in the section of the component (C) can be obtained in the first embodiment. The content of the component (D) is arbitrary, but is preferably in the same range as the content of the component (D) described above in the first embodiment. Thereby, the same advantages as described in the section 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] to the alkaline 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, and particularly preferably 15 nm / sec. It is 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 prevent the dissolution rate of the resin composition from being dissolved in the alkaline developer from becoming excessively slow or fast. Therefore, it is possible to suppress the local occurrence of a portion that melts too much unintentionally and a portion that does not melt unintentionally. Therefore, the undercut resistance can be improved, and preferably the side surface of the opening pattern can be brought closer to perpendicular to the layer plane.

As a method of keeping the weighted average value S _(A) of the dissolution rate of the component (A) within the above-mentioned range, for example, a method of adopting the component (A) including the component (A-1) can be mentioned. However, for example, even if the type and amount of the component (A) other than the component (A-1) are appropriately adjusted to keep the weighted average value S _(A) of the dissolution rate of the component (A) within the above range. good.

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

<Component (E), component (F) and component (G)>
The resin composition according to the present embodiment may further contain (E) a reactive diluent, (F) an organic solvent, (G) and other additives, if necessary. Regarding the component (E), the component (F) and the component (G) that can be contained in the resin composition according to the second embodiment, the component (E) and the component (F) that can be contained in the resin composition according to the first embodiment. And (G) are the same as the component. Thereby, the same advantages as those of 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 performed by a kneading means such as a three-roll, ball mill, bead mill, sand mill, or a stirring means such as a super mixer or a planetary mixer. The resin composition can be obtained as a resin varnish by containing, for example, (F) an organic solvent.

<Physical characteristics and uses of resin composition>
A cured product obtained by photo-curing the resin composition according to the first embodiment or the resin composition according to the second embodiment and then heat-curing at 190 ° C. for 90 minutes has a characteristic of excellent undercut resistance. show. That is, it provides an insulating layer and a solder resist having excellent undercut resistance. The undercut is preferably +10 μm or less, more preferably +5 μm or less, still more preferably +4 μm or less, still more preferably +3 μm or less, from the viewpoint of suppressing the forward taper shape. 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 undercut value can be measured according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

Further, a cured product obtained by photo-curing the resin composition according to the first embodiment or the second embodiment of the present invention and then heat-curing at 190 ° C. for 90 minutes tends to exhibit excellent developability. .. Therefore, normally, there is no residue such as resin in the unexposed portion. The minimum via hole diameter without residue is preferably 100 μm or less, more preferably 90 μm or less, and further preferably 80 μm or less. The lower limit is not particularly limited, but may be 1 μm or more. The developability can be evaluated according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

The cured product obtained by photo-curing the resin composition according to the first embodiment or the second embodiment of the present invention and then heat-curing at 190 ° C. for 90 minutes tends to exhibit a characteristic that the average linear thermal expansion coefficient is low. be. That is, it provides an insulating layer and a solder resist having a low average coefficient of linear thermal expansion. The average coefficient of linear thermal expansion is preferably 45 ppm / ° C. or lower, more preferably 40 ppm / ° C. or lower, still more preferably 36 ppm / ° C. or lower, and 35 ppm / ° C. or lower. The lower limit is not particularly limited, but may be 10 ppm / ° C. or higher. The average coefficient of linear thermal expansion can be measured according to the method described in <Measurement of average coefficient of linear thermal expansion and glass transition temperature> described later.

A cured product obtained by photo-curing the resin composition according to the first embodiment or the second embodiment of the present invention and then heat-curing at 190 ° C. for 90 minutes tends to exhibit a characteristic that the glass transition temperature is high. That is, it provides an insulating layer and a solder resist having a high glass transition temperature. The glass transition temperature is preferably more than 135 ° C., more preferably 170 ° C. or higher, still more preferably 180 ° C. or higher. 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.

A cured product obtained by photo-curing the resin composition according to the first embodiment or the second embodiment of the present invention and then heat-curing at 190 ° C. for 90 minutes exhibits a characteristic of excellent crack resistance. That is, it provides an insulating layer and a solder resist having excellent crack resistance. No cracks or peeling were observed even after repeating the temperature rise test between -65 ° C and 150 ° C 500 times. The crack resistance can be evaluated according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

The use of the resin composition according to the first embodiment or the second embodiment of the present invention is not particularly limited, but is limited to a photosensitive film, a photosensitive film with a support, an insulating resin sheet such as a prepreg, and a circuit board (utilized laminated board). , Multi-layer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, fill-in-the-blank resins, component-embedded resins, etc., can be used in a wide range of applications requiring resin compositions. Among them, a resin composition for an insulating layer of a printed wiring board (a printed wiring board in which a cured product of a resin composition is used as an insulating layer) and a resin composition for an interlayer insulating layer (a cured product of a resin composition is used as an interlayer insulating layer). Printed wiring board), resin composition for plating (printed wiring board with plating formed on the cured product of the resin composition), and resin composition for solder resist (printed using the cured product of the resin composition as a solder resist). It can be suitably used as a wiring board).

[Photosensitive film]
By using the resin composition according to the first embodiment or the second embodiment of the present invention, a photosensitive film containing the resin composition can be obtained. For example, the resin composition can be applied on a support substrate in a resin varnish state and dried with an organic solvent to form a resin composition layer to form a photosensitive film. Further, it is also possible to use a photosensitive film formed on the support in advance by laminating it on the support substrate. The photosensitive film can be laminated on various support substrates. Examples of the support substrate mainly include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like.

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

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.

Examples of commercially available supports include product names "Alfan MA-410" and "E-200C" manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product names "PS-25" manufactured by Teijin Limited. Examples include, but are not limited to, polyethylene terephthalate films such as PS series. These supports are preferably coated with a release agent such as a silicone coating agent on the surface in order to facilitate the removal of the resin composition layer. 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 prevent the support from being torn during the support peeling performed before development, and by setting the thickness to 50 μm or less, when exposing from above the support. The resolution can be improved. Also, a low fisheye support is preferred. Here, fisheye means that when a material is thermally melted, kneaded, extruded, biaxially stretched, casted, or the like is used to produce a film, foreign substances, undissolved substances, oxidative deterioration substances, etc. of the material are incorporated into the film. It is a thing.

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

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

For the photosensitive film with a support of the present invention, for example, a resin varnish in which the resin composition of the present invention is dissolved in an organic solvent is prepared according to a method known to those skilled in the art, and the resin varnish is applied onto the support. It can be produced by drying an organic solvent by heating, blowing hot air, or the like to form a resin composition layer. Specifically, first, after completely removing bubbles in the resin composition by a vacuum defoaming 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 furnace, and the resin is dried. Then, a photosensitive film with a support can be produced by laminating a protective film on the obtained resin composition layer, if necessary. 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 case of the resin varnish containing 30% by mass to 60% by mass of the organic solvent, the temperature is 3 at 80 ° C to 120 ° C. It can be dried in 1 to 13 minutes. The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less, preferably 2% by mass or less, based on the total amount of the resin composition layer, from the viewpoint of preventing the diffusion of the organic solvent in a later step. Is more preferable. Those skilled in the art can appropriately set suitable drying conditions by a simple experiment. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm from the viewpoint of improving handleability and suppressing deterioration of the sensitivity and resolution inside the resin composition layer, and is preferably 10 μm to 200 μm. It is more preferably in the range of 15 μm to 150 μm, further preferably in the range of 20 μm to 100 μm, and even more preferably in the range of 20 μm to 60 μm.

Examples of the coating method of the resin composition include a gravure coat method, a micro gravure coat method, a reverse coat method, a kiss reverse coat method, a die coat method, a slot die method, a lip coat method, a comma coat method, a blade coat method, and a roll coat. Examples thereof include a 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 in several times, may be applied once, or may be applied in combination of a plurality of different methods. Of these, the die coat method, which is excellent in uniform coatability, is preferable. Further, in order to prevent foreign matter from being mixed in, it is preferable to carry out the coating step in an environment such as a clean room where foreign matter is less generated.

[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 embodiment or the second embodiment of the present invention. The insulating layer is preferably used as a solder resist.

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

<Applying and drying process>
A photosensitive film is formed on the circuit board by applying the resin composition directly on the circuit board in a resin varnish state and drying the organic solvent.

Examples of the circuit board include a glass epoxy board, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like. Here, the circuit board refers to a board on which a conductor layer (circuit) patterned on one side or both sides of the board is formed as described above. Further, in a multilayer printed wiring board in which conductor layers and insulating layers are alternately laminated, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a conductor layer (circuit) in which a pattern is processed is also used here. It is included in the circuit board. The surface of the conductor layer may be roughened in advance by blackening treatment, copper etching, or the like.

As the coating method, full-page printing by a screen printing method is generally used, but any other coating method as long as it can be uniformly coated may be used. 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 coat method. , Brush coating, and all other normal coating methods can be used. After application, dry in a hot air oven or far infrared oven if necessary. The drying conditions are preferably 80 ° C. to 120 ° C. for 3 to 13 minutes. In this way, the photosensitive film is formed on the circuit board.

<Laminating process>
When a photosensitive film with a support is used, the resin composition layer side is laminated on one side or both sides of the circuit board using a vacuum laminator. In the laminating step, if the photosensitive film with a support has a protective film, the protective film is removed, and if necessary, the photosensitive film with a support and the circuit board are preheated to form a resin composition layer. Is pressure-bonded to the circuit board while pressurizing and heating. In the photosensitive film with a support, a method of laminating on a circuit board under reduced pressure by a vacuum laminating method is preferably used.

The conditions of the laminating step are not particularly limited, but for example, the crimping temperature (laminating temperature) is preferably 70 ° C. to 140 ° C., and the crimping pressure is preferably 1 kgf / cm ² to 11 kgf / cm ² (9. 8 × 10 ⁴ N / m ² to 107.9 × 10 ⁴ N / m ² ), the crimping time is preferably 5 to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less for laminating under reduced pressure. Is preferable. Further, the laminating step may be a batch type or a continuous type using a roll. The vacuum laminating method can be performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Co., Ltd., a roll type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. In this way, the photosensitive film is formed on the circuit board.

<Exposure process>
After the photosensitive film is provided on the circuit board by the coating and drying steps or the laminating step, the resin composition layer of the irradiation portion is irradiated with active light to a predetermined portion of the resin composition layer through a mask pattern. Is subjected to an exposure process of photocuring. Examples of the active ray include ultraviolet rays, visible rays, electron beams, X-rays and the like, and ultraviolet rays are 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 in which the mask pattern is brought into close contact with the printed wiring board and a non-contact exposure method in which the mask pattern is exposed by using parallel rays without being brought into close contact, but either of them may be used. When the support is present on the resin composition layer, it may be exposed from above the support or may be exposed after the support is peeled off.

Since the solder resist uses the resin composition of the present invention, it is excellent in developability. Therefore, as an exposure pattern in the mask pattern, for example, the ratio (L / S) of the circuit width (line; L) to the width (space; S) between circuits is 100 μm / 100 μm or less (that is, the wiring pitch is 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 or less (wiring pitch 120 μm or less) can be used. Is. The pitch does not have to be the same throughout the circuit board.

<Development process>
After the exposure step, if a support is present on the resin composition layer, the support is removed, and then wet development is performed to remove the non-photocured portion (unexposed portion) for development. Allows the pattern to be formed.

In the case of the above wet development, an alkaline solution is usually used as the developing solution, and the developing step using an alkaline aqueous solution is particularly preferable. Further, as a developing method, known methods such as spraying, rocking dipping, brushing, and scraping are appropriately adopted.

Examples of the alkaline solution used as the developing solution include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and sodium bicarbonate, or bicarbonates and sodium phosphate. , An aqueous solution of an alkali metal phosphate such as potassium phosphate, an alkali metal pyrophosphate such as sodium pyrophosphate and potassium pyrophosphate, and an aqueous solution of an organic base containing no metal ion such as tetraalkylammonium hydroxide. An aqueous solution of tetramethylammonium hydroxide (TMAH) is preferable because it does not contain metal ions and does not affect the semiconductor chip.
These alkaline developers can contain a developing solution such as a surfactant and an antifoaming agent in order to improve the developing effect. The pH of the alkaline solution is, for example, preferably in the range of 8 to 13, more preferably in the range of 9 to 12, and even more preferably in the range of 10 to 12. The base concentration of the alkaline developer is preferably 0.1% by mass to 10% by mass. The temperature of the alkaline developer can be appropriately selected according to the developability of the resin composition layer, but is usually room temperature, preferably 20 ° C to 50 ° C.

The organic solvent used as the developing solution 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, diethylene glycol. It is a monobutyl ether.

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

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

According to the resin composition according to the first embodiment or the second embodiment described above, the occurrence of undercut can be effectively suppressed in the above-mentioned developing step.

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

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

After forming the solder resist, if desired, a drilling step is performed on the solder resist formed on the circuit board to form via holes and through holes. The drilling step can be performed by, for example, a known method such as a drill, a laser, or plasma, and if necessary, these methods can be combined, but a drilling step using a laser such as a carbon dioxide laser or a YAG laser is preferable.

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

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

Examples of the dry-type desmear treatment include desmear treatment using plasma. The desmear treatment using plasma can be carried out by using a commercially available plasma desmear treatment apparatus. Among the commercially available plasma desmear processing devices, examples suitable for the production of printed wiring boards include a microwave plasma device manufactured by Nissin, a normal pressure plasma etching device manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of the wet desmear treatment include desmear treatment using an oxidizing agent solution. When the desmear treatment is performed using the oxidant solution, it is preferable to perform the swelling treatment with the swelling solution, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralizing solution in this order. Examples of the swelling liquid include "Swelling Dip Security Guns P" and "Swelling Dip Security Guns SBU" manufactured by Atotech Japan. The swelling treatment is preferably performed by immersing a substrate on which a via hole or the like is formed in a swelling liquid heated to 60 ° C to 80 ° C for 5 to 10 minutes. The oxidizing agent solution is preferably an alkaline permanganate aqueous solution, 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 carried out by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dozing Solution Security P" manufactured by Atotech Japan. The neutralization treatment with the neutralizing solution is preferably carried out by immersing the substrate after the oxidation treatment in the neutralizing solution at 30 ° C. to 50 ° C. for 3 to 10 minutes. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include "Reduction Solution Securigant P" manufactured by Atotech Japan.

When the dry-type desmear treatment and the wet-type desmear treatment are carried out in combination, the dry-type desmear treatment may be carried out first, or the wet-type desmear treatment may be carried out first.

When the insulating layer is used as the interlayer insulating layer, it can be performed in the same manner as in the case of the solder resist, and the drilling step, the desmear step, and the plating step may be performed after the thermosetting step.

The plating process is a process of forming a conductor layer on the insulating layer. The conductor layer may be formed by combining electroless plating and electrolytic plating, or a plating resist having a pattern opposite to that of the conductor layer may be formed, and the conductor layer may be formed only by electroless plating. As a method for forming a pattern thereafter, for example, a subtractive method or a semi-additive method 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 by using the printed wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electric products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

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

The method for mounting a semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

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

(Synthesis Example 1: Synthesis of resin solution (A-1a))
Epoxy resin A containing a naphthalene skeleton represented by the following formula (8) (1,1'-bis (2,7-diglycidyloxynaphthyl) methane, epoxy equivalent 162, "EXA-4700" manufactured by Dainippon Ink and Chemicals Co., Ltd.) 162 parts were placed in a flask equipped with a gas introduction tube, a stirrer, a condenser and a thermometer, 340 parts of carbitol acetate was added, and the mixture was heated and dissolved, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. .. The mixture was heated to 95-105 ° C., 72 parts of acrylic acid was gradually added dropwise, and the mixture was reacted for 16 hours. The reaction product was cooled to 80-90 ° C., 80 parts of tetrahydrophthalic anhydride was added, and the reaction was allowed to cool for 8 hours. In this way, a resin solution having an acid value of 90 mgKOH / g (nonvolatile content 70%, hereinafter abbreviated as "resin solution (A-1a)") was obtained.

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

(Synthesis Example 2: Synthesis of resin solution (A-1b))
In Synthesis Example 1, the naphthalene skeleton-containing epoxy resin A was changed to 325 parts of a naphthol aralkyl type epoxy resin B (epoxy equivalent 325, “ESN-475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) represented by the following formula (10). Except for the above items, the same operation as in Synthesis Example 1 was performed. In this way, a resin solution having an acid value of 60 mgKOH / g as a solid material (nonvolatile content 70%, hereinafter abbreviated as "resin solution (A-1b)") was obtained.

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

<Examples 1 to 7, Comparative Examples 1 to 2>
Each component was blended in the blending ratio shown in Table 1 below, and a resin varnish was prepared using a high-speed rotary mixer. Next, a PET film ("Lumilar T6AM" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., "Release PET", which was mold-released with an alkyd resin-based mold release agent ("AL-5" manufactured by Lintec Corporation) as a support. ") Was prepared. The prepared resin varnish is uniformly applied with a die coater to the surface treated with the alkyd resin-based mold release agent of the mold release PET so that the thickness of the resin composition layer after drying is 40 μm, and the temperature is changed from 80 ° C to 110. By drying at ° C. for 6.5 minutes, a photosensitive film with a support having a resin composition layer on the release PET was obtained.

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

<Evaluation of dissolution rate of resin composition>
The resin solution (A-1a), the resin solution (A-1b), and the resins ZFR-1491H, ZAR-2000, and ZCR-1569H described later were added to propylene glycol monomethyl ether acetate (PGMEAc), respectively, to add 35% by weight of the non-volatile component. A solution was prepared. The solution was applied onto a silicon wafer and spin coated to obtain a coating film. Then, 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 Seimitsu Co., Ltd.). Then, the resin film was immersed in a 1% by mass sodium carbonate aqueous solution (pH: 11.7) as an alkaline solution at 23 ° C. together with the silicon wafer. Then, the disappearance time until the resin film disappeared was measured. The disappearance of the resin film was confirmed by visually observing the disappearance of the interference fringes due to the reflected light on the surface of the resin film. Therefore, the disappearance time is the time from the time when the resin film is dipped in the alkaline solution to the time when the disappearance is confirmed. Then, for each resin film, the dissolution rate [nm / sec] indicating the amount of decrease in the thickness [nm] of the resin film per second was calculated. For the resin film in which dissolution was not observed even after immersion for 30 minutes, the dissolution rate was set to 1 nm / sec. The results were as follows.
(A-1) Ingredient:
A-1a: 100 nm / sec
-A-1b: 6 nm / sec
(A-2) Ingredient:
-ZFR-1491H: 131 nm / sec
-ZAR-20000: 39 nm / sec
-ZFR-1491H: 1 nm / sec
In each of the 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) to the alkaline solution was calculated by the following formula (IV).
S _(A) = Σ {s (A) × R _(A) } ・ ・ ・ (IV)
Here, in the above formula (IV), s (A) is the dissolution rate of each component (A) in an alkaline solution. In the above formula (IV), R _(A) is the mass ratio of each resin (A) when the non-volatile component in the component (A) is 100% by mass.

<Evaluation of developability, crack resistance, and undercut resistance>
(Formation of laminate for evaluation)
A surface treatment agent containing an organic acid (CZ8100, manufactured by MEC) roughens the copper layer of a glass epoxy substrate (copper-clad laminate) in which a circuit in which a copper layer having a thickness of 18 μm is patterned is formed. Was given. Next, the resin composition layer of the photosensitive film with a support obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was arranged so as to be in contact with the copper circuit surface, and a vacuum laminator (manufactured by Nikko Materials, VP160) was arranged. ) Was crimped to form a laminated body in which the copper-clad laminate, the resin composition layer, and the support were laminated in this order. The crimping conditions were a vacuuming time of 30 seconds, a crimping temperature of 80 ° C., a crimping pressure of 0.7 MPa, and a pressurizing time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or more, and was exposed to ultraviolet rays from the support side of the laminate using a quartz glass mask and a pattern forming apparatus on which an exposure pattern for forming a round hole was formed. The quartz glass mask used was provided with a pattern capable of drawing all six types of round holes having a diameter of 50 μm / 60 μm / 70 μm / 80 μm / 90 μm / 100 μm. After allowing to stand at room temperature for 30 minutes, the support was peeled off from the laminated body. A 1% by mass sodium carbonate aqueous solution at 30 ° C. as an alkaline developer was spray-developed on the entire surface of the resin composition layer on the laminated plate at a spray pressure of 0.2 MPa for 2 minutes. As a result, in Examples 1 to 7 and Comparative Example 2, the round hole portion was eluted and a via hole was formed in the resin composition layer, while in Comparative Example 1, a via hole was not formed. After spray development, ultraviolet irradiation of 1 J / cm ² 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 the copper-clad laminate was obtained. Further, in Comparative Example 1, an evaluation laminate having an insulating layer on which a via hole was not formed was obtained on a copper-clad laminate.

(Evaluation of developability)
The via holes formed in the evaluation laminate were observed by SEM (magnification 1000 times), and the minimum via hole diameter without residue was specified among all 6 types of via holes. When the opening (via hole) could not be confirmed in the evaluation laminate, it was judged that the minimum via hole diameter could not be specified, and the evaluation was evaluated as “x”.

(Evaluation of crack resistance)
The evaluation laminate was exposed to the air at −65 ° C. for 15 minutes, then heated at a heating rate of 180 ° C./min, then exposed to the atmosphere at 175 ° C. for 15 minutes, and then 180 ° C./min. A test was conducted in which the treatment by the heat cycle of lowering the temperature at the lowering rate of the above was repeated 500 times. After the test, the degree of cracking and peeling of the evaluation laminate 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: Cracks and / or peeling are observed.

(Evaluation of undercut resistance)
FIG. 1 is a cross-sectional view of the evaluation laminate used in the examples. As shown in FIG. 1, the evaluation laminate 100 has a via hole 130 having a diameter of 100 μm as an opening in an insulating layer 120 made of a cured product of a resin composition provided on a copper-clad laminate 110. rice field. The insulating layer 120 of the evaluation laminate 100 is cut along a plane passing through the central axis of the via hole 130, and the cross section thereof is observed by SEM to obtain the radius (x [μm]) of the opening top surface 140 shown in FIG. The undercut value [μm] was calculated by measuring the radius (y [μm]) of the bottom surface of the opening 150 and obtaining the difference xy [μm]. When an opening (via hole) could not be confirmed in the evaluation laminate, it was judged that the undercut value could not be calculated, and the evaluation was 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 ultraviolet rays of 100 mJ / cm ² and photo-cured. Then, a 1% by mass sodium carbonate aqueous solution at 30 ° C. as an alkaline developer was spray-developed on the entire surface of the resin composition layer at a spray pressure of 0.2 MPa for 2 minutes. After spray development, ultraviolet irradiation of 1 J / cm ² was performed, and further heat treatment was performed at 190 ° C. for 90 minutes to form a cured product. Then, the support was peeled off to obtain a cured product for evaluation.

(Measurement of average coefficient of linear thermal expansion)
The cured product for evaluation was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a thermomechanical weighting method using a thermomechanical analyzer (Thermo Plus TMA8310, manufactured by Rigaku). After the test piece was attached to the apparatus, measurements were made twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. The average coefficient of linear thermal expansion (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 test pieces having a width of about 5 mm and a length of about 15 mm, and thermomechanical analysis was performed by a tensile weight method using a dynamic viscoelasticity measuring device (EXSTAR6000, manufactured by SII Nanotechnology Inc.). .. After the test piece was attached to the apparatus, the measurement was carried out under the measurement conditions of a load of 200 mN and a heating rate of 2 ° C./min. The peak top of the obtained tan δ was calculated as the glass transition temperature (° C.).

The ingredients used are as follows.
(A) Ingredient:
(A-1) Component-A-1a: Resin solution (A-1a) synthesized in Synthesis Example 1
-A-1b: Resin solution synthesized in Synthesis Example 2 (A-1b)
(A-2) Ingredients-ZFR-1491H: Bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, non-volatile component concentration 70%)
-ZAR-2000: Bisphenol A type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, non-volatile component concentration 70%)
-ZCR-1569H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 98 mgKOH / g, non-volatile component concentration 70%)
(B) Ingredient:
SC2050: Surface treatment with 0.5 parts by mass of aminosilane (KBM573, manufactured by Shin-Etsu Chemical Co., Ltd.) for 100 parts by mass of molten silica (manufactured by Admatex, average particle size 0.5 μm, specific surface area 5.9 m ² / g). (C) component:
-NC3000H: Biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 272)
1031S: Tetrakis hydroxyphenylethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 200)
(D) Ingredient:
-Irgacure TPO: Bis (2,4,6-trimethylbenzoyl) -Phenylphosphinoxide) (manufactured by BASF)
(E) Ingredient:
-DPHA: Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent about 96)
(F) Ingredient:
-EDGAc: Diethylene glycol monoethyl ether acetate-MEK: Methyl ethyl ketone-Contents of component (B): Content of component (B) when the non-volatile component of the resin composition is 100% by mass [mass%]
-Weighted average value of dissolution rate S _(A) : Weighted average value based on the mass ratio of the dissolution rate [nm / sec] of the component (A) to the alkaline solution-Undercut value: Undercut value in a via hole with a diameter of 100 μm [Μm]

<Examination>
From the results in Table 1 above, it was found that Examples 1 to 7 using the resin composition of the present invention had excellent undercut resistance. This means that the component (A-1) itself can be dissolved in an alkaline solution (for example, an alkaline developer) at a dissolution rate in an appropriate range, and the resin composition containing the component (A-1) can be dissolved in an alkaline developer. It is considered that this is because it is possible to suppress the local generation of a portion that is unintentionally melted too much and a portion that is not unintentionally melted in the resin composition when developed. It is presumed that one of the reasons is that the component (A-1) was well mixed with the components (C) to (E) and the bias of the composition in the resin composition could be suppressed.

Further, it was found that Examples 1 to 7 had better developability, heat resistance, mechanical strength and crack resistance as compared with Comparative Examples 1 and 2. Specifically, it was also found that in Examples 1 to 7, the average coefficient of linear thermal expansion was low and the glass transition temperature was high. This is because when the component (A-1) uses a naphthalene skeleton-containing resin, the rigidity of the molecule is usually increased, so that the movement of the molecule in the resin composition is suppressed, and as a result, the resin composition is cured. It is considered that this is because the glass transition temperature of the material becomes higher and the average linear thermal expansion coefficient of the cured material becomes lower. Further, it is considered that the action of the component (A-1) usually improves the resistance of the cured product to the internal stress caused by thermal expansion or contraction, so that the damage of the cured product due to the temperature change can be suppressed. Be done.

Further, according to Examples 4 to 6, the weighted average value S _(A) of the dissolution rates of Examples 1 to 4 and 7 is obtained by using the component (A-1) and the component (A-2) in combination. It can be seen that the values of the average linear thermal expansion rate and the glass transition temperature can be adjusted. Further, according to the comparison between Examples 1 to 5 and Examples 6 and 7, the minimum via hole diameter can be kept small by using the resin solution (A-1a), and the undercut value is set to +10 μm or more. It tends to remain a positive value even within the range of -5 μm, while the dissolution rate by using the resin solution (A-1b) is higher than that when the resin solution (A-1a) is used alone. It can be seen that the load mean value S _(A) of can be increased, whereby the side surface of the opening pattern can be brought closer to perpendicular to the layer plane.

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

In each example, it has been confirmed that even when the component (E) or the like is not contained, the result is the same as that in the above-mentioned example, although the degree is different.

100 Evaluation laminate 110 Copper-clad laminate 120 Insulation layer 130 Via hole 140 Open top surface 150 Open bottom

Claims (26)

(A) Resin containing ethylenically unsaturated group and carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) A resin composition containing a photopolymerization initiator.
(A) Ingredient is
(A-1) Contains a naphthalene skeleton-containing resin,
Here, the average particle size of the component (B) is the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method.
Resin composition (However, when (B) barium sulfate is contained as the inorganic filler, the resin composition in which the content of barium sulfate with respect to the total mass of the (B) inorganic filler is 88% by mass or more is excluded). (B) The resin composition according to claim 1, wherein the average particle size of the components is 2.5 μm or less. (A) Resin containing ethylenically unsaturated group and carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) A resin composition containing a photopolymerization initiator.
The component (A) contains (A-1) a naphthalene skeleton-containing resin,
The component (B) is silica,
Here, the average particle size of the component (B) is the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method.
Resin composition. (B) The resin composition according to claim 3, wherein the average particle size of the components is 2.5 μm or less. (A) Resin containing ethylenically unsaturated group and carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more and 2.5 μm or less.
(C) Epoxy resin and
(D) A resin composition containing a photopolymerization initiator.
The component (A) contains (A-1) a naphthalene skeleton-containing resin,
Here, the average particle size of the component (B) is the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method.
Resin composition. The resin composition according to any one of claims 1 to 5, wherein the component (A-1) is a naphthol aralkyl type resin. The resin composition according to any one of claims 1 to 6, wherein the content of the component (A-1) is 5% by mass or more when the non-volatile component in the component (A) is 100% by mass. .. The resin composition according to any one of claims 1 to 7, wherein the content of the component (A) is 10% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 1 to 8, wherein the content of the component (B) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. (A) Ingredient is
(A-2) The resin composition according to any one of claims 1 to 9, which contains 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) to the alkaline solution is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
The filling,
Here, the dissolution rate is such that when a resin film having a thickness of about 2 μm is formed and immersed in a 1% by mass sodium carbonate aqueous solution (pH: 11.7) as an alkaline solution at 23 ° C., the resin film per second. The amount of decrease in the thickness [nm] is shown here, and the formation of the resin film having a thickness of about 2 μm is performed by forming a coating film by spin coating and then drying the coating film at 120 ° C. for 3 minutes. ,
The resin composition according to any one of claims 1 to 10. (A) A resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) 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) to the alkaline solution is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
The filling,
here,
The average particle size of the component (B) is the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method.
The dissolution rate was such that when a resin film having a thickness of about 2 μm was formed and immersed in a 1% by mass sodium carbonate aqueous solution (pH: 11.7) as an alkaline solution at 23 ° C., the thickness of the resin film per second [ The amount of decrease in nm] is shown, and the formation of the resin film having a thickness of about 2 μm is carried out by forming a coating film by spin coating and then drying the coating film at 120 ° C. for 3 minutes.
Resin composition (However, when (B) barium sulfate is contained as the inorganic filler, the resin composition in which the content of barium sulfate with respect to the total mass of the (B) inorganic filler is 88% by mass or more is excluded). (B) The resin composition according to claim 12, wherein the average particle size of the components is 2.5 μm or less. (A) A resin containing an ethylenically unsaturated group and a carboxyl group,
(B) Inorganic filler having an average particle size of 0.5 μm or more,
(C) Epoxy resin and
(D) 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) to the alkaline solution is the following formula (I):
5 ≤ S _(A) ≤ 110 ... (I)
The filling,
The component (B) is silica,
here,
The average particle size of the component (B) is the median diameter of the volume-based particle size distribution measured by the laser diffraction / scattering method.
The dissolution rate was such that when a resin film having a thickness of about 2 μm was formed and immersed in a 1% by mass sodium carbonate aqueous solution (pH: 11.7) as an alkaline solution at 23 ° C., the thickness of the resin film per second [ The amount of decrease in nm] is shown, and the formation of the resin film having a thickness of about 2 μm is carried out by forming a coating film by spin coating and then drying the coating film at 120 ° C. for 3 minutes.
Resin composition. (B) The resin composition according to claim 14, wherein the average particle size of the component is 2.5 μm or less. The resin composition according to any one of claims 12 to 15, wherein the component (A) contains (A-1) a naphthalene skeleton-containing resin. The resin composition according to claim 16, wherein the component (A-1) is a naphthol aralkyl type resin. The resin composition according to claim 16 or 17, wherein the content of the component (A-1) is 5% by mass or more when the non-volatile component in the component (A) is 100% by mass. (A) Ingredient is
(A-2) The resin composition according to any one of claims 16 to 18, which contains an acid-modified epoxy (meth) acrylate resin other than the component (A-1). The resin composition according to any one of claims 12 to 19, wherein the content of the component (A) is 10% by mass or more and 30% by mass or less when the non-volatile component in the resin composition is 100% by mass. thing. The resin composition according to any one of claims 12 to 20, wherein the content of the component (B) is 60% by mass or more when the non-volatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 21, which is a resin composition for forming a solder resist of a printed wiring board. A photosensitive film containing the resin composition according to any one of claims 1 to 22. A photosensitive film with a support having a support and a resin composition layer provided on the support and containing the resin composition according to any one of claims 1 to 22. A printed wiring board including an insulating layer formed of a cured product of the resin composition according to any one of claims 1 to 22. A semiconductor device comprising the printed wiring board according to claim 25.

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