JP7322988B2 - Resin composition, photosensitive film, photosensitive film with support, printed wiring board and semiconductor device - Google Patents

Description

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

A printed wiring board is sometimes provided with a solder resist as a permanent protective film to prevent solder from adhering to areas where solder is not required and to prevent corrosion of the circuit board. As a solder resist, for example, a photosensitive resin composition as described in Patent Document 1 is generally used.

JP 2014-115672 A

A solder resist is required to have a fine opening pattern that partially exposes a conductor layer having a wiring pattern, in order to connect substrates by soldering. In addition, from the viewpoint of solder adhesion, the cross-sectional shape of the opening is required not to be inversely tapered, and in particular, the side surface of the opening is required to be nearly perpendicular to the layer plane. there is Here, the reverse tapered cross-sectional shape refers to a shape in which the diameter of the opening increases toward the back, and specifically refers to a shape in which the bottom surface of the opening is wider than the top surface of the opening. In this specification, such a property that the cross-sectional shape is less likely to become a reverse tapered shape is sometimes referred to as being excellent in "undercut resistance". In addition, the above-mentioned subject is a subject which arises also when forming a soldering resist using a resin composition.

An object of the present invention is to provide 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 intensive studies to solve the above problems, the present inventors have found that (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, ( 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 , found that the above problems can be solved, and completed the present invention.

In addition, as a result of intensive studies to solve the above problems, the present inventors have 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 , (C) an epoxy resin, and (D) a resin composition containing a photopolymerization initiator, wherein the weighted average value based on the mass ratio of the dissolution rate [nm/sec] of the component (A) in an alkaline solution S _(A) is represented by the following formula (I):
5≦S _(A) ≦110 (I)
The inventors have found that the above problems can be solved by using a resin composition that satisfies the above, and have completed the present invention.

That is, the present invention includes the following contents.
[1] (A) a resin containing an ethylenically unsaturated group and a carboxyl group;
(B) an inorganic filler having an average particle size of 0.5 μm or more;
(C) an epoxy resin, and
(D) A resin composition containing a photopolymerization initiator,
A resin composition in which component (A) contains (A-1) a naphthalene skeleton-containing resin.
[2] The resin composition according to [1], wherein the component (A-1) is a naphthol aralkyl resin.
[3] The resin composition according to [1] or [2], wherein the content of component (A-1) is 5% by mass or more when the non-volatile component in component (A) is 100% by mass. .
[4] Any one of [1] to [3], wherein the content of 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. of the resin composition.
[5] The resin composition according to any one of [1] to [4], wherein the content of 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 component (A) contains an acid-modified epoxy (meth)acrylate resin other than component (A-2) (A-1). .
[7] The weighted average value S (A) based on the mass ratio of the dissolution rate [nm/sec] of component _(A) in an alkaline solution is represented by the following formula (I):
5≦S _(A) ≦110 (I)
The resin composition according to any one of [1] to [6], which satisfies
[8] (A) a resin containing an ethylenically unsaturated group and a carboxyl group;
(B) an inorganic filler having an average particle size of 0.5 μm or more;
(C) an 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 component (A)} in an alkaline solution is represented by the following formula (I):
5≦S _(A) ≦110 (I)
A resin composition that satisfies
[9] The resin composition according to any one of [1] to [8], which is a resin composition for forming a solder resist for printed wiring boards.
[10] A photosensitive film containing the resin composition according to any one of [1] to [9].
[11] A support-attached photosensitive film comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [9] provided on the support.
[12] A printed wiring board comprising an insulating layer formed from 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 Examples of the present invention, schematically showing a state when cut along a plane passing through the 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 A resin composition containing a resin and (D) a photopolymerization initiator. The (A) component 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, and (G) other additives, if necessary. Each component contained in the resin composition will be described in detail below.

<(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 vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadimide group, and (meth)acryloyl group. from the viewpoint of (meth)acryloyl group is preferred. A "(meth)acryloyl group" includes a methacryloyl group, an acryloyl group, and combinations thereof. Since the component (A) contains an ethylenically unsaturated group, photoradical polymerization is possible. The number of ethylenically unsaturated groups per molecule of component (A) may be one, or two or more. Moreover, when the component (A) contains two or more ethylenically unsaturated groups per molecule, those 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 component (A) may be one or two or more.

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

<(A-1) Naphthalene skeleton-containing resin>
The (A-1) component is a resin belonging to the (A) component, and thus is a resin containing an ethylenically unsaturated group and a carboxyl group. Therefore, the component (A-1) is capable of radical photopolymerization, and any resin composition containing the component (A-1) exhibits solubility in an alkaline solution.

Component (A-1) preferably has a plurality of ethylenically unsaturated groups in one molecule. Thereby, the mechanical strength and dissolution resistance of the cured product of the resin composition can be enhanced. In addition, the component (A-1) preferably has two or less ethylenically unsaturated groups per naphthalene skeleton. Thereby, the cross-linking position (cross-linking point) can be adjusted, so that the mechanical strength and dissolution resistance of the cured product of the resin composition can be controlled. More preferably, the ethylenically unsaturated group is included in the substituents of the naphthalene skeleton. In order to include an ethylenically unsaturated group in the substituent of the naphthalene skeleton, for example, the H atom of the OH group of naphthol is substituted with an epoxy group-containing substituent (e.g., epoxy group, glycidyl group) is prepared, and the first precursor is obtained by adding a compound having an ethylenically unsaturated bond (e.g., unsaturated carboxylic acid, preferably (meth)acrylic acid). can be done. Thereby, an ethylenically unsaturated group can be introduced into the substituent of the naphthalene skeleton.

Component (A-1) preferably has a plurality of carboxyl groups in one molecule. This can increase the solubility of the resin composition in an alkaline solution (for example, an alkaline developer). Component (A-1) preferably has two or less carboxyl groups per naphthalene skeleton. This allows solubility control. More preferably, the carboxyl group is included in the substituents of the naphthalene skeleton. In order to include a 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 a substituent containing an epoxy group is prepared as the first precursor, A compound having an ethylenically unsaturated bond (e.g., unsaturated carboxylic acid, preferably (meth)acrylic acid) is added to one precursor 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. Thereby, both an ethylenically unsaturated group and a carboxyl group can be introduced into the substituent of the naphthalene skeleton.

Also, the (A-1) component is a naphthalene skeleton-containing resin. A naphthalene skeleton-containing resin refers to a compound containing one or more naphthalene skeletons in one molecule. Since component (A-1) can be well mixed with components (C) to (E), uneven composition in the resin composition can be suppressed. In addition, component (A-1) can be dissolved in an alkaline solution (eg, alkaline developer) at a dissolution rate within an appropriate range. In addition, when the resin composition containing the component (A-1) is developed with an alkaline developer, unintentionally excessively soluble or unintentionally insoluble portions may be 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 made nearly perpendicular to the layer plane.

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

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

Component (A-1) is, for example, a resin containing a structure represented by the following formula (1). Component (A-1) may have a plurality of structures represented by formula (1) below (for example, 1 to 10, preferably 1 to 6), and may have a plurality of structures represented by formula (1) below. When it has one, 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 bound to R ¹ may be bound to any bondable carbon atom among the carbon atoms of the naphthalene skeleton. Therefore, the bond to which R ¹ is bonded is the same carbon atom of the benzene ring as the bond in formula (1) bonded to anything other than R ¹ and OR' (hereinafter sometimes referred to as "terminal bond"). may be bonded to or may be bonded to carbon atoms of different benzene rings. For example, the combinations of the positions of the terminal bond in the naphthalene skeleton and the bond bonded to R ¹ are 1,2, 1,3, 1,4, 1,5, 1,6, 1 , 7th, 1,8th, 2,3rd, 2,6th, 2,7th.

In formula (1) above, R ¹ and R ² each independently represent an optionally substituted alkylene group. The number of carbon atoms in R ¹ is generally 1-20, preferably 1-10, more preferably 1-6. In addition, the alkylene group may be linear or branched. Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, and the like.

Substituents that R ¹ and R ² may each independently have include, 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 in X is generally 6-30, preferably 6-20, more preferably 6-10. Arylene groups are, for example, phenylene groups, anthracenylene groups, phenanthrenylene groups and biphenylene groups.

Examples of substituents that X may have include the same substituents that R ¹ and R ² may have.

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

In the above formula (1), s represents 0 or 1. where s and t are the number of groups R ¹ and R ² respectively. Moreover, in the above formula (1), t represents 0 or 1. However, as for s and t, s+t does not become 0. Among them, when a=1, both s and t are preferably 1. If a=0, preferably one of s and t is 0.

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

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

In the above formula (2), R ³ represents a trivalent group, preferably a trivalent hydrocarbon group optionally having a substituent (provided that the carbon-carbon bond (CC bond) A heteroatom may be interposed therebetween), and trivalent aliphatic hydrocarbon groups optionally having substituents are particularly preferred. This R ³ may be a trivalent residue of an optionally substituted epoxy group-containing substituent. Examples of substituents that R ³ may have include the same substituents that R ¹ and R ² may have.

In formula (2) above, R ⁴ represents an organic group containing an ethylenically unsaturated group. A preferred example of an organic group containing an ethylenically unsaturated group is a (meth)acryloyloxy group. A "(meth)acryloyloxy group" includes an acryloyloxy group, a methacryloyloxy group, and combinations thereof.

In formula (2) above, R ⁵ is an organic group containing a carboxyl group. An example of an organic group containing a carboxyl group is -OCO-R ⁶ -COOH. Here, R ⁶ represents a divalent group. R ⁶ is preferably an optionally substituted divalent hydrocarbon group. The number of carbon atoms in R ⁶ is generally 1-30, preferably 1-20, more preferably 1-6. Examples of divalent hydrocarbon groups include linear or branched acyclic alkylene groups such as methylene group, ethylene group, propylene group and butylene group; saturated or unsaturated divalent alicyclic carbonized hydrogen group; phenylene group, arylene group such as naphthylene group, and the like. Among them, a divalent alicyclic hydrocarbon group and an arylene group are preferred, and a 4-cyclohexenylene group and a phenylene group are particularly preferred. Examples of substituents that R ⁶ may have include the same substituents that R ¹ and R ² may have. --CO--R ⁶ --COOH in --OCO--R ⁶ --COOH is usually a residue of carboxylic acid anhydride. Examples of carboxylic anhydrides are maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid di It is an anhydride.

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

<First example of component (A-1) (a = 1)>
A preferred example of the component (A-1) is a naphtholaralkyl type resin. A "naphtholaralkyl type resin" is a resin containing a group having a structure obtained by removing the H atom of an OH group from a naphtholaralkylene group.

A preferable naphthol aralkyl resin is a resin containing the structure of a=1 in the above formula (1), for example, a resin containing the structure shown in the following formula (3).

In formula (3) above, R ¹ , R ² , X, s, t, R' and c are the same as described above. Both s and t are preferably one.

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

In formula (4) or (5) above, R ¹ , R ² , 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. Naphthol aralkyl type epoxy resin B is available, for example, as "ESN-475V" (epoxy equivalent: 325) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.

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

In formula (6) above, R ¹ , 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 using naphthalene skeleton-containing epoxy resin A (1,1′-bis(2,7-diglycidyloxynaphthyl)methane, epoxy equivalent of 162) as a material. (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 component (A-1) is preferably 500 or more, more preferably 1000 or more, even more preferably 1500 or more, and 2000 or more, from the viewpoint of film-forming properties. 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. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by 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, the acid value is preferably 150 mgKOH/g or less, more preferably 120 mgKOH/g or less, from the viewpoint of suppressing the fine pattern of the cured product from eluting into an alkaline solution and improving the undercut resistance. More preferably, it is 100 mgKOH/g or less. Here, the acid value is the residual acid value of the carboxyl groups present in the component (A-1), and the acid value can be measured by the following method. First, about 1 g of the resin solution to be measured is accurately 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 as an indicator is added to the solution, and titration is performed using a 0.1N KOH aqueous solution. Then, the acid value is calculated by the following formula (7).
Formula: A = 10 x Vf x 56.1/(Wp x I) (7)

In the above formula (7), A represents the acid value [mgKOH / g], Vf represents the titration amount of KOH [mL], Wp represents the measured resin solution mass [g], and I represents the measured resin solution. represents the ratio [% by mass] of the non-volatile components of

The weighted average value S (A-1) based on the mass ratio of the dissolution rate [nm/sec] of component _(A-1) in an alkaline solution is expressed by the following formula (II):
5≦S _(A-1) ≦110 (II)
is preferably satisfied. 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 component _{(A-1) is} more preferably 6 nm/sec or more, still more 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, still more preferably 80 nm/sec or less. The weighted average value S of the dissolution rate of component (A-1) _(A-1) is within the above range, so that the dissolution rate of the resin composition in the alkaline developer is excessively slowed down or accelerated. can be suppressed. Therefore, it is possible to suppress the local occurrence of unintentionally excessive melting portions and unintended unmelting portions. Therefore, the undercut resistance can be improved, and preferably the side surfaces 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 component (A-1), the dissolution rate [nm/sec] of each of the naphthalene skeleton-containing resins is within the above range. This ensures that the weighted average value S _(A-1) satisfies the range.

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

From the viewpoint of adjusting the solubility of the resin composition in an alkaline solution, the content of component (A-1) should be 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. is preferred, 10% by mass or more is more preferred, and 15% by mass or more is even more preferred. From the viewpoint of improving undercut resistance, the upper limit is preferably 30% by mass or less, more preferably 29% by mass or less, and even more preferably 28% by mass or less.

<Method for producing component (A-1)>
Component (A-1) is not limited to the above-described examples and is not particularly limited as long as it is a compound having a resin containing a naphthalene skeleton, an ethylenically unsaturated group, and a carboxyl group. Examples thereof include acid-modified unsaturated naphthalene skeleton-containing epoxy ester resins obtained by reacting an unsaturated carboxylic acid with a naphthalene-type epoxy compound having a naphthalene skeleton (naphthalene skeleton-containing epoxy compound) 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, a naphthalene skeleton-containing epoxy compound is reacted with an unsaturated carboxylic acid to obtain an unsaturated naphthalene skeleton-containing epoxy ester resin, and then the unsaturated naphthalene skeleton-containing epoxy ester resin is reacted with a carboxylic acid anhydride. Thus, 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. , naphthalene-type epoxy resins obtained by condensation reaction of polyhydroxynaphthalene and aldehydes, naphthalene-type epoxy resins having a naphthalene skeleton in the molecule, such as binaphthol-type epoxy resins. Any one of these may be used alone, or two or more thereof may be used in combination.

Monohydroxynaphthalene type epoxy resins include, for example, 1-glycidyloxynaphthalene and 2-glycidyloxynaphthalene. Dihydroxynaphthalene type epoxy resins include, for example, 1,3-diglycidyloxynaphthalene, 1,4-diglycidyloxynaphthalene, 1,5-diglycidyloxynaphthalene, 1,6-diglycidyloxynaphthalene, 2,3-di glycidyloxynaphthalene, 2,6-diglycidyloxynaphthalene, 2,7-diglycidyloxynaphthalene and the like.

Examples of polyhydroxy binaphthalene type epoxy resins include 1,1′-bi-(2-glycidyloxy)naphthyl, 1-(2,7-diglycidyloxy)-1′-(2′-glycidyloxy)binaphthyl, 1,1'-bi-(2,7-diglycidyloxy) naphthyl and the like.

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

Among these, polyhydroxybinaphthalene-type epoxy resins having two or more naphthalene skeletons in one molecule and naphthalene-type epoxy resins obtained by the condensation reaction of polyhydroxynaphthalene and aldehydes are preferred, and in particular epoxy 1,1′-bis(2,7-diglycidyloxynaphthyl)methane having 3 or more groups, 1-(2,7-diglycidyloxynaphthyl)-1′-(2′-glycidyloxynaphthyl)methane, 1-(2,7-diglycidyloxy)-1′-(2′-glycidyloxy)binaphthyl and 1,1′-bi-(2,7-diglycidyloxy)naphthyl have It is preferable in terms of excellent heat resistance.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, cinnamic acid and crotonic acid, and these may be used alone or in combination of two or more. Among them, acrylic acid and methacrylic acid are preferable from the viewpoint of improving the photocurability of the photosensitive resin composition. In this specification, the naphthalene-type epoxy compound ester resin, which is a reaction product of the 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 generally substantially extinguished by 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 carboxylic anhydrides include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenonetetracarboxylic acid. dianhydrides, etc., and any one of these may be used alone, or two or more thereof may be used in combination. Among these, succinic anhydride and tetrahydrophthalic anhydride are preferred from the viewpoint of improving the developability of the cured product and insulation reliability.

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. An epoxy ester resin and a carboxylic acid anhydride may be reacted.

The amount of the catalyst used at this time is preferably 2% by mass or less, more preferably 0.0005% by mass or less, 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 mass %, more preferably in the range of 0.001 mass % to 0.5 mass %. Examples of catalysts include N-methylmorpholine, pyridine, 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]nonene-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 salts, tetraethylphosphonium salts, tetrapropylphosphonium salts, tetrabutylphosphonium salts, trimethyl(2-hydroxypropyl)phosphonium salts, triphenylphosphonium salts, benzylphosphonium salts, etc., and representative counter anions are Phosphonium salts having chlorides, bromides, carboxylates, hydroxides, etc.; sulfonium salts such as trimethylsulfonium salts, benzyltetramethylenesulfonium salts, phenylbenzylmethylsulfonium salts or phenyldimethylsulfonium salts; sulfonium salts having carboxylates, hydroxides, etc.; 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 at this time 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. % to 1% by mass, more preferably 0.001% to 0.5% by mass.

As the acid-modified unsaturated naphthalene skeleton-containing epoxy ester resin, an acid-modified naphthalene skeleton-containing epoxy (meth)acrylate is preferred. 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 an unsaturated carboxylic acid. .

In another aspect of the component (A-1), a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid is reacted with an epoxy compound containing an ethylenically unsaturated group and a naphthalene skeleton. An unsaturated modified naphthalene skeleton-containing (meth)acrylic resin into which an ethylenically unsaturated group is introduced can be mentioned. Furthermore, it is also possible to react a carboxylic anhydride with a hydroxyl group produced during the introduction of an unsaturated group. As the carboxylic acid anhydride, the same acid anhydride as described above can be used, and the preferred range is also the same.

<(A-2) Acid-modified epoxy (meth)acrylate resin>
The acid-modified epoxy (meth)acrylate resin as component (A-2) is a compound having a structure in which a carboxyl group is introduced into (meth)acrylate of an 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 with a carboxylic acid anhydride. A modified bisphenol type epoxy (meth)acrylate and the like are included. In detail, a 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)acrylates 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 with a carboxylic acid anhydride. Specifically, a 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)acrylates can be obtained.

Still another embodiment of the component (A-2) includes an acid-modified epoxy (meth)acrylate obtained by reacting an epoxy compound other than the epoxy compounds described above with (meth)acrylic acid and further reacting with a carboxylic acid anhydride. . Such epoxy compounds include, for example, novolac epoxy resins such as phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A novolac epoxy resins, and alkylphenol novolak epoxy resins; perfluoroalkyl epoxy resins, and the like. Fluorine-containing epoxy resin, bixylenol type epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; tert-butyl-catechol type epoxy resin; epoxy resin containing condensed ring skeleton such as anthracene type epoxy resin; 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; methylol type epoxy resin; tetraphenylethane type epoxy resin; glycidyl group-containing acrylic resin such as polyglycidyl (meth)acrylate, copolymer of glycidyl methacrylate and acrylic acid ester; fluorene type epoxy resin; be done.

Such an acid-modified epoxy (meth)acrylate can be a commercially available product. acid and succinic anhydride), "ZFR-1491H" (acid-modified bisphenol type epoxy acrylate: reaction product of bisphenol F type epoxy resin, acrylic acid and acid anhydride), "ZFR-1533H" (acid-modified 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 reaction product), Showa Denko's "PR-300CP" (a reaction product of cresol novolac type epoxy resin, acrylic acid, and acid anhydride), and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As another aspect of the component (A-2), a (meth)acrylic resin having a structural unit obtained by polymerizing (meth)acrylic acid is reacted with a (meth)acrylate of an epoxy compound to obtain ethylenically unsaturated Unsaturated modified (meth)acrylic resins into which groups are introduced can be mentioned. (Meth)acrylates of epoxy compounds include, for example, glycidyl methacrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, 3,4-epoxycyclohexylmethyl (meth)acrylate and the like. Furthermore, it is also possible to react a carboxylic anhydride with a hydroxyl group produced during the introduction of an unsaturated group. As the carboxylic anhydride, the same carboxylic anhydride as described above can be used, and the preferred range is also the same.

Commercial products can be used as such unsaturated modified (meth)acrylic resins. Specific examples include "SPC-1000" and "SPC-3000" manufactured by Showa Denko KK, and "Cychromer" manufactured by Daicel Allnex. P (ACA) Z-250", "Cychromer P (ACA) Z-251", "Cychromer P (ACA) Z-254", "Cychromer P (ACA) Z-300", "Cychromer P ( ACA) Z-320” and the like.

The weight-average molecular weight of component (A-2) is preferably 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, from the viewpoint of film-forming properties. From the viewpoint of developability, the upper limit is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 14,000 or less. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) method.

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

The weighted average value S (A-2) based on the mass ratio of the dissolution rate [nm/sec] of component _(A-2) in an alkaline solution is expressed by the following formula (III):
1≦S _(A-2) ≦150 (III)
It is preferred to satisfy, more preferably the following formula (IIIa):
1≦S _(A-2) ≦131 (IIIa)
meet. Thereby, the undercut resistance can be controlled by adjusting the solubility of the resin composition in an alkaline solution in consideration of the content of the component (A-1). 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 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 This ensures that the weighted average value S _(A-2) satisfies the range.

From the viewpoint of adjusting the solubility in an alkaline solution, the content of component (A-2) is the same as the content of component (A-1) when the non-volatile component of component (A) is 100% by mass. Or preferably less than that, more preferably, the content of component (A-2) is 50% of the content of component (A-1) when the non-volatile component of component (A) is 100% by mass % by mass or less, more preferably 45% by mass or less. The content of 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. , More preferably 20% by mass or less, more preferably 15% by mass or less, the lower limit is usually 0% by mass, but when used in combination with component (A-1), the lower limit is 0 .1% by mass or 0.2% by mass.

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

<(A-3) Any Resin Containing an Ethylenically Unsaturated Group and a Carboxyl Group>
Component (A) may be combined with components (A-1) and (A-2) described above, and may further contain (A-3) any resin containing an ethylenically unsaturated group and a carboxyl group. . The (A-3) component does not include the (A-1) component and the (A-2) component.

The weight-average molecular weight and acid value of component (A-3) are arbitrary, but are preferably in the same range as the weight-average molecular weight and acid value of component (A-2) described above. This makes it possible to obtain the same advantages as explained in the section on the (A-2) component.

<Overall Characteristics of Component (A)>
The lower limit of the weight average molecular weight of component (A) is preferably 500 or more or 1,000 or more, more preferably 1,500 or more, and even more preferably 2,000 or more, from the viewpoint of film-forming properties. From the viewpoint of developability, the upper limit is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 14,500 or less. A weight average molecular weight is a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC) method.

The weighted average value S (A _{) based on the mass ratio of the dissolution rate [nm/sec] of component (A)} in an alkaline solution is expressed by the following formula (I):
5≦S _(A) ≦110 (I)
is preferably satisfied. 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 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. Below, it is preferably 100 nm/sec or less, more preferably 90 nm/sec or less, and still more preferably 80 nm/sec or less. When the weighted average value S _(A) of the dissolution rate of the component (A) is within the above range, the dissolution rate of the resin composition in the alkaline developer can be prevented from becoming excessively slow or excessive. Therefore, it is possible to suppress the local occurrence of unintentionally excessive melting portions and unintended unmelting portions. Therefore, the undercut resistance can be improved, and preferably the side surfaces of the opening pattern can be brought closer to perpendicular to the layer plane.

More preferably, when using resins containing multiple types of ethylenically unsaturated groups and carboxyl groups as component (A), the dissolution rate [nm/sec] of each of the resins containing ethylenically unsaturated groups and carboxyl groups is It is more preferable to be within the above range. This ensures that the weighted average value S _(A) satisfies the range.

From the viewpoint of adjusting the solubility of the resin composition in an alkaline solution, component (A) preferably has a content of 10% by mass or more when the non-volatile component in the resin composition is 100% by mass. , more preferably 15% by mass or more, more preferably 20% by mass or more. From the viewpoint of improving undercut resistance, the upper limit is preferably 30% by mass or less, more preferably 29.5% by mass or less, and even more preferably 29% by mass or less.

<(B) Inorganic filler having an average particle 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 if the average particle diameter of the inorganic filler is large), it is possible to provide a resin composition that can obtain a cured product with excellent undercut resistance. becomes. Moreover, 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 examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. As silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler is 0.5 μm or more, preferably 0.8 μm or more, 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, even more preferably 1.5 μm or less, and still more preferably from the viewpoint of suppressing light reflection during exposure and obtaining excellent developability. is 1.3 μm or less. Examples of commercially available inorganic fillers having such an average particle size include "SC4050" and "ADMAFINE" manufactured by Admatechs, "SFP Series" manufactured by Denki Kagaku Kogyo, and "SP" manufactured by Nippon Steel & Sumikin Materials. (H) Series”, Sakai Chemical Industry Co., Ltd. “Sciqas Series”, Nippon Shokubai Co., Ltd. “Seahoster Series”, Nippon Steel & Sumikin Materials Co., Ltd. “AZ Series”, “AX Series”, Sakai Chemical Industry Co., Ltd. “ B series", "BF series", and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering particle size distribution analyzer, and the median diameter thereof can be used as the average particle size for measurement. As the measurement sample, one obtained by ultrasonically dispersing an inorganic filler in water can be preferably used. As the laser diffraction scattering type particle size distribution analyzer, Horiba's "LA-500", Shimadzu Corporation's "SALD-2200" and 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, particularly preferably 5 m ² /g or more, from the viewpoint of obtaining a cured product having excellent undercut resistance. Although there is no particular upper limit, it 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 Mountec) according to the BET method and calculating the specific surface area using the BET multipoint method. .

Inorganic fillers include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilane compounds, organosilazane compounds, titanates, from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated 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., Shin-Etsu Chemical Industry Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" ( hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), and the like.

From the viewpoint of obtaining a cured product having a low average linear thermal expansion coefficient, the content of 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. 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 to obtain excellent developability.

<(C) Epoxy resin>
The resin composition contains (C) an epoxy resin. By including 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 dissolution resistance of the cured product of the resin composition can increase However, the component (C) here does not include epoxy resins belonging to the component (A).

Examples of component (C) include fluorine-containing epoxy resins such as bisphenol AF type epoxy resins and perfluoroalkyl type epoxy resins; bisphenol A type epoxy resins; bisphenol F type epoxy resins; bisphenol S type epoxy resins; Epoxy resin; dicyclopentadiene type epoxy resin; trisphenol type epoxy resin; naphthol novolak type epoxy resin; phenol novolac type epoxy resin; tert-butyl-catechol type epoxy resin; naphthalene type epoxy resin; Resin; Glycidylamine type epoxy resin; Glycidyl ester type epoxy resin; Cresol novolac type epoxy resin; Biphenyl type epoxy resin; Linear aliphatic epoxy resin; cyclic epoxy resin; heterocyclic epoxy resin; spiro ring-containing epoxy resin; cyclohexane dimethanol type epoxy resin; naphthylene ether type epoxy resin; trimethylol type epoxy resin; Bisphenol F-type epoxy resins and biphenyl-type epoxy resins are preferred, and biphenyl-type epoxy resins are more preferred, from the viewpoint of improving adhesion. From the viewpoint of improving heat resistance, naphthalene-type epoxy resins, naphthol-type epoxy resins, anthracene-type epoxy resins, naphthylene ether-type epoxy resins, and tetraphenylethane-type epoxy resins are preferable, and tetraphenylethane-type epoxy resins are more preferable. . An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. From the viewpoint of improving adhesion and heat resistance, the component (C) preferably contains at least one of a biphenyl-type epoxy resin and a tetraphenylethane-type epoxy resin, more preferably both.

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 mass %, at least 50 mass % or more of the epoxy resin preferably has two or more epoxy groups in one molecule. As component (C), two or more epoxy resins may be used in combination.

Specific examples of epoxy resins include "HP4032", "HP4032D", "HP4032SS", and "HP4032H" (naphthalene type epoxy resins) manufactured by DIC Corporation, "828US" and "jER828EL" (bisphenol A type epoxy resins) 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 & Sumikin Chemical Co., Ltd. (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "YD-8125G" (bisphenol A type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" manufactured by Nagase ChemteX Corporation (glycidyl ester type epoxy resin), Daicel's "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton), "PB-3600" (epoxy resin having a butadiene structure), Nippon Steel Chemical Co., Ltd.'s "ZX1658", " ZX1658GS" (liquid 1,4-glycidylcyclohexane), Mitsubishi Chemical's "630LSD" (glycidylamine type epoxy resin), Daikin Industries Ltd.'s "E-7432", "E-7632" (perfluoroalkyl type epoxy resin), DIC's "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4" , "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin), Nippon Kayaku "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin) , “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthol aralkyl type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., “ESN485” (naphthol novolac type epoxy resin) , "YSLV-80XY" (tetramethylbisphenol F type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" ( anthracene-type epoxy resin), Osaka Gas Chemicals' "PG-100" and "CG-500", Mitsubishi Chemical's "YL7800" (fluorene-type epoxy resin), Mitsubishi Chemical's "1010" (solid bisphenol A type epoxy resin), "1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin), and the like.

From the viewpoint of enhancing the mechanical strength and solubility resistance of the cured product of the resin composition, the content of component (C) is preferably 1% by mass or more, when the non-volatile component of the resin composition is 100% by mass. It is preferably 5% by mass or more, more preferably 8% by mass or more. The upper limit of the epoxy resin content 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, and 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. ~3000g/eq. , more preferably 80 g/eq. ~2000g/eq. , even more preferably 110 g/eq. ~1000g/eq. is. Within this range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of epoxy groups.

The weight average molecular weight of the epoxy resin is preferably 100-5000, more preferably 250-3000, still more preferably 400-1500. Here, the weight average molecular weight of the epoxy resin is the polystyrene equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

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

Component (D) is not particularly limited, but examples include 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-morpholinopropan-1-one and other α-aminoalkylphenones Photopolymerization initiator; oxime ester photopolymerization initiator such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) benzophenone, methylbenzophenone, o-benzoylbenzoic acid, benzoylethyl ether, 2,2-diethoxyacetophenone, 2,4-diethylthioxanthone, diphenyl-(2,4,6-trimethylbenzoyl)phosphine oxide, ethyl-(2 ,4,6-trimethylbenzoyl)phenylphosphinate, 4,4′-bis(diethylamino)benzophenone, 1-hydroxy-cyclohexyl-phenylketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1 -[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and the like. Also, a sulfonium salt-based photopolymerization initiator and the like can 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 "Omnirad907", "Omnirad369", "Omnirad379", "Omnirad819", and "OmniradTPO" manufactured by IGM, and "IrgacureTPO", "IrgacureOXE-01", and "IrgacureOXE" manufactured by BASF. -02”, and “N-1919” manufactured by ADEKA.

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

Further, the resin composition contains, in combination with the component (D), N,N-dimethylaminobenzoic acid ethyl ester, N,N-dimethylaminobenzoic acid isoamyl ester, pentyl-4-dimethylamino Tertiary amines such as benzoate, triethylamine and triethanolamine may be included, and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, thioxanthones and the like may be included. 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. Photoreactivity can be improved by including the component (E). Component (E) can be, for example, a photosensitive (meth)acrylate compound that has one or more (meth)acryloyl groups in one molecule and is liquid, solid or semi-solid at 25°C. A "(meth)acryloyl group" refers to an acryloyl group and a methacryloyl group.

Representative photosensitive (meth)acrylate compounds include, for example, hydroxyalkyl acrylates such as 2-hydroxyethyl acrylate and 2-hydroxybutyl acrylate, and glycols such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol and propylene glycol. Mono- or diacrylates, acrylamides such as N,N-dimethylacrylamide and N-methylol acrylamide, aminoalkyl acrylates such as N,N-dimethylaminoethyl acrylate, trimethylolpropane, pentaerythritol and dipentaerythritol Polyhydric acrylates of ethylene oxide, propylene oxide or ε-caprolactone adducts thereof, phenols such as phenoxy acrylate and phenoxyethyl acrylate, or their ethylene oxide or propylene Examples 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. For example, trivalent acrylates or methacrylates include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane EO-added tri(meth)acrylate, glycerin PO-added tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetrafurfuryl alcohol oligo(meth)acrylate, ethyl carbitol oligo(meth)acrylate, 1,4-butanediol Oligo(meth)acrylate, 1,6-hexanediol oligo(meth)acrylate, trimethylolpropane oligo(meth)acrylate, pentaerythritol oligo(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate ) acrylates, N,N,N′,N′-tetrakis(β-hydroxyethyl)ethyldiamine (meth)acrylic acid esters, and trivalent or higher acrylates or methacrylates include tri(2- (Meth)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) Phosphoric acid triester (meth)acrylates such as acryloyloxyethyl)phosphate may 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 when blending the component (E) 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 cured. % to 10% by mass, more preferably 3% to 8% by mass.

<(F) Organic solvent>
The resin composition may further contain (F) an organic solvent. The viscosity of the resin varnish can be adjusted by including the component (F). (F) Examples of organic solvents include ketones such as ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene, methyl cellosolve, butyl cellosolve, methyl carbitol, butyl carbitol, and propylene glycol. monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol diethyl ether, glycol ethers such as triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, butyl cellosolve acetate, carbitol acetate (EDGAc: diethylene glycol monoethyl ether acetate), Examples include esters such as ethyl diglycol acetate, aliphatic hydrocarbons such as octane and decane, and petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These are used individually by 1 type or in combination of 2 or more types. When using an organic solvent, the content can be appropriately adjusted from the viewpoint of coating properties of the resin composition.

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

<Manufacturing method>
The resin composition can be produced by mixing the components described above. In mixing, kneading or stirring may be carried out by kneading means such as a triple roll, ball mill, bead mill, sand mill, etc., or agitating means such as a super mixer, planetary mixer, etc., if necessary. The resin composition can be obtained as a resin varnish by including (F) an organic solvent, for example.

[2. Resin composition according to the second embodiment of the present invention]
Hereinafter, the resin composition according to the second embodiment of the 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 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 component ( _A ) in an alkaline solution is represented by 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. Examples of the alkaline solution include a developer usually used for development. In order to make the dissolution rates comparable, it is preferable to use a 1% by mass sodium carbonate aqueous solution with 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 it does 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.

<(A) component, (B) component, (C) component and (D) component>
Regarding the (A) component, (B) component, (C) component and (D) component contained in the resin composition according to the second embodiment, even if the (A) component does not contain the (A-1) component The good thing is that the weighted average value S of the dissolution rate of component (A) _(A) , except that (A) satisfies the formula (I), is included in the resin composition according to the first embodiment. ) component, (C) component and (D) component. 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 component (A) are arbitrary, but are preferably in the same range as the content, weight average molecular weight and acid value of component (A) described above in the first embodiment. . This makes it possible to obtain the same advantages as those described in the section on component (A) in the first embodiment. The content, average particle size, and specific surface area of component (B) are arbitrary, but are preferably in the same range as the content, average particle size, and specific surface area of component (B) described above in the first embodiment. . This makes it possible to obtain the same advantages as those explained in the section of component (B) in the first embodiment. The content of component (C), the epoxy equivalent weight and the weight average molecular weight are arbitrary, but are preferably in the same range as the content of the component (C), the epoxy equivalent weight and the weight average molecular weight described above in the first embodiment. . This makes it possible to obtain the same advantages as those described in the section on component (C) in the first embodiment. Although the content of component (D) is arbitrary, it is preferably in the same range as the content of component (D) described above in the first embodiment. This makes it possible to obtain the same advantages as those explained in the section of component (D) in the first embodiment.

The weighted average value S _(A) based on the mass ratio of the dissolution rate [nm/sec] of component (A) in the resin composition according to the present embodiment in an alkaline solution satisfies the above formula (I). More specifically, the weighted average value S ₍ A) of the dissolution rate of 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 110 nm/sec or less, preferably 100 nm/sec or less, more preferably 90 nm/sec or less, and still more preferably 80 nm/sec or less. When the weighted average value S _(A) of the dissolution rate of the component (A) is within the above range, the dissolution rate of the resin composition in the alkaline developer can be prevented from becoming excessively slow or excessive. Therefore, it is possible to suppress the local occurrence of unintentionally excessive melting portions and unintended unmelting portions. Therefore, the undercut resistance can be improved, and preferably the side surfaces of the opening pattern can be brought closer to perpendicular to the layer plane.

Weighted average value S of dissolution rate of component _{(A) As a method of keeping (A)} within the above range, for example, a method of using component (A) including component (A-1) can be mentioned. However, for example, by appropriately adjusting the type and amount of the component (A) other than the component (A-1), the weighted average value S _(A) of the dissolution rate of the component (A) may be kept within the range described above. good.

When using resins containing multiple types of ethylenically unsaturated groups and carboxyl groups as component (A), the dissolution rate [nm/sec] of each of the resins containing ethylenically unsaturated groups and carboxyl groups is within the above range. is more preferable. The component (A) having a dissolution rate [nm/sec] in the range of 5 to 110, more preferably in the range of 5 to 100 includes a resin solution (A-1a) obtained in Synthesis Example 1 described below, 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 succinic anhydride) can be mentioned.

<(E) component, (F) component and (G) component>
The resin composition according to the present embodiment may further contain (E) a reactive diluent, (F) an organic solvent, and (G) other additives, if necessary. Regarding the (E) component, (F) component and (G) component that the resin composition according to the second embodiment may contain, the (E) component and (F) component that the resin composition according to the first embodiment may contain and (G) 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 components described above. In mixing, kneading or stirring may be carried out by kneading means such as a triple roll, ball mill, bead mill, sand mill, etc., or agitating means such as a super mixer, planetary mixer, etc., if necessary. The resin composition can be obtained as a resin varnish by including (F) an organic solvent, for example.

<Physical properties and applications of the resin composition>
After photocuring the resin composition according to the first embodiment or the resin composition according to the second embodiment of the present invention, the cured product obtained by heat curing at 190 ° C. for 90 minutes has the property of being excellent in undercut resistance. show. That is, it provides an insulating layer and a solder resist that are excellent in undercut resistance. The undercut is preferably +10 μm or less, more preferably +5 μm or less, even more preferably +4 μm or less, and even more preferably +3 μm or less, from the viewpoint of suppressing the forward tapered shape. The lower limit is preferably −5 μm or less, more preferably −4 μm or less, and still more preferably −3 μm or less, from the viewpoint of suppressing the reverse tapered shape. The undercut value can be measured according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

In addition, after photocuring the resin composition according to the first embodiment or the second embodiment of the present invention, the cured product obtained by heat curing at 190 ° C. for 90 minutes tends to exhibit excellent developability. . For this reason, there is usually no residue of resin or the like in the unexposed area. The minimum via hole diameter without residue is preferably 100 μm or less, more preferably 90 μm or less, and even more preferably 80 μm or less. Although the lower limit is not particularly limited, it may be 1 μm or more. Developability can be evaluated according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

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

A cured product obtained by photocuring the resin composition according to the first embodiment or the second embodiment of the present invention and then thermally curing the composition at 190° C. for 90 minutes tends to exhibit a high glass transition temperature. That is, an insulating layer and a solder resist having a high glass transition temperature are obtained. The glass transition temperature is preferably higher than 135°C, more preferably 170°C or higher, and even more preferably 180°C or higher. Although the upper limit is not particularly limited, it may be 300° C. or less. The glass transition temperature can be measured according to the method described in <Measurement of Average Coefficient of Linear Thermal Expansion and Glass Transition Temperature> below.

A cured product obtained by photocuring the resin composition according to the first embodiment or the second embodiment of the present invention and then thermally curing the composition at 190° C. for 90 minutes exhibits excellent crack resistance. That is, it provides an insulating layer and a solder resist having excellent crack resistance. Cracks and peeling are not observed even after repeating the heating test between -65°C and 150°C 500 times. Crack resistance can be evaluated according to the method described in <Evaluation of developability, crack resistance, and undercut resistance> described later.

Applications of the resin composition according to the first embodiment or the second embodiment of the present invention are not particularly limited. , multilayer printed wiring board applications, etc.), solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole-filling resins, component-embedding resins, etc. Among them, a resin composition for an insulating layer of a printed wiring board (a printed wiring board having a cured product of a resin composition as an insulating layer), a resin composition for an interlayer insulating layer (a cured product of a resin composition having an interlayer insulating layer printed wiring board), resin composition for plating (printed wiring board in which plating is formed on the cured product of the resin composition), and resin composition for solder resist (printed with the cured product of the resin composition as solder resist It can be suitably used as a wiring board).

[Photosensitive film]
A photosensitive film containing the resin composition can be obtained by using the resin composition according to the first embodiment or the second embodiment of the present invention. For example, the resin composition is coated on a support substrate in a resin varnish state, and the organic solvent is dried to form a resin composition layer, whereby a photosensitive film can be obtained. Alternatively, a photosensitive film preliminarily formed on a support may be used by being laminated on the support substrate. The photosensitive film can be laminated to various supporting substrates. Examples of the support substrate mainly include substrates such as glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates.

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

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

Commercially available supports include, for example, product names “Alphan MA-410” and “E-200C” manufactured by Oji Paper Co., Ltd., polypropylene films manufactured by Shin-Etsu Film Co., Ltd., and product name “PS-25” manufactured by Teijin Limited. Polyethylene terephthalate films such as the PS series, etc., but not limited to these. These supports preferably have a release agent such as a silicone coating agent applied to the surface to facilitate 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 suppress breakage of the support when the support is peeled off before development. Resolution can be improved. Also preferred are supports with low fisheyes. Here, the fish eye refers to foreign matter, undissolved matter, oxidative deterioration, etc. of the material being incorporated into the film when the film is produced by heat-melting the material, kneading, extruding, biaxial stretching, casting, etc. It is a thing.

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

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

The support-attached photosensitive film of the present invention can be prepared according to methods known to those skilled in the art, for example, by dissolving the resin composition of the present invention in an organic solvent to prepare a resin varnish, coating the resin varnish on the support, It can be produced by drying the organic solvent by heating or blowing hot air 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 oven or a far-infrared oven, and the substrate is dried. A support-attached photosensitive film 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 organic solvent in the resin varnish. It can be dried in minutes to 13 minutes. The amount of the residual organic solvent in the resin composition layer is preferably 5% by mass or less, more preferably 2% by mass or less, relative to the total amount of the resin composition layer in order to prevent diffusion of the organic solvent in subsequent steps. is more preferable. A person skilled in the art can appropriately set suitable drying conditions by simple experiments. The thickness of the resin composition layer is preferably in the range of 5 μm to 500 μm, more preferably 10 μm to 200 μm, from the viewpoint of improving handleability and suppressing deterioration of sensitivity and resolution inside the resin composition layer. more preferably in the range of 15 μm to 150 μm, still more preferably in the range of 20 μm to 100 μm, and most preferably in the range of 20 μm to 60 μm.

Examples of coating methods for the resin composition include gravure coating, micro gravure coating, reverse coating, kiss reverse coating, die coating, slot die, lip coating, comma coating, blade coating, and roll coating. method, knife coating method, curtain coating method, chamber gravure coating method, slot orifice method, spray coating method, dip coating method and the like.
The resin composition may be applied in several times, may be applied in one time, or may be applied by combining a plurality of different methods. Among them, the die coating method is preferable because of its excellent uniform coatability. Also, in order to avoid contamination by foreign substances, it is preferable to perform the coating process in an environment such as a clean room where foreign substances are less likely to occur.

[Printed wiring board]
A 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 produced using the above-described photosensitive film or photosensitive film with a support. A case where the insulating layer is a solder resist will be described below.

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

Examples of circuit boards include glass epoxy boards, metal boards, polyester boards, polyimide boards, BT resin boards, and thermosetting polyphenylene ether boards. Here, the term "circuit board" refers to a board having a patterned conductor layer (circuit) formed on one side or both sides of the board as described above. In addition, in a multilayer printed wiring board formed by alternately laminating conductor layers and insulating layers, a substrate in which one or both sides of the outermost layer of the multilayer printed wiring board is a patterned conductor layer (circuit) is also included here. 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 a coating method, screen printing is generally used for full surface printing, but any other coating method may be used as long as it can be applied uniformly. For example, spray coating method, hot melt coating method, bar coating method, applicator method, blade coating method, knife coating method, air knife coating method, curtain flow coating method, roll coating method, gravure coating method, offset printing method, dip coating method. , brushing, or any other conventional application method can be used. After coating, drying is performed in a hot air oven, a far infrared oven, or the like, if necessary. The drying conditions are preferably 80° C. to 120° C. for 3 minutes to 13 minutes. Thus, a photosensitive film is formed on the circuit board.

<Lamination process>
When a photosensitive film with a support is used, the resin composition layer side is laminated on one side or both sides of a circuit board using a vacuum laminator. In the lamination step, when the photosensitive film with a support has a protective film, after removing the protective film, the photosensitive film with a support and the circuit board are preheated as necessary to form a resin composition layer. is pressurized and heated to the circuit board. In the support-attached photosensitive film, a method of laminating on a circuit board under reduced pressure by a vacuum lamination method is preferably used.

The conditions of the lamination step are not particularly limited, but for example, the pressure bonding temperature (laminating temperature) is preferably 70° C. to 140° C., and the pressure bonding 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 pressure bonding time is preferably 5 seconds to 300 seconds, and the air pressure is 20 mmHg (26.7 hPa) or less. is preferred. Moreover, the lamination process may be of a batch type or a continuous type using rolls. A vacuum lamination method can be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum applicator manufactured by Nikko Materials, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a roll-type dry coater manufactured by Hitachi Industries, and a vacuum laminator manufactured by Hitachi AIC. be able to. Thus, a photosensitive film is formed on the circuit board.

<Exposure process>
After the photosensitive film is provided on the circuit board by the coating and drying process or the lamination process, then, through the mask pattern, a predetermined portion of the resin composition layer is irradiated with actinic rays, and the irradiated portion of the resin composition layer is exposed. An exposure step for photocuring is performed. Actinic rays include, for example, ultraviolet rays, visible rays, electron beams, X-rays, and the like, and ultraviolet rays are particularly preferred. The dose of ultraviolet rays is about 10 mJ/cm ² to 1000 mJ/cm ² . The exposure method includes a contact exposure method in which a mask pattern is brought into close contact with a printed wiring board and a non-contact exposure method in which a parallel light beam is used for exposure without close contact. Either method may be used. Further, when a support is present on the resin composition layer, exposure may be performed from above the support, or exposure may be performed after the support is peeled off.

Since the solder resist uses the resin composition of the present invention, it has excellent developability. Therefore, as the exposure pattern in the mask pattern, for example, the ratio (L/S) of the circuit width (line; L) and the width (space; S) between the circuits is 100 μm/100 μm or less (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. It should be noted that the pitch need not be the same throughout the circuit board.

<Development process>
After the exposure step, if there is a support on the resin composition layer, remove the support, and then perform wet development to remove portions that have not been photocured (unexposed portions). can form a pattern.

In the case of the wet development, an alkaline solution is usually used as the developer, and a developing step using an alkaline aqueous solution is particularly preferred. As a developing method, known methods such as spraying, rocking immersion, brushing, scraping, and the like are appropriately employed.

Examples of the alkaline solution used as the developer include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; carbonates or bicarbonates such as sodium carbonate and sodium bicarbonate; and sodium phosphate. , alkali metal phosphates such as potassium phosphate, aqueous solutions of alkali metal pyrophosphates such as sodium pyrophosphate and potassium pyrophosphate, and aqueous solutions of organic bases containing no metal ions 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 surfactants, antifoaming agents, etc. in order to improve the development effect. The pH of the alkaline solution is, for example, preferably in the range of 8-13, more preferably in the range of 9-12, and even more preferably in the range of 10-12. Further, 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 it is usually room temperature, preferably 20°C to 50°C.

Organic solvents used as developers include, for example, acetone, ethyl acetate, alkoxyethanol having an alkoxy group having 1 to 4 carbon atoms, ethyl alcohol, isopropyl alcohol, butyl alcohol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol. It is 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 developer. Moreover, the temperature of such an organic solvent can be adjusted according to the developability. Furthermore, such organic solvents can be used alone or in combination of two or more. Organic solvent-based developers used alone include, for example, 1,1,1-trichloroethane, N-methylpyrrolidone, N,N-dimethylformamide, cyclohexanone, methyl isobutyl ketone, and γ-butyrolactone.

In pattern formation, if necessary, two or more of the above-described developing 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, etc. The high-pressure spray method is suitable for improving resolution. When the spray method is employed, 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, it is possible to effectively suppress the occurrence of undercuts in the development process.

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

<Other processes>
After forming the solder resist, the printed wiring board may further include a drilling step and a desmear step. These steps may be carried out according to various methods known to those skilled in the art for use in manufacturing printed wiring boards.

After forming the solder resist, if desired, the solder resist formed on the circuit board is subjected to a drilling step to form via holes and through holes. The drilling step can be carried out by a known method such as drilling, laser, plasma, or a combination of these methods if necessary, but a drilling step using a laser such as a carbon dioxide gas laser or a YAG laser is preferred.

A desmear process is a process of desmearing. Resin residue (smear) generally adheres to the inside of the opening formed in the drilling process. Since such smears cause electrical connection failures, processing for removing smears (desmear processing) is performed in this step.

Desmearing may be performed by dry desmearing, wet desmearing, or a combination thereof.

Dry desmearing includes, for example, desmearing using plasma. Desmearing using plasma can be performed using a commercially available plasma desmearing device. Among commercially available plasma desmear treatment apparatuses, suitable examples for use in manufacturing printed wiring boards include a microwave plasma apparatus manufactured by Nissin Co., Ltd., and an atmospheric pressure plasma etching apparatus manufactured by Sekisui Chemical Co., Ltd., and the like.

Examples of 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 liquid, the oxidation treatment with the oxidant solution, and the neutralization treatment with the neutralization solution in this order. Examples of the swelling liquid include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. The swelling treatment is preferably carried out by immersing the substrate having via holes and the like formed therein in a swelling liquid heated to 60° C. to 80° C. for 5 to 10 minutes. As the oxidizing agent solution, an aqueous alkaline permanganate solution is preferable. For example, a solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide can be mentioned. The oxidation treatment with the oxidizing agent solution is preferably performed by immersing the substrate after the swelling treatment in the oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Examples of commercially available alkaline permanganate aqueous solutions include "Concentrate Compact CP" and "Dosing Solution 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. As the neutralizing liquid, an acidic aqueous solution is preferable, and commercially available products include, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan.

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

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

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

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

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, 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. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively. Examples include a mounting method using a buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, "a mounting method using a build-up layer without bumps (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these examples. In the following description, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

(Synthesis Example 1: Synthesis of resin solution (A-1a))
Naphthalene skeleton-containing epoxy resin A (1,1′-bis(2,7-diglycidyloxynaphthyl)methane, epoxy equivalent 162, “EXA-4700” manufactured by Dainippon Ink and Chemicals, Inc.) represented by the following formula (8): 162 parts were placed in a flask equipped with a gas inlet tube, stirrer, condenser and thermometer, 340 parts of carbitol acetate was added and dissolved by heating, and 0.46 parts of hydroquinone and 1 part of triphenylphosphine were added. . This mixture was heated to 95 to 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, reacted for 8 hours, and cooled. In this manner, a resin solution (non-volatile content of 70%, hereinafter abbreviated as “resin solution (A-1a)”) having a solid matter acid value of 90 mgKOH/g was obtained.

It was confirmed that the resin solution (A-1a) contained at least a 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). The same operation as in Synthesis Example 1 was performed except for the above items. Thus, a resin solution (70% non-volatile content, hereinafter abbreviated as “resin solution (A-1b)”) having an acid value of 60 mgKOH/g of solid matter was obtained.

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

<Examples 1 to 7, Comparative Examples 1 to 2>
Each component was blended at the blending ratio shown in Table 1 below, and a resin varnish was prepared using a high-speed rotating mixer. Next, a PET film (“Lumirror T6AM” manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130 ° C., “release PET ”) was prepared. The prepared resin varnish was evenly applied with a die coater to the surface of the release PET treated with the alkyd resin release agent so that the thickness of the resin composition layer after drying was 40 μm, and heated at 80° C. to 110° C. C. for 6.5 minutes to obtain a support-attached photosensitive film having a resin composition layer on the release PET.

A measurement method and an evaluation method in physical property evaluation will be described.

<Evaluation of Dissolution Rate of Resin Composition>
Resin solution (A-1a), resin solution (A-1b), and resins ZFR-1491H, ZAR-2000 and ZCR-1569H, which will be described later, were added to propylene glycol monomethyl ether acetate (PGMEAc), respectively, to obtain a non-volatile component of 35% by weight. A solution was prepared. The solution was applied onto a silicon wafer and spin-coated to obtain a coating film. Thereafter, the coating film was dried at 120° C. for 3 minutes to form a resin film having a thickness of about 2 μm. The film thickness of the resin film was measured with a stylus film thickness meter ("SURFCOM 130A" manufactured by Tokyo Seimitsu Co., Ltd.). Thereafter, the resin film together with the silicon wafer was immersed in a 1 mass % sodium carbonate aqueous solution (pH: 11.7) as an alkaline solution at 23°C. Then, the disappearance time until the resin film disappeared was measured. The disappearance of the resin film was confirmed by visually confirming 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 starts to be immersed in the alkaline solution to the time when the disappearance is confirmed. Then, for each resin film, a dissolution rate [nm/sec] indicating a decrease in the thickness [nm] of the resin film per second was calculated. The dissolution rate was set at 1 nm/sec for the resin film that did not dissolve even after being immersed for 30 minutes. The results were as follows.
(A-1) Component:
・A-1a: 100 nm/sec
・A-1b: 6 nm/sec
(A-2) Component:
・ZFR-1491H: 131nm/sec
・ZAR-20000: 39nm/sec
・ZFR-1491H: 1 nm/sec
In each of Examples and Comparative Examples, the weighted average value S _(A) based on the mass ratio of the dissolution rate [nm/sec] of component (A) in an alkaline solution was calculated using 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 _{2 (A)} is the mass ratio of each resin (A) when the non-volatile component in component (A) is taken as 100% by mass.

<Evaluation of developability, crack resistance, and undercut resistance>
(Formation of laminate for evaluation)
The copper layer of a glass epoxy substrate (copper-clad laminate) on which a circuit is formed by patterning a copper layer with a thickness of 18 μm is roughened by treatment with a surface treatment agent (CZ8100, manufactured by MEC Co., Ltd.) containing an organic acid. was applied. Next, the resin composition layer of the support-attached photosensitive film obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was placed in contact with the copper circuit surface, and a vacuum laminator (manufactured by Nikko Materials Co., VP160 ) to form a laminate in which the copper-clad laminate, the resin composition layer, and the support are laminated in this order. The crimping conditions were as follows: evacuation time of 30 seconds, crimping temperature of 80° C., crimping pressure of 0.7 MPa, and pressurization time of 30 seconds. The laminate was allowed to stand at room temperature for 30 minutes or longer, and was exposed to ultraviolet rays from the support side of the laminate using a quartz glass mask having an exposure pattern for forming round holes and a pattern forming device. The quartz glass mask used was provided with a pattern capable of drawing a total of six types of round holes with diameters of 50 μm/60 μm/70 μm/80 μm/90 μm/100 μm. After standing at room temperature for 30 minutes, the support was peeled off from the laminate. The entire surface of the resin composition layer on the laminate was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as an alkaline developer 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 holes were eluted and via holes were formed in the resin composition layer, while in Comparative Example 1, no via holes were formed. After spray development, 1 J/cm ² ultraviolet irradiation was performed, and further heat treatment was performed at 180° C. for 30 minutes. As a result, the resin composition layer was cured, and in Examples 1 to 7 and Comparative Example 2, laminates for evaluation having insulating layers having openings (via holes) on the copper-clad laminate were obtained. Further, in Comparative Example 1, a laminate for evaluation having an insulating layer in which no via holes were formed on a copper-clad laminate was obtained.

(Evaluation of developability)
The via holes formed in the laminate for evaluation were observed with an SEM (magnification: 1000), and the minimum via hole diameter free of residue was specified among all the six types of via holes. When an opening (via hole) could not be confirmed in the laminate for evaluation, it was judged that the minimum via hole diameter could not be specified, and was evaluated as "x".

(Evaluation of crack resistance)
After exposing the laminate for evaluation in the atmosphere at −65° C. for 15 minutes, the temperature was raised at a rate of 180° C./minute, and then exposed in the atmosphere at 175° C. for 15 minutes, followed by 180° C./minute. was repeated 500 times. After the test, the degree of cracking and peeling of the laminate for evaluation was observed with an optical microscope (manufactured by Nikon Corporation, "ECLIPSE LV100ND") and evaluated according to the following criteria.
◯: Neither crack nor peeling is observed.
x: One or both of cracks and peeling are observed.

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

<Measurement of average linear thermal expansion coefficient and glass transition temperature>
(Formation of cured product for evaluation)
The resin composition layers of the support-attached photosensitive films obtained in Examples and Comparative Examples were exposed to ultraviolet light at 100 mJ/cm ² and photocured. After that, the entire surface of the resin composition layer was developed by spraying a 1% by mass sodium carbonate aqueous solution at 30° C. as an alkaline developer 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. After that, the support was peeled off to obtain a cured product for evaluation.

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

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

The ingredients used are as follows.
(A) Component:
(A-1) Component A-1a: Resin solution synthesized in Synthesis Example 1 (A-1a)
· A-1b: resin solution synthesized in Synthesis Example 2 (A-1b)
(A-2) Component ZFR-1491H: Bisphenol F type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 99 mgKOH/g, nonvolatile component concentration 70%)
・ ZAR-2000: Bisphenol A type epoxy acrylate (Nippon Kayaku Co., Ltd., acid value 99 mgKOH / g, nonvolatile component concentration 70%)
・ ZCR-1569H: Biphenyl type epoxy acrylate (manufactured by Nippon Kayaku Co., Ltd., acid value 98 mgKOH / g, nonvolatile component concentration 70%)
(B) Component:
・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 fused silica (manufactured by Admatechs, average particle size 0.5 μm, specific surface area 5.9 m ² /g) What was done (C) component:
・ NC3000H: biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 272)
・ 1031S: Tetrakis hydroxyphenyl ethane type epoxy resin (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 200)
(D) Component:
・ Irgacure TPO: bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide) (manufactured by BASF)
(E) Component:
・ DPHA: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., acrylic equivalent about 96)
(F) Component:
EDGAc: diethylene glycol monoethyl ether acetate MEK: methyl ethyl ketone Content of component (B): Content of component (B) when the non-volatile component of the resin composition is 100% by mass [% by mass]
- Weighted average value of dissolution rate S _(A) : Weighted average value based on the mass ratio of the dissolution rate [nm/sec] of component (A) in an alkaline solution - Undercut value: Undercut value in a via hole with a diameter of 100 µm [μm]

<Consideration>
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 (eg, an alkaline developer) at a dissolution rate within an appropriate range, and the resin composition containing the component (A-1) can be dissolved in an alkaline developer. It is thought that this is because it is possible to suppress the local occurrence of unintended excessively soluble portions and unintended undissolved portions in the resin composition when developed. It is presumed that one of the reasons for this is that component (A-1) is well mixed with components (C) to (E), and uneven composition in the resin composition can be suppressed.

Moreover, it was found that Examples 1 to 7 had better developability, heat resistance, mechanical strength and crack resistance than Comparative Examples 1 and 2. Specifically, it was found that Examples 1 to 7 had a low average coefficient of linear thermal expansion and a high glass transition temperature. This is because when a resin containing a naphthalene skeleton is used as the component (A-1), 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 hardened. This is probably because the glass transition temperature of the cured product becomes higher and the average coefficient of linear thermal expansion of the cured product becomes lower. Furthermore, due to the action of the component (A-1), the resistance of the cured product to internal stress normally caused by thermal expansion or thermal contraction is improved, so it is thought that damage to the cured product due to temperature changes could be suppressed. be done.

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

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

In each example, it has been confirmed that the same results as those of the above examples are obtained even if the component (E) is not contained, although there is a difference in degree.

REFERENCE SIGNS LIST 100 evaluation laminate 110 copper clad laminate 120 insulating layer 130 via hole 140 opening top surface 150 opening bottom surface

Claims (13)

(A) a resin containing an ethylenically unsaturated group and a carboxyl group (however, the reaction product of a polynuclear epoxy compound (a) represented by the following general formula (Z) and an unsaturated group-containing monocarboxylic acid (b) is often Excluding the active energy ray-curable resin obtained by reacting the basic acid anhydride (c)),
(B) an inorganic filler having an average particle size of 0.5 μm or more;
(C) an epoxy resin, and
(D) A resin composition containing a photopolymerization initiator,
(A) component contains (A-1) naphthalene skeleton-containing resin,
The weighted average value S (A) based on the mass ratio of the dissolution rate [nm/sec] of component _(A) in an alkaline solution is represented by the following formula (I):
5≦S _(A) ≦110 (I)
The filling,
Here, the average particle diameter of the component (B) is the median diameter of the volume-based particle size distribution measured by a laser diffraction/scattering method,
The dissolution rate is the thickness of the resin film per second [ nm], where a resin film with a thickness of about 2 μm is formed by forming a coating film by spin coating and then drying the coating film at 120 ° C. for 3 minutes.
Resin compositions (however, when barium sulfate is included as the (B) inorganic filler, resin compositions in which the content of barium sulfate relative to the total mass of the (B) inorganic filler is 88% by mass or more are excluded).

(A) a resin containing an ethylenically unsaturated group and a carboxyl group (however, the reaction product of a polynuclear epoxy compound (a) represented by the following general formula (Z) and an unsaturated group-containing monocarboxylic acid (b) is often Excluding the active energy ray-curable resin obtained by reacting the basic acid anhydride (c)),
(B) an inorganic filler having an average particle size of 0.5 μm or more;
(C) an epoxy resin, and
(D) A resin composition containing a photopolymerization initiator,
(A) component contains (A-1) naphthalene skeleton-containing resin,
The weighted average value S (A) based on the mass ratio of the dissolution rate [nm/sec] of component _(A) in an alkaline solution is represented by the following formula (I):
5≦S _(A) ≦110 (I)
The filling,
(B) component is silica,
Here, the average particle diameter of the component (B) is the median diameter of the volume-based particle size distribution measured by a laser diffraction/scattering method,
The dissolution rate is the thickness of the resin film per second [ nm], where a resin film with a thickness of about 2 μm is formed by forming a coating film by spin coating and then drying the coating film at 120 ° C. for 3 minutes.
Resin composition.

3. The resin composition according to claim 2 , wherein component (B) has an average particle size of 2.5 [mu]m or less. The resin composition according to any one of claims 1 to 3 , wherein component (A-1) is a naphthol aralkyl resin. The resin composition according to any one of claims 1 to 4 , wherein the content of component (A-1) is 5% by mass or more when the non-volatile component in component (A) is 100% by mass. . The resin composition according to any one of claims 1 to 5 , wherein the content of 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 6 , wherein the content of component (B) is 60% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. (A) component is
(A-2) The resin composition according to any one of claims 1 to 7 , which contains an acid-modified epoxy (meth)acrylate resin other than component (A-1). The resin composition according to any one of claims 1 to 8 , which is a resin composition for forming a solder resist for printed wiring boards. A photosensitive film containing the resin composition according to any one of claims 1 to 9 . A photosensitive film with a support, comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 9 provided on the support. A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 9 . A semiconductor device comprising the printed wiring board according to claim 12 .

Images