TW201638136A - Carboxyl group-containing resin, photo-sensitive resin composition, dry film, printed wiring board, and manufactural method of carboxyl group-containing resin - Google Patents

Abstract

Provided is a resin containing a carboxyl group, which is suitable as a component of a photosensitive resin composition, can impart excellent developability with an alkaline aqueous solution to a photosensitive resin composition even though the resin has a fluorene skeleton, and can also impart high electric insulation properties and plating resistance to a cured product of a photosensitive resin composition. The resin containing a carboxyl group is a reaction product of an intermediate with an acid dianhydride and an acid monohydride, wherein the intermediate is a reaction product of an epoxy compound having a bisphenol fluorene skeleton represented by formula (1) with a carboxylic acid containing an unsaturated group. The degree of polydispersion of the resin containing a carboxyl group is in the range from 1.2 to 2.8.

Description

Carboxyl group-containing resin, photosensitive resin composition, dry film, printed wiring board and Method for producing carboxyl resin

The present invention relates to a carboxyl group-containing resin, a photosensitive resin composition, a dry film, a printed wiring board having an interlayer insulating layer, a printed wiring board having a solder resist layer, and a method for producing the carboxyl group-containing resin, and the photosensitive resin composition The dry film is a dried product of the photosensitive resin composition, and the interlayer insulating layer contains a cured product of the photosensitive resin composition, and the solder resist layer contains a cured product of the photosensitive resin composition. .

In the past, an electrically insulating resin composition was used to form an electrically insulating layer such as a solder resist layer, a plating resist layer, an etch resist layer, and an interlayer insulating layer of a printed wiring board. Such a resin composition is, for example, a photosensitive resin composition.

It has been proposed to incorporate a carboxyl group-containing resin in a photosensitive resin composition for imparting a higher layer to a layer formed of a photosensitive resin composition. The heat resistance of the carboxyl group-containing resin has a bisphenol fluorene skeleton. For example, Japanese Patent No. 4,508, 929 discloses the use of a carboxyl group-containing resin having an anthracene skeleton obtained by reacting a fluorene epoxy (meth) acrylate with a polyvalent carboxylic acid or an anhydride thereof.

The layer formed of the photosensitive resin composition also requires high electrical insulation and plating resistance. Therefore, it is necessary to increase the molecular weight of the carboxyl group-containing resin having a bisphenol fluorene skeleton.

However, if the molecular weight of the carboxyl group-containing resin having a bisphenol fluorene skeleton is increased, it is difficult to develop the photosensitive resin composition by containing an alkaline aqueous solution containing at least one of an alkali metal salt and an alkali metal hydroxide. . In recent years, in order to improve the working environment and reduce the burden of disposal at the disposal site, the use of an organic amine-containing developer has been gradually avoided. Therefore, it is strongly required that the photosensitive resin composition can contain an alkali metal salt and an alkali metal hydroxide. At least one of the alkaline aqueous solutions is used for development.

An object of the present invention is to provide a carboxyl group-containing resin, a photosensitive resin composition, a dry film, a printed wiring board having an interlayer insulating layer, a printed wiring board having a solder resist layer, and a method for producing a carboxyl group-containing resin. The composition is suitable as a component of the photosensitive resin composition, and has an anthracene skeleton, and is capable of imparting excellent developability by an aqueous alkaline solution to the photosensitive resin composition, and is capable of hardening the photosensitive resin composition. The material imparts high electrical insulation and plating resistance, and the photosensitive resin composition contains the above-mentioned carboxyl group-containing resin, and the dry film is the aforementioned photosensitive A dried product of the resin composition, wherein the interlayer insulating layer contains a cured product of the photosensitive resin composition, and the solder resist layer contains a cured product of the photosensitive resin composition.

One of the carboxyl group-containing resins (A1) of the present invention is a reactant of an intermediate, an acid dianhydride (a3) and an acid anhydride (a4), which is an epoxy compound (a1) and an unsaturated group. A reaction product of the carboxylic acid (a2), wherein the epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the following formula (1): in the following formula (1), R ₁ ~R _{8 is} each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen, and the polydispersity of the carboxyl group-containing resin (A1) is in the range of 1.2 to 2.8.

A photosensitive resin composition of one aspect of the present invention, comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; and a photopolymerization initiator (C); and an epoxy compound (D); wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1).

A dry film of one aspect of the present invention is a dried product of the photosensitive resin composition.

A printed wiring board according to an aspect of the present invention includes an interlayer insulating layer containing a cured product of the photosensitive resin composition.

A printed wiring board according to one aspect of the present invention includes a solder resist layer containing a cured product of the photosensitive resin composition.

One aspect of the production method of the present invention is a method for producing a carboxyl group-containing resin (A1) having a polydispersity in the range of 1.2 to 2.8, which comprises the steps of: making an epoxy compound (a1) and an unsaturated group. a step of reacting a carboxylic acid (a2) to obtain an intermediate; and reacting the intermediate, acid dianhydride (a3) and acid anhydride (a4) to synthesize the carboxyl group-containing resin (A1) The epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the formula (1). In the formula (1), R ₁ to R ₈ are each independently hydrogen and carbon number. 1 to 5 alkyl groups, or halogen.

According to one aspect of the present invention, it is possible to obtain a carboxyl group-containing resin which is suitable as a component of a photosensitive resin composition and which has an anthracene skeleton and which can impart an excellent alkaline aqueous solution to the photosensitive resin composition. The developability of development and the high electrical insulating property and plating resistance of the cured product of the photosensitive resin composition can be imparted.

Moreover, according to one aspect of the present invention, a photosensitive resin composition, a dry film, a printed wiring board having an interlayer insulating layer, a printed wiring board having a solder resist layer, and a method for producing the carboxyl group-containing resin can be obtained. The photosensitive resin composition contains the carboxyl group-containing resin, and the dry film is a dried product of the photosensitive resin composition, and the interlayer insulating layer contains A cured product of the photosensitive resin composition, and the solder resist layer contains a cured product of the photosensitive resin composition.

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧Conductor line (first conductor line)

4‧‧ ‧ film

5‧‧‧Unexposed parts

6‧‧‧ hole

7‧‧‧Interlayer insulation

8‧‧‧Second conductor line

9‧‧‧Perforated plating

10‧‧‧through holes

11‧‧‧Printed circuit board

1A to 1E are cross-sectional views showing a manufacturing step of a multilayer printed wiring board.

Fig. 2 is a GPC elution curve obtained by colloidal permeation chromatography of the carboxyl group-containing resin (A-1) obtained in Synthesis Example A-1.

Hereinafter, one embodiment of the present invention will be described. In the following description, "(meth)acrylic acid" means at least one of "acrylic acid" and "methacrylic acid". For example, (meth) acrylate means at least one of methacrylate and acrylate.

The carboxyl group-containing resin (A1) of the present embodiment is suitable as a component of the photosensitive resin composition. a photosensitive resin composition containing, for example, a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; a photopolymerization initiator (C); An oxygen compound (D); wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1).

The carboxyl group-containing resin (A1) is a reaction of an intermediate, an acid dianhydride (a3) and an acid anhydride (a4), and the intermediate is a reaction of an epoxy compound (a1) with an unsaturated carboxylic acid (a2). Things. The epoxy compound (a1) has a bisphenol fluorene skeleton, which is represented by the following formula (1), and in the formula (1), R ₁ to R ₈ are each independently hydrogen and have a carbon number of 1 to 1; 5 alkyl or halogen.

The carboxyl group-containing resin (A1) is synthesized by reacting an epoxy compound (a1) with an unsaturated group-containing carboxylic acid (a2), and then obtaining an intermediate obtained therefrom with an acid dianhydride (a3). And react with acid anhydride (a4). The polydispersity of the carboxyl group-containing resin (A1) is in the range of 1.2 to 2.8. Further, the polydispersity is a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the carboxyl group-containing resin (A1). The polydispersity of the carboxyl group-containing resin (A1) was calculated from the measurement results of the molecular weight, and the measurement results of the molecular weight were obtained by performing colloidal permeation chromatography (GPC) under the following conditions.

GPC device: manufactured by Showa Denko, trade name SHODEX SYSTEM 11; pipe column: SHODEX KF-800P, KF-005, KF-003, KF-001 4-tube series; mobile phase: tetrahydrofuran (THF); flow rate: 1ml/ Minute; column temperature: 45 ° C; detector: refractive index (RI) detector; conversion: polystyrene.

R ₁ to R ₈ in the formula (1) may each be hydrogen or may be an alkyl group having 1 to 5 carbon atoms or a halogen. This is because, even if the hydrogen in the aromatic ring is replaced by a low molecular weight alkyl group or a halogen, the carboxyl group-containing resin (A1) is not adversely affected, and the carboxyl group-containing resin (A1) is sometimes promoted. The heat resistance or flame retardancy of the cured product of the photosensitive resin composition.

In the present embodiment, since the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton derived from the epoxy compound (a1), it is possible to impart a cured product to the photosensitive resin composition containing the carboxyl group-containing resin (A1). High heat resistance and insulation reliability. Further, since the polydispersity of the carboxyl group-containing resin (A1) is in the range of 1.2 to 2.8, the viscosity of the film formed of the photosensitive resin composition can be reduced, and good insulation reliability and plating resistance of the cured product can be ensured. (for example, whitening resistance at the time of electroless nickel/gold treatment), it is possible to impart excellent developability to the photosensitive resin composition. In other words, by making the polydispersity 1.2 or more, the viscosity of the film can be reduced, and the insulation reliability and the plating resistance can be improved. By making the polydispersity 2.8 or less, the alkaline aqueous solution can be improved. Development developability. Therefore, it is also possible to obtain a photosensitive resin composition which can be developed by an aqueous alkaline solution containing at least one of an alkali metal salt and an alkali metal hydroxide.

The carboxyl group-containing resin (A1) is more specifically described. In order to synthesize the carboxyl group-containing resin (A1), first, an epoxy group (refer to the formula (2)) of at least a part of the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2) to thereby synthesize an intermediate. . The intermediate has a structure (S3) represented by the following formula (3) which is produced by a ring-opening addition reaction of an epoxy group with an unsaturated group-containing carboxylic acid (a2). That is, the intermediate has a secondary hydroxyl group in the structure (S3) which is produced by a ring-opening addition reaction of an epoxy group with an unsaturated group-containing carboxylic acid (a2). In the formula (3), A is an unsaturated group-containing carboxylic acid residue.

Then, a part of the secondary hydroxyl groups in the intermediate is reacted with the acid dianhydride (a3), and another portion of the secondary hydroxyl groups in the intermediate is reacted with the acid monoanhydride (a4). Thereby, the carboxyl group-containing resin (A1) can be synthesized. Therefore, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton represented by the formula (1), a structure (S4) represented by the following formula (4), and a structure represented by the following formula (5) (S5). ).

The structure (S4) is produced by reacting the secondary hydroxyl group in the structure (S3) of the intermediate with the acid anhydride group in the acid anhydride (a4) should. In the formula (4), A is an unsaturated group-containing carboxylic acid residue, and B is an acid-anhydride residue.

The structure (S5) is produced by reacting two acid anhydride groups in the acid dianhydride (a3) with two secondary hydroxyl groups in the intermediate. That is, the structure (S5) is produced by crosslinking two secondary hydroxyl groups by acid dianhydride (a3). Furthermore, there may be a case where two secondary hydroxyl groups present in one molecule of the intermediate are cross-linked to each other, and two secondary hydroxyl groups respectively present in the intermediate of two molecules are cross-linked to each other. The situation. If two secondary hydroxyl groups respectively present in the intermediate of two molecules are cross-linked to each other, the molecular weight increases. In the formula (5), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

The carboxyl group-containing resin (A1) may further have a structure (S6) represented by the following formula (6). The structure (S6) is produced by reacting only one of the two acid anhydride groups in the acid dianhydride (a3) with the secondary hydroxyl group in the intermediate. In the formula (6), A is an unsaturated group-containing carboxylic acid residue, and D is an acid dianhydride residue.

When the intermediate is synthesized, when a part of the epoxy group in the epoxy compound (a1) is left unreacted, the carboxyl group-containing resin (A1) may have a structure (S2) as shown in the formula (2). base. Further, when a part of the structure (S3) in the intermediate remains without reaction, the carboxyl group-containing resin (A1) may have a structure (S3).

However, in the present embodiment, the number of structures (S2) and structures (S6) in the carboxyl group-containing resin (A1) is reduced by optimizing the reaction conditions for synthesizing the carboxyl group-containing resin (A1), or The carboxyl group-containing resin (A1) almost removes the structure (S2) and the structure (S6).

According to the above, the carboxyl group-containing resin (A1) has a bisphenol fluorene skeleton represented by the formula (1), a structure (S4), and a structure (S5). Further, the carboxyl group-containing resin (A1) may have at least one of the structure (S2), the structure (S3), and the structure (S6).

In addition, when the epoxy compound (a1) itself has a secondary hydroxyl group, that is, for example, when n=1 or more in the following formula (7), the carboxyl group-containing resin (A1) may have the following manner. Structure produced: The secondary hydroxyl group in the epoxy compound (a1) is reacted with at least one of the acid dianhydride (a3) and the acid anhydride (a4).

Further, the structure of the carboxyl group-containing resin (A1) is rationally derived based on technical common sense, and in reality, the structure of the carboxyl group-containing resin (A1) cannot be specified by analysis. The reason is as follows. When the epoxy compound (a1) itself has a secondary hydroxyl group (for example, when n is 1 or more in the formula (7)), the carboxyl group-containing resin is different depending on the amount of the secondary hydroxyl group in the epoxy compound (a1) ( The structure of A1) will vary greatly. Further, when the intermediate is reacted with the acid dianhydride (a3), as described above, there may be a case where the two secondary hydroxyl groups present in one molecule of the intermediate are crosslinked by the acid dianhydride (a3). And the case where two secondary hydroxyl groups present in the two molecules in the intermediate are crosslinked by the acid dianhydride (a3). Therefore, the final obtained Since the carboxy resin (A1) contains a plurality of molecules having different structures from each other, even if the carboxyl group-containing resin (A1) is analyzed, the structure cannot be specified.

The carboxyl group-containing resin (A1) has photoreactivity because it has an ethylenically unsaturated group derived from the unsaturated group-containing carboxylic acid (a2). Therefore, the carboxyl group-containing resin (A1) can impart photosensitivity (specifically, ultraviolet curability) to the photosensitive resin composition. Further, since the carboxyl group-containing resin (A1) has a carboxyl group derived from the acid dianhydride (a3) and the acid anhydride (a4), it is possible to impart developability to development of the photosensitive resin composition by an aqueous alkaline solution. The alkaline aqueous solution contains at least one of an alkali metal salt and an alkali metal hydroxide. Further, the molecular weight of the carboxyl group-containing resin (A1) depends on the amount of crosslinking by the acid dianhydride (a3). Therefore, the carboxyl group-containing resin (A1) whose acid value and molecular weight are appropriately adjusted can be obtained. That is, by controlling the amounts of the acid dianhydride (a3) and the acid anhydride (a4), and the amount of the acid anhydride (a4) relative to the acid dianhydride (a3), the desired molecular weight and acid value can be easily obtained. The carboxyl group-containing resin (A1). Therefore, the carboxyl group-containing resin (A1) having a polydispersity in the range of 1.2 to 2.8 can be obtained.

The weight average molecular weight of the carboxyl group-containing resin (A1) is preferably in the range of from 1,000 to 5,000. When the weight average molecular weight is 1000 or more, the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. In addition, when the weight average molecular weight is 5,000 or less, the developability of development of the photosensitive resin composition by an aqueous alkaline solution can be particularly improved.

It is preferred that the weight average molecular weight of the carboxyl group-containing resin (A1) is in the range of from 1,000 to 5,000, and the region having a molecular weight of 200 or more and less than 1700 under the GPC elution curve of the carboxyl group-containing resin (A1) (AR1) The ratio of the area to the area of the region (AR2) having a molecular weight of 1700 or more under the GPC elution curve is in the range of 1:0.5 to 1:2.5. In this case, it is possible to further suppress the viscosity of the film formed of the photosensitive resin composition, and to ensure good insulating reliability and plating resistance of the cured product, and to provide more excellent developability to the photosensitive resin composition. In other words, when the area of the region (AR1) is 1, the area of the region (AR2) is 0.5 or more, whereby the viscosity of the film formed of the photosensitive resin composition can be suppressed, and the cured product can be further improved. Insulation reliability and plating resistance. Further, when the area of the region (AR1) is 1, the area of the region (AR2) is made 2.5 or less, and the developability of the photosensitive resin composition by the alkaline aqueous solution can be further improved.

Furthermore, the area of the region under the GPC elution curve refers to the area of the region between the GPC elution curve and the line indicating the differential refractive detection intensity (mV) = 0 on the graph of the GPC elution curve. The graph of the GPC elution curve is such that the horizontal axis is the elution time (minutes) and the vertical axis is the differential refractive detection intensity (mV). A calibration curve is used to convert the elution time to molecular weight. Further, the GPC elution curve of the carboxyl group-containing resin (A1) was also obtained from the measurement results by colloidal permeation chromatography.

The solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH/g. At this time, it is possible to enhance the sensitivity The developability of the resin composition. The solid content acid value is more preferably in the range of 80 to 135 mgKOH/g, still more preferably in the range of 90 to 130 mgKOH/g.

The raw material of the carboxyl group-containing resin (A1) and the reaction conditions when the carboxyl group-containing resin (A1) is synthesized will be described in detail.

The epoxy compound (a1) has a structure (S7) represented by the following formula (7), for example. n in the formula (7) is, for example, a number in the range of 0 to 20. In order to make the molecular weight of the carboxyl group-containing resin (A1) an appropriate value, the average of n is particularly preferably in the range of 0 to 1. If the average of n is in the range of 0 to 1, it is easy to suppress an excessive increase in molecular weight due to the addition of the acid dianhydride (a3).

The unsaturated carboxylic acid (a2) may contain, for example, a compound having only one ethylenically unsaturated group in one molecule. More specifically, the unsaturated group-containing carboxylic acid (a2) may contain, for example, at least one compound selected from the group consisting of acrylic acid, methacrylic acid, and ω-carboxy-polycaprolactone (n≒). 2) monoacrylate, crotonic acid, cinnamic acid, succinic acid mono(2-propenyloxyethyl) ester, succinic acid mono(2-methylpropenyloxyl) Ethyl)ester, mono(2-propenylmethoxyethyl) phthalate, mono(2-methylpropenyloxyethyl) phthalate, mono(2-propene phthalate) Mercapto oxypropyl) ester, mono(2-methylpropenyloxypropyl) phthalate, mono(2-propenyl methoxyethyl) maleate, maleic acid mono(2- Methyl propylene decyl oxyethyl ester, β-carboxyethyl acrylate, mono(2-propenyl methoxyethyl) tetrahydrophthalate, mono (2-methyl propylene) tetrahydrophthalate Mercaptooxyethyl) ester, mono(2-propenylmethoxyethyl) hexahydrophthalate, and mono(2-methylpropenyloxyethyl) hexahydrophthalate. The unsaturated carboxylic acid (a2) preferably contains acrylic acid.

When the epoxy compound (a1) and the unsaturated group-containing carboxylic acid (a2) are reacted, a known method can be employed. For example, an unsaturated group-containing carboxylic acid (a2) is added to a solvent solution of the epoxy compound (a1), and a thermal polymerization inhibitor and a catalyst are further added as needed, and stirred and mixed, whereby a reactive solution is obtained. The reactive solution can be preferably reacted at a temperature of from 60 to 150 ° C by a conventional method, and it is particularly preferred to carry out the reaction at a temperature of from 80 to 120 ° C to obtain an intermediate. The solvent may contain, for example, at least one component selected from the group consisting of ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; ethyl acetate and butyl acetate; , acetic acid such as cellosolve acetate, butyl cyproterone acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, etc. Esters; and, dialkyl glycol ethers. The thermal polymerization inhibitor may contain, for example, at least one of hydroquinone and hydroquinone monomethyl ether. The catalyst may contain, for example, at least one selected from the group consisting of a component: a tertiary amine such as benzyldimethylamine or triethylamine; a quaternary ammonium salt such as trimethylbenzylammonium chloride or methyltriethylammonium chloride; and triphenylphosphine And triphenyl stibine.

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferred to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in the presence of triphenylphosphine. In this case, the ring-opening addition reaction of the epoxy group in the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) can be particularly promoted, and a reaction of 95% or more, 97% or more, or almost 100% can be achieved. Rate (conversion rate). Therefore, an intermediate having the structure (S3) can be obtained in a high yield. Further, in the layer containing the cured product of the photosensitive resin composition, the occurrence of ion migration can be suppressed, and the insulation reliability of the layer can be further improved.

When the epoxy compound (a1) is reacted with the unsaturated group-containing carboxylic acid (a2), the amount of the unsaturated group-containing carboxylic acid (a2) is 1 mol of the epoxy group of the epoxy compound (a1). Preferably, it is in the range of 0.8 to 1.2 moles. At this time, a photosensitive resin composition having excellent photosensitivity and storage stability can be obtained.

It is also preferred to react the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) in a state in which bubbles are generated. At this time, since the addition polymerization reaction of the unsaturated group can be suppressed, the increase in the molecular weight of the intermediate and the gelation of the solution of the intermediate can be suppressed. Further, excessive coloring of the final product, that is, the carboxyl group-containing resin (A1) can be suppressed.

The intermediate obtained in such a manner has a hydroxyl group which is produced by a reaction of an epoxy group of the epoxy compound (a1) with a carboxyl group of the unsaturated group-containing carboxylic acid (a2).

The acid dianhydride (a3) is a compound having two acid anhydride groups. The acid dianhydride (a3) may contain an acid anhydride of a tetracarboxylic acid. The acid dianhydride (a3) may contain, for example, at least one compound selected from the group consisting of 1,2,4,5-benzenetetracarboxylic dianhydride, diphenyl ketone tetracarboxylic dianhydride, methyl Cyclohexene tetracarboxylic dianhydride, tetracarboxylic dianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, ethylene tetracarboxylic dianhydride, 9,9'-bis(3,4-dicarboxyphenyl) Sebacic anhydride, glycerol bis(hydrogen trimellitate) monoacetate, ethylene glycol bis(hydrogen trimellitate), 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride 1,3,3a,4,5,9b-hexahydro-5(tetrahydro-2,5-di-oxy-3-furanyl)naphtho[1,2-c]furan-1,3- Diketone, 1,2,3,4-butanetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride. In particular, it is preferred that the acid dianhydride (a3) contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. That is, it is preferred that D in the formula (5) and the formula (6) contains a 3,3',4,4'-biphenyltetracarboxylic dianhydride residue. In this case, the good developability of the photosensitive resin composition can be ensured, and the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. The amount of 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferably in the range of 20 to 100 mol%, more preferably 40 to 100, based on the total of the acid dianhydride (a3). Moore% is within the scope, but is not limited to these ranges.

The acid monoanhydride (a4) is a compound having one acid anhydride group. The acid monoanhydride (a4) may contain an acid anhydride of a dicarboxylic acid. Acidic anhydride (a4), which may contain For example, at least one compound selected from the group consisting of phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl Methyl nadic acid anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, succinic anhydride, methyl succinic anhydride, maleic anhydride, citraconic anhydride, glutaric anhydride, cyclohexane Alkane-1,2,4-tricarboxylic acid-1,2-anhydride, and itaconic anhydride. In particular, it is preferred that the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. That is, it is preferred that B in the formula (4) contains a 1,2,3,6-tetrahydrophthalic anhydride residue. In this case, the good developability of the photosensitive resin composition can be ensured, and the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the insulation reliability and plating resistance of the cured product can be further improved. The amount of 1,2,3,6-tetrahydrophthalic anhydride is preferably in the range of 20 to 100 mol%, more preferably 40 to 100 mol, relative to the total acid anhydride (a4). Within the range of % of ears, but not limited to these ranges.

At least one of the acid dianhydride (a3) and the acid monohydride (a4) may include an acid anhydride (a5) having a carboxyl group and having an alicyclic skeleton. At this time, the amount of the carboxyl group contained in the carboxyl group-containing resin (A1) can be increased. Thereby, the developability of developing the photosensitive resin composition by an aqueous alkaline solution can be further improved. In addition, since the carboxyl group-containing resin (A1) has an alicyclic skeleton derived from the acid anhydride (a5), the viscosity of the film formed of the photosensitive resin composition can be further suppressed, and the plating resistance and the solder heat resistance can be further improved. Sex.

Preferably, the acid dianhydride (a4) contains an acid anhydride (a5). That is, it is preferred that B in the formula (4) contains a residue of the acid anhydride (a5). Anhydride (a5), containing For example, at least one of the following alicyclic compounds: a cycloalkane, a cycloalkene, a bicyclic compound, a polycyclic compound, a spiro compound, and the like. In particular, it is preferred that the acid anhydride (a5) is a compound containing a cycloalkane. Examples of the naphthenes include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, and the like. Further preferably, the acid anhydride (a5) is a compound containing cyclohexane. Further, the acid anhydride (a5) preferably has a carboxyl group directly bonded to the alicyclic skeleton. Further, the acid anhydride group in the acid anhydride (a5) is preferably directly bonded to the alicyclic skeleton. The acid anhydride (a5) may not contain an aromatic ring. Further, the acid anhydride (a5) may be an acid anhydride of a tricarboxylic acid.

More preferably, the acid anhydride (a5) contains cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride. That is, it is preferred that B in the formula (4) contains a cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride residue. In this case, since the structure (S4) has two carboxyl groups and an alicyclic skeleton, the viscosity of the film formed of the photosensitive resin composition can be reduced, and the insulation reliability and plating resistance of the cured product can be improved and ensured. Good developability. Further, since cyclohexane-1,2,4-tricarboxylic acid-1,2-anhydride has high water solubility and good reactivity, it is easy to produce a carboxyl group-containing resin (A1).

When the intermediate is reacted with the acid dianhydride (a3) and the acid anhydride (a4), a known method can be employed. For example, acid dianhydride (a3) and acid anhydride (a4) are added to a solvent solution of the intermediate, and a thermal polymerization inhibitor and a catalyst are further added as needed, and stirred and mixed, whereby a reactive solution is obtained. The reactive solution can be reacted at a temperature of 60 to 150 ° C by a conventional method, and it is particularly preferable to carry out the reaction at a temperature of 80 to 120 ° C to obtain a carboxyl group-containing resin. (A1). As the solvent, catalyst, and polymerization inhibitor, a suitable solvent, catalyst, and polymerization inhibitor can be used, and a solvent, a catalyst, and a polymerization inhibitor used in the synthesis of the intermediate can be used as it is.

In particular, it is preferred that the catalyst contains triphenylphosphine. That is, it is preferred to react the intermediate with the acid monoanhydride (a4) and the acid dianhydride (a3) in the presence of triphenylphosphine. In this case, the reaction of the secondary hydroxyl group in the intermediate with the acid monoanhydride (a4) and the acid dianhydride (a3) can be particularly promoted, and a reaction of 90% or more, 95% or more, 97% or more, or almost 100% can be achieved. Rate (conversion rate). Therefore, the carboxyl group-containing resin (A1) having the structure (S4) and the structure (S5) can be obtained in a high yield. Further, in the layer containing the cured product of the photosensitive resin composition, the occurrence of ion migration can be suppressed, and the insulation reliability of the layer can be further improved.

It is also preferred to react the intermediate with the acid monoanhydride (a4) and the acid dianhydride (a3) in a state in which bubbles are generated. In this case, it is possible to suppress an excessive increase in the molecular weight of the produced carboxyl group-containing resin (A1), and thus it is possible to suppress an excessive increase in polydispersity, whereby development of development of the photosensitive resin composition by an alkaline aqueous solution can be particularly enhanced. Sex.

When the intermediate is reacted with the acid monoanhydride (a4) and the acid dianhydride (a3), the amount of the acid dianhydride (a3) is preferably 1 mol of the epoxy group (a1). It is in the range of 0.05~0.24 moles. Further, the amount of the acid monoanhydride (a4) is preferably in the range of 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). At this time, the carboxyl group-containing resin (A1) whose acid value and molecular weight are appropriately adjusted can be easily obtained. Further, it is possible to suppress an excessive amount of the generated carboxyl group-containing resin (A1). Since the amount of the particles is increased, it is possible to suppress an excessive increase in the polydispersity and an excessive increase in the area of the region having a molecular weight of 1700 or more under the GPC elution curve, whereby the development of the photosensitive resin composition by the alkaline aqueous solution can be particularly enhanced. Developability.

When the intermediate, the acid monoanhydride (a4) and the acid dianhydride (a3) are reacted, the intermediate, the acid monoanhydride (a4) and the acid dianhydride (a3) can be simultaneously reacted.

When the intermediate, the acid monoanhydride (a4) and the acid dianhydride (a3) are reacted, the product can be first synthesized by reacting the intermediate with the acid dianhydride (a3), and the product can be synthesized with an acid. The monoanhydride (a4) is reacted. That is, the carboxyl group-containing resin (A1) may be a reactant of the product and the acid monoanhydride (a4), which is a reaction product of an intermediate and an acid dianhydride (a3). In this case, the reaction between the intermediate and the acid dianhydride (a3) proceeds stably without competing with the reaction of the acid monoanhydride (a4), so that the structure is easily formed stably (S5). Further, the molecules in the product are less likely to cause structural deviations from each other. Therefore, in the carboxyl group-containing resin (A1) obtained by reacting the product with the acid monoanhydride (a4), the molecules are less likely to cause structural deviation. Therefore, it is possible to stably produce, for example, a carboxyl group-containing resin (A1) having a specific molecular weight distribution or further having a specific acid value, which is a weight average molecular weight in the range of 1,000 to 5,000, and an area (A1) of an area (A1) The ratio of the area of AR2) is in the range of 1:0.5 to 1:2.5.

A component other than the carboxyl group-containing resin (A1) in the photosensitive resin composition will be described.

As described above, the photosensitive resin composition contains, for example, a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; and a photopolymerization initiator (C); And an epoxy compound (D); wherein the carboxyl group-containing resin (A) contains a carboxyl group-containing resin (A1).

The carboxyl group-containing resin (A) may contain only the carboxyl group-containing resin (A1), and may further contain a carboxyl group-containing resin (hereinafter also referred to as a carboxyl group-containing resin (F)) other than the carboxyl group-containing resin (A1).

The carboxyl group-containing resin (F) may contain, for example, a compound having a carboxyl group but not having photopolymerization (hereinafter referred to as a component (F1)). The component (F1) contains a polymer such as an ethylenically unsaturated monomer, and the ethylenically unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated compound having a carboxyl group may contain the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, and the like. The ethylenically unsaturated compound having a carboxyl group may further contain a reaction product with a dibasic acid anhydride such as pentaerythritol triacrylate or pentaerythritol trimethacrylate. The ethylenically unsaturated monomer may further contain the following ethylenically unsaturated compound having no carboxyl group: 2-(meth)acryloxyethyl phthalate, 2-(methyl) propylene phthalate A (meth) acrylate or the like which is a methoxyethyl 2-hydroxyethyl ester, a linear or branched aliphatic or alicyclic group in which a ring may have a part of an unsaturated bond.

The carboxyl group-containing resin (F) may contain a compound having a carboxyl group and an ethylenically unsaturated group (hereinafter referred to as a component (F2)). Further, the carboxyl group-containing resin (F) may contain only the component (F2). a component (F2) containing a resin (hereinafter referred to as a first resin (g)), which is, for example, an intermediate and a selected one a reactant of at least one compound (g3) in a group of a carboxylic acid and an anhydride thereof, the intermediate being an epoxy compound (g1) having two or more epoxy groups in one molecule and an ethylenically unsaturated compound (g2) The reactants. The first resin (g), for example, can be obtained by reacting an epoxy group in the epoxy compound (g1) with a carboxyl group in the ethylenically unsaturated compound (g2), and then adding the compound (g3) to the obtained intermediate. . The epoxy compound (g1) may contain an appropriate epoxy resin: a cresol novolac type epoxy resin, a phenol novolak type epoxy resin, or the like. The epoxy compound (g1) may contain a polymer of the ethylenically unsaturated compound (h). The ethylenically unsaturated compound (h) contains an epoxy group-containing compound (h1) such as glycidyl (meth)acrylate or further contains 2-(methyl)propenyloxyethyl phthalate. The compound (h2) which does not have an epoxy group. The ethylenically unsaturated compound (g2) preferably contains at least one of acrylic acid or methacrylic acid. The compound (g3) contains, for example, one or more compounds selected from the group consisting of polycarboxylic acids such as phthalic acid, tetrahydrophthalic acid, and methyltetrahydrophthalic acid; Anhydrides of these polycarboxylic acids.

The component (F2) may further contain a resin (referred to as a second resin (i)) which is a reactant of a polymer such as an ethylenically unsaturated monomer and an ethylenically unsaturated compound having an epoxy group. The ethylenically unsaturated monomer contains an ethylenically unsaturated compound having a carboxyl group. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. The second resin (i) can be obtained by reacting an ethylenically unsaturated compound having an epoxy group with a part of carboxyl groups in the polymer. The ethylenically unsaturated monomer may further contain an ethylenically unsaturated compound having no carboxyl group. An ethylenically unsaturated compound having a carboxyl group, for example, the following compounds: acrylic acid, methacrylic acid, ω-carboxy-polycaprolactone (n≒2) monoacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, etc. . An ethylenically unsaturated compound having no carboxyl group, and containing, for example, the following compound: 2-(methyl)propenyloxyethyl phthalate, 2-(methyl)propenyloxyethyl phthalate- 2-hydroxyethyl ester, a linear or branched aliphatic or alicyclic (wherein the ring may have a part of an unsaturated bond) (meth) acrylate or the like. The ethylenically unsaturated compound having an epoxy group preferably contains glycidyl (meth)acrylate.

The carboxyl group-containing resin (A) contains only the carboxyl group-containing resin (A1) or the carboxyl group-containing resin (A1) and the carboxyl group-containing resin (F). The carboxyl group-containing resin (A) preferably contains 30% by mass or more of the carboxyl group-containing resin (A1), more preferably 50% by mass or more, and still more preferably 100% by mass. In this case, the heat resistance and insulation reliability of the cured product of the photosensitive resin composition can be particularly improved. Moreover, the viscosity of the film formed from the photosensitive resin composition can be sufficiently reduced. Further, the developability of development of the photosensitive resin composition by an aqueous alkaline solution can be ensured.

The unsaturated compound (B) can impart photocurability to the photosensitive resin composition. The unsaturated compound (B) may contain, for example, at least one compound selected from the group consisting of: a monofunctional (meth) acrylate such as 2-hydroxyethyl (meth)acrylate; and, Alcohol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, Pentaerythritol tetra(meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ε-caprolactone modified pentaerythritol hexaacrylate, tricyclodecane dimethanol di(II) Poly) (meth) acrylate such as acrylate.

In particular, the unsaturated compound (B) is preferably a trifunctional compound, that is, a compound having three unsaturated bonds in one molecule. In this case, when the film formed of the photosensitive resin composition is exposed and developed, the resolution can be improved, and the developability of the photosensitive resin composition by the alkaline aqueous solution can be particularly improved. The trifunctional compound may contain, for example, at least one compound selected from the group consisting of trimethylolpropane tri(meth)acrylate, EO-modified trimethylolpropane tri(meth)acrylate , pentaerythritol tri (meth) acrylate, ethoxylated isocyanuric acid tri(meth) acrylate, ε-caprolactone modified ginseng (2-propenyl methoxyethyl) iso-cyanuric acid Ester, and ethoxylated glycerol tri(meth) acrylate.

The unsaturated compound (B) preferably also contains a phosphorus-containing compound (phosphorus-containing unsaturated compound). At this time, the flame retardancy of the curing of the photosensitive resin composition can be improved. The phosphorus-containing unsaturated compound may contain, for example, at least one compound selected from the group consisting of 2-methylpropenyloxyethyl phosphate (as a specific example, manufactured by Kyoeisha Chemical Co., Ltd.) Product type LIGHT ESTER P-1M, and LIGHT ESTER P-2M), 2-propenyl methoxyethyl phosphate (as a specific example, the product model LIGHT ACRYLATE P-1A manufactured by Kyoeisha Chemical Co., Ltd.), Diphenyl-2-methylpropenyloxyl phosphate Ethyl ethyl ester (commodity model MR-260 manufactured by Daiba Industry Co., Ltd.) and HFA series manufactured by Showa Polymer Co., Ltd. (as a specific example, dipentaerythritol hexaacrylate and HCA (9, 10) -Additional reactants of -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) are also commercially available models HFA-6003 and HFA-6007, caprolactone-modified dipentaerythritol hexaacrylate and HCA ( The addition reactant of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is also the commercial models HFA-3003 and HFA-6127, and the like.

The unsaturated compound (B) may contain a prepolymer. The prepolymer may contain, for example, at least one compound selected from the group consisting of polymerizing a monomer having an ethylenically unsaturated bond and then adding an ethylenically unsaturated group. And, oligomeric (meth) acrylate prepolymers. The oligomeric (meth) acrylate prepolymer may contain, for example, at least one component selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, Amine ester (meth) acrylate, alkyd resin (meth) acrylate, oxime resin (meth) acrylate, and spirane resin (meth) acrylate.

The photopolymerization initiator (C) contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). In other words, the photosensitive resin composition contains, for example, a fluorenylphosphine oxide-based photopolymerization initiator (C1). In this case, although the photosensitive resin composition contains the carboxyl group-containing resin (A1), it is possible to impart high sensitivity to ultraviolet light to the photosensitive resin composition. Further, in the layer containing the cured product of the photosensitive resin composition, the occurrence of ion migration can be suppressed, and the insulation reliability of the layer can be further improved.

Further, the fluorenylphosphine oxide-based photopolymerization initiator (C1) is less likely to interfere with the electrical insulation of the cured product. Therefore, by subjecting the photosensitive resin composition to exposure curing, a cured product excellent in electrical insulating properties can be obtained, and the cured product is suitable as, for example, a solder resist layer, a plating resist layer, an etch resist layer, and an interlayer insulating layer.

The fluorenylphosphine oxide-based photopolymerization initiator (C1) may contain, for example, at least one component selected from the group consisting of 2,4,6-trimethylbenzylidene-diphenyl- Monodecylphosphine oxide photopolymerization initiator such as phosphine oxide, 2,4,6-trimethylbenzimidyl-phenyl-phosphonic acid ethyl ester; and, bis-(2,6-dichlorobenzene) Mercapto) phenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)- 4-propylphenylphosphine oxide, bis-(2,6-dichlorobenzhydryl)-1-naphthylphosphine oxide, bis-(2,6-dimethoxybenzylidene)phenyl oxide Phosphine, bis-(2,6-dimethoxybenzylidene)-2,4,4-trimethylpentylphosphine oxide, bis-(2,6-dimethoxybenzylidene)- 2,5-Dimethylphenylphosphine oxide, bis-(2,4,6-trimethylbenzylidene)phenylphosphine oxide, (2,5,6-trimethylbenzylidene)- A bis-indenylphosphine oxide-based photopolymerization initiator such as 2,4,4-trimethylpentylphosphine oxide. In particular, it is preferred that the fluorenylphosphine oxide-based photopolymerization initiator (C1) contains 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, and is preferably a fluorenylphosphine oxide-based light. The polymerization initiator (C1) contains only 2,4,6-trimethylbenzimidyl-diphenyl-phosphine oxide.

The photopolymerization initiator (C) preferably contains a hydroxyketone-based photopolymerization initiator (C2) in addition to the fluorenylphosphine oxide-based photopolymerization initiator (C1). That is, the photosensitive resin composition preferably contains a hydroxyketone A photopolymerization initiator (C2). In this case, it is possible to impart further high photosensitivity to the photosensitive resin composition as compared with the case where the hydroxyketone-based photopolymerization initiator (C2) is not contained. Thereby, when the coating film formed from the photosensitive resin composition is irradiated with ultraviolet light to be cured, the coating film can be sufficiently cured from the surface to the deep portion. Examples of the hydroxyketone-based photopolymerization initiator (C2) include 1-hydroxy-cyclohexyl-phenyl-ketone, methyl phenylglyoxylate, and 1-[4-(2-hydroxyethoxy). -phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzene Methyl]phenyl}-2-methyl-propan-1-one, and 2-hydroxy-2-methyl-1-phenyl-propan-1-one.

The mass ratio of the fluorenylphosphine oxide-based photopolymerization initiator (C1) to the hydroxyketone-based photopolymerization initiator (C2) is preferably in the range of 1:0.01 to 1:10. In this case, the hardenability in the vicinity of the surface of the coating film formed of the photosensitive resin composition and the hardenability in the deep portion can be uniformly adjusted.

The photopolymerization initiator (C) preferably also contains bis(diethylamino)diphenyl ketone (C3). In other words, the photosensitive resin composition preferably contains a fluorenylphosphine oxide-based photopolymerization initiator (C1) and bis(diethylamino)diphenyl ketone (C3), or a photosensitive resin composition. The photosensitive resin composition contains a mercaptophosphine oxide photopolymerization initiator (C1), a hydroxyketone photopolymerization initiator (C2), and bis(diethylamino)diphenyl ketone (C3). At this time, when the coating film formed of the photosensitive resin composition is partially exposed and developed, the hardening of the portion which is not exposed is suppressed, so that the resolution is particularly high. Therefore, it is possible to form a very fine map A cured product of the photosensitive resin composition. In particular, when an interlayer insulating layer of a multilayer printed wiring board is produced from a photosensitive resin composition, and a hole having a small diameter for a through hole is provided in the interlayer insulating layer by photolithography (see FIG. 1) It is possible to form a hole with a small diameter precisely and easily.

The amount of bis(diethylamino)diphenyl ketone (C3) is preferably in the range of 0.5 to 20% by mass based on the fluorenylphosphine oxide-based photopolymerization initiator (C1). When the amount of bis(diethylamino)diphenyl ketone (C3) is 0.5% by mass or more with respect to the fluorenylphosphine oxide-based photopolymerization initiator (C1), the resolution is particularly high. In addition, when the amount of bis(diethylamino)diphenyl ketone (C3) is 20% by mass or less based on the fluorenyl phosphine oxide-based photopolymerization initiator (C1), bis(diethylamino group) Diphenyl ketone (C3) does not easily impede the electrical insulation of the cured product of the photosensitive resin composition.

The photosensitive resin composition may further contain a known photopolymerization accelerator, a sensitizer, or the like. The photosensitive resin composition may contain, for example, at least one component selected from the group consisting of benzoin and its alkyl ethers; acetophenones such as acetophenone and benzoin dimethyl ketal; - anthracene such as methyl hydrazine; 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, a thioxanthone such as 2,4-diisopropylthioxanthone; a diphenyl ketone such as diphenyl ketone or 4-benzylidene-4'-methyldiphenyl sulfide; , xanthone such as 4-diisopropylxanthone; and α-hydroxyketones such as 2-hydroxy-2-methyl-1-phenyl-propan-1-one; 2-A Keto-1-[4-(methylthio)phenyl]-2-(N-morpholinyl)-1-propanone, etc. A compound containing a nitrogen atom. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), ethyl p-dimethylbenzoate, p-dimethylamino benzoic acid isoamyl ester, and 2-dimethylamino benzoate. A known photopolymerization accelerator or sensitizer such as a tertiary amine such as ethyl ester. The photosensitive resin composition may contain at least one of a photopolymerization initiator for visible light exposure and a photopolymerization initiator for near-infrared exposure, as needed. The photosensitive resin composition may contain, in addition to the photopolymerization initiator (C), a sensitizer for laser exposure, that is, coumarin such as 7-diethylamino-4-methylcoumarin A derivative, a carbocyanine pigment, a xanthene pigment, or the like.

The epoxy compound (D) can impart thermosetting properties to the photosensitive resin composition. The epoxy compound (D) preferably has at least 2 epoxy groups in one molecule. The epoxy compound (D) may be an epoxy compound which is insoluble in a solvent, or a solvent-soluble epoxy compound which is widely used. The epoxy compound (D) preferably contains, for example, one or more components selected from the group consisting of phenol novolak-type epoxy resins (as a specific example, the product model EPICLON N manufactured by DIC Corporation) -775), a cresol novolac type epoxy resin (a specific example, a product model EPICLON N-695 manufactured by DIC Corporation), and a bisphenol A novolac type epoxy resin (as a specific example, manufactured by DIC Corporation) Product model EPICLON N-865), bisphenol A type epoxy resin (as a specific example, product type jER1001 manufactured by Mitsubishi Chemical Corporation), bisphenol F type epoxy resin (as a specific example, Mitsubishi Chemical Corporation Manufactured product model jER4004P), bisphenol S type epoxy resin (as a specific example, product model EPICLON EXA-1514 manufactured by DIC Corporation), bisphenol AD type epoxy resin, biphenyl type epoxy resin (as a specific example, Mitsubishi Chemical Product model YX4000) manufactured by Co., Ltd., biphenyl aldehyde varnish type epoxy resin (as a specific example, product type NC-3000 manufactured by Nippon Kayaku Co., Ltd.), hydrogenated bisphenol A type epoxy resin (as a specific example) , product type ST-4000D manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., and naphthalene type epoxy resin (as a specific example, the product model EPICLON HP-4032, EPICLON HP-4700, EPICLON HP-4770 manufactured by DIC Corporation) ), hydroquinone type epoxy resin (as a specific example, the product model YDC-1312 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and tertiary catechol epoxide type epoxy resin (as a specific example, DIC shares are limited) The company's product model EPICLON HP-820), dicyclopentadiene type epoxy resin (as a specific example, DIC Corporation's product model EPICLON HP-7200), adamantane type epoxy resin (as a specific example, light Product model: ADAMANTATE XE-201), bisphenol epoxy resin (as a specific example, the product model YSLV-80XY manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), diphenyl ether epoxy resin (As a specific example, the product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) and bismuth (hydroxyphenyl) ethane type epoxy resin (as a specific example, the product model GTR manufactured by Nippon Kayaku Co., Ltd.) -1800), epoxy resin having a bisphenol fluorene skeleton (as a specific example, an epoxy resin having a structure (S7)), a rubbery core-shell polymer A modified bisphenol A type epoxy resin (a specific example, a product model MX-156 manufactured by KANEKA CORPORATION) and a rubbery core-shell polymer modified bisphenol F type epoxy resin (as a specific example, a product manufactured by KANEKA CORPORATION) Model MX-136), and special difunctional epoxy resin (as a specific example, the product model YL7175-500 manufactured by Mitsubishi Chemical Corporation, and YL7175-1000; the product model EPICLON TSR-960 manufactured by DIC Corporation, EPICLON TER-601, EPICLON TSR-250-80BX, EPICLON 1650-75MPX, EPICLON EXA-4850, EPICLON EXA-4816, EPICLON EXA-4822, and EPICLON EXA-9726; YSLV-120TE).

The epoxy compound (D) preferably contains a crystalline epoxy resin. At this time, the developability of the photosensitive resin composition can be improved. Further, the crystalline epoxy resin means an epoxy resin having a melting point. The crystalline epoxy resin may contain, for example, at least one component selected from the group consisting of triglycidyl isocyanurate (1,3,5-para (2,3-epoxypropyl) Base)-1,3,5-three -2,4,6(1H,3H,5H)-trione), hydroquinone-type crystalline epoxy resin (as a specific example, trade name YDC-1312 manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), biphenyl A crystalline epoxy resin (a specific name, YX-4000, manufactured by Mitsubishi Chemical Corporation), and a diphenyl ether-type crystalline epoxy resin (as a specific example, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) Product model YSLV-80DE), bisphenol type crystalline epoxy resin (for example, YSLV-80XY, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), bismuth (hydroxyphenyl) ethane type crystalline epoxy Resin (for example, a product model GTR-1800 manufactured by Nippon Kayaku Co., Ltd.) and a bisphenol fluorene-type crystalline epoxy resin (having an epoxy resin having a structure (S7) as a specific example).

The amount of the crystalline epoxy resin is preferably in the range of 10 to 100% by mass, more preferably in the range of 30 to 100% by mass, even more preferably in the range of 35 to 100% by mass based on the epoxy compound (D). Within the range of 100% by mass. In this case, in the step up to the thermal curing of the photosensitive resin composition, the thermosetting reaction of the carboxyl group-containing resin and the epoxy resin can be suppressed, and the developability can be improved.

In particular, the crystalline epoxy resin preferably contains a crystalline epoxy resin having a melting point of 110 ° C or lower. That is, the epoxy compound (D) preferably contains a crystalline epoxy resin having a melting point of 110 ° C or lower. In this case, the developability of development of the photosensitive resin composition by an aqueous alkaline solution can be particularly enhanced. The crystalline epoxy resin having a melting point of 110 ° C or less may contain, for example, at least one component selected from the group consisting of biphenyl type epoxy resins (for example, a model number YX4000 manufactured by Mitsubishi Chemical Corporation) ), diphenyl ether type epoxy resin (as a specific example, the product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), and bisphenol type epoxy resin (as a specific example, Nippon Steel & Sumitomo Chemical Co., Ltd.) The product model manufactured by the company is YSLV-80XY).

The epoxy compound (D) may contain triglycidyl isocyanurate. In particular, triglycidyl isocyanurate, preferably a beta body, has three epoxy linkages relative to S-three. The ring skeleton surface is a structure formed in the same direction; or, preferably, a mixture of the β body and the α body, the α body having one epoxy bond in relation to the S-three The ring skeleton surface has a structure different from the other two epoxy groups.

The crystalline epoxy resin preferably also contains a crystalline epoxy resin having a melting point of less than 100 °C. That is, the epoxy compound (D) is also preferably a crystalline epoxy resin having a melting point of less than 100 °C. At this time, the developability of the photosensitive resin composition can be further improved. In addition, since the crystalline epoxy resin having a melting point of less than 100° C. has a high compatibility with a component other than the epoxy resin (D) or a solvent in the photosensitive resin composition, it is easily dispersed in the photosensitive resin composition. Homogenize. Further, when the photosensitive resin composition contains a crystalline epoxy resin having a melting point of less than 100 ° C, crystallization does not easily occur even at a low temperature. Therefore, it is possible to impart high storage stability to the photosensitive resin composition. Further, since the crosslinking reaction between the carboxyl group and the epoxy group in the photosensitive resin composition can be suppressed at a low temperature, it is possible to maintain high developability of the photosensitive resin composition and to impart high preservation to the photosensitive resin composition. stability.

The crystalline epoxy resin having a melting point of less than 100 ° C may contain, for example, at least one component selected from the group consisting of: diphenyl ether type epoxy resin (as a specific example, Nippon Steel & Sumitomo Chemical Co., Ltd. The product model YSLV-80DE manufactured by the company, and the bisphenol epoxy resin (as a specific example, the product manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd. Model YSLV-80XY), an epoxy resin having a bisphenol fluorene skeleton (as a specific example, an epoxy resin having a structure (S7)).

When the epoxy compound (D) contains a crystalline epoxy resin having a melting point of less than 100 ° C, the equivalent of the epoxy group contained in the crystalline epoxy resin having a melting point of less than 100 ° C is contained with respect to the carboxyl group-containing resin (A). One equivalent of the carboxyl group is preferably in the range of 0.2 to 2.0, more preferably in the range of 0.25 to 1.7, and even more preferably in the range of 0.3 to 1.5.

The epoxy compound (D) may contain a phosphorus-containing epoxy resin. At this time, the flame retardancy of the cured product of the photosensitive resin composition can be improved. Phosphorus-containing epoxy resin, for example, phosphoric acid-modified bisphenol F-type epoxy resin (as a specific example, DIC Corporation's product model EPICRON EXA-9726, and EPICRON EXA-9710), Nippon Steel & Sumitomo Chemical Co., Ltd. The product model EPOTORT FX-305 manufactured by the company.

The photosensitive resin composition may contain melamine. The photosensitive resin composition may contain a component (E) containing at least one of melamine and a melamine derivative. In this case, the adhesion between the cured product of the photosensitive resin composition and a metal such as copper can be made high. Therefore, the photosensitive resin composition is particularly suitable as an insulating material for a printed wiring board. Moreover, the plating resistance of the cured product of the photosensitive resin composition can be improved, that is, the whitening resistance at the time of electroless nickel/gold treatment.

Melamine is 2,4,6-triamino-1,3,5-three And can be obtained from generally commercially available compounds. Further, the melamine derivative has one of three in one molecule thereof. The compound of the ring and the amine group may be used. As the melamine derivative, for example, guanamine; methyl decylamine; phenyl decylamine; 2,4-diamino-6-methylpropenyl oxyethyl-S-III 2-vinyl-4,6-diamino-S-three 2-vinyl-4,6-diamino-S-three /Iso-cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three /Iso-cyanuric acid adducts, etc. S-three a derivative; and a reaction of melamine with an anhydride such as melamine-tetrahydrophthalic acid. More specific examples of the melamine derivative include the product name VD-1 of Shikoku Chemical Industry Co., Ltd., the product name VD-2, and the product name VD-3.

The photosensitive resin composition may contain an organic solvent. The organic solvent is used for liquidification or varnishing of a photosensitive resin composition, adjustment of viscosity, adjustment of coatability, adjustment of film formability, and the like.

The organic solvent may contain, for example, at least one compound selected from the group consisting of: linear, branched, quaternary or polyhydric alcohols such as ethanol, propanol, isopropanol, hexanol, ethylene glycol; Ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene and xylene; Swasol series (manufactured by Maruzen Petrochemical Co., Ltd.), Solvesso series (manufactured by ExxonMobil Chemical Company), etc. Petroleum aromatic mixed solvent; celecoxib, butyl acesulfame, etc.; carbitol, carbitol, propylene glycol methyl ether and other propylene glycol alkyl ether; a polypropylene glycol alkyl ether such as propylene glycol methyl ether; an acetate such as ethyl acetate, butyl acetate, celecoxib acetate or carbitol acetate; and a dialkyl glycol ether.

The amount of the component in the photosensitive resin composition is appropriately adjusted so that the photosensitive resin composition has photocurability and can be developed by an alkaline solution.

The amount of the carboxyl group-containing resin (A) is preferably in the range of 5 to 85% by mass, more preferably in the range of 10 to 75% by mass, based on the solid content of the photosensitive resin composition. It is further preferably in the range of 30 to 60% by mass.

The amount of the unsaturated compound (B) is preferably in the range of 1 to 50% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 10 to 45% by mass. Further preferably, it is in the range of 40% by mass. In particular, when the amount of the unsaturated compound (B) is in the range of 21 to 40% by mass based on the carboxyl group-containing resin (A), it is possible to impart excellent photocurability to the photosensitive resin composition and to provide photosensitivity. The developability of the resin composition is further improved, and the viscosity of the film formed of the photosensitive resin composition is further reduced. In other words, when the amount of the unsaturated compound (B) is 21% by mass or more based on the carboxyl group-containing resin (A), the photocurability of the photosensitive resin composition can be improved and the developability of the photosensitive resin composition can be improved. Further improvement. In addition, when the amount of the unsaturated compound (B) is 40% by mass or less based on the carboxyl group-containing resin (A), the viscosity of the film formed of the photosensitive resin composition can be further reduced.

The amount of the photopolymerization initiator (C) is preferably in the range of 0.1 to 30% by mass based on the carboxyl group-containing resin (A), and more preferably in the range of 1 to 25% by mass.

The amount of the epoxy compound (D) is preferably 0.7 to 2.5 in terms of the equivalent amount of the epoxy group contained in the epoxy compound (D) with respect to 1 equivalent of the carboxyl group contained in the carboxyl group-containing resin (A). In the range of 0.7 to 2.3, it is more preferably in the range of 0.7 to 2.0, and further preferably in the range of 0.7 to 2.0.

When the photosensitive resin composition contains melamine, the amount of melamine is preferably in the range of 0.1 to 10% by mass based on the carboxyl group-containing resin (A), and further preferably in the range of 0.5 to 5% by mass. .

When the photosensitive resin composition contains the component (E) containing at least one of the melamine and the melamine derivative, the amount of the component (E) is preferably the amount of the carboxyl group-containing resin (A). It is in the range of 0.1 to 10% by mass, and more preferably in the range of 0.5 to 5% by mass.

When the photosensitive resin composition contains an organic solvent, the amount of the organic solvent is preferably such that the organic solvent can be quickly volatilized and disappeared when the coating film formed of the photosensitive resin composition is dried, that is, The organic solvent is adjusted in such a manner that it does not remain in the dried film. In particular, the amount of the organic solvent is preferably in the range of 0 to 99.5% by mass, and more preferably in the range of 15 to 60% by mass, based on the entire photosensitive resin composition. Further, the appropriate ratio of the organic solvent varies depending on the coating method and the like. Therefore, it is preferred to appropriately adjust the ratio depending on the coating method.

In addition, the solid content amount is a total amount of all the components remaining after the volatile component such as a solvent is removed from the photosensitive resin composition.

The photosensitive resin composition may further contain components other than the above components within a range that does not impair the effects of the embodiment.

For example, the photosensitive resin composition may contain an inorganic filler. At this time, it is possible to reduce the hardening and shrinkage of the film formed of the photosensitive resin composition. The inorganic filler may contain, for example, at least one material selected from the group consisting of barium sulfate, crystalline cerium oxide, nano cerium oxide, carbon nanotube, talc, bentonite, Aluminum hydroxide, magnesium hydroxide, and titanium dioxide. The photosensitive resin composition contains a white material such as titanium oxide or zinc oxide to whiten the photosensitive resin composition and the cured product. The ratio of the inorganic filler in the photosensitive resin composition can be appropriately set, and the amount of the inorganic filler is preferably in the range of 0 to 300% by mass based on the carboxyl group-containing resin (A).

The photosensitive resin composition may contain at least one resin selected from the group consisting of toluene diisocyanate and morpholine diisocyanate which are blocked with caprolactam, hydrazine, malonate or the like. , isophorone diisocyanate and hexamethylene diisocyanate blocked isocyanate; melamine resin, n-butyl melamine resin, isobutylated melamine resin, butylated urea resin, butylated melamine urea co-condensation resin, An amide-based resin such as a benzoguanamine-based co-condensation resin; a thermosetting resin other than the above; an ultraviolet curable epoxy (meth) acrylate; and a (meth)acrylic acid in a bisphenol A type a resin obtained by an epoxy resin such as a phenol novolak type, a cresol novolac type, or an alicyclic type; and a polymer compound such as a diallyl phthalate resin, a phenoxy resin, an amine ester resin, or a fluororesin .

The photosensitive resin composition may contain a curing agent for curing the epoxy compound (D). The hardener may contain, for example, at least one component selected from the group consisting of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl Imidazole derivatives such as imidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole; dicyandiamide, benzene Methyl dimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl -N,N-dimethylbenzylamine and other amine compounds; ruthenium compounds such as hexamethylenedifluoride and ruthenium dioxime; phosphorus compounds such as triphenylphosphine; acid anhydride; phenol; thiol; Lewis acid amine And; 鎓 salt. Commercial products of these components include, for example, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, and 2P4MHZ manufactured by Shikoku Chemicals Co., Ltd. (all trade names of imidazole compounds); manufactured by San-Apro Co., Ltd. U-CAT3503N, U-CAT3502T (trade names of blocked isocyanate compounds of dimethylamine); DBU, DBN, U-CATSA102, U-CAT5002 (all of which are bicyclic guanidine compounds and salts thereof).

The photosensitive resin composition may contain an adhesiveness imparting agent other than the component (E). The adhesion imparting agent is, for example, decylamine; methyl decylamine; phenyl decylamine; and 2,4-diamino-6-methylpropenyl oxyethyl-S-three 2-vinyl-4,6-diamino-S-three 2-vinyl-4,6-diamino-S-three /Iso-cyanuric acid adduct, 2,4-diamino-6-methylpropenyloxyethyl-S-three /Iso-cyanuric acid adducts, etc. S-three derivative.

The photosensitive resin composition may contain at least one component selected from the group consisting of a curing accelerator; a colorant; a copolymer of polyfluorene oxide, acrylate, etc.; a leveling agent; Cohesive imparting agent such as a coupling agent; a thixotropic agent; a polymerization inhibitor; an antihalation agent; a flame retardant; an antifoaming agent; an antioxidant; a surfactant; and a polymer dispersing agent.

The content of the amine compound in the photosensitive resin composition is preferably as small as possible. When it is carried out in this manner, the electrical insulation of the layer composed of the cured product of the photosensitive resin composition is not easily impaired. In particular, the amount of the amine compound is preferably 6% by mass or less based on the carboxyl group-containing resin (A), and more preferably 4% by mass or less.

The photosensitive resin composition can be prepared by blending a raw material of the photosensitive resin composition as described above, and by using, for example, a three-roll mill, a ball mill, and a sand. A well-known kneading method such as a sand mill is used for kneading. When the raw material of the photosensitive resin composition contains a liquid component or a component having a low viscosity, the photosensitive resin composition can be prepared by first adding a component having a low viscosity in addition to a liquid component in the raw material. The other portions are kneaded, and then a liquid component, a component having a low viscosity, and the like are added to the obtained mixture and mixed.

In consideration of storage stability and the like, the first agent can be prepared by mixing a part of components of the photosensitive resin composition, and the second agent can be prepared by mixing the remaining components. That is, the photosensitive resin composition may have a first agent and a second agent. At this time, for example, by using a photosensitive resin composition The unsaturated compound (B), a part of the organic solvent, and the thermosetting component in the component are mixed and dispersed in advance to prepare a first agent, and the remaining components of the components of the photosensitive resin composition are mixed and dispersed. Modulate the second dose. At this time, the required amount of the first agent and the second agent may be mixed at appropriate to prepare a mixed solution, and the mixed solution is hardened to obtain a cured product.

The photosensitive resin composition of this embodiment is suitable for an electrically insulating material used for a printed wiring board. In particular, the photosensitive resin composition is suitable for a material such as a solder resist layer, a plating resist layer, an etch resist layer, or an interlayer insulating layer.

The photosensitive resin composition of the present embodiment preferably has a property of being developed by an aqueous solution of sodium carbonate even in the case of a film having a thickness of 25 μm. In this case, since a sufficiently thick electrically insulating layer can be produced from the photosensitive resin composition by photolithography, the photosensitive resin composition can be widely applied to the production of an interlayer insulating layer in a printed wiring board. Flux layer, etc. Of course, it is also possible to produce an electrically insulating layer thinner than the thickness of 25 μm from the photosensitive resin composition.

Whether or not the film having a thickness of 25 μm can be developed by an aqueous solution of sodium carbonate can be confirmed by the following method. The wet coating film was formed by coating a photosensitive resin composition on a suitable substrate, and then the wet coating film was heated at 80 ° C for 40 minutes to form a film having a thickness of 25 μm. Exposure was carried out by irradiating the film with ultraviolet rays at a condition of 500 mJ/cm ² in a state in which the negative mask was directly adhered to the film, and the negative mask had an exposure portion for blocking ultraviolet rays and shielding. Non-exposure part of ultraviolet light. After the exposure, the following treatment was carried out: a 1% sodium carbonate (Na ₂ CO ₃ ) aqueous solution at 30 ° C was sprayed on the film at an injection pressure of 0.2 MPa for 90 seconds, and then pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. . When the film was observed after the treatment, and the portion corresponding to the non-exposed portion in the film was removed and the residue could not be confirmed, it was confirmed that the film having a thickness of 25 μm could be developed by an aqueous solution of sodium carbonate.

Hereinafter, an example of a method of manufacturing a printed wiring board having an interlayer insulating layer formed of the photosensitive resin composition of the present embodiment will be described with reference to FIGS. 1A to 1E. In the method, a through hole is formed on the interlayer insulating layer by photolithography.

First, as shown in Fig. 1A, the core material 1 is prepared. The core material 1 is provided with, for example, at least one insulating layer 2 and at least one conductor line 3. The conductor line 3 provided on one side of the core material 1 is hereinafter referred to as a first conductor line 3. As shown in Fig. 1B, a film 4 is formed on one surface of the core material 1 from a photosensitive resin composition. The method of forming the film 4 includes, for example, a coating method and a dry film method.

In the coating method, for example, a photosensitive resin composition is applied onto the core material 1 to form a wet film. The coating method of the photosensitive resin composition may be selected from known methods, for example, a group consisting of a dipping method, a spray method, a spin coating method, a roll coating method, and a curtain coating method. (curtain coating), and screen printing. Then, in order to volatilize the organic solvent in the photosensitive resin composition, for example, the wet coating film is dried at a temperature in the range of 60 to 120 ° C, whereby the film 4 can be obtained.

In the dry film method, first, a photosensitive resin composition is applied onto a suitable support made of polyester or the like, and dried, whereby a dried product of a photosensitive resin composition is formed on the support, that is, dried. membrane. Thereby, a laminated body having a dry film and a support for supporting the dry film is obtained. First, the dry film in the laminate is superposed on the core material 1, and then the dry film is pressed against the core material 1, and then the support is peeled off from the dry film, thereby transferring the dry film to the core from the support. On the material 1. Thereby, the film 4 composed of the dry film is provided on the core material 1.

As shown in Fig. 1C, the film 4 is partially cured by exposure to the film 4. Therefore, for example, the negative mask is attached to the film 4, and the film 4 is irradiated with ultraviolet rays. The negative photomask includes an exposure portion that allows ultraviolet rays to pass through, and a non-exposure portion that blocks ultraviolet rays, and the non-exposed portion is provided at a position that coincides with the position of the through hole 10. The negative mask is, for example, a photo tool such as a mask film or a dry plate. The ultraviolet light source may be selected from the group consisting of a chemical lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, and a metal halide lamp.

Further, the exposure method may be a method other than the method using a negative mask. For example, the film 4 can be exposed by a direct drawing method in which ultraviolet rays emitted from a light source are irradiated only on the portion of the film 4 to be exposed. The light source suitable for the direct drawing method can be selected, for example, as a group consisting of a high pressure mercury lamp, an ultra high pressure mercury lamp, Metal halide lamp, g line (436 nm), h line (405 nm), I line (365 nm); and a combination of two or more of the g line, the h line, and the I line.

Further, in the dry film method, the dry film of the laminate may be laminated on the core material 1, and then the film 4 composed of the dry film may be irradiated with ultraviolet rays through the support without peeling off the support. Thereby, the film 4 is exposed, and then the support is peeled off from the film 4 before the development process.

Then, the unexposed portion 5 of the film 4 shown in FIG. 1C is removed by performing development processing on the film 4, whereby the through hole 10 is formed at a position as shown in FIG. 1D. Hole 6. In the development treatment, an appropriate developer can be used depending on the composition of the photosensitive resin composition. The developing solution is, for example, an alkaline aqueous solution or an organic amine containing at least one of an alkali metal salt and an alkali metal hydroxide. The alkaline aqueous solution, more specifically, contains, for example, at least one component selected from the group consisting of sodium carbonate, potassium carbonate, ammonium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, ammonium hydrogencarbonate, sodium hydroxide , potassium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide, and lithium hydroxide. The solvent in the alkaline aqueous solution may be only water or a mixture of water and a hydrophilic organic solvent such as a lower alcohol. The organic amine may contain, for example, at least one component selected from the group consisting of monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

The developer is preferably an aqueous alkaline solution containing at least one of an alkali metal salt and an alkali metal hydroxide, and particularly preferably an aqueous sodium carbonate solution. At this time, it is possible to achieve an increase in the working environment and a reduction in the burden of waste disposal.

Then, the film 4 is hardened by heating it. The heating conditions, for example, the heating temperature is in the range of 120 to 200 ° C, and the heating time is in the range of 30 to 120 minutes. When the film 4 is thermally cured in this manner, the properties such as strength, hardness, and chemical resistance of the interlayer insulating layer 7 can be improved.

The film 4 is further irradiated with ultraviolet rays before or after heating, or before and after heating, as needed. At this time, the photocuring of the film 4 can be further performed.

According to the above, the interlayer insulating layer 7 can be provided on the core material 1, and the interlayer insulating layer 7 is composed of a cured product of a photosensitive resin composition. The second conductor line 8 and the perforated plating 9 may be provided on the interlayer insulating layer 7 by a known method such as an additive method. Thereby, as shown in FIG. 1E, a printed wiring board 11 having the first conductor line 3, the second conductor line 8, and the interlayer insulating layer 7 interposed between the first conductor line 3 and the second conductor line can be obtained. 8 , and a through hole 10 electrically connecting the first conductor line 3 and the second conductor line 8 . Further, in the first E-figure, the perforated plating 9 has a tubular shape in which the inner surface of the hole 6 is covered, but the perforated plating 9 may be entirely filled inside the hole 6.

An example of a method of manufacturing a printed wiring board comprising a solder resist layer formed of the photosensitive resin composition of the present embodiment will be described.

First, prepare the core material. The core material is provided with, for example, at least one insulating layer and at least one conductor line. A film is formed from a photosensitive resin composition on a surface of the core material on which the conductor line is provided. As a method of forming a film, The coating method and the dry film method are listed. As the coating method and the dry film method, the same method as in the case of forming the interlayer insulating layer described above can be employed. The portion is hardened by exposing the film. The exposure method may be the same as the above-described method of forming the interlayer insulating layer. Then, the unexposed portion of the film is removed by subjecting the film to development treatment, whereby the exposed portion of the film remains on the core material. Then, the film on the core material is thermally hardened by heating it. The developing method and the heating method may be the same as those in the case of forming the interlayer insulating layer described above. The film is further irradiated with ultraviolet rays before or after heating, or before and after heating. At this time, the photocuring of the film can be further performed.

According to the above, the solder resist layer can be provided on the core material, and the solder resist layer is composed of a cured product of the photosensitive resin composition. Thereby, it is possible to obtain a printed wiring board comprising: a core material having an insulating layer and a conductor line thereon; and a solder resist layer partially covering the surface of the core material on which the conductor line is provided.

[Examples]

(1-1) Synthesis of Synthesis Examples A-1 to A-24 and B-1 to B-6

The synthesis examples A-1 to A-24 and B-1 to B-6 were prepared in the following manner.

In a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer, the raw material components shown in the "first reaction" column in Tables 1 to 3 are added, and these are stirred in the presence of bubbles. Raw material ingredients, thereby blending the mixture. In a four-necked flask, in the presence of bubbles While stirring the mixture, the mixture was heated at the reaction temperature and reaction time shown in the "Reaction conditions" column of the "First reaction" column. Thereby, a solution of the intermediate is formulated.

Then, the raw material components shown in the "second reaction" column of Tables 1 to 3 were placed in the solution of the intermediate in the four-necked flask, and the solution in the four-necked flask was stirred while the bubbles were generated. The heating was carried out by the reaction temperature and the reaction time shown in the column of "Reaction conditions (1)" in the "second reaction" column. Then, in addition to the synthesis examples A-17, A-18, B-1, B-4, B-5, and B-6, the solution in the four-necked flask was stirred while the bubbles were generated. The reaction temperature and the reaction time shown in the column of "reaction conditions (2)" in the "second reaction" column are heated. Thereby, a 65 mass% solution of a carboxyl group-containing resin was obtained (wherein, the synthesis example B-4 was a 57% solution). The weight average molecular weight, polydispersity and acid value of the carboxyl group-containing resin are shown in Tables 1 to 3. The molar ratio between the components is also shown in Tables 1-3.

(1-2) Synthesis of Synthesis Example A-25

250 parts by mass of the following epoxy compound 1, 72 parts by mass of acrylic acid, and 60 parts by mass of propylene glycol monomethyl ether acetate were placed in a four-necked flask equipped with a reflux condenser, a thermometer, an air blowing tube, and a stirrer. 140 parts by mass of diethylene glycol monoethyl ether acetate, 0.2 parts by mass of methylhydroquinone, 1.5 parts by mass of triphenylphosphine, and agitating these raw materials in a state in which bubbles are generated, thereby blending mixture. The mixture was stirred at 115 ° C for 12 hours while stirring the mixture in a four-necked flask. Thereby, a solution of the intermediate is formulated.

Then, 58.8 parts by mass of 3,3',4,4'-biphenyltetracarboxylic dianhydride and 20 parts by mass of propylene glycol monomethyl ether acetate were charged into the solution of the intermediate in the four-necked flask, and The mixture was stirred at 115 ° C for 3 hours while stirring the bubbles.

Then, 60.8 parts by mass of 1,2,3,6-tetrahydrophthalic anhydride and 18.7 parts by mass of propylene glycol monomethyl ether acetate were charged into the solution of the intermediate in the four-necked flask, and In the state in which the bubbles were generated, the raw material components were stirred while heating at 115 ° C for 3 hours, and then the raw material components were stirred while being bubbled, and the mixture was heated at 80 ° C for 1 hour.

Thereby, a 65 mass% solution of the carboxyl group-containing resin was obtained. The weight average molecular weight of the carboxyl group-containing resin was 2758, the acid value was 105, and the polydispersity was 1.76.

Regarding the carboxyl group-containing resin obtained in Synthesis Example A-1, a GPC elution curve obtained by colloidal permeation chromatography is shown in Fig. 2 . In the GPC elution curve, the peak area of the elution time of 27.363 is the area corresponding to the molecular weight of 205 to 1617 under the GPC elution curve, and the ratio of the peak area is 46.5229%. The peak area of the elution time of 26.017 is the area corresponding to the molecular weight of 1747 to 3341 under the GPC elution curve, and the ratio of the peak area is 30.8301%. The peak area of the elution time of 25.471 is the area corresponding to the molecular weight of 3524 to 11576 under the GPC elution curve, and the ratio of the peak area is 22.530%. Solubilized by the GPC The area ratio of the area of the region (AR1) to the area of the region (AR2) was obtained, and the result was 1:1.2.

With respect to Synthesis Examples B-1, B-2, B-3, and B-4, the area ratio of the area of the region (AR1) to the area of the region (AR2) was obtained, and the results were 1:0, 1:2.8, and 1, respectively. :1 and 1:3.6.

The details of the components shown in the column (a1) in Tables 1 to 3 are as follows.

‧Epoxy compound 1: A bisphenol fluorene type epoxy compound having an epoxy equivalent of 250 g/eq, which is represented by the formula (7), and all of R ₁ to R ₈ in the formula (7) are hydrogen.

‧Epoxy compound 2: a bisphenol fluorene type epoxy compound having an epoxy equivalent of 279 g/eq, which is represented by the formula (7), and R ₁ and R ₅ in the formula (7) are each a methyl group, R ₂ ~ R ₄ and R ₆ to R ₈ are all hydrogen.

‧Epoxy compound 3: a bisphenol fluorene type epoxy compound having an epoxy equivalent of 650 g/eq, which is represented by the formula (7), and R ₁ to R ₈ in the formula (7) are all hydrogen, R ₂ to R ₄ and R ₆ to R ₈ are all hydrogen.

‧ Cresol novolac type epoxy resin: cresol novolac type epoxy resin having an epoxy equivalent of 203 g/eq.

(2) Dispensing a photosensitive resin composition

Examples 1 to 97 and Comparative Examples 1 to 6 were prepared in the following manner.

The components shown in the "composition" column of Tables 4 to 14 described later were blended in a three-roll mill, and the components were stirred and mixed in a flask to obtain a photosensitive resin composition. Furthermore, the details of the components are as follows.

‧ Unsaturated Compound A: Trimethylolpropane triacrylate.

‧ Unsaturated Compound B: Trimethylolpropane trimethacrylate.

‧Unsaturated Compound C: Dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product model KAYARAD DPHA.

‧ Unsaturated Compound D: Difunctional aliphatic amine ester acrylate, manufactured by DAICEL-ALLNEX LTD., product model EBECRYL 8402.

‧ Unsaturated compound E: ε-caprolactone modified dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., product model DPCA-60.

‧ Unsaturated compound F: Tricyclodecane dimethanol diacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., product type A-DCP.

‧Photopolymerization initiator A: 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, manufactured by BASF Corporation, trade name Irgacure TPO.

‧Photopolymerization initiator B: 1-hydroxy-cyclohexyl-phenyl-ketone, manufactured by BASF Corporation, trade name Irgacure 184.

‧ Photopolymerization initiator C: 4,4'-bis(diethylamino)diphenyl ketone.

‧Photopolymerization initiator D: 2-methyl-1-(4-methylthiophenyl)-2-(N-morpholinyl)propan-1-one, manufactured by BASF Corporation, trade name Irgacure 907.

‧Photopolymerization initiator E: 2,4-diethylthioxan-9-one.

‧Photopolymerization initiator F: bis(2,4,6-trimethylbenzylidene)phenylphosphine oxide, manufactured by BASF Corporation, trade name Irgacure 819.

‧Photopolymerization initiator G: 2-hydroxy-2-methyl-1-phenyl-propan-1-one, manufactured by BASF Corporation, product model Irgacure 1173.

‧ Crystalline Epoxy Resin A: Biphenyl type crystalline epoxy resin, manufactured by Mitsubishi Chemical Corporation, product type YX4000, melting point 105 ° C, epoxy equivalent 187 g / eq.

‧ Amorphous epoxy resin B: bisphenol A type epoxy resin containing a long chain carbon chain, manufactured by DIC Corporation, product model EPICLON EXA-4816, liquid resin, epoxy equivalent 410 g / eq.

‧ A solution of amorphous epoxy resin B: A solution obtained by dissolving amorphous epoxy resin B in a solvent of diethylene glycol monoethyl ether acetate to a solid content of 90%.

‧ Crystalline Epoxy Resin C: Bisphenol type crystalline epoxy resin, manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., product model YSLV-80XY, melting point 75-85 ° C, epoxy equivalent 192 g/eq.

‧A solution of amorphous epoxy resin D: a cresol novolac type epoxy resin (manufactured by DIC Co., Ltd., product model EPICLON N-695, softening point) with solvent diethylene glycol monoethyl ether acetate A solution obtained by dissolving in a solid content of 75% at 90 to 100 ° C and an epoxy equivalent of 214 g/eq.

‧Crystalline epoxy resin E: 1,3,5-parade (2,3-epoxypropyl)-1,3,5-three -2,4,6(1H,3H,5H)-trione (high melting point), melting point 150-158 ° C, epoxy equivalent 99 g / eq.

‧ Crystalline Epoxy Resin F: Hydroquinone-type crystalline epoxy resin, manufactured by Nippon Steel Chemical Co., Ltd., model number YDC-1312, melting point 138-145 ° C, epoxy equivalent 176 g / eq.

‧ Crystalline epoxy resin G: Diphenyl ether type crystalline epoxy resin, product model YSLV-80DE manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., melting point 80 to 90 ° C, epoxy equivalent 163 g / eq.

‧ Amorphous epoxy resin H: Rubber-like core-shell polymer modified bisphenol A epoxy resin, manufactured by KANEKA CORPORATION, product model MX-120, liquid resin, epoxy equivalent 243 g/eq.

‧A solution of amorphous epoxy resin I: Amorphous biphenyl aldehyde varnish type epoxy resin (trade name NC-3000, manufactured by Nippon Kayaku Co., Ltd., softening point 53) is 80% solid content ~63 ° C, epoxy equivalent: 280 g / eq) A solution obtained by dissolving diethylene glycol monoethyl ether acetate (the epoxy equivalent in terms of 80% solid content is 350 g / eq).

‧ Amorphous epoxy resin J: bisphenol F-type epoxy resin containing rubber particles, manufactured by KANEKA CORPORATION, model number Kane Ace MX-130.

‧ Melamine: Made by Nissan Chemical Industry Co., Ltd., melamine micropowder.

‧ Melamine dispersion varnish: Dispersed varnish made of Nissan Chemical Industry Co., Ltd., melamine micropowder. 1.5 parts of melamine fine powder and 3.5 parts of unsaturated compound trimethylolpropane triacrylate were dispersed by a bead mill.

‧ Melamine Derivative: The reaction of melamine with 1,2,3,6-tetrahydrophthalic anhydride is also melamine-tetrahydrophthalate.

‧Antioxidant: A hindered phenolic antioxidant, manufactured by BASF, under the trade designation IRGANOX 1010.

‧ Blue pigment: phthalocyanine blue.

‧Yellow pigment: 1,1'-[(6-phenyl-1,3,5-three -2,4-diyl)diimido]bis(9,10-nonanedione).

‧ Barium sulfate: manufactured by 堺Chemical Industries Co., Ltd., product model BARIACE B31.

‧ Talc: Made by Japan Talc, product model SG-2000.

‧ Bentonite: Organic bentonite, manufactured by Rheox, Inc., model number BENTONE SD-2.

‧ Defoamer: manufactured by Shin-Etsu Lee Co., Ltd., product model KS-66.

‧ Surfactant A: Manufactured by DIC Corporation, product model MEGAFACE F-477.

‧ Surfactant B: manufactured by DIC Corporation, product model MEGAFACE F-556.

‧ Rheology regulator: manufactured by BYK Japan KK, product model BYK-430.

‧ Solvent A: Diethylene glycol monoethyl ether acetate.

‧ Solvent B: methyl ethyl ketone.

(3) Making test films

Except for the examples and comparative examples other than Examples 17, 35, 56, 88 and 97, test pieces were produced in the following manner.

A glass epoxy copper clad laminate (FR-4 type) having a copper foil having a thickness of 35 μm was prepared. On the glass epoxy-clad laminate, a comb-shaped electrode as a conductor line was formed by subtraction, whereby a core material having a line width/pitch of 50 μm/50 μm was obtained. In the case of Examples 90 to 97 and Comparative Examples 5 to 6, an etchant (organic acid-based etchant manufactured by MEC Co., Ltd., product model CZ-8100) was used to dissolve and remove the conductor wiring of the core material. The surface layer portion having a thickness of about 1 μm is used to roughen the conductor line. A photosensitive resin composition is applied onto the entire surface of one side of the core material by a screen printing method to form a wet coating film. The wet coating film was heated at 80 ° C for 40 minutes (Examples 90 to 96 and Comparative Examples 5 to 6 were 30 minutes), and preliminary drying was carried out to form a film having a film thickness of 25 μm. In a state where the negative mask having the non-exposed portion is directly in contact with the film, the film is irradiated with ultraviolet rays under conditions of 500 mJ/cm ² to perform exposure, and the non-exposed portion has a circular shape including a diameter of 50 μm (if implemented) In the cases of Examples 27 to 36 and 62 to 83, the patterns are circular shapes of 50 μm and 70 μm. The developed film is subjected to development treatment. At the time of development processing, a 1% sodium carbonate aqueous solution of 30 ° C was sprayed on the film at an ejection pressure of 0.2 MPa for 90 seconds. Then, the film was washed by spraying pure water on the film at an ejection pressure of 0.2 MPa for 90 seconds. Thereby, the unexposed portion of the film is removed and a hole is formed. Then, in the case of Examples 1 to 16, 18 to 26, Comparative Examples 1 to 4, Examples 37 to 55, 57 to 61, 84 to 87, 89 to 96, and Comparative Examples 5 and 6, the first was 1000 mJ/cm. ^The film was irradiated with ultraviolet rays under the conditions of ² , and then heated at 160 ° C for 60 minutes. However, in the case of Examples 16 and 87 which did not contain a pigment, the ultraviolet ray at the time of exposure was set to the condition of 300 mJ/cm<^2> . In the case of Examples 27 to 34, 36 and 62 to 83, the film was first heated at 160 ° C for 60 minutes, and then the film was irradiated with ultraviolet rays at a condition of 1000 mJ/cm ² . Thereby, a layer composed of a photosensitive resin composition is formed on the core material. Thereby a test piece is obtained.

Examples 17, 35, 56, 88 and 97 were produced in the following manner to prepare test pieces.

First, the photosensitive resin composition was applied onto a film made of polyethylene terephthalate by an applicator, and then dried by heating at 95 ° C for 25 minutes, thereby drying the film. A dry film having a thickness of 25 μm was formed thereon.

A glass epoxy copper clad laminate (FR-4 type) having a copper foil having a thickness of 35 μm was prepared. On the glass epoxy-clad laminate, a comb-shaped electrode as a conductor line was formed by subtraction, whereby a core material having a line width/pitch of 50 μm/50 μm was obtained. In the case of Examples 35 and 97, an etchant (organic acid-based etchant manufactured by MEC Co., Ltd., product model CZ-8100) was used to dissolve and remove the surface portion of the conductor line having a thickness of about 1 μm. Thereby, the conductor line is roughened. The core material was heated and laminated by a vacuum laminator to form a dry film on the entire surface of one of the core materials. The conditions for heating the lamination were 0.5 MPa, 80 ° C, and 1 minute. Thereby, a film having a thickness of 25 μm composed of a dry film was formed on the core material. In the case of Examples 17, 56, 88, and 97, the film was subjected to exposure, development, and ultraviolet irradiation treatment under the same conditions as in Example 1. In the case of Example 35, The film was subjected to exposure, development, and ultraviolet irradiation treatment under the same conditions at 27 o'clock. Further, a film made of polyethylene terephthalate was peeled off from the dry film (film) after exposure and before development. Thereby, a photosensitive tree is formed on the core material A layer of a cured product of a lipid composition (also referred to as a cured product of a dry film). Thereby a test piece is obtained.

(4) Evaluation test

(4-1) Viscosity

In addition to the examples and comparative examples other than Examples 17, 35, 56, 88 and 97, in the preparation of the test piece, the degree of viscosity of the film when the negative mask was removed from the film after exposure of the film was as follows. to evaluate.

A: There was no feeling of resistance when the negative mask was removed from the film, and the adhesion was not confirmed on the film after the negative mask was removed.

B: A feeling of resistance was obtained when the negative mask was removed from the film, and a mark of adhesion was confirmed on the film after the negative mask was removed.

C: It is difficult to remove the negative mask from the film, and if the negative mask is forcibly removed, the film is broken.

Further, regarding Comparative Examples 1 and 6 in which the viscosity evaluation was C, the evaluation of (4-3) to (4-7) was not performed.

(4-2) developability

Examples and comparative examples other than Examples 17, 35, 56, 88, 90-97 and Comparative Examples 5 and 6 were coated by screen printing on the entire surface of one side of the printed wiring board. A photosensitive resin composition is thereby formed into a wet coating film. The wet coating film was heated at 80 ° C for 40 minutes or 60 minutes to form a film having a film thickness of 25 μm. The development treatment is performed on the film without performing exposure. In the development treatment, the film was sprayed with a 1% sodium carbonate aqueous solution at 30 ° C for 90 seconds at a spray pressure of 0.2 MPa, and then Pure water was sprayed at a jet pressure of 0.2 MPa for 90 seconds. The treated printed wiring board was observed and the results were evaluated in the following manner.

A: In any case where the heating time of the wet coating film was 40 minutes and 60 minutes, all the film was removed.

B: When the heating time of the wet film was 40 minutes, the film was completely removed, but at 60 minutes, a part of the film remained on the printed wiring board.

C: In any case where the heating time of the wet coating film was 40 minutes and 60 minutes, a part of the film remained on the printed wiring board.

In Example 1 and Comparative Example 2, evaluation was also performed for the case where the conditions of the development treatment were changed. That is, Example 1 and Comparative Example 2 were also evaluated for the case where the film was first immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C during development treatment. For 60 seconds, pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

Further, in Comparative Examples 3 and 4 in which the developability was evaluated as C, the evaluations of the following (4-3) to (4-7) were not carried out. In Comparative Example 2, since the evaluation when using a 1% sodium carbonate aqueous solution was C, when the 1% sodium carbonate aqueous solution was used, the following evaluations of (4-3) to (4-7) were not performed.

Further, in Examples 17, 35, 56, 88, 90 to 97 and Comparative Example 5, development was possible without any problem in the development step after the exposure of the test piece.

(4-3) Resolution

For the examples and comparative examples, the pores formed in the layer composed of the cured product in the test piece were observed, and the results were evaluated in the following manner.

A: The diameter of the bottom of the hole is 40 μm or more.

B: The diameter of the bottom of the hole is 25 μm or more but less than 40 μm.

C: The diameter of the bottom of the hole is less than 25 μm, or a clear hole cannot be formed.

Among them, Examples 27 to 36 and 62 to 83 evaluate the resolution in the following manner.

A: A non-exposed portion of a circular shape of 50 μm has been opened.

B: The non-exposed portion of a circular shape of 70 μm was opened, but the non-exposed portion of a circular shape of 50 μm was not opened.

C: Both the non-exposed portion of a circular shape of 70 μm and the non-exposed portion of a circular shape of 50 μm were not opened.

In Example 1 and Comparative Example 2, evaluation was also carried out in the following cases: in the development treatment at the time of producing the test piece, in the state where the film was immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C, The film was vibrated for 60 seconds, and pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

(4-4) Plating resistance

First, on the exposed portions of the conductor traces of the test pieces of the examples and the comparative examples, a commercially available electroless nickel bath was used to form a nickel plating layer, and a commercially available electroless gold bath was used to form a gold plating layer. Thereby, a metal layer composed of a nickel plating layer and a gold plating layer is formed. Visually observed by the hardened material Layer and metal layer. Further, a cellophane adhesive tape peeling test was carried out on the layer composed of the cured product. The results were evaluated in the following manner.

A: The appearance of the layer composed of the cured product and the metal layer could not be confirmed to be abnormal, and the peeling of the metal layer due to the cellophane adhesive tape peeling test did not occur.

B: Discoloration was confirmed in the layer composed of the cured product, but the peeling of the metal layer due to the cellophane adhesive tape peeling test did not occur.

C: It was confirmed that the layer composed of the cured product floated, and the peeling of the metal layer due to the peeling test of the cellophane adhesive tape occurred.

With respect to Example 1 and Comparative Example 2, evaluation was also carried out in the following cases: in the state of developing treatment at the time of producing a test piece, the film was immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C, first The film was vibrated for 60 seconds, and pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

(4-5) Insulation between wires

A conductor circuit (comb electrode) in the test piece of the embodiment and the comparative example was applied with a direct current (DC) bias voltage of 30 V, and the printed wiring board was exposed to 121 ° C and a relative humidity of 97% ( The test environment of RH) was 150 hours (100 hours for Examples 27 to 36, 90 to 97, and Comparative Example 5). The resistance value between the comb-shaped electrodes of the layer composed of the cured product was continuously measured in this test environment, and the results were evaluated in accordance with the following evaluation criteria.

A: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to 150 hours (100 hours in the case of Examples 27 to 36, 90 to 97, and Comparative Example 5).

B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 100 hours (80 hours for the examples 27 to 36, 90 to 97, and the comparative example 5), but the test was started. The resistance value was less than 10 ⁶ Ω until 150 hours (100 hours for the examples 27 to 36).

C: The resistance value was less than 10 ⁶ Ω from the start of the test to 100 hours (in the case of Examples 27 to 36, 90 to 97, and 80 hours in Comparative Example 5).

In Example 1 and Comparative Example 2, evaluation was also carried out in the following cases: in the development treatment at the time of producing the test piece, in the state where the film was immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C, The film was vibrated for 60 seconds, and pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

(4-6) interlayer insulation

Conductive tape was adhered to the layer composed of the cured material in the test pieces of the examples and the comparative examples. While applying a bias voltage of DC 100 V to the conductive tape, the printed wiring board was exposed to a test environment of 121 ° C and 97% RH for 60 hours (in the case of Examples 27 to 36, 90 to 97, and Comparative Example 5, 50 hours). Continuous measurement in the test environment by hardening The resistance value between the conductor line of the layer formed by the object and the conductive tape was evaluated according to the following evaluation criteria.

A: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test to the lapse of 60 hours (40 hours in the case of Examples 27 to 36, 90 to 97, and Comparative Example 5).

B: The resistance value was maintained at 10 ⁶ Ω or more from the start of the test until 50 hours (in the case of Examples 27 to 36, 90 to 97, and 30 hours in Comparative Example 5), but the test was started. The resistance value was less than 10 ⁶ Ω until 60 hours (40 hours for Examples 27 to 36).

C: The resistance value was less than 10 ⁶ Ω from the start of the test to 50 hours (30 hours in the case of Examples 27 to 36, 90 to 97, and Comparative Example 5).

With respect to Example 1 and Comparative Example 2, evaluation was also carried out in the following cases: in the state of developing treatment at the time of producing a test piece, the film was immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C, first The film was vibrated for 60 seconds, and pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

(4-7) Pressure cooker test (PCT)

The test pieces of the examples and the comparative examples were placed in an environment of 121 ° C and 100% RH for 100 hours (50 hours for the cases of Examples 27 to 36), and then evaluated by the hardened materials according to the following evaluation criteria. The appearance of the layer.

A: No abnormality was observed in the layer composed of the cured product.

B: Discoloration was observed in the layer composed of the cured product.

C: A large discoloration was observed in the layer composed of the cured product, and a part of the expansion occurred.

In Example 1 and Comparative Example 2, evaluation was also carried out in the following cases: in the development treatment at the time of producing the test piece, in the state where the film was immersed in a 1.2% tetramethylammonium hydroxide solution at 28 ° C, The film was vibrated for 60 seconds, and pure water was sprayed at a spray pressure of 0.2 MPa for 90 seconds. In Table 5, the evaluation when using a 1% aqueous sodium carbonate solution is shown on the left side, and the evaluation when using a 1.2% tetramethylammonium hydroxide solution is shown on the right side.

(4-8) Solder heat resistance

A water-soluble flux (manufactured by London Chemical Co., Ltd., trade name LONCO 3355-11) was applied to the test pieces of Examples 27 to 36, and the test piece was then immersed in a molten solder bath at 260 ° C for 10 seconds, followed by washing with water. . This series of operations was repeated three times, and then the appearance of the layer (the solder resist layer) composed of the cured material in the test piece was observed, and evaluated according to the following evaluation criteria.

A: No abnormality can be observed.

B: Discoloration of the layer composed of the cured product can be observed.

C: It was observed that the layer composed of the cured product was peeled off.

(4-9) low temperature stability

The photosensitive resin compositions of Examples 62 to 83 were stored at 3 ° C for 7 days. When the storage was started, it was confirmed whether or not the crystalline epoxy resin in the photosensitive resin was crystallized after passing through the weather for one day, and the evaluation was carried out in accordance with the following evaluation criteria.

A: When the crystallization of the crystalline epoxy resin was not confirmed, the photosensitive resin composition was kept in a uniform state.

B: When the crystallization of the crystalline epoxy resin was not observed, the photosensitive resin composition was kept in a uniform state, but the crystallization was confirmed after 5 days, and the photosensitive resin was observed. The composition has become uneven.

C: When one day passed at 3 ° C, crystallization was confirmed, and the photosensitive resin composition had become uneven.

(4-10) Glass transition temperature

In Examples 90 to 97 and Comparative Example 5, a layer composed of a cured product was formed on a member made of Teflon (registered trademark). The method of forming the layer composed of the cured product is the same as that in the case of forming a layer composed of a cured product in the test piece. The layer composed of the cured material was first peeled off from the member, and the glass transition temperature of the layer was measured by Thermal Mechanical Analysis (TMA).

The results of the above evaluation tests are shown in Tables 4 to 14 below.

In addition, the "crystalline epoxy E/A having a melting point of less than 100 ° C" in Tables 11 and 12 is an epoxy resin contained in a crystalline epoxy resin having a melting point of less than 100 ° C with respect to the carboxyl group-containing resin (A). The equivalent of the base; the "crystalline epoxy E/A having a melting point of 100 ° C or higher" is equivalent to the epoxy group contained in the crystalline epoxy resin having a melting point of 100 ° C or higher with respect to the carboxyl group-containing resin (A); The oxygen overall E/A" is an equivalent of the epoxy group contained in the epoxy compound (D) with respect to the carboxyl group-containing resin (A).

[Table 1]

[Table 2]

[table 3]

[Table 4]

[table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

[Table 14]

According to the above-described embodiment, the carboxyl group-containing resin (A1) of the first aspect is a reactant of an intermediate, an acid dianhydride (a3) and an acid anhydride (a4), and the intermediate is an epoxy compound ( A1) a reaction product with an unsaturated carboxylic acid (a2), wherein the epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the following formula (1), in the formula (1) R ₁ to R ₈ are each independently hydrogen, an alkyl group having 1 to 5 carbon atoms, or a halogen, and the polydispersity of the carboxyl group-containing resin is in the range of 1.2 to 2.8.

In the carboxyl group-containing resin (A1) of the second aspect, for the first aspect, the weight average molecular weight of the carboxyl group-containing resin is in the range of 1,000 to 5,000.

In the first or second aspect, the solid content acid value of the carboxyl group-containing resin (A1) is preferably in the range of 60 to 140 mgKOH/g.

The carboxyl group-containing resin (A1) of the third aspect, the carboxyl group-containing resin having the following molecular weight distribution for the second aspect: the area of the region having a molecular weight of 200 or more and less than 1700 under the GPC elution curve and the GPC elution curve The ratio of the area of the region having a molecular weight of 1700 or more is in the range of 1:0.5 to 1:2.5.

In the carboxyl group-containing resin (A1) of the fourth aspect, the acid anhydride (a4) contains 1,2,3,6-tetrahydroortylene for any of the first to third aspects. Formic anhydride.

In the carboxyl group-containing resin (A1) of the fifth aspect, the acid dianhydride (a3) contains 3,3',4,4'-biphenyl IV for any of the first to fourth aspects. Formic acid dianhydride.

In the carboxyl group-containing resin (A1) of the sixth aspect, for any of the first to fifth aspects, the acid anhydride is relative to 1 mol of the epoxy group of the epoxy compound (a1) ( The amount of a4) is in the range of 0.3 to 0.7 mol.

In the carboxyl group-containing resin (A1) of the seventh aspect, for any of the first to sixth aspects, the acid dianhydride is (1 mol) with respect to the epoxy compound (a1). The amount of a3) is in the range of 0.05 to 0.24 moles.

An eighth aspect of the photosensitive resin composition comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; and a photopolymerization initiator (C) And an epoxy compound (D); wherein the carboxyl group-containing resin (A) contains the carboxyl group-containing resin (A1) in any of the first to seventh aspects.

In the ninth aspect, the photosensitive resin composition has the property that the photosensitive resin composition having a thickness of 25 μm can be developed by an aqueous solution of sodium carbonate.

In the photosensitive resin composition of the tenth aspect, in the eighth or ninth aspect, the unsaturated compound (B) contains a compound having three unsaturated bonds in one molecule.

In the photosensitive resin composition of the eleventh aspect, the epoxy compound (D) contains a crystalline epoxy resin in any of the eighth to tenth aspects.

In the eleventh aspect, the content of the unsaturated compound (B) may be in the range of 21 to 40% by mass based on the carboxyl group-containing resin (A).

In the photosensitive resin composition of the twelfth aspect, in the eleventh aspect, the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of 110 ° C or lower.

In the eleventh or twelfth aspect, the crystalline epoxy resin may contain a crystalline epoxy resin having a melting point of less than 100 °C.

In the photosensitive resin composition of the thirteenth aspect, the photopolymerization initiator (C) contains a mercaptophosphine oxide-based photopolymerization initiator for any of the eighth to twelfth aspects. (C1).

In the photosensitive resin composition of the fourteenth aspect, in the thirteenth aspect, the photopolymerization initiator (C) contains a hydroxyketone photopolymerization initiator (C2).

In the photosensitive resin composition of the fifteenth aspect, the photopolymerization initiator (C) contains bis(diethylamino)diphenyl ketone (C3) for the thirteenth or fourteenth aspect. .

In the fourteenth or fifteenth aspect, the mass ratio of the fluorenylphosphine oxide-based photopolymerization initiator (C1) to the hydroxyketone-based photopolymerization initiator (C2) may be from 1:0.01 to 1: Within the scope of 10.

In a sixteenth to fifteenth aspect, the photosensitive resin composition contains the component (E) containing melamine and melamine derived, in any one of the eighth to fifteenth aspects. At least one of the things.

The dry film of the seventeenth aspect is a dried matter of the photosensitive resin composition of any of the eighth to sixteenth aspects.

An eighteenth aspect of the printed wiring board comprising an interlayer insulating layer comprising a cured product of the photosensitive resin composition of any of the eighth to sixteenth aspects.

A printed wiring board according to a nineteenth aspect, comprising: a solder resist layer comprising a cured product of the photosensitive resin composition of any of the eighth to sixteenth aspects.

The twentieth aspect manufacturing method is a method for producing a carboxyl group-containing resin (A1) having a polydispersity in the range of 1.2 to 2.8, which comprises the steps of: bringing an epoxy compound (a1) and an unsaturated group-containing carboxyl group a step of obtaining an intermediate by reacting an acid (a2); and a step of synthesizing the intermediate, the acid dianhydride (a3) and the acid anhydride (a4) to synthesize a carboxyl group-containing resin (A1); wherein the ring The oxygen compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the formula (1). In the formula (1), R ₁ to R ₈ are each independently hydrogen and an alkyl group having 1 to 5 carbon atoms. Or halogen.

In the method for producing a carboxyl group-containing resin according to the twenty first aspect, the weight average molecular weight of the carboxyl group-containing resin (A1) in the twentieth aspect is in the range of 1,000 to 5,000.

In the method for producing a carboxyl group-containing resin according to the twenty-second aspect, in the twentieth or twenty-first aspect, the carboxyl group-containing resin has a molecular weight distribution having a molecular weight of 200 or more under a GPC elution curve and The ratio of the area of the region of less than 1700 to the area of the region having a molecular weight of 1700 or more under the GPC elution curve is in the range of 1:0.5 to 1:2.5.

In the method for producing a carboxyl group-containing resin according to the twenty-third aspect, for any of the twentieth to twelfth aspects, the 1 mol of the epoxy group relative to the epoxy compound (a1) The amount of the acid anhydride (a4) is in the range of 0.3 to 0.7 mol.

In the method for producing a carboxyl group-containing resin according to the twenty-fourth aspect, for any of the twentieth to twenty-third aspect, the 1 mol of the epoxy group relative to the epoxy compound (a1) The amount of the acid dianhydride (a3) is in the range of 0.05 to 0.24 moles.

In the method for producing a carboxyl group-containing resin according to the twenty-fifth aspect, the epoxy compound (a1) and the unsaturated carboxylic acid (a2) are used in any one of the twentieth to twenty-fourth aspects. The reaction is carried out in the presence of triphenylphosphine.

In the method for producing a carboxyl group-containing resin according to the twenty-sixth aspect, the intermediate, the acid dianhydride (a3), and the acid anhydride (a4) are used in any one of the twentieth to twenty-fifth aspect. The reaction is carried out in the presence of triphenylphosphine.

1‧‧‧ core material

2‧‧‧Insulation

3‧‧‧Conductor line (first conductor line)

4‧‧ ‧ film

5‧‧‧Unexposed parts

6‧‧‧ hole

7‧‧‧Interlayer insulation

8‧‧‧Second conductor line

9‧‧‧Perforated plating

10‧‧‧through holes

11‧‧‧Printed circuit board

Claims (26)

a carboxyl group-containing resin which is a reactant of an intermediate, an acid dianhydride (a3) and an acid anhydride (a4), which is a reaction product of an epoxy compound (a1) and an unsaturated group-containing carboxylic acid (a2). The epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the following formula (1): in the following formula (1), R ₁ to R ₈ are each independently hydrogen and carbon. a number of 1 to 5 alkyl groups or halogens, and the polydispersity of the carboxyl group-containing resin is in the range of 1.2 to 2.8, The carboxyl group-containing resin according to claim 1, wherein the carboxyl group-containing resin has a weight average molecular weight in the range of from 1,000 to 5,000. The carboxyl group-containing resin according to claim 2, wherein the carboxyl group-containing resin has a molecular weight distribution: an area of a region having a molecular weight of 200 or more and less than 1700 under a GPC elution curve and a molecular weight of 1700 or more under a GPC elution curve. The ratio of the area of the area is 1:0.5 ~1:2.5 in the range. The carboxyl group-containing resin according to claim 1 or 2, wherein the acid monoanhydride (a4) contains 1,2,3,6-tetrahydrophthalic anhydride. The carboxyl group-containing resin according to claim 1 or 2, wherein the acid dianhydride (a3) contains 3,3',4,4'-biphenyltetracarboxylic dianhydride. The carboxyl group-containing resin according to claim 1 or 2, wherein the amount of the acid anhydride (a4) is in the range of 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). Inside. The carboxyl group-containing resin according to claim 1 or 2, wherein the amount of the acid dianhydride (a3) is in the range of 0.05 to 0.24 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). Inside. A photosensitive resin composition comprising: a carboxyl group-containing resin (A); an unsaturated compound (B) having at least one ethylenically unsaturated bond in one molecule; a photopolymerization initiator (C); The oxygen-containing compound (D), wherein the carboxyl group-containing resin (A) contains the carboxyl group-containing resin (A1) according to any one of claims 1 to 7. The photosensitive resin composition according to claim 8, wherein the photosensitive resin composition has a property that a film of a photosensitive resin composition having a thickness of 25 μm can be subjected to an aqueous solution of sodium carbonate. development. The photosensitive resin composition according to claim 8 or 9, wherein the unsaturated compound (B) contains a compound having three unsaturated bonds in one molecule. The photosensitive resin composition according to claim 8 or 9, wherein the epoxy compound (D) contains a crystalline epoxy resin. The photosensitive resin composition according to claim 11, wherein the crystalline epoxy resin contains a crystalline epoxy resin having a melting point of 110 ° C or lower. The photosensitive resin composition according to claim 8 or 9, wherein the photopolymerization initiator (C) contains a fluorenylphosphine oxide-based photopolymerization initiator (C1). The photosensitive resin composition according to claim 13, wherein the photopolymerization initiator (C) contains a hydroxyketone photopolymerization initiator (C2). The photosensitive resin composition according to claim 13 or 14, wherein the photopolymerization initiator (C) contains bis(diethylamino)diphenyl ketone (C3). The photosensitive resin composition according to claim 8 or 9, wherein the photosensitive resin composition further contains a component (E) containing at least one of melamine and a melamine derivative. A dry film which is a dried product of the photosensitive resin composition according to any one of claims 8 to 16. A printed wiring board comprising an interlayer insulating layer, wherein the interlayer insulating layer comprises a cured product of the photosensitive resin composition according to any one of claims 8 to 16. A printed wiring board comprising a solder resist layer, wherein the solder resist layer contains a cured product of the photosensitive resin composition according to any one of claims 8 to 16. A method for producing a carboxyl group-containing resin, which is a method for producing a carboxyl group-containing resin (A1) having a polydispersity in the range of 1.2 to 2.8, which comprises the steps of: an epoxy compound (a1) and an unsaturated carboxylic acid-containing compound (a2) a step of reacting to obtain an intermediate; and a step of reacting the intermediate, the acid dianhydride (a3) and the acid anhydride (a4) to synthesize the carboxyl group-containing resin (A1); The epoxy compound (a1) has a bisphenol fluorene skeleton, and the bisphenol fluorene skeleton is represented by the following formula (1), and in the following formula (1), R ₁ to R ₈ are each independently hydrogen, An alkyl group having 1 to 5 carbon atoms, or a halogen, The method for producing a carboxyl group-containing resin according to claim 20, wherein the carboxyl group-containing resin (A1) has a weight average molecular weight of from 1,000 to 5,000. The method for producing a carboxyl group-containing resin according to claim 20, wherein the carboxyl group-containing resin has a molecular weight distribution: an area of a region having a molecular weight of 200 or more and less than 1700 under a GPC elution curve and a GPC elution curve. The ratio of the area of the region having a molecular weight of 1700 or more is in the range of 1:0.5 to 1:2.5. The method for producing a carboxyl group-containing resin according to claim 20, wherein the amount of the acid anhydride (a4) is from 0.3 to 0.7 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). Within the range of the ear. The method for producing a carboxyl group-containing resin according to claim 20, wherein the amount of the acid dianhydride (a3) is 0.05 to 0.24 mol with respect to 1 mol of the epoxy group of the epoxy compound (a1). Within the range of the ear. The preparation of the carboxyl group-containing resin as described in claim 20 or 21 In the method, the reaction of the epoxy compound (a1) with the unsaturated group-containing carboxylic acid (a2) is carried out in the presence of triphenylphosphine. The method for producing a carboxyl group-containing resin according to claim 20, wherein the reaction of the intermediate, the acid dianhydride (a3) and the acid anhydride (a4) is carried out in the presence of triphenylphosphine. .